Citation
Studies in the chemistry of cyclic and acyclic nitrogen compounds

Material Information

Title:
Studies in the chemistry of cyclic and acyclic nitrogen compounds
Creator:
White, Roslyn Lorraine, 1967-
Publication Date:
Language:
English
Physical Description:
vii, 179 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Amines ( jstor )
Carbon ( jstor )
Imines ( jstor )
Ions ( jstor )
Mass spectroscopy ( jstor )
Molecular ions ( jstor )
Nitrogen ( jstor )
Piperidines ( jstor )
Pyridines ( jstor )
Triazoles ( jstor )
Chemistry thesis, Ph. D
Dissertations, Academic -- Chemistry -- UF
Organonitrogen compounds ( lcsh )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1995.
Bibliography:
Includes bibliographical references (leaves 170-178).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Roslyn Lorraine White.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
002052093 ( ALEPH )
33448219 ( OCLC )
AKP0054 ( NOTIS )

Downloads

This item has the following downloads:


Full Text













STUDIES IN THE CHEMISTRY OF
CYCLIC AND ACYCLIC NITROGEN COMPOUNDS











By

ROSLYN LORRAINE WHITE


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

1995



























To my husband, Abdul, for his loving support














ACKNOWLEDGEMENTS


First and foremost, I would like to give praises to the Almighty God,


whom al


without


life would not be possible.


Secondly, I would like to thank my supervisor, Dr. Alan R Katritzky, for allowing


me the opportunity to become a member of his research group.


gratitude for his guidance during my stay here.


I would also like to express


I would especially like to thank him for


challenging me, for it is those challenges which have pushed me to look deep within myself

and to strive to become a better, stronger chemist.

For the time spent and helpful suggestions given, I would like to express sincere


thanks to my supervisory committee members, Dr


James A.


Deyrup, Dr.


William R.


Dolbier


Vaneica Young and Dr. Jonathan F. K. Earle.


I would also like to express special thanks to Dr. Richard A.


Barcock and Dr.


Steven M. Allin for their help over the years.


Also special


thanks go to


Elena S.


Ignatchenko.

It has been a rather unique experience working with the members of the Katritzky

Research Group and these memories will remain with me always.

I am truly grateful to my entire and extended family and friends for their love and

support.


Finally,


forever


indebted


husband,


Abdul


whose


love,


understanding, support and encouragement has been a constant source of inspiration.










TABLE OF CONTENTS


page


ACKNOWLEDGEMENTS.

ABSTRACT.


CHAPTERS


GENERAL INTRODUCTION.


General Introduction to Nitrogen Compounds.
Introduction. .


FIRST DEMONSTRATION OF SPECIFIC C-C BOND SCISSION
OF THE PYRIDINE RING: REACTIONS OF PIPERIDINE, PYRIDINE
AND SOME OFTHEIR METHYLDERIVATIVES.


Introduction. .
Synthesis of Compounds.
Results.
General Discussion.
Conclusions.
Experimental. .


REACTIONS OF VARIOUS ALIPHATIC AMINES WITH FORMIC
ACID: 1-OCTYLAMINE, DI-1-OCTYLAMINE, N,N-DIMETHYL-
OCTYLAMINE, 1-DODECYLAMINE AND N,N-DIMETHYL-1-
DODECYLAMINE.. .


Introduction.
Synthesis of Compounds.
Results.
General Discussion.
Conclusions.
Experimental. .










IV BENZOTRIAZOLE-1-CARBOXAMIDINIUM TOSYLATE:
ANALTERNATIVE METHOD FOR THE CONVERSION OF AMINES
TO GUANIDINES.. 76

Introduction 76
Results and Discussion. 81
Conclusions. 86
Experimental.. 87

V INVESTIGATIONS OF 4-AMINO-1,2,4-TRIAZOLE: APPROACHES
TO THE DEVELOPMENT OF A NEW ELECTROPHIIC AMINATING
AGENT & METHODOLOGY FOR THE PREPARATION OF
4-(ALKYLAMINO)- 1,2,4-TRIAZOLES. 93

Introduction. . 93
Results and Discussion. 99
Conclusions. 117
Experimental. 119


APPENDICES

A MASS SPECTRAL FRAGMENTATION PATTERNS OF
PIPERIDINE PRODUCTS. 126

B MASS SPECTRAL FRAGMENTATION PATTERNS OF
ALIPHATIC PRODUCTS. 144

C X-RAY CRYSTAL STRUCTURE OF
BENZOTRIAZOLE-1-CARBOXAMIDINIUMTOSYLATE. 166


REFERENCES. 170


BIOGRAPHICAL SKETCH. 179













Abstract of Dissertation Presented to the Graduate School of the University of Florida in
Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy

STUDIES IN THE CHEMISTRY
OF CYCLIC AND ACYCLIC NITROGEN COMPOUNDS


By

Roslyn Lorraine White


May


Chairman:


1995


Alan R. Katritzky, FRS


Major Department: Chemistry


Formic acid variously acts as a formylating, methylating, reducing and oxidizing

agent in its reactions with piperidine, pyridine and some of their methyl derivatives under


aquathermolysis conditions.


Both pyridine and piperidine are converted in significant


amounts into 1-methyl-,


1-ethyl-,


1-propyl-


and 1-pentyl-piperidines.


1-alkyl


groups, isotopic labelling shows that only 1-methyl derives from the formic acid, while the

1-ethyl and 1-propyl arise from heterocyclic ring C-C bond fission by retro-vinylogous-

bis-aza-Aldol reactions. Detailed analysis of the products for pyridine, piperidine, and their

4-methyl derivatives, reacted separately and mixed, supports mechanisms in which a


piperidine adds 1


to a pyridinium cation, or to a di-


or tetra-hydropyridine, to initiate


reaction sequences leading to the product slates found.


Two primary aliphatic amines (1-octylamine,


1-dodecylamine),


one secondary


aliphatic amine (di-1-octylamine) and two tertiary aliphatic amines (N


,N-dimethyl-1-









dominant reaction pathways viz., (i) N-formylation with subsequent reduction to give N-
methyl- and N,N-dimethyl-alkylamines, and (ii) elimination of NH3 and smaller amines to


the corresponding alkenes followed by partial double bond isomerization.


The secondary


amine mainly underwent conventional N-formylation with subsequent reduction to the N-


methyl derivative.


Tertiary amines underwent reductive cleavages to secondary and


primary amines, which subsequently followed the reaction sequences seen for primary

amines.

Benzotriazole-1-carboxamidinium tosylate was synthesized from benzotriazole,


cyanamide and


p-toluenesulfonic acid.


This tosylate salt underwent nucleophilic


displacement of the benzotriazole anion by various primary and secondary amines to

generate substituted guanidines under mild conditions.

Two derivatives of 4-amino-l,2,4-triazole were synthesized and their chemistries


investigated.


Condensation of 4-amino-l,2,4-triazole and fluorenone led to N-(1


triazol-4-yl)fluorenimine.


aminating agent.


This novel imine was investigated as a potential electrophilic


4-(Benzotriazol-l-ylmethylamino)-1,2,4-triazole was synthesized by the


condensation of 4-amino-l,2,4-triazole and hydroxymethylbenzotriazole.


This adduct


undergoes nucleophilic displacement by Grignard reagents to generate 4-(alkylamino)-

1,2,4-triazoles.














CHAPTER I
GENERAL INTRODUCTION



General Introduction to Nitrogen Compounds


Nitrogen is one of the principal elements in all living creatures.


Therefore, nitrogen


containing compounds are ubiquitous in nature.


A large number of


medically and


biologically important compounds are N-compounds--in particular various amines and


amino acids.


Many of these compounds have powerful physical and psychological effects.


Nitrogen compounds are also important industrially.


The petrochemical industry provides


raw materials for liquid petroleum and natural gas feed stocks in the form of amines, nitro-


compounds, heterocyclic N-compounds, dyes, drugs etc.


Due to the importance of


nitrogen to the growth of plants and animals, it is not surprising that nitrogen compounds

(particularly fertilizers) rank very high in total annual commercial production. The

objective of this dissertation is to investigate the chemistry of cyclic and acyclic nitrogen

compounds, for which the results will be reported in the following four chapters.



Introduction


Chapters II and III deal with the aquathermolysis


of various classes of nitrogen


compounds.


Chapter II focuses upon the aquathermolysis of piperidine,


pyridine and


some of their methyl derivatives,


while chapter III deals with the aauathermolvsis


-a





2


can be used to remove the deleterious nitrogen compounds found in crude petroleum and

synthetic oils. Normally, organic compounds do not react with water under standard

reaction conditions. However, organic molecules which are unreactive in liquid water can

be subjected to many chemical reactions when the temperature of water is raised to 250 *C -


350 oC.


Compounds such as ethers (1


-001) and esters (1


-002) undergo cleavage and


hydrolysis,


respectively, with ease [90EF488] (Scheme 1


the above reactions):


catagenesis, takes place in nature.


An analogous process (to


Catagenesis, is the process by


which cross-linked macromolecular structures (solid petroleum kerogens) are converted in


source rock into liquid petroleum.


In nature, catagenesis has a time frame of millions of


years, and occurs at temperatures less than 200 *C,


in aqueous environments at about


61MPa of pressure [91SCI231].


HO


-O-R1
-001


- 3500C


R-H


+ HO


cleavage products


H20


-0-


- 350C


-OH


+ "OR1


-002


hydrolysis
products


RC-


Scheme 1-1


When water is heated at elevated temperatures significant changes in its physical

and chemical properties take place. As the temperature of water is increased from 25 to 350

*C the following changes take place:
/\; ,'m.A j4, gf ^,f ,4.., /l/^. ^ /,Fn, <-/^-. f\ rw7 *- / ,'1I l-- -^ to1 jr rT ,-n


-R1


-R1





3


The physical changes allow water at 300 C to behave similar to acetone at


[91SCI231],


creating an environment for ionic reactions.


Chapter IV discusses the synthesis of benzotriazol


e- 1-carboxamidinium tosylate


and the related application of benzotriazole methodology in the synthesis of guanidines


from amines.


A useful synthetic auxiliary, benzotriazole (1


-003) and its chemistry has


been exploited within the Katritzky research laboratories and has also found favorable use


industrially.


The N-N double bond of benzotriazole has strong electron-withdrawing


ability which enhances the acidic properties and therefore transforms the benzotriazole


anion into an excellent leaving group.


A wide variety of organic compounds including


primary,


secondary


tertiary


amines,


hydroxylamines,


hydrazines,


amides,


polyfunctional amino compounds, ethers and esters have been synthesized [91T2683].


N-N

N
I
NH2


-003


The structurally related 4-amino-1,2,4-triazole (1


-004


-004) has also been investigated.


This amino-triazole can be condensed with ketones to generate the corresponding imine. In

addition, this triazole can also be condensed with benzotriazole and formaldehyde to


generate the corresponding benzotriazole-triazole adduct.


Chapter VI deals with the


derivatization of 4-amino-l,2,4-triazole and its application in the attempted synthesis of


imines and 4-(alkylamino)-1


,4-triazoles.















CHAPTER II
FIRST DEMONSTRATION OF SPECIFIC C-C BOND SCISSION OF THE PYRIDINE
RING: REACTIONS OF PIPERIDINE, PYRIDINE AND SOME OF THEIR METHYL
DERIVATIVES IN AQUEOUS FORMIC ACID



Introduction


Nitrogen, sulfur and oxygen are among the heteroatoms which are found in coals


[92EF439].


In order to convert solid coals and oil shale kerogens to liquids which can be


used as synthetic fuels (the) cross-links of the above mentioned heteroatoms need to be


broken. This process of the liquification of coal normally requires a variety of catalysts

[89EF160]. Unfortunately, a specific catalyst is required for the removal of a specific


heteroatom and can become quite costly.


Liquids derived from N-containing coals often contain large amounts of N-

impurities [84MI]. Compounds which contain nitrogen are detrimental for the following

three reasons:-

(i) they poison and deactivate catalyst used later in refining processes,

(ii) they form toxic nitrogen oxides upon combustion, and

(iii) they confer instability on the product fuel, causing discoloration and other

detrimental reactions [92EF439, 93TL4739].

The nitrogen-containing compounds found in petroleum or synthetic oils include both

heterocycles, for example pyridines and pyrroles, and non-heterocycles such as aliphatic


amines


With N-heterocvcles. the normal mode of removal has been denitrogenation


r
I


~~l.





5


hydrogenolysis of strong aromatic C-N bonds which subsequently requires significant

prehydrogenation of the heteroaromatic and/or aromtic rings [92EF439].

Extensive investigations have been carried out within the Katritzky Research Group

on nitrogen removal from heterocyclic nitrogen model compounds in aqueous systems


[92EF439, 92EF450].


Formally, we have been investigating the aquathermolysis2.1


- i.e.


thermal transformations of organic compounds in aqueous environments


- of a variety of


N-compounds.


Recently, we found that at 350 *C,


49% aqueous formic acid induces the


hydrogenation of the pyridine ring to piperidine in significant amounts and also induces the


scission of the pyridine ring [93TL4739].


Over the last 50 years, much evidence has


accumulated that the common heterocycles can undergo (often reversibly) ring opening


under a variety of conditions.


However, all examples involve the scission of heteroatom-


carbon


bonds;


the analogy


been


made of heterocycles as carbon chains


with


heteroatoms as padlocks which enable opening by a suitable key.

We set out to propose appropriate mechanistic pathways for the various products of

pyridine ring scission, by synthesizing authentic compounds and investigating their


authentic mass spectral


fragmentation


pathways to


confirm


products


aquathermolysis runs.


2.2,2.3 Therefore, we studied the effect of 49% aqueous formic acid


on piperidine (2-004)2.4


, 1-methylpiperidine (2-007),


4-methylpiperidine (2-008),


pyridine (2-005) and 4-methylpyridine (2-012) (Scheme


The work to be described


had its origin in our extensive studies [92EF439, 92EF450] of hydrodenitrogenation of

2.1 This project formed part of a joint collaboration between the Katritzky Research Group at the
University of Florida and groups at Exxon Research and Engineering Co.
2.2 All aquthermolysis reactions were conducted jointly by Mamudai Balasubramanian, Richard A.


Barcock and Elena S.


Ignatchenko at the University of Florida.


A.-- L


~ll..,rt,~. ,E,,,,,..,1, ,,~ ...I,, ,.,,I,,,,,, _-~-1 1~~.~-Il__rl_.__!.~ .._1_.~~1 d









heteroaromatic models of compounds found in fuel resource streams.


In addition to


reporting the unique behavior of these compounds under aquathermolysis conditions, we


now


disclose


first examples of


specific


C-C-bond


scission


unactivated


heterocyclic system of pyridine,


and demonstrate how the long-studied


ndustrially


important processes by which pyridine rings are formed from C1,


2 and C3 aldehydes are


in principle reversible.


2-004


2-005


2-007


2-008


2-012


Scheme


The gas chromatographic (GC) behavior (retention times) of all the compounds

employed in this study (starting materials and products) are summarized in Table 2-1.2.5


Tables

results.


Table


, and 2-4 contain the compiled mass spectral data for the analysis of the

.-2 contains the sources and purities of the starting materials used and have


been compiled based upon the direct comparison of the GC retention times, and of the mass


spectral (MS) fragmentation patterns with those of the authentic compounds.


Table 2-3


contains compounds which have been compared with literature mass spectral data for the


same compound.


Those compounds for which no suitable literature MS data were


available


have


been


identified


fragmentation


patterns (obtained from


aquathermolysis runs) and have been compiled in Table 2-4.


Further explanation of the


Tables


--2-4


given


in section


Experimental.


results


from


from










Table 2-1.


Structure and Identification of Starting Materials and Products.


tR (min)


Structure


Eq. Wt


Basis a


Factor b


2-001

2-002

2-003

2-004

2-005

2-006

2-007

2-008

2-009

2-010

2-011

2-012


potenne

3-methyl- 1-pentene

pentyiamine

pperidine

pyridine

1-(13C)-methylpiperidine

1-methylpiperidine

4-methylpiperidine

N,N-dimethylpentylamine

1,4-dimethylpiperidine

1-ethylpiperidine

4-methylpyridine


Table 2-2

Table 2-2

Table 2-2

Table 2-2

Table 2-2

Table 24

Table 2-2

Table 2-2

Table 24

Table 2-2

Table 2-2

Table 2-2


2-013


N,N-dimethyl-2-
methylpentylamine


Table 24


2-014

2-015


l-ethyl-4-methylpiperidine


Table 24

Table 2-4


1 -propylpiperidine


2-016


1-popyl-4-methylpiperidine


2-017


l-butylpiperidine


2-018


1-butyl-4-methylpiperidine


2-019

2-020

2-021


1-(2-methylbutyl)piperidine

1-pentylpiperidine

1-(pent-4-en-yl)piperidine

1-(13C)-formylpiperidine

1-formylpipezidine


2-022

2-023


Table 2-4


Table 2-3


Table 24


Table 2-4

Table 2-3

Table 24


Table 2-4

Table 2-2





8




Table 2-- 1 continued


tR (min)


Structure


Eq. Wt


Basis a


Factor b


2-027


1-formyl-4-methylpiperidine


Table 2-4


2-028


l-(3-methylpentyl)-4
-methylpiperidine


2-029

2-030


Table 2-4


1-(5aminopentyl)piperidine

1-acetyl-4-methylpiperidine


Table 2-4

Table 2-4


2-031


1-(3-methyl-5-aminopentyl)-4
-methylpiperidine


Table 24


tR (min)


Retention time in minutes. MW = molecular weight. Eq. Wt = equivalent weight.


a = Identification Basis, see appropriate tables. b = Response Factor, see ref [89TCM17].










Table


Authentic Compounds Used as Starting Materials and for the Identification
of Products.


Compound


Purity


m/z (% relative intensity)


Ref. b
spectra#


2-001


pentene


70(35); 55(60); 42(100); 41(45);
39(35)


2-002

2-003

2-004


2-005


2-007


2-008


3-methyl-l-pentene


pentylamine

piperidine


84(30); 69(80); 55(100); 41(80)

87(5); 70(3); 55(2); 42(3); 30(100)

85(55); 84(100); 70(10); 56(40);
55(45)


pyridine


79(60); 55(20); 52(100); 50(60);
44(70)


1-methylpiperidine


99(35); 98(100); 84(10); 70(30);
58(10)


4-methylpiperidine


99(60); 98(95); 84(40); 70(10);
56(100)


67826


68696


68691


2-009


N.N-dimethyl
pentylamine


115(6); 58(100); 44(4); 42(10)


2-010

2-011


1,4-dimethylpiperidine

1-ethylpiperidine


113(10); 112(100); 98(5); 70(20)

113(25); 112(20); 98(100); 84(10)


80481

3071


2-012


4-methylpyridne


93(100); 66(50); 65(25);


51915)


68420


2-013


N,N-dimethyl-
2-methylpentylamine


129(5); 100(5); 86(10); 58(100)


2-019


-(2-methylbutyl)-


piperidine


155(7); 98(100); 84(10); 70(6); 56(10)


2-023


1 -formylpiperidine


13(100); 112(50); 103(30); 98(50)


2-024


1-(3-methylpentyl)-


piperidine


2-026


1-acetylpiperidine


MW = molecular weight. a A


1690); 154(9); 98(100); 84(5); 70(4)


127(100); 112(20); 84(45); 70(25);
56(30)


= Aldrich, S = synthesized authentic compound (see experimental section).


b spectral numbers of the mass spectral data for the compounds found from a search of the Wiley











Q^.o



4> 0


o >

ed
C



mS
U, --









i j~
'al









0
Saa




gol
'E
I &d
o<'



3 *0



sSs
0
idI








o a

p1Qr
i'^




















.ci
0 m T?











Esk
1 1.
b. *cr t;
,0 ^ 5


*l-'


4) I
I





I
I
I
Irt^











I
;O I
a c






S
I



I
981


'0'a
ItI




& 2 I
ral
ii1
^- [
cn


Emq






11




Table 2-4. Identification of Piperidines from Mass Spectral Fragmentation Patterns


1iperidine
Substituent


Fragmentation Pattern m/z (% rel. intensity,
structure of fragment ion)


2-006


1-(13C)-methyl-


100(75, M+); 99(100, M-H); 71(25, M-Et); 70(10);
58(10, C3HgN); 43(30, C2H5N)


2-014


1-ethyl-4-methyl-


127(20, M+);


112(100, M-CH3); 84(20, C5H10N+); 80(15);


70(40); 52(25); 42(60); 33(99)


2-015


2-016


2-018


1-propyl-


M+); 126(20, M-H); 98(100, M-Et); 57(5, C3H7N)


1-propyl-4-methyl-


1-butyl-4-methyl-


141(5, M+); 112(100, M-Et); 70(25); 55(10); 44(30);
42(30)


155(10, M+); 112(100, M-Pr); 98(10); 70(35); 55(20);
44(60); 33(95)


2-021


1-(pent-4-en-1-yl)-


153(1,


M+); 98(100, M-C4H7); 84(4); 70(12)


2-022


14-13C)-formyl-


114(100, M+);113(35, M-H); 98(30, M-CH);
84(20, M-13CHO); 70(15, M-C3H6)


2-025


l-pentyl-4-methyl-


169(5, M+); 112(100, M-C4H9); 84(5); 70(30); 55(5);
44(30)


2-027


1-formyl-4-methyl-


128(100, M+


27(10, M+); 126(5); 112(25, M-CH3);


98(10, M-CHO); 84(10, C5H1 N+)


2-028


1-(3-methylpentyl)-


4-methyl-


2-029


2-030


183(5, M+); 112(100, M-C5H11); 70(
55(5); 44(20); 42(10); 41(15)


1 -(5-aminopentyl)-


l-acetyl-4-methyl-


M-C7H15N);


170(40, M+); 140(10, M-CH2=NH2+); 112(5); 98(100);
84(10); 70(20); 58(15); 41(15); 42(35)


142(100, M+ + 1); 141(25, M+); 140(10, M-H);


126(35, M-CH3); 98(35,


M-COCH3); 84(30)


2-031


1-(3-methyl-5-amino-
pentyl)-4-methyl-


198(1


M+); 197(5); 196(15); 112(100); 70(15); 55(10);


44(20); 42(15); 41(20)


+ 1); 1





12


percentages of moles of starting material as described in detail previously [90EF493] and


have been corrected with regard to their response factors [89TCM17].


demonstrates the percentages of


Table


the various simple N-alkylpiperidines formed from


pyridine and their 4-methyl derivatives, singly and admixed.


Structures and proposed


mechanistic pathways for the formation of these products (which are justified later in this


chapter) are given in Schemes 2-3,


2-8--2-


In these reaction Schemes, numbers greater


than 2-


100 are used for postulated intermediates not detected by the GC/MS analyses.


Synthesis of Compounds


project


outlined


above


undertaken


our


laboratories


on the


aquathermolysis of piperidine, pyridine and some of their methyl derivatives in 49%


aqueous formic acid solutions,


we were speculating upon


the formation of


some


alkylpiperidines and tertiary aliphatic amine derivatives as the aquathermolysis reactions


progressed.


However, the gas chromatographic/mass spectral data was inconclusive for


the compounds were hitherto unknown.

various 1-alkylpiperidines and N, N-din


Thus, we were interested in synthesizing these


lethylalkylamines and determining their authentic


mass spectral fragmentation pathways, to confirm the identity of these products in the

aquathermolyses, as well as giving us an idea about the identity of similar derivatives.

The compounds synthesized were authentic samples of two tertiary amines, N,N-


dimethylpentylamine (2-009) and N,N-dimethyl-2-methylpentylamine (2


-013), and three


1-alkylpiperidines, 1-(2-methylbutyl)piperidine (2-019), 1-(3-methylpentyl)piperidine (2-


024) and 1-(4-methylpentyl)piperidine (2-032) (Scheme 2-2).


(2-019,


The novel cyclic amines


2-024) and the known cyclic amine (2-032) were prepared in respectable yields









N


RN
R2


R3MgBr


Et20O


R3CH-N'
R2


2-033R1
2-034R'


= -(CH,)5-


2-009, 2


-Me


2-019,


-013,


2-024,


2-032


Compound


2-033
2-034


(%) yield


-(CH2)5-


2-009


CH2CH2CH2CH2


2-013


CH3CH2CH2(CH3)CH


2-019


-(CH2)5-


2-024


2-032


CH3CH2(CH3)CH

CH3CH2CH(CH3)CH2

(CH3)2CHCH2CH2


H-C-H


EtOH


+ H-NF
R


N
N


R2


2-033R1
2-034 R1


= -(CH2)5-


-Me


Scheme


-(CH2)5-


-(CH2)5-


_R2





14


bromobutane, 1-bromo-2-methylbutane and 1-bromo-3-methylbutane, respectively.


The tertiary, acyclic amines (2-009,


2-013) were prepared by the reaction of 1-(N,N-


dimethylaminomethyl) benzotriazole (2-034) with the corresponding Grignard reagents of

n-butyl bromide and 2-bromopentane, respectively (see section 2.6 Experimental).


1-(Piperidinomethyl)benzotriazole (2-033)


[52JA3868,


87JCS(P1)799] and


(N,N-dimethylaminomethyl)benzotriazole (2-034)


[46JA2496,


92JOC4932


were


prepared in high yields employing literature procedures.


The benzotriazole adduct 2-033


was synthesized by condensation of benzotriazole formaldehyde and piperidine, while

adduct 2-034 was synthesized by the condensation of benzotriazole, formaldehyde and


dimethylamine (Scheme 2.2).


Further discussion of the mass spectral identification and


interpretation of the amines


is covered in the Discussion (2.4),


Experimental (


6) and


Appendix.


Results


Piperidine (2-004).


On heating with aqueous 49% HCO2H at 350


*C for


piperidine (2


-004) was completely consumed (Table 2-5).


The major product was


formylpiperidine (2-023,


93.9%)


together


with


an appreciable


amount


methylpiperidine (2-007


However, 1-ethyl-


(2-011


0.3%),


1-propyl-


(2-015,


0.8%) and 1-acetyl-piperidine (2-026, 0.8%) were all detected as minor products along


with traces of 1-pentylpiperidine (2-020, 0.1%).


After 8 h at 350 *C in 49% HCO2H, the


yield of 1-formylpiperidine (2-023) was roughly halved (42.4%) and the aforementioned


1-alkylpiperidines, noticeably 1-pentylpiperidine (2-020, 19.3


) were all formed in larger


amounts.


1-(2-Methylbutyl)piperidine (2


-019) was formed in trace amount (0.6%).


clear that


1-formylpiperidine (2


-023)


initially


formed


later converted


later


converted






15


Table 2-5. Products Obtained from 1-Methylpiperidine (1-MePip), 4-Methylpiperidine (4-MePip),
Piperidine (Pip).


Mech


1-MePip


4-MePip


Additive


(see text)


Time (h)
No. Structure


2-001
2-003
2-004
2-005
2-007
2-009
2-010
2-011
2-013


2-014
2-015
2-016
2-017
2-018
2-019
2-020


2-021
2-023
2-025
2-026
2-027
2-028


2-029
2-030
2.ilT 1


pentene
pentylamine
piperidine


pyridine


(25.6)+


1-methylpiperidine


23.2 3.9


N, N-dimethylpentylamine
1,4-dimethylpiperidine


1ethylpiperidine


1.5 4.8


0.9 0.6


NN-dimethyl-2-methyl-
pentyamine
1-ethyl-4-methylpiperidine


1-propylpiperidine


2.4 0.5


1-propyl-4-methylpiperidine
1-butylpiperidine
1 -butyl-4-methylpiperidine
1-(2-methylbutyl)piperidine


1 -pentylpiperidine


19.3 0.1


1-(pent-4en-1-yl)piperidine


1-formylpiperidine


42.4 94.9


1 -pentyl-4-methylpiperidine
1-acetylpiperidine
1-formyl-4-methylpiperidine
1-(3-methylpentyl)-4-methyl
piperidine


1-(5-aminopentyl)piperidine
1 -acetyl-4-methylpiperidine
1 -.-mathvl- gmltnrmowntulk









Piperidine (2-004) plus 1-pentene (2-001).


The same reaction of piperidine was


carried out in the presence of 1-pentene (2-001) (1 equivalent) in 49% HCQ2H at 350 oC


2 h and gave the same slate of products as in the absence of pentene, i.e. 1-methyl-(2-


,3.9%) and 1-formyl-piperidine (2-023, 94.9%),


products.


together with the same minor


In particular, no significant increase in 1-pentylpiperidine (2-020) was found


this run, suggesting that olefins are not intermediates in these reactions.


1-Methvlpiperidine (2-007).


This


compound showed a 46.


conversion after


just 0.5 h at 350 *C in 49% HCO2H.


29.0%).


The major product was 1-formylpiperidine (2-023,


This product is probably formed via the N-formylation of 1-methylpiperidine


with the subsequent elimination of a methyl cation probably assisted by the format ion.


Other products included piperidine (2-004,


1.8%),


and small quantities of 1-ethyl-


, 1.5%),


1-propyl-


(2-015,


0.9%),


1-butyl-


(2-017


1.6%) and 1-pentylpiperidine


(2-020, 3.7%).


Extending the reaction time to 2 h yielded a similar product slate,


although a higher conversion (52.1%) was observed.


formylpiperidine (2- 0 2 3, 28.3 %).


The major product was again 1-


The N-alkylpiperidines observed in the above reaction


(350 *C, 0.5 h) were again seen here,


but in increased amounts (see Table


Extending


the reaction time further to 4 h, led to a 48.3


conversion, which is only slightly lower


than that observed for the


2h run.


The major product here is again 1-formylpiperidine (2-


023, 1


, N-Dimethyl-2-methylpentylamine (2-013) was formed in trace amount


(0.3%), while N


, N-dimethylpentylamine (2


-009) was observed slightly higher (2.


2%).


However, it seems likely that during the extended time of this reaction, some of the 1-


formylpiperidine is reduced


hydride


from


formic


acid


to return


to 1-


methylpiperidine (2-007)


in view


the increased amounts of


the same higher N-


alkylpiperidines which were observed (see Table 2-5).


On heating at 350 OC for 8 h with









and 1-pentyl-piperidine (2-020,


4.8%).


,N-Dimethylpentylamine (2-009) was formed


in 23.1


After 8 h,


1-formylpiperidine (2-023) was present only in a small amount


(2.4%).


4-Methvlpiperidine (2-008).


This compound underwent complete conversion after


h(see


Table 2-5) and the major products were 1,4-dimethylpiperidine (2


1-formyl-4-methylpiperidine (2-027,


70.1


-010, 27.5%),


1-(3-methyl-5-aminopentyl)-4-


methylpiperidine (2-031,


2.3%).


A trace amount of 1-ethyl-4-methylpiperidine (2-014,


) was also seen.


At 350 *C


for 8 h


n 49% HCO2H,


4-methylpiperidine (2-008)


underwent a complete conversion to give


1,4-dimethylpiperidine (2-010,


38.0%),


formyl-4-methylpiperidine (2-027, 33.3%),


together with smaller amounts of 1-ethyl-


014, 6.9%),


1-propyl-


-016


1-butyl-


(2-018, 0.


) and 1-pentyl-


(2-025,


1-(3-methylpentyl)-4-methylpiperidines (2-028,


7.0%).


demonstrated that the N-alkyl groups on the nitrogen-functionality are now derived from

the 4-methylpiperidine (2-008) ring.


4-Methvlpiperidine (2-008) plus 3-methvl-1-pentene (2-002).


This


run was


carried out to determine whether or not 3-methyl-1-pentene (2-002) is an intermediate in


the formation of 2-028 from 2-008.


HCO2H at 350 *C for


002),


4-Methylpiperidine (2-008) on heating with 49%


2 h, in the presence of one equivalent of 3-methyl-l-pentene (2-


underwent a 100% conversion with the major products being 1,4-dimethylpiperidine


(2-010, 13.


) and 1-formyl-4-methylpiperidine (2-027


83.1%).


The product slate


from this


run (Table 2-5) suggests that 3-methy


1-pentene (2-002) does not play a


significant role in the generation of the products, especially as

methylpiperidine(2-028), was not seen in increased amounts.


Pvridine (2-005).


1-(3-methylpentyl)-4-


Pyridine (2-005) on heating with 49% HCO2H 350 *C for












Table 2-6.


Products Obtained from 4-Methylpyridine (4-MePy), Pyridine (Py).


Mech


Additive
Time (h)
No.


2-004
2-005
2-006
2-007
2-010
2-011
2-012
2-014
2-015
2-016
2-017
2-018
2-019
2-020


4-MePy


(see text)


Structure


piperidine

pyridine


1-(3C)Q-methylpiperidine
1-methylpiperidine
1,4-dimethylpiperidine


14.9 0.4


1-ethylpipridine
4-methylpyridine


1 -ethyl-4-methylpiperidine
1-propylpiperidine
1-propyl-4-methylpiperidine
1-butylpiperidine
1-butyl-4-methylpiperidine
1 -(2-methylbutyl)piperidine


1 -pentylpiperidine


11.7 6.7


2-022
2-023
2-024
2-025
2-026
2-027
2-028


2-029
2-030


1-(13C)-fonnylpieridine


1 -formylpiperidine


1-(3-methylpentyl)piperidine
1-pentyl-4-methylpiperidine


1-acetylpiperidine


1-formyl-4methylpiperidine
1-(3-methylpentyl)-4-methyl
piperidine
1-(n5aminopentyl)piperidine
1-acetyl-4-methylpiperidine





19


16% to 59.7% and produced all the foregoing products in much increased quantities,


together with


1-acetylpiperidine (2-026,


2.1%), 1-(2-methylbutyl)piperidine (2-019,


1.8%) and 1-(5-aminopentyl)-piperidine (2


-029,


1%).


On heating in 100% H13CO2H at 350 *C for


2 h, pyridine (2-005) showed a


conversion into a similar slate of products (but in increased amounts, probably


facilitated by the use of 100% HCO2H


- see Table 2-6) as seen for the run in 49% HCO2H


at 350 *C for


Significantly, only the 1-methylpiperidine (2-006,


1.9%) and the


1-formylpiperidine (2-022, 19


) were labelled, and each contained just one C label.


The fact that 1-ethyl-


(2-011,


1-propyl- (2-015,


1%),


1-pentyl-piperidine


(2-020, 6.7%) produced simultaneously had no 13C labelled carbons shows conclusively


that the ethyl, propyl and pentyl groups in 2-011,


2-015 and 2


-020, respectively, are all


derived completely from pyridine carbon atoms and not from carbons of the formic acid.


4-Methvlpvridine (2-012).


4-Methylpyridine (2-012) on heating in 49% HCO2H


at 350 *C for


2 h showed a 59.6% conversion into


1,4-dimethyl-


(2-010,


14.9%),


formyl-4-methyl-


-027


) and


-methylpentyl)-4-methyl-piperidine (2-028,


together with


smaller amounts


1-ethyl-


(2-014,


1.4%)


-butyl-4-


methylpiperidine (2-018,


) (Table 2-6).


Evidently,


the ethyl and butyl groups


required for the N-alkylation of 4-methylpiperidine were derived by fragmentation of 4-


methylpyridine molecules.


amount (0.3%).


1-(3-Methylpentyl)piperidine (2-024) was observed in trace


4-Methylpyridine (2-012) on heating in 49% HCO2H at 350 *C for 6 h


underwent a 64.6% conversion to 1,4-dimethylpiperidine (2-010,


18.2%),


1-formyl-4-


methylpiperidine (2-027,


30. 1


and 1-(3-methylpentyl)-4-methylpiperidine (2-028,


9.7%).


Other products included small amounts of 1-ethyl-


-014), 1-propyl-


(2-016),


-butyl-


(2-018),


1-pentyl-


(2-025)


2-acetyl-


(2-030) -4-methylpiperidines.









4-Methylpiperidine (2-008) plus pvridine (2-005).


To understand the types of


intermediates involved in the C-C and C-N bond cleavages, we ran an aquathermolysis of

4-methylpiperidine (2-008) mixed with pyridine (2-005) (1 mole equivalent) in 49%


HCO2H at 350 *C for


2 h (Table 2-5).


4-Methylpiperidine (2-008)


underwent a 100%


and pyridine a


74.6% conversion


under these conditions.


Various


N-substituted


piperidines (2-007


2-011


2-015


, 2-019,


2-020,


2-023 and


2-029) were formed


together with the following N-substituted-4-methylpiperidines


1,4-dimethyl-


(2-010,


7%),


methyl-


1-ethyl-4-methyl-


(2-025,


(2-014, 1.1


1-propyl-4-methyl-


1-(3-methylpentyl)-4-methyl-


(2-016, 1.9%), 1-pentyl-4-


(2-028,


1-(3-methyl-


aminopentyl) -4-methyl-


(2-031,


2.3%


1-formyl-4-methylpiperidine (2-027


4-Methvlpvridine (2-012) plus piperidine (2-004).


This reaction was carried out


in order to compare the results with those obtained from the 4-methylpiperidine (2-008)

plus pyridine (2-005) run. 4-Methylpyridine (2-012) showed a 58.9% conversion with
49% HCO2H at 350 oC for 2 h and the same slate of products was seen as in the case of 4-


methylpiperidine (2-008) plus pyridine (2-005) (Table 2-6).


The long list of products


can be classified


nto two groups:


(i) N-substituted piperidines (2-007,


2-011


, 2-015,


2-017


, 2-020,


2-023


2-024


and 2-026) and (ii) 4-methyl-N-substituted piperidines


(2-010,


2-014,


2-016, 2-018,


2-028,


2-030).


No piperidine (2-004) or 4-


methylpiperidine (2


-008) (reduction product of 4-methylpyridine {2-012}) was left in the


reaction mixture which indicates that they were completely consumed in further reactions.



General Discussion








from the ring carbon atoms.


The fact that piperidine (2-004) forms a rather similar slate of


products to that obtained from pyridine (2


-005), suggest that formic acid acts not only as a


reducing, but also evidently toward piperidine (2-004) as an oxidizing agent, although we


have been unable to find literature precedence for this.


We believe that most of the


products formed can be explained by four types of mechanistic routes:

(i) Conventional reactions where the formic acid is behaving as a hydride ion donor
and as a formylating agent

(ii) Retro-vinylogous-bis-aza-aldol reactions of products formed by the addition of

piperidines to dihydropyridines.

(iii) Simple ring-opening of amidine or aminal type intermediates formed by addition of

piperidine to dihydro- or tetrahydro-pyridines followed by reduction.

(iv) Ring-opening of isomers of products formed by addition of piperidines to a

quaternized pyridinium cation.

We now discuss each of these mechanistic pathways in turn.


(i) Conventional formic acid reduction/formvlation.


Formic acid reductions of


quaternary salts of pyridine and of 1-methylpyridinium cation to the corresponding fully


hydrogenated products, viz. piperidine (2


-004) and 1-methylpiperidine (2-007), are well


documented [55ZOK1947


57ZOK3021


, 65CCC1700, 65MI1058]


The mechanistic


pathway [38CCC66, 47CCC71] to these compounds (Scheme 2-3) involves formic acid


(or format anion) donating hydride ion to the C-4 of the pyridinium cation (2-


101)


resulting in 1,4-dihydropyridine (2-


102).


Further successive protonations and attacks of


hydride ion at C-6 and C


yield piperidines (2-004


2-008).


Piperidine (2-004)


undergoes


formylation


to 1-formylpiperidine (2-023)


which


reduced


methylpiperidine(2-007) in the presence of formic acid as shown in Scheme 2-3.


In the












HCO2H


2-005R


2-012


=H
=Me


101)


2-004
2-008


-H
=Me


102)


103)


CH3
2-007R


HCOH


HCO2H


2-010

R :


=Me


2H,
2 H+


CHO


CHO


CHO


104)


105)


2-023
2-027


-Me


Scheme


Retro-vinvlogous-bis-aza-Aldol reaction route.


The Aldol reaction [680R1]


and its reverse, the retro-Aldol reaction [89MI 199], are among the most important reactions


in organic chemistry.


Mono-aza-Aldol reactions are also well known [68AG(E)7].


Although the self-condensation of nitriles (Scheme 2-4) is a well known "named reaction"


(Thorpe-reaction) [06JCS 1906],


we have been unable to find any example of the similar








which should thus involve the fragmentation of a 3-amino-imine (2-


109 and 2-


111) into two imines


110) also appears to be unknown (Scheme 2-5).


RCH2CN


RCH2CN


R-CH2,-


NHCN
I %PC


106)


107)


108)


alkyl,


Scheme 2-4


H i"
RC-C-R
R5


R'HN
R2-C-
R3


C-R7


R2, R3


109)


R'-R7


=alky


110)


111)


,aryl


Scheme


As regards vinylogs of the Aldol reaction, although the reactions of aldehydes at the


y-position of an a,j-unsaturated ketone (Scheme 2-6) is well known [680R1],


we have


been unable to find any example when this reaction stops at the intermediate hydroxy

compound.


RCHO + R'CH2CH=CHCOR


112)


113)


C-CR
H


= alkyl,


R-C=C-C=C-CR2


R H-
FI I


R.R1


u L









Aza analogs of


vinylogous Aldol reactions also appear to be uninvestigated


although such reactions are almost certainly involved in the commercially important


preparation of pyridines from aliphatic aldehydes and ammonia (see later).


Based on the


previous arguments, 6.amino-y6-unsaturated imines could be expected to undergo retro-


vinylogous-bis-aza-Aldol (RVBAA) reactions cf 2-115


-> 2-116 & 2-


(Scheme


R
'NH
I 4-
R-3C r>


R
R N
-_ II 7
-C-C-R


R,
-N R
II I
R~r^_r^-


R F~IHR
+ C=C-R
R


115)


= H, alkyl


116)


117)


Scheme


Compounds of type 2-


115 are tautomers of 6-bis-imines, and the related cations


(cf 2-


120) are capable of formation by ring-opening of the addition products (2-


a secondary amine (R2NH) to a 1,4-(or


) dihydropyridine (2-


119) of


118) (see Scheme 2-8).


The RVBAA reaction of 2-


120 thus causes scission into protonated acrylaldehyde imine


122) and the N-vinyl derivative (2-


vinyl compound (2-


123) of the original secondary amine.


123) is rapidly converted by successive H+


This N-


and H- addition (both


supplied by formic acid) into the corresponding N-ethyl derivative (2-


129).


In addition,


intermediate 2-


120 can undergo proton loss and proton addition to give the isomeric 6-


amino-y6-unsaturated imine cation 2-


121.


RVBAA


reaction


of 2-


121 affords


vinylamine 2-124


and the unsaturated imine cation 2-


the latter which is converted


rapidly, by successive additions of


H-, H+


and H-


, into the propyl derivative 2-


127 of


the wnri oinal snomndarv marine


Ths narstpfl AnriVtihni 7.


1 r an 9alar n f,, ,wr-mn- f,-m,,m i


. FL










R2N H


NR+
NR2


118)


119)


120)


121)


HCQCH2

H2N 22)
(2-12 2)


OfH2


123)

H+


CH2
fCH
H2N


124)


CH

NR
125)


9H3
HCR +
NR,


126)


CH3CH2NR2


CH3CH2CH2NR2


127)


H20,-2H/
CH3


129)


"NR2
128)


Scheme 2-8


The formation of 1-ethyl- (2


-011)


and 1-propyl-piperidine (2


-015)


from


reaction of pyridine (2-005), (and of piperidine {2-004}) with formic acid are thus


explained by the transformation of Scheme


Moreover, it would be expected that 4-














2-005


118)


130)


H2N


134)


131)


R


HN:
(2-


132)


-1H2N


135)


2-011


2-014R


=Me
R


133)
H20


136)


2-015R


2-016


2-026
2-030


=H
=Me


=H
= Me


Scheme 2-9


Further evidence for the mechanism proposed can be derived from the selected data


of Tables


5 and 2-6 which have been abstracted into


Table


This compares the


H










Table


Comparison of the Percentages of some of the N-Alkvlpiperidines formed


from Pyridine (Py) and Piperidine (Pip) and their 4-Methyl Derivatives, Singly and
Admixed in 49% HCO2H at 350 C for 2 h.
----------------l-----it ------------------l-l-i----.--l----l-----l 4-------- --i---- i------ ------nBe--l-- I 1-I i---i---I- ---l l -- Il I Illl ll Il IDql I d*i Il 10 --


Entry No.


Piperidine
Product
Substituent


Origin of t


4-MePy


4-MePy 4-MePip


N-alkyl


4-MePip Py


2-011


1-ethyl-


Either


2-014


2-015

2-016


2-017

2-018


2-020

2-024


2-025


2-028


1-ethyl-
4-methyl-


Either


1-propyl-

1-propyl-
4-methyl-


1-butyl-

1-butyl-
4-methyl


1-pentyl-

l-(3-methyl-
pentyl)-


N-pentyl-
4methyl-


1-(3-methyl
pentyl)-4-methyl-


2-011, 015, 017, 020, 024*

2-014, 016, 018, 025, 028*


2-015, 016, 020, 025*

2-017, 018, 024, 028*


Either


Either


Either

Either


i---" -" -----i --eI---l--B--i-.-----------------"-1-i-1----l---0- ---#ii ..---i1 ---.-e --. ---ii ---.---l -


t H is from Py or Hp; Me is from 4-MePy or 4-MePip


* = total for compounds listed.


1--1111 M-mumh ~-_II ICI~-II-CIY-~I-









amounts


simple


N-alkylpiperidines


formed


from


piperidine (2-004)


methylpiperidine (2-008),


those from the two mixed runs.


pyridine (2-005),


Table


and 4-methylpyridine (2-012) alone with


7 demonstrates very clearly that the products


expected from the mechanistic routes discussed, and only the expected products, are

formed in the runs from a single substrate.

Furthermore, Table 2-7 provides good evidence for the mechanism postulated from


the nature, and the proportions of the products formed in the mixed runs.


Thus, when 4-


methylpiperidine (2-008)


pyridine


(2-005)


were


reacted


together,


methylpiperidine (2-008) predominately provided the ring component of the piperidines


formed (compare 3.


to 1.5%


Entries xii and xi


, respectively),


whereas pyridine


predominately provided the piperidine N-alkyl substituent (compare


9% to 0.5%


Entries


xiii and xiv, respectively).


methylpyridine (2


Conversely, when a mixture of piperidine (2-004) and 4-


-012) was reacted a total of 3.9% of products formed was derived from


piperidine (2


-004) reacting as the amine HNR2,


compared


with 3.7%


from


the 4-


methylpyridine (2-012) reacting as HNR2.


Again, the N-alkyl groups of the piperidine


products


were


formed


from


the starting piperidine and 3.5%


from


methylpyridine.


This is in good agreement with the mechanism proposed in Scheme 2-9 in


which the saturated secondary amine adds to a dihydropyridine in a key step.


Addition to 23,4,5-tetrahvdropvridinium cations.


addition of R2NH to a 2,3,4,5-tetrahydropyridinium ring (2-


A simpler sequence of

137) followed by ring-


opening and reduction leads to amines of type R2N(CH2)5NH2 and this explains the


formation of 2-029 and 2-031 (Scheme


2-10).


Ring opening of isomers of products of addition of pioeridines to auaternized


ovridines


Addition of a secondary amine to a ouaternized nvridine (2-


1421 will Five


.








converts 2-


145 into the saturated product 2-


146.


We believe mechanisms of these types


to be involved in the formation of products 2-020, 2-024, 2-025,


2-028, and 2


-029


(Scheme 2-12).


140)


H

Me


H


137)


138)


NH2


NH2


141)


139)


NH2


NH2


2-031


=Me


2-029


Scheme


















142)


143)


144)


4H+


146)


= alkyl,


NR1

145)


= H, alkyl


Scheme
















150)


H

Me


101)


147)


151)


148)


152)

I 4H+


4H+


2-025


2-028 R


= Me


2-020


149)
S2H,
\2H


2-021


R=H


2-024 R


Scheme






32


Conclusions


Formic acid variously acts as a formylating, methylating, reducing and oxidizing

agent when it reacts with piperidine, pyridine and some of their methyl derivatives under

aquathermolysis conditions. In similar reactions both piperidine and pyridine are converted


to significant amounts of 1-alkylpiperidines, namely 1-methyl-,


1-ethyl-,


1-propyl- and 1-


pentyl-piperidines

aquathermolyses.


1-(4-Methylpentyl)piperidine was not observed as product from the


Through the use of isotropic labelling it has been demonstrated that only


the 1-methyl-


derivative originated from formic acid.


That is


, during the course of the


reactions piperidine and pyridine were both formylated and then subsequently reduced to


the 1-methyl derivatives.


The 1-ethyl- and 1-propyl derivatives arise from the heterocyclic


rng C-C bond fission by retro-vinylogous-bis-aza-Aldol reactions.


These unique C-C


bond scissions show for the first time that heterocyclic rings are susceptible to opening


other than at the heteroatoms.


Other reaction pathways elucidated during the course of this


work include conventional


formic acid reduction/formylation, addition


to 2,3


,4,5-


tetrahydropyridinium cations and ring opening of isomers of products formed by addition

of piperidines to a quaternized pyridinium cation.

It has been shown that formic acid at 350 *C converts pyridine and piperidine into a


defined


mixture


specific


N-alkylpiperidines.


4-Methylpyridine


methylpiperidine


similarly


converted


corresponding


1-alkyl-4-


methylpiperidines.


It has been demonstrated that al


1-alkyl groups (except for 1-


methyl) arise from a second molecule of the heterocyclic ring compound and not from the


formic acid.


The formation of all products can be rationalized by addition of a piperidine


mninletnll tnr a nn-din nr i rnr tnf _hirnrn-r;rA;nn oinol nn





33


synthesis of pyridine involves the formation of the Cs unit in situ by one or more base-


catalyzed condensation reactions.

cyclization is usually spontaneous.


With ammonia or an amine as the condensing agent,

On the industrial scale, self condensation of simple


aldehydes with ammonia lead to a variety of pyridines [79MI64].


Perhaps, the mechanistic


pathways may be viewed as cleavage into two molecules of aldehyde, the subsequent

intermediate can enable retro-aldol cleavage of the pyridines.


Experimental


1H NMR spectra were recorded either on a Varian VXR 300 (300 MHz) or a


General Electric QE 300 (300 MHz) spectrometer.


13C NMR spectra were recorded at 75


MHz on the same spectrometers. Chemical shifts are reported in parts per million (ppm)


downfield from tetramethylsilane (TMS) used as the internal standard.


(J values) are reported in Hz.

using oven dried apparatus.


Coupling constants


All Grignard reactions were run under an inert atmosphere

Solvents and anhydrous liquid reagents were dried prior to


use: diethyl ether was distilled over sodium benzophenone ketyl.


Analytical thin layer


chromatography (TLC) was performed using pre-coated silica gel 60 F 254 plastic plates

(0.2 mm thick) using iodine as indicator.


I-(Piperidinomethvl)benzotriazole (2-033) was prepared by applying the literature


procedure [87JCS(P1)799].


Benzotriazole (5.0 g, 42 mmol) was dissolved in EtOH (50.0


mL).


Next was added 37% aqueous formaldehyde (6.60 mL, 64.0 mmol)


and piperidine


mL, 42.0 mmol) and the reaction was stirred vigorously at room temperature (18 h).


Precipitation was induced by addition of HO (2 mL).


The product obtained was washed









4H, J


7.0) (piperidine),


5.43 (s,


2H) (CH2),


7.4 (m, 1H) (Bt),


(Bt),


2 (d,


1H, J


= 8.0) (Bt).


13C NMR (CDCl3)


: 6 23


70.1


110.1


118.2


119.7


123.7


126.3


127.3.


1-(N,N-Dimethvlaminomethvl)benzotriazole (2


-034) was prepared according to


the literature procedure [92JOC4932].


Benzotriazole (5.13 g,


43 mmol) was dissolved in


EtOH (42.0 mL).


Next was added 37% aqueous formaldehyde (6.60 mL, 64.0 mmol).


The mixture was stirred vigorously and cooled to 0 *C.


After the initial precipitate formed,


, N-dimethylamine (6.4 mL, 129 mmol) was added dropwise via an addition funnel and


the reaction was allowed to warm up to room temperature (18 h).

crude product was induced by cooling the mixture to -18 *C. The


filtered and washed with EtOH (20 mL).


Crystallization of the


Crude white solid was


Recrystallization from ethanol yielded white


prisms (6.3 g,


M.p. 95-97 *C (lit.[52JA3868]


m.p. 99-100.5 *C).


1H NMR


(CDC13):


(Bt),


6 2.4 (s,


7.7 (d, 1H,


6H) (2CH3),


= 8.2) (Bt),


5.4 (s,


2H) (CH2),


8.1 (d, 1H,


7.4 (m, 1H) (Bt),


7.3) (Bt).


(t, 1H, J


13C NMR (CDCl3) 6:


42.3,


69.8, 109.8, 119.5, 123.7,


127.3,


133.76, 145.


General procedure for the synthesis of N-alkvlpioeridines


1 -(2-Methvlbutvl)piperidine (2-019)


. Mg


metal


(1.7


mmol)


was


suspended with an iodine chip in Et20 (20 mL).


2-Bromobutane (9.5 g, 69.4 mmol) was


dissolved in Et20 (50 mL) and added dropwise to the Mg metal.


After the addition was


complete,


mixture


was


heated


under


reflux


stirred


(Piperidinomethyl)benzotriazole (5.0 g, 23.0 mmol)


was


- -Y a V m


Soxhlet


then


added


via a









removed in vacuo to yield a crude yellow oi


, which was purified by Kugelrohr distillation.


A colorless oil (


20 g, 62


) was isolated: B.p. 65 *C/0.65 mm


1H NMR (CDCl3):


6 0.8 (d,


3H, J


= 8.0) (CH3),


0.9 (t, 3H, J


= 8.0) (CH3), 1.0-1.1 (m,


1H) (CH), 1


4H) (2CH2 [ring]),


1.6 (quintet,


= 6.0, 8.0) (CH2N aliphaticc]),


4H, J


2-2.4 (br m,


= 8.0) (CH2 [ring]),


4H) (CH2N [ring]).


1.0-2.1 (d of d, 2H,
13C NMR (CDC13):


6 11.3


, 24.6, 26.1,


27.9,


66.4.


HR MS (70 eV


1666 (7) [M+],


98(100) [CSH11N+];


C10H21N requires 155.1674.


1-(3-Methvlpentvl)piperidine (2-024).


This product was obtained as a crude


yellow oil and was purified by Kugelrohr distillation to give a colorless oil (3.0 g, 76%);


*C/0.


mm Hg


1H NMR (CDC13):


6 0.8-0.9 (d & t, 6H, J


= 8.0) (2CH3),


.2 (quintet, 1H, J


(CH2 [ring]),
aliphaticc]), 2.


= 8.0) (CH),


(quintet,


-2.4 (br


.2-1.4 (m,


= 8.0)


s, 4H) (CH2N [ring])


4H) (2CH2 aliphaticc]),


2CH2


[ring]),


13C NMR (CDCl3):


1.4-1


.5 (m,


(CH2N


611


26.0, 29.6, 33.3,

(100) [C5H 11N+]


54.7.


HR MS (70 eV


169.1827 (7),


C11H23N requires 169.1830.


1-(4-Methvlpentvl)piperidine (2


-032).


This product was obtained as a crude


yellow oil and was purified by Kugelrohr distillation to give a pale yellow oil (2


B.p. 65 *C/0.1 mm Hg;


1H NMR (CDCl3):


6 0.9 (d, 6H, J


= 8.0) (2CH3),


.2 g, 57%);
.2 (quintet,


2H, J


= 9.0) (CH2),


.5 (m,


4H) (piperidine),


4H) (piperidine),


(t, 2H, J


7.0) (CH2 [ring]),


2.4 (br.


s, 3H) aliphaticc).


13C NMR (CDCI3):


6 22.2


24.7


9, 36.8, 54.5, 59.8.


HR MS (70 eV


169.1


98 (100)


[CsH 11N+1


Ci1HnoN requires 169.1830.


[M+],


.5 (m,


[M+],





36


General procedure for the synthesis of acvclic amines


N,N-Dimethvlentvlamine (2- 009).


n-Buty


bromide (11.68 g, 85.2


mmol) was


dissolved in Et20 (65 mL) and added dropwise to Mg metal (2.05 g,


85.2


mmol) in the


presence of an iodine chip. After the addition was complete, the mixture was heated under


gentle


reflux


stirred


0.5 h.


After


period


time


dimethylaminomethyl)benzotriazole (5.0 g, 28.4 mmol) was added via Soxhiet extractor.


The mixture was stirred and refluxed for 18 h.


aqueous NaOH (30 mL).


The reaction was cooled and quenched with


The bulk of the Et20O was decanted from the solid and the


remainder filtered through celite, dried (MgSO4) and concentrated in vacuo to give a crude


yellow oil


- GC yield 79%.


The crude product was purified by Kugelrohr distillation to


give a colorless oil (27%


*C/0.9 mm Hg (lit. [46MI165] b.p.


122-123 "C/760


mm Hg).


1H NMR (CDCl3):


6 0.9 (t, 3H, J


= 6.0) (CH3),


1.50-1.60 (m, 6H) (3CH2),


2.20 (s,


6H) (2CH3N),


2.30 (d, 2H,


= 6.0) (CH2N).


13C NMR (CDCl3)


6 13.9,


22.5,


, 29.6,


59.7.


HR MS (70 eV


EI): ml


(%) 11


1364 (8%) [M+],


(100) [C5H11N+]


C7H17N requires 11


1361.


N,N-Dimethvl-2-methvlpentvlamine (2-013).


This product was obtained crude as


a yellow oil which was purified by Kugelrohr distillation to give a colorless oil (1.02 g,


28%


*C/2 mm Hg (lit.[50CCC512]


*C/760 mm Hg).


1H NMR


(CDCl3):


6 0.7-0.8 (t, 3H,


= 6.0) (CH3 [terminal]),


0.9 (d, J


= 6.0)3H) (CH3),


1.02-


= 6.0) (CHa),


.2 (d, 1H, J


= 6.0) (CHb),


1.4 (m,


2H) (CH2),


1.7-1.8


1H) (CH [CH3]),


.4 (d of d, 6H, J


= 6.0, 6.0) (CH2N),


2.4 (s, 6H) (2CH3N).


13C NMR (CDCIj):


6 14.3


-- ---- -


,30.8, 37.8,


45.9, 67.4.


HR MS (70 eV


-(N,N-


1.1 (q, 1H,









Aquathermolysis: General2.7


All starting materials were checked by GC prior to use;


purified to >98%.


where necessary they were


49% Aqueous formic acid was deoxygenated with argon for 1 h prior to


use. The model compound (1 g) and the formic acid (7 mL) were charged into a nitrogen-

blanketed 1" Swagelok stainless steel bomb (plug and cap) which was then sealed. The

reactor was then kept, without agitation, in a fluidized sand bath (model SBS-4) set at 350

*C using a Techne temperature controller (TC-8D) for the specified time period. The


temperature profile was measured by a Barnant 115

placed in the sandbath adjacent to the reaction vessel.


thermocouple thermometer (type J)

After the reaction period, the reactor


was immediately cooled with a stream of cold air and then quenched i

reaction mixture was then worked up as previously described [90EF493],


n dry ice.


and subjected to


GC analyses on a Hewlett Packard 5890 instrument (flame ionization detector, [FID]) with

a 15 m capillary column (SPB-1) and a temperature program of 10 *C min-1 from 50-250


GC/MS


analyses


compounds


were


performed


on a Varian 3400 gas


chromatograph and a Finnigan MAT 700 ion trap detector.


Product identification.


The GC behavior of all the compounds in this chapter


(starting material and products) are collated in Table


earlier papers [90EF493]).


1 (in the format as explained in


Within the reaction mixtures, the identities of all the starting


materials and some of their reaction products [2-001--2-005,


2-007--2-013, 2-019,


023, 2-024, 2-026] were confirmed by direct comparisons of retention times and mass

spectral fragmentation patterns with those of the authentic compounds, under essentially the


same mass spectral operating conditions.


Table 2-2 records the major features of the mass


spectra together with a literature reference to the MS of the compounds (where available).


Table 2-3 recnrds the man. enar.tral fraomentatinn nattomo rnf nrmlnteo (


n.n '7


'- nA'


i





38


the reference spectrum is always given and the major features of both the experimental and


the reference spectrum are recorded.


Table 2-4 records the MS patterns of products [2-


006, 2


-014--2-016, 2-018, 2-021,


2-022,


2-025


2-027--2


-031] for which no


published MS data could be


found.


These products were assigned from


their MS


fragmentation patterns, together with a consideration of the reaction conditions, starting


materials

materials,


, and a reasonable mechanistic pathway for their formation from the starting

p Also, the mass spectral fragmentation patterns for the synthesized compounds


(see Appendix A) 2-009,


2-013


,2-019, and 2-024 are represented.














CHAPTER III
REACTION OF VARIOUS ALIPHATIC AMINES WITH FORMIC ACID:
1-OCTYLAMINE, DI-1-OCTYLAMINE, N,N-DIMETHYL- 1-OC'TYLAMINE,
1-DODECYLAMINEAND N,N-DIMETHYL-1 -DODECYLAMINE



Introduction


As stated in Chapter


, nitrogen is among the heteroatoms


found in coals


[92EF439].


Due to the deleterious effects of N impurities (as mentioned in Chapter II),


remaining in synthetic oils


it is highly economical to remove them easily and cost


effectively.


Normal


mode


purification


involve


denitrogenation


hydrodenitrogenation


[92EF439,


93TL4739].


Aquathermolysis,


thermal


transformation of organic compounds in aqueous environments, holds potential economic

incentive as an alternative purification method for the conversion and purification of fossil

fuels such as coal.3.1


Denitrogenation can


a costly


process


removal


nitrogen form


heterocyclic nitrogen containing compounds due to the large excess of hydrogen needed to


afford hydrogenolysis of the heterocyclic ring (as mentioned in Chapter II),


but aliphatic


amines should undergo denitrogenation quite rapidly since there is no need to use excess


hydrogen.


With six-membered heterocycles, progressive decarboxylation and C-C, C-N


bond cleavages occur, leading to the generation of alkane chains [92EF439].


The aliphatic


amine already contains the alkane chain, and would therefore undergo fragmentation









directly.


There would be no need for significant prehydrogenation of the system.


Aliphatic


amines are among the nitrogen compounds found in petroleum or synthetic oils.


Our main objective was to uncover the general


pattern of


reactivity under


aquathermolysis3


functional groups.


3.3 conditions of some common, naturally occurring amine-related

Literature reports have shown that formic acid at temperatures ranging


from 100


-200 *C


, readily reduces basic N-heterocyclic rings.


Thus pyridine, quinoline,


isoquinoline and acridine can be easily reduced to piperidine, 1,2,3,4-tetrahydroquinoline,


1,2,3,4-tetrahydroisoquinoline, and 9,10-dihydroacridine respectively.


The analogous


salts


yield


the corresponding N-substituted compounds


[65CCC 1700,


65CLI1058,


55ZOK1947, 57ZOK3021].


More recently, it has been demonstrated in our laboratories


that formic acid induces the hydrogenation of the pyridine ring and subsequently leads to its

scission [93TL4739].

As previously stated, it was demonstrated in our laboratories [93TL4739] that in


49%


aqueous


formic


at 350


pyridine


was


converted


predominantly


formylpiperidine accompanied by several N-alkylpiperidines as minor products.


connection with


elucidation


mechanism


formation


alkylpiperidines,


we have also studied the effect of


49%


aqueous


formic acid on


representative primary [1-octylamine (3


-008)3 .4, 1-dodecylamine (3


-023)],


secondary


[di-1-octylamine (3


-033)]


tertiary


, N-dimethyl--1-octylamine (3


-013)


dimethyl- 1-dodecylamine (3-028)] alkylamines (Scheme 3-1).


3.2 All synthetic work and mass spectral investigations
White at the University of Florida.


All nna thennrmonvli reritinm w rnne nrwn/,,tp hr fenaf


interpretations were performed by Rolsyn L.


Tnn !anatnlnnlrn at t1a T Tn4,onrtrr nIf fLji.-Al










CeH17NH2
3.008


CeH17NMe2


3.013


12H25NH2
3.023


C12H2sNMe2
3.028


(CsH17)2NH
3.033


Scheme 3-1


The gas chromatographic (GC) behavior of al


study and the products are recorded in Table 3


the compounds employed for this


Table 3-2, 3-3 and 3-4 contain the


compiled mass spectral data for the analysis of results.


Table 3


contains the sources and


purities of the starting materials used and have been compiled based upon the direct

comparison of the GC retention times and of the mass spectral (MS) fragmentation pattern


with those of the authentic compound.


Table 3-3 contains compounds which have been


identified by comparison of MS patterns with literature MS data for the same compound.

Those compounds for which no suitable literature MS data were available have been

identified by their MS fragmentation patterns (obtained from the aquathermolysis runs) and

have been compiled in Table 3-4. A more detailed explanation of Tables 3-2--3-4 is given


in section 3


.5 Experimental.


The results from the aquathermolyis of each amine are


collected in Tables 3-5--3-11


All product yields (molar %) are represented as a percentage


of moles as described in detail previously [90EF493] and have been corrected with regard

to their response factors [89TCM17].3.6


Structures and proposed reaction pathways for the formation of these products


given in Schemes 3-6--3-9 (see section 3.4 Discussion).


numbers


In these reaction Schemes,


> 3-100 are used for postulated intermediates not detected by the GC/MS


analyses.










Table 3-1.


Structure and Identification of Starting Materials and Products


tR(min)


Compound


Eq. W


Basisa


Factor


3-001
3-002
3-003
3-004
3-005
3-006
3-007
3-008
3-009
3-010
3-011
3-012
3-013
3-014
3-015
3-016
3-017
3-018
3-019
3-020
3-021


3-022
3-023
3-024
3-025
3-026
3-027
1-ton


N,N-dimethyl- 1-butylamine


1-hexanol


N, N-dimethy-1 -hexylamine
N-methyldi-1 -butylamine


2-octamone


N,N-dimethyl-2-ethyl- 1-hexylamine
N-methyl-N-1 -butylformamide


1-octylamine


N, N-dimethyl-3-octylamine


1-octanol


N-methyl-3-octylamine
N-methyl-1-octylamine
N,N-dimethyl-1 -octylamine


Table 3-2
Table 3-3
Table 3-2
Table 3-4
Table 3-2
Table 3-3
Table 3-4
Table 3-2
Table 3-3
Table3-2
Table 34
Table 3-3
Table 3-2
Table 3-3
Table 3-3
Table3-2
Table 3-3
Table 34
Table 3-3
Table 3-3
Table34


tri-1-butylamine


10.73
10.87
10.94
11.03
11.10
11.57
12.06
14.52
14.64
14.84


2-todecee


N-methyl-N-1-hexylformamide


N, N-di-l-butylformamide
N-methyldi-1 -hexylamine


N- l-octylfarmamide


14odecylamine


N-methyl-N-1 -octylfonnamide


N-1-otylacetaritde


15.06
15.18
.e -'


1-dodecanl


N-methyl-1 -dodecylamine


-* I nri a' sr.hn ,h.a.Aj A.a u U' r *


Table 3-3
Table 3-2
Table 34
Table 34
Table 3-2
Table 3-4


I Af


3-dodeceexa










Table 3-1 continued


tR(min)


Compound


Eq.W


Basisa


Factor


3-032
3-033
3-034
3-035
3-036
3-037
3-038
3-039
3-040
3-041
3-042
3-043
3-044


18.12
18.41
18.76
19.54
19.99
20.56
21.43
21.44
22.37
22.62
24.58
28.91
29.26


N-methyldi-1 -octylamine


di-l-oaylamine


127.5
120.5
134.5


N- l-octyl-N-3-octylformamide


N-l-odec4yfonamide


N-methyl-N- 1-dodecylfonnamide
N-methyl-N-1dodecylaetamide
N-acetyl-N-1-dodecylfomamide
N-methyl-N-3-octyl- 1-octylamine


N,N-dil-octylfomamide
N,N-di- 1-octylactamide


127.5
134.5
141.5
117.7
183.5
176.5


tri-1-octylamine


di-odecylaminem


Table 3-3
Table 3-2
Table 34
Table 3-2
Table 34
Table 3-4
Table3-4
Table 3-4
Table 3-3
Table 3-3
Table 3-3
Table34
Table 3-3


tR(min)


= Retention time in minutes.


= molecular weight.


= equivalent weight.


a = Identification


Basis, see appropriate table. b = Response Factor, see ref [89TCM17].


N-methyldi-1 -dodecylamine






44


Table 3-2. Properties of Authentic Compounds used as Starting Materials and for the
Identification of Products


Compound


a Purity


m/z (% relative intensity)


Spectra#


3-001

3-003

3-005

3-008


3-010


3-013


N,N-dimethyl- -butylamine

N, N-dimethyl-1 -hexylamine

2-octanone

1-octylamine


1-octanol


A 99

A 99

K 97

A >99


A 97


N, N-dimethyl-1.-octylamine


A 95


101(9); 72(1); 58(100); 44(5); 42(12)

129(7); 114(1); 84(1); 58(100); 42(9)

128(12); 113(5); 85(9); 58(96); 43(100)

129(2); 100(3); 86(5); 58(6); 45(8);
41(10); 30(100)


112(2); 84(43); 83(46); 70(69); 56(100);
55(89)


157(6);
42(6)


118158

6209

120848

120973


121161


143(2); 59(4); 58(100); 44(41);


3-016


A 99


170(8); 85(46); 71(64); 57(100); 56(22);
55(18)


126002


3-023


3-026


-dodecyamine


F 99


l-dodecano


A 98


185(2); 184(1); 55(9); 44(10); 43(10);
41(15); 30(100)


168(1); 140(8); 97(43); 83(65); 69(81);
55(100)


28046


127402


3-028


N,N-dimethyl-1-
dodecyamine


A 97


213(4); 212(1); 84(2); 59(4); 58(100)


40885


3-033


di-1-octylamine


A >99


241(5)
44(36)


143(10); 142(100); 57(7); 56(4);


53027


3-035


N-1-dodecyifomamide


213(18)
44(19)


184(15); 72(39); 59(100); 58(68);


34318


3-042


tri-1-octylamine


A 98


353(2); 352(2); 256(2); 255(19); 254(100);
156(8)


135035


aA = Aldrich, F


Fluka, K


= Eastman Kodak; L


Lancaster, S = synthesized authentic compound (see


experimental section). b = spectral numbers of the mass spectral data for the compounds found from a search of the
Wiley. 138L / MSP. c = no spectra available.


dodeane






45





rO s-4r I
T ... -a ..o i n** c
(N -8' 4 ..
4- *. ci S o I'^ --S S S f
N^ C S .. r h- .
n ^o 8 h oS fS
IQ S: -n s ''E & ^ S ^
'8 -
-g S 4-' *
o' ^*~ ci C iS r fi -'
a C .4. c I Sr l


aNI 2 v 1 0 4/.0 0 -0 -s N^ N N' "l
-* -t l- tl '




5S I^ 'o %; ^ SS EEEI E5M ^0
o3 Vn
U NNN

I S
45i n '3 o



Qc a
'S~~~ =tc'-


00 N NO



L*I ^S ^~- 4' 4 N ..r^c ^v S
*.
-a '4 lat ta tat -



.24~t~ -o
10 S a S''
OI~yI
S ^ y p~ggl~r i~s






g. g EZ' a a .ai 8 I
Vj> ^ lQ'& ^ .^ ^ ^ y


0 .~




^SSf N ff4r S S) ^ ^ ;'B
S 8'"y'^' do s^' r^ t' -^ -i ^- r^S
.0 9 I ^ '^^ ^ ^'^ ^ S'^ ^ ^ r
ISd





II ('D( (' *S*' ^ ^ *t *l
'-~~~~L E0 rPa 00^ t ^ i ^ ^ ^ ^ lN f f
sa~~h >i g r 3 ?(i% 8^
^~ S '5

^ a 1
~~^ o8-, 'laIll'
'S~~~ *s. 11 *ci *
"{ F*&: S t a






I IinJ 1t
1~h I






o I .
I
Us "
j'i I
h h ~ hy ~y gVs




















h rl

- N



- t
-
U
E


+ +


- *a


00


*



-
" i0
J








U 8
ar
C r







- as
-
^ e4
* aS
N^
is
'o6
*


MAl


r 00
c^ w
3 -' h




v^
+2'r
&?^
aa





47


Synthesis of Compounds


After extensive mass spectral interpretation and subsequent identification of all the

products/unknowns obtained from the aquathermolysis runs there were several compounds


whose formation remained obscure.


Therefore


, five compounds were selected to


synthesized. They included N-1-octylacetamide (3


-025) N


, N-dimethyl-3-octylamine (3-


009),


, N-dimethyl-2-octylamine (3


-045), 2-dodecylamine (3


-049) and 3-dodecylamine


(3-050).


Amine 3-025 was chosen because it appeared to be an unlikely product based


upon the expected reaction pathways,


while amines 3


-009 and 3


-045 were chosen


because no direct mechanistic pathway for their formation could be suggested.


primary amines (3-049, 3


-050) were synthesized to investigate whether or not amination


of the alkenes formed during aquathermolysis was occurring.


N-1-Octylacetamide (3-025) was synthesized using


1-octylamine (3-008) and


acetic anhydride and was isolated as a clear oil in 68% yield (Scheme 3-2).


Analysis of the


MS fragmentation pattern of our authentic N-l-octylacetamide (3-025) shows that its


pattern is identical


to that of the literature (see Table 3-3) and suggests that amide 3-025


could be a product from the aquathermolysis of 1-octylamine (3-008).


C8H17NH2


acetic anh.


50 *C


C8H17NHCOCHa


3-008


3-025


Scheme 3


, N-Dimethyl-3-octylamine (3


[94TL2401].


-009) was synthesized using a literature method


This method uses titanium (IV) isopropoxide [Ti(OiPr)4] and sodium





48


is thought that the Ti(OiPr)4 functions as a Lewis acid catalyst as well as a water scavenger


(Scheme 3-

octanone (3


5).


3-Octylamine (3-046) was prepared from the corresponding ketone, 3-


-047) using the literature method [83JCS(P1)3027] (Scheme 3-3).


3-046


(HCHO)n

Ti(OiPr)4
diglyme


a


+ CH2
HN


NaBH4


Me2


3-009


NH2


NaBH3CN


3-047


NH4OAc,
reflux


EtOH


3-046


Scheme 3-3


Mass


spectral


analysis


the authentic N


, N-dimethyl-3-octylamine (3-009)


revealed that the MS fragmentation pattern is identical to that of the literature (see Table 3-3)


and suggests that amine 3-009 could be a product from N


, N-dimethyl-1-octylamine (3-


013).


The proposed compound (i.e.


from the fragmentation found in the aquathermolysis


runs),


the library match and the synthesized compound are identical (see Table 3-3).


, N-Dimethyl-2-octylamine (3


-045)


was


also synthesized


using


the above


literature procedure [94TL2401] from 1-methylheptylamine (3-048) (Scheme 3-4).


suggested that the compound proposed to be N


It was


, N-dimethyl-2-ethyl-1-hexylamine (3-006)











NH2


3-048


(HCHO)n
Ti(OiPr)4
diglyme


H -
+N=
)N=CH2


NaBH4


NMe2


3-045


Scheme 3-4


2-Dodecylamine(3-049) and 3-dodecylamine (3


corresponding


-050) were synthesized from the


and 3-dodecanone using a literature method [83JCS(P1)3027] (Scheme


As with amine 3-046, the ketone is reductively aminated to the corresponding


amine.


These primary amines were synthesized to tell whether the 2-dodecene (3


-017)


and 3-dodecene (3-019) formed (see section 3.3 Results) were being converted back to the


corresponding amines.


This hypothesis


was disproven, as neither of the amines (3-049


nor 3-050) were observed as products.


Further discussion of these and the above


compounds will be covered in the Discussion (section 3.4).


0
CH3(CH 2)0C- CH3


NaBHaCN


N H4OAc,
reflux


EtOH


!JH2
CH3(CH2)9-CHCH,
3-049


0
CH3(0H2)8C- CH2CH3


NaBH3CN


NH4OAc, EtOH
reflux


CH3(CH 2)8-CHCH 2CH3
3-050


3-5).


-- .=





50




Results


-1-Octvlamine (3


-008) (Table 3-5).


The reaction of 1-octylamine (3


-008) with


49% aqueous formic acid (HCO2H) at 350 C for 0.5 h showed a 50.4% conversion to the


major products N-1-octylformamide (3-022,


17.5%),


1-octylamine (3-033,


11.6%).


Other minor products included 1-octanol (3-010,


7%),


N-methyl-1 -octylamine


-012, 5.4%),


N-methyl-N- 1-octylformamide (3-024, 3.0%),


N- 1-octylacetamide (3-


025,


N-methyldi- 1 -octylamine (3


-032, 1.0%) and N


, N-di-1-octylformamide (3-


040,


3.7%).


,N-Dimethyl-1-octylamine (3-013,


0.3%),


N-methyl-N-3-octyl-1-


octylamine (3-039, 0.


) and tri-1-octylamine (3-042, 0.


) were formed in trace


amounts.


Extending the reaction time to


2 h resulted in a 60.1


conversion with N-1-


octylformamide (3-022,


10.4%),


-octylamine


(3-033,


N-di-1-


octylformamide (3-040,


7.9%)


1-octylamine (3


-042,


2.7%


as the major


products.


Similar minor and trace products were observed as in the 0.5 h reaction.


Reactions at lower temperature gave significant formamide product formation.


250 *C in 49% aqueous HCO2H for 0.


1-octylamine (3


-008) underwent a 98.1


conversion to products with N-l1-octylformamide (3-022, 91.5%) as the major product


along with N-methyl-N-1-octylformamide (3-024,


) and N-l-octylacetamide (3-


025,


Increasing the reaction time to


2 h gave a somewhat lower conversion


(90.9%) to the major products N-l-octylformamide (3-022,


N-methyl-N-l-


octylformamide (3


-024, 9.8%) and N-l-octylacetamide(3-025,


6%).


N, N-Dimethyl-


-octylamine


-013)


N-acetyl-N- 1-octylformamide


-030)


N,N-di-1-


octylformamide (3-040) were each observed in less than


1-Octanol (3-010),


-


_ I
















I
r*
i**


0
I
-*


'0
S*


\0
fl


'6
* *


I
I S









N-methyl-N-1-octylformamide (3-024,


10.5%), di-


1-octylamine (3


-033,


9.7%)


,N-di-l-octylformamide (3


-040, 1


0%) as major products.


A similar slate of minor


products as seen previously was also observed.


The product slate suggests that formylation of 3


-008 yields N-l-octylformamide


-022) which can subsequently undergo reduction to furnish N-methyl-1-octylamine (3-


012).


Similarly,


, N-dimethyl- 1-octylamine (3


-013) can be derived from N-methyl-l-


octylamine (3-012),


but this conversion appears to occur in small amounts.


Di-1-


octylamine (3-033) can be obtained by further reaction of 3


-013 with 1-octylamine (3-


008).


Reaction


di-1-octylamine


(3-033)


with


HCO2H


leads


to N


N-di-1-


octylformamide (3-040) which can be subsequently reduced to N-methyldi-1-octylamine


(3-032).


Tri-1-octylamine (3


-042) can be obtained by reaction of 3


-033 with 3-013.


The increasing amount of 1-octylamine (3


-008) remaining with increasing reaction


time and temperature is unexpected.


Since reaction at 250


"C 0.5


h indicates 98.1


conversion, it appears that with increasing time and temperature all the 1-octylamine (3-

008) is converted to the observed products, some of which revert to starting material.


Di-1-octvlamine (3-033) (Table 3-6).


After 0.5 h, the reaction of di-1-octylamine


(3-033) with 49% aqueous HCO2H at 350 C showed 75.


conversion to 1-octylamine


(3-008, 3.9%),


1-octanol (3


-010, 2.4%),


N-methyldi-1 -octylamine (3


-032,


,N-di-1-octylformamide (3-040,


18.5%) and tri-1-octylamine (3


-042


Methyl-


1-octylamine


-012),


- 1-octylformamide


(3-022)


N-methyl-N-l-


octylformamide (3-024) and N


,N-di-1 -octylacetamide (3


-041) were formed in less than


Trace


amounts


octylformamide (3-034) were observed.


, N-dimethyl-1-octylamine (3-013)


Heating with 49% HCO2H for


N-l-octyl-N-3-

2 h led to the


formation of i-octvlamine (3


A 1\


--o u- J 'I *f .-


-n. l


Ao\


1-netannl (3


nin


A/-methvldi-1


. ..


-













,-

I*


-4
rl


-4

Vd
v


'I


0
I ni


0:


, C ,


00








t Co









were each observed in less than


Traces of N


, N-dimethyl- 1-octylamine (3-013) and


N-l-octyl-N-3-octylformamide (3-034) were observed in <0.1


and 0.8%, respectively.


The first step in the reaction sequence could be the cleavage of di-1-octylamine (3-


033) to give 1-octylamine (3-008).


1-Octylamine (3


-008) thus obtained,


could further


react to give a similar product slate to that discussed.


Once again, formamide formation was dominant at lower temperatures.


At 250


reaction


time


to N-methyldi-1-octylamine (3


-032,


6.8%),


N-di-1-


octylformamide (3-040, 82.


2%) and tri-1-octylamine (3-042, 3.0%) as major products.


The following four compounds were identified, each in less than 1


1-octylamine (3-


00 8),


, N-dimethyl-1-octylamine (3


-013),


N- 1-octyl-N-3-octylformamide (3


-034) and


N-methyl-N-3-octyl- 1-octylamine (3


-039).


Extending the reaction time to


2 h gave N-


methyldi- 1-octylamine (3


-032,


10.0%),


, N-di-1-octylformamide (3


-040,


70.7%) and


tri-1-octylamine (3-042,


4.8%) with an 88.3


conversion to products,


while the


10 h


reaction gave N-methyldi-1-octylamine (3-032,


, N-di-1-octylformamide (3-


040,


41.6%)


tri-1-octylamine (3-042,


with


an 81.3%


conversion


products. Again, there appears to be some equilibrium reversion to starting material.


2 h reaction also gave a small amount of N-l-octyl-N-3-octylformamide (3-034,


trace amounts of


1-octylamine (3-008),


1-octanol


(3-010)


N, N-dimethyl-1-


octylamine (3-013),


N-1-octylformamide (3-022)


024),

039).


N-methyl-N- 1-octylacetamide (3-029)

Similarly, the 10 h reaction gave small


and N-methyl-N-3-octyl-l-octylamine (3-


amounts of N-1-octylformamide (3-022,


N-methyl-1-octylformamide (3


-024,


0%),


N-l -octyl-N-3-octylformamide (3-


034, 1


) and N


, N-di- 1-octylacetamide (3


-041


,1.6%),


and traces of 1-octylamine (3-


n008f


1 -octanol


(3-010m


v t -- -


.N-dimethvl- 1-octvlamine (3


-013).


N-methyl-N-1-


N-methyl-N-1-octylformamide (3-









N. N-Dimethvl- 1-octvlamine (3-013) (Table 3-7).


At 350 *C in HCO2H for 10 h,


, N-dimethyl-1-octylamine (3


-013) showed a 64.0% conversion.


Products observed


include


1-octanol (3-010,


octylamine (3


N-methyldi-1-octylamine (3


-033, 10.2%) and tri-l-octylamine (3-042,


were identified in lesser amounts:


2-octanone (3-005,


4.6%).

4.3%),


-032,


.6%),


The following products

1-octylamine (3-008,


2.0%),


N-methyl-N-l -octylformamide (3


-024, 3


.2%),


and N


, N-di- 1-octylformamide (3-


040,


0%), with N-methyl-l-octylacetamide (3


-029) and N-l-octyl-N-3-octylamine (3-


031) in traces.


At lower temperatures N


,N-dimethyl-1-octylamine (3-013) was not very reactive


with 49% aqueous HCO2H.


At 250 *C for


2h, a


25.8


% conversion led to N-methyl-N-1-


octylformamide (3-024, 10.8%) as the major product.


Other products identified include


, N-dimethyl-2-ethyl- 1-hexylamine (3


-006


,1.8%),


, N-dimethyl-3-octylamine (3-011,


-032


- 1-octylformamide


After 10 h a 19.9% conversion led to N-methyl-3-octylamine (3


-011


(3-049,


) and


N-methyldi- 1-octylamine (3


-032,


7.5%


N-methyl- 1-octylformamide (3


-024,


3.2%


, N-dimethyl-3-octylamine (3-009, 1.4%) and 1-octylamine (3


-008,


<0.1


1-Dodecvlamine (3-023)


(Table


3-8).


1-Dodecylamine (3-023)


was


very


reactive in 49% aqueous formic acid. A 97.1% conversion was observed after 0.


six major products were 1-dodecanol (3


-026, 6.1


, N-dimethyl- 1-dodecylamine (3-


028, 8.6%),


-036,


N- 1-dodecylformamide (3


11.9%),


-035


,19.3%),


N-methyldi-1-dodecylamine (3


N-methyl-N-1 -dodecylformamide


-043, 20.0%)


and di-1-dodecylamine


-044,


9%).


Minor products observed were dodecane (3-016, 6.1%),


2-dodecene


(3-017,


0.3%),


1-dodecanol (3


-026


, 6.1%),


N-methyl-N-1-dodecylacetamide (3-037


1.4%) and N-acetvl-N- 1-dodecvlformamide (3


-.ia


A4AOt\


A ftPr


--UU 'tU / i. f LU!


10 hI a significant


N-methyldi- 1-octylamine (3




















N
lb*


, ,


00
I r-


I *


00
I
-4


0
Sci


-4





I I





1 cn
~W








FH


00
I *
N


0
* ri


F*













vi


' d


0,
I *
ci


'0
I 00


r-


I
I


,I
V3


I;
I *


* *r









The major products were 1-dodecanol (3


-026, 14.3%),


N-methyl-N-1 -dodecylformamide


(3-036,


10.0%),


N-methyldi-1-dodecylamine (3-043,


and di-1-dodecylamine


(3-044, 30.0%).


Also minor amounts of three isomers of dodecene (3-015,


3-017


019) were observed.


Lower temperature runs also showed moderate to high reactivity.


After 1 h, in


49% HCO2H at 150


dodecylformamide (3


*C, 1-dodecylamine (3


-035


-023) showed 58.2


) and a trace of di-1-dodecylamine (3


conversion to N-1-


-044,


After 0.5 h at 250 *C an 88.6% conversion was observed with N-1-dodecylformamide (3-


) and N-methyl-N-1-dodecylformamide (3


-036,


7.5%


as products.


conversion was observed after 10 h with N


, N-dimethyl- 1-dodecylamine (3


-028,


7.6%),


N-1-dodecylformamide (3


-035


N-methyl-N- 1-dodecylformamide


(3-036, 34.7%) as the major products.


Minor products identified were N-methyl-N-l-


dodecylacetamide (3


-037


, 2.1%),


N-acetyl-N-1-dodecylformamide (3


-038,


1.6%),


methyldi- 1-dodecylamine (3


-043, 3.3%) and di-1-dodecylamine (3


', N-Dimethvl- 1-dodecvlamine (3


-028) (Table 3-9).


-044,


A 46.0% conversion was


observed after reacting N


, N-dimethyl- 1-dodecylamine (3-028)


with


aqueous


HCO2H for


2 h at 350


The major products observed were


1-dodecanol (3-026,


14.8


N-methyldi-


1-dodecylamine (3


-043,


27.8


N-Methyl-N-l-


dodecylformamide (3


-036),


1-dodecene (3


-015) and dodecane (3


-016) were formed in


minor amounts.


Extending the reaction time to 10 h led to a 57.8% conversion with a


significant number of


minor products


- dodecane (3-016,


N-methyl-N-1-


dodecylacetamide (3


-037


, 0.4%) and di-


1-dodecylamine (3


-044,


The major


product was again N-methyldi- 1-dodecylamine (3


-043, 39.5%).


Two isomeric dodecenes


(3-015, 3-017) were also formed in this run in minor amounts.


























00








Irl


t*i


00









, N-Dimethyl-1-dodecylamine (3-028)


was much less reactive at 250 *C in


HCO2H for 0.5


Only a 7.3% conversion was observed with 1-dodecanol (3


-026,


), and N-methyl-N-1-dodecylformamide (3


-036,


as the


major products.


Traces of 1-dodecene (3-015,


0.4%),


dodecane (3-016, 0.


2-dodecene (3-017,


2%) and 3-dodecene (3


-019, 0.1%) were also identified.


Extending the reaction time to


10 h showed a 28.9% conversion with 1-dodecanol (3-026,


N-methyl-N-1-


dodecylformamide (3-036,


8%) and N-methyldi-1-dodecylamine (3


-043,


the only products (Table 3-9).


Since a clear mechanistic pathway (see


Discussion) could not be proposed for the


formation of


the rearranged product 3-009,


two additional


aquathermolyses were


performed to see whether similar rearranged products would be formed and whether a clear


mechanistic pathway could be determined.


butylamine (3-001) and N


The amines of choice were N


, N-dimethyl- 1 -hexylamine (3-003).


, N-dimethyl-1-


These two tertiary amines


were heated at 250 *C for 2 h in 49% HCO2H since these were the conditions under which

N, N-dimethyl-3-octylamine(3-009) was observed.


, N-Dimethvl-1 -butvlamine (3-001) (Table 3-10).


On heating with aqueous 49%


HCO2H


at 250


2 h, N


, N-dimethyl-1-butylamine (3


-001)


showed


a 63.1


conversion (Table 3-10).


The two major products were N-methyldi-1-butylamine (3-004,


32.3%) and N-methyl-N- 1-butylformamide (3


-007


2%).


Tri-1-butylamine (3-014,


1.1%) and N


,N-di- 1-butylformamide (3-020,


1.5%) were detected in minor amounts.


There was no detection of any rearranged product, that is, no N


, N-dimethyl-2-butylamine.








Table 3-10.


Products from N


, N-Dimethyl-1-butylamine (3-001) 49% HCO2H


Temp.(*C)
Time(h)


Compound


Identification


3-001
3-004
3-007
3-014
3-020


N, N-dimethyl- 1-butylamine
N-methyldi- 1-butylamine
N-methyl-N- 1-butylformamide


tri-1-butylamine


, N-di-1-butylformamide


Table 3-2
Table 3-4
Table 3-4
Table 3-3
Table 3-3


36.9
32.3
28.2


= molecular weight


. N-Dimethvl-1-hexvlamine (3


-003) (Table 3-11).


, N-Dimethyl- 1-hexylamine


-003) showed a 37.5% conversion after 2 h at 250 *C in 49% aqueous HCO2H (Table


3-11).


The major product was N-methyl-N-1-hexylformamide (3


-018, 23.9%).


Other


products included


1-hexanol (3-002,


2.8%)


N-methyldi-1-hexylamine (3-021,


10.8%).


There was no detection of any rearranged products.


Table 3-11.


Products from N


, N-Dimethyl-1-hexylamine(3-003) 49% HCO2H


Temp.(*C)
Time(h)


Compound


Identification


3-002
3-003
3-018
3-021


1-hexanol


Table 3-3


N, N-dimethyl- 1-hexylamine
N-methyl-N-1 -hexylformamide
N-methyldi-1 -hexylamine


Table 3


Table 3-4
Table3-4


62.5
23.9
10.8


- mal1 nn* n1rt fnt





62


General Discussion


The aliphatic primary amines showed the dominant reaction


formylation with subsequent reduction to give N-methyl and N


pathway as N-


N, -dimethylalkylamines.


That is, under the above mentioned aquathermolysis conditions the aliphatic amines are

involved in conventional reactions where the formic acid is behaving as a hydride donor


and as a formylating agent.


In the case of 1-dodecylamine (3


-023), in addition to the


above mentioned pathway, elimination of NH3 and HNMe2 to the corresponding alkene


was also observed; which could then undergo isomerization.


The secondary amine, di-1-


octylamine (3-033) underwent conventional N-formylation and subsequent reduction to


the N-methyl derivative.


Also, formation of the mono- and tri-


1-octyl derivatives is


representative of a cleavage process.


The tertiary amines underwent reductive cleavages to


primary and secondary amines, which subsequently followed the reaction sequences seen

for the primary amines.

Formation of N-l-octylformamide (3-022) and subsequent reduction products


was the major reaction pathway for 1-octylamine (3-008) (Scheme 3-6).


It is evident that


ower temperatures


there


is significant formamide


product


formation as well.


Subsequent reduction of the N-formylation product is supported by the presence of N-


methyl-1 -octyamine (3-012) and N


, N-dimethyl- 1-octylamine (3


-013).


Amine 3-012,


the reduced product of formamide 3-022 underwent a second formylation to give N-


methyl-N- 1-octylformamide (3-024).


Subsequent reduction of amide 3


-024


eads to


N, N-dimethyl- 1-octylamine (3-013).


Tri-1-octylamine (3-042) can be formed by the


reaction of amine 3-013 with di-1-octylamine (3-033).


In this process, amine 3-013


undergoes loss of N.N-dimethvlamine.


Di- 1-octvlamine (3


-033) is the product of self






















0
I c
0(3


V r
(I
++z
I I


0


I +
I


O
II


I I
I


+
I


p p


N
I I

0 .
I

XN *
O
LI
'a
0"
pII


I
0

z i
I




o+o
Iur

Ir


O= O
I
0=0
(0,

0o


CM
. n
2 ?2
Z 03
I
zo

0


I


N
1
o 5
I

I
CO


I
z
^N
I A
10









N-l-Octylacetamide (3


-025)


may have been produced under aquathermolysis


conditions via a rearrangement of N-methyl-N-1-octylformamide (3-024) (Scheme 3-6),

although we have been unable to find an example of an acid promoted rearrangement of a


formamide to an acetamide.


The other acetyl derivatives would have been formed from


further reaction of 3-025.


N-Acetyl-N- 1-octylformamide (3


-030) is produced from the


N-formylation of acetamide 3-025.


Subsequently, reduction of amide 3-030 would


generate N-methyl-N- 1-octylacetamide (3-029) (Scheme 3-6).


Similarly,


other primary


amine,


-dodecylamine


(3-023)


gave


N-l-


dodecylformamide (3


-035) as the main product under all reaction conditions,


subsequent reduction was supported by formation of the various N-methyl derivatives.


contrast to implied formation of 1-octene, formation of 1-dodecene is observed as well as


and 3- isomer (Scheme 3-7).


Under


aquathermolysis


conditions


1-dodecylamine


-023)


underwent


conventional N-formylation to

Subsequent reduction of amide 3


give N-1-dodecylformamide (3-035)

-035 generates the N-methyl derivative 3


(Scheme


-027


3-7).


. Loss of


methylamine from 3-027 results in the formation of 1-dodecene (3-015).


alkene 3


Alternately,


-015 may be generated either by the loss of ammonia from 1-dodecylamine (3-


023) or by the loss of N


, N-dimethylamine from N


, N-dimethyl-1-dodecylamine (3-028).


In turn, the amine 3


-028 is generated from the reduction of N-methyl-N-1-octylformamide


(3-036) which is produced by the N-formylation of N-methyl-1-dodecylamine (3-027).


1-Dodecene can undergo isomerization to both the


(3-017) and the 3-


(3-019)


derivative (Scheme 3-7).


Reduction of either of these alkenes would lead to dodecane (3-


016).


In addition, loss of ammonia from 1-dodecylamine (3


-023) and a formic acid


catalyzed reaction


with


water generated


1-dodecanol


(3-026). N


.N-Dimethvl-1-


_ _~~____




















I
0
I


NO
"O
0 I
No


BI
IO
O

O


o
4-z
10
I-z
I
Cu
I
CM
0


(O "
* S


CZ
I
z


N
I



9,
ri
5
A


IC
I0
o0


+


C


CO

ff ^
f0,
C o
a '

O
c'0


I4
I









The acetyl derivatives may


justified


amide 3-036,


though


corresponding N-1-dodecylacetamide (3-


108) was not detected by the GC/MS analysis


(Scheme 3-7).


N-Acetyl-N- 1-dodecylformamide (3


-038)


be explained via


formylation


3-108,


with


subsequent


reduction


leading


N-methyl-N-l-


dodecylacetamide (3-037).


Again, there is no literature precedence for the formation of


acetamide 3 -


108 from the formamide 3


-036.


As expected di-1-octylamine (3


-033)


underwent N-formylation.


a simple


reduction were the only possible reaction pathway, then N-methyldi-1-octylamine (3


would be the only next logical product.

takes place (on the starting amine), du


-032)


However, it is apparent that reductive cleavage

e to the presence in the product slate of similar


products to those obtained from 1-octylamine (3-008) (Scheme 3-6). Formation of N-1-

octyl-N-3-octylformamide (3-034) and N-methyl-N-3-octyl- 1-octylamine (3 -03 9) appear

to be from the isomerization of the octyl moiety before the formulation and reduction take

place (Table 3-9).

Since the tertiary amine could not undergo N-formylation directly, N-formyl and

subsequent reduction products would have to be formed after reductive cleavage of the


starting amine.


Reductive cleavage explains


methyldialkylamine major products from


both N


formation


alcohol


, -dimethyl-1-octylamine (3


-013)


(Scheme 3-6) and N, N-dimethyl-1-dodecylamine (3


N, -Dimethyl- 1-octylamine (3


-028) (Scheme 3-7).


-013) may be reductively cleaved to amine 3-008


and/or amine 3-012, which can each undergo the reaction pathways outlined in Scheme 3-


As shown in Chapter II,


formic acid may act both as a reducing and as an oxidizing


agent.


Its role as an oxidizer may explain the formation of octanone (3


-005).


Again the


rearranged derivatives 3


-006


,3-009, 3-011 and 3


-031 (Table 3-7) may be from the





67


tertiary amine 3-001 would undergo reductive cleavage to the primary amine before


formylation took place.


However, the corresponding primary amine, 1-butylamine (3-


109) was not detected by GC/MS.


, N-methyl-N-l-butylformamide (3


-007) does


support the above pathway, since its (3-007) formation may be viewed through the


formylation of 3-


109, to form 3-


112, which would subsequently be reduced to 3-


finally,


formylated once again


to give


amide


3-007.


Likewise


N, N-di-1-


butylformamide (3-020) is formed via formylation of 3-


. The intermediate 3-


111 is


generated from condensation of 3-


110 and 3-


109 accompanied by the loss of N


dimethylamine.


Tri-1-butylamine (3


-014) is a self condensation product via intermediate


3-109.


Simple reduction of 3


-020 leads to N-methyldi-1l-butylamine (3


-004) (Scheme


3-8).


The products from N


,N-dimethyl- l1-hexylamine (3


-003) are formed similarly to


those of amine 3


-001 (Scheme 3-9).


As seen with amine 3-001


, formation of N-methyl-


N-1-hexylformamide suggests the presence of intermediates 3-


114,


3-115 and 3-


116,


though they were not detected by the GC/MS analysis.


N-Formylation of intermediate 3-


114 would give 3-


115, which could undergo reduction to 3-


116.


Subsequent reduction


of intermediate 3-

not detected (3-1


116 would generate formamide 3-018.


14--3-


Since these intermediates were


116), this may suggest that they are being consumed within the


reactions.


N-Methydi-1-hexylamine (3-021) may be explained similarly, via formylation


and reduction of 3-


119 and


3-120, respectively.


As with


1-octylamine (3-008),


formation of 1-hexanol (3-002) implies the presence of an alkene


- 1-hexene (3-


117)


(Scheme 3-9).

























I
O
O
I
0

I
O
I
0




O


I
O
I
Z
oP
0


U.
0


0
I

z
0


CM
I
z0
I
O


0 2


'.
~^ c


Z
-a
'^s


CM
Cr


t
0o







































(U)
I
ro

0)

I '
co'

0
*p


I
a
I
O
0
Z4
z'


0)
I
cc


O
I

CM
I
0
Ii


z0
I
OI
0
r
0.


p
0
0
I
z
C,--
I
<0
p p


I I
CM
I
C)
cu e
0 T
~e .


I t
CM~
I:

r
I'
^'c
O0


I
0
o
II
I
o
0
02

.0
or
7
o


CM

i s
z o

I
_-CO


rC-





70


Conclusions


The general trend observed from the results obtained is that N-formylation is the


dominant reaction pathway.


Under the above mentioned aquathermolysis conditions the


aliphatic amines were involved in conventional reactions where the formic acid behaved


both as a hydride donor and as a formylating agent.


The aliphatic primary amines showed


the dominant reaction pathway as N-formylation with subsequent reduction to give N-


methyl and N


, N-dimethylalkylamines.


In addition to the above mentioned pathway,


there


was


also elimination of simple amines to yield the corresponding alkene which could


further undergo isomerization.


The secondary amine also underwent conventional N-


formylation and subsequent reduction to the N-methyl derivative, with formation


mono- and tri-1-octyl


of the


derivatives is representative of a reductive cleavage process.


tertiary amines underwent reductive cleavages to primary and secondary amines, which

subsequently followed the reaction sequences seen for the primary amines.


1-Octylamine (3-008)


displayed


significant amounts


N-formylation and


subsequent reduction products.


This trend was observed at 350 *C as well as at


ower


temperatures.


There was also some self condensation products


- di-1-octylamine (3


-033)


and tri- 1-octylamine (3-042).


Synthesis of authentic N-1-octylacetamide (3


-025) and investigation of its MS


pattern suggest that it could be a plausible product under the aquathermolysis conditions.

However, since the suggested pathway for its formation lacks literature precedence and is


an anomaly, amide 3


-025 may be alternately explained as an obscure impurity


1-Dodecylamine (3


-023)


gave significant N-formylation.


In addition,


formation of alkenes was observed via the 1


oss of ammonia and N, N-dimethylamine.









Di-1-octylamine (3-033),


also gave N-formylation, but it was not significant.


This secondary amine also underwent reductive cleavage and subsequent reduction, with


products similar to those from 1-octylamine (3


-008).


Both tertiary amines (3


-013, 3


-028) were, as expected, less reactive than the


primary and secondary amines.


Most products were generated from a primary or


secondary amine, which was produced by reductive cleavage of the corresponding tertiary

amine.


A number of rearranged products were identified, but may well be inadvertent


impurities.


Though, MS investigations indicate N


,N-dimethyl-3-octylamine (3-009) as a


possible product, aquathermolysis of N


, -dimethyl-1-butylamine (3-001)


and N


dimethyl- 1-hexylamine (3


-003) revealed no rearranged products similar to amine 3-009


and therefore could shed no light on a possible rearrangement pathway.


It is very likely


that the rearranged amine 3


-009


might


have


been


an impurity.


appears


rearrangement is not a normal pathway under the reaction conditions.


Experimental


1H NMR spectra were recorded either on a Gemini 300 (300 MHz) Varian VXR


300 (300 MHz) or a General Electric QE (300 MHz) spectrometer.


13C NMR spectra were


recorded at 75 MHz on the same spectrometers. Chemical shifts are reported in parts per

million (ppm) downfield from tetramethylsilane (TMS) used as an internal standard.


Coupling constants (J values)


are reported in


hertz


(Hz).


Analytical


layer


chromatography (TLC) was performed using pre-coated silica gel 60 F254 plastic plates

(0.2 mm thick) using iodine as an indicator to visualize the product compounds.









General procedure for the synthesis of N


.N-dimethvloctvlamines


, N-Dimethvl-3-octvlamine (3-009)


. 3-Octylamine (1 eq.,


2.4 g,


18.8 mmol),


formaldehyde (4 eq.,


3 g, 75.0 mmol) and titanium tetraisopropoxide (2 eq.


10.4 g,


mmol) was refluxed in diglyme (


0 ml) at 70


After


2 h the reaction was cooled to


room temperature and sodium borohydride (1.


reaction was then stirred at room temperature (7 h).


reaction was diluted with Et20 (


5 eq, 1.1 g, 28.1 mmol) was added.


After cooling to room temperature, the


mL) and aqueous ammonium hydroxide was added to


precipitate the inorganic product, which was filtered and washed with excess Et2O.


organic layer was dried over Na2SO4 and concentrated in vacuo.


Dyglime was removed by


distillation in vacuo.


A pale colored oil (1.6 g, 57%) was isolated.


1H NMR (CDCI3):


0.9 (t, 3H, J


= 6.5) (CHtCH2),


1.0 (t, 3H, J


= 7.0) (CHICH2CH),


.2 (s,


8H) (4CH2),


1.4 (m, 2H) (CH3CH2CH),


2.3 (s,


6H) (NMe2),


6 (m, 1H) (CH).


13C NMR (CDCI3):


13.9


0, 31


58.9.


= m/z


(C10H23N); base peak


m/z 86 (C5H12N).


,N-Dimethvl-2-octvlamine (3


-045).


This product was obtained as an off-white


oil which solidified upon cooling.


1H NMR (CDCl3)


6 0.9 (t, 3H, J


= 7.0) (CHCH2),


1.1 (d, 3H, J


= 6.7) (CH_3CH),


1.3 (s,


8H) (4CH2),


1.7 (m, 2H) (Ci2CH),


2 (S,


(NMe2),


2.9 (m, 1H) (CH).


13C NMR (CDCl3):


6 13.9,


6, 23


26.0, 29.4, 29.6,


31.8, 39.5, 54.9.


LR MS M+


= m/z 157 (C10H23N)


base peak


= m/z 72 (C4HIoN).


N-1-Octvlacetamide (3-025).


-Octylamine (iml)


was dissolved


n acetic


anhydride (2.


7 mL) and warmed for about 0.5 h.


The mixture was then cooled to room









7.4),


0 (s, 3H),


(q, 2H, J


= 6.7),


6.3 (s,


13C NMR (CDCl3): 6


13.9,


,26.8, 29.1


29.4, 31.7,


39.6,


170.2.


LR MS M+


= m/z 171


(CloH21NO);


base peak


= m/z 30 (CH4N)


N- 1-Dodecvlformamide (3-03 5)


1-Dodecylamine (10.0 g, 54 mmol)


was


suspended in an excess of aqueous formic acid (88%) (


48 g, 108 mmol).


The mixture


was refluxed in benzene (150 mL) under Dean-Stark conditions for the azeotropic removal


of water.


The reaction was refluxed for 18 h; cooled to room temperature and the solvent


removed in vacuo.


The pale yellow solid was recrystallized from petroleum ether to give


the title compound as white flakes (9.70 g, 84%) (m.p.


33.5-35


C) (Lit. [59MI388] m.p.


35-36 "C)


1H NMR (CDCl3): 6


0.9 (t, 3H, J


= 7.0), 1.3 (s,


18H),


.5 (t, 2H, J


= 7.0),


2 (q,


2H, J


7.0),


7 (br.


s, 1H), 8.2


(s, 1H); 13C NMR (CDCI3): 6 14.1,


.6, 26.8,


29.5


(2C),


6, 29.7,


31.8, 38.


161.1


HR MS m/z


213.2090 (M+


, C13H27NO requires


213.2090).


General procedure for the synthesis of orimarv anmines


3-Octvlamine(3-046).


Sodium cyanoborohydride (7.0 eq, 17.8 g, 273


mmol)


was suspended in absolute EtOH (100 mL) and 3-octanone (1.0 eq,


absolute EtOH (50 ml) was added dropwise via addition funnel.


39.1 mmol) in


Ammonium acetate (10.0


eq, 30.1 g, 390.1 mmol) was then added and the mixture was allowed to reflux at 70 *C.


After

to pH


5 h the reaction mixture was cooled to room temperature, acidified with cone.


then basified with 20% NaOH.


The aqueous layer was then extracted with CHCl3


..1 -


dried over Na-SOa and concentrated to give a nale fellow viscous oil (3.1 .


lm)X(1( 3 X)


I jk VV .at[









2H) (NH2).


13C NMR (CDC13):


22.8,


, 27.0, 31


32.8, 35.0, 58.9.


LR MS M+


129 (CgH19N),


base peak


= m/z 58 (C3H2N).


2-Dodecylamine(3- 049).


This compound was obtained crude as a pale yellow


viscous oil by the procedure outline above for 3

Kugelrohr distillation to produce a colorless oil (:


-046.


The sample was then purified by


0 g, 66%).


1H NMR (CDC13):


6 0.9


(t, 3H, J


(CI-!CH),


= 6.3) (CHICH2),


1.3 (s,


1.0 (t, 3H, J


16H) (8CH2),


1.7 (s,


= 6.9) (C.H3CH2),


2H) (CH),


1.1 (d of d, 3H, J


3 (d, 1H, J


7.0) (CH).


= 6.4, 6.3)

13C NMR


(CDCl3):


6 14.0,


23.7, 26.3, 29.


29,5


2C),


29.6, 31.8,


40.0,


46.8.


HR MS


185.2167 (M+


0.5%


, C12H27NO requires 185.


2167).


3-Dodecvlamine (3-050).


This compound was obtained crude as a pale yellow


viscous oil by the procedure outline above for 3


-046.


The sample was then purified by


Kugelrohr distillation to produce a colorless oil (07 g, 68%).


1H NMR (CDCl3):


60.9


6H) (NCH3CH2


CH3CH2),


1.0 (t, 3H,


= 6.9) (CH3CH2),


1.3 (s,


16H) (8CH2),


1.4 (m, 2H) (CHCH_2),


2H) (NH2),


6 (m,


1H) (CH).


13C NMR (CDCl3):


, 14.0,


6, 23.7


29,5,


29.6, 29.8, 30.6, 31.8, 37


52.6.


HR MS


m/z 185.2158 (M+


0.5%


, C2H27NO requires 185.2


158).


Aquathermolvsis: General.3 7


The purities of all starting materials


were checked by GC prior to use


Aqueous formic acid was deoxygenated with argon for


h prior to use.


49%


The model


compound (1 g) and the acid (7 mL) were charged into a nitrogen blanketed stainless steel


bomb which was then sealed.


The reactor was then kept without agitation in a fluidized


= m/


.5 (m,









The reaction mixture was then worked up as previously described [90EF493],


subjected to GC analyses on a Hewlett Packard 5890 instrument (flame ionization detector,


FID) fitted with a 15 m capillary column (SPB-


1) and an oven temperature program of 10


*C/min from 50


-250 C.


Gas chromatographic/mass spectral analyses were obtained on a


Hewlett Packard 5890 Series II Gas Chromatograph with a HP 5972A Mass Selective

Detector (MSD).


Product identification.


Within the reaction mixtures, the identities of all the starting


materials, and some of the products [3-005


3-006, 3-008, 3


-009, 3-010, 3


-012--3-


024, 3


-026, 3-027


,3-028, 3


-032, 3-033, 3-035,


3-040--3


-042 and 3


-044] were


confirmed by comparison of their retention times and mass spectral fragmentation patterns

with those of the authentic compounds, commercially available or prepared independently.


Table 3


-2 records the source and mass spectral fragmentation patterns of the authentic


compounds used, either as starting materials or for the identification of products.


For some


other products [3-006, 3-009,


3-012,


3-015,


3-017--3


-022,


3-026,


3-032,


040, 3-041 and 3


-044 for which authentic samples were not available, identification was


by comparison of their mass spectral (MS) fragmentation patterns with published mass


spectra (Table 3-3).


The structure for the remaining products (Table 3-4) [3


-011


,3-024,


3-025


3-027


3-029--3


-031


,3-034, 3


-036--3


-039 and 3


-043] were assigned by


consideration of their mass spectral fragmentation patterns together with the starting

materials, reaction conditions and reasonable mechanistic pathways for their formation


from the starting materials.


Tables 3-3 and 3-4


record the mass spectral fragmentation


pattern of those compounds for which authentic samples were not available


the structural


assignments of these were based either on the fragmentation pattern of that same compound


reported in the literature (Table 3-3IL


or deduced from the fragmentation nhberved and















CHAPTER IV
BENZIOTRIAZOLE- 1-CARBOXAMIDINIUMTOSYLATE: AN ALTERNATIVE
METHOD FOR THE CONVERSION OF AMINES TO GUANIDINES



Introduction


Much research has been directed toward the synthesis of guanidines as many


biologically active compounds contain guanidine moieties.


Established methods for the


preparation of guanidines include the use of cyanamide [04CB 1681, 50CB1260, 270S46,


46HCA324,


50JOC884,


50JOC890


, 51CJC718,


51JCS1252,


71JA5542],


alkylthiouronium salts and derivatives [430S345,


63JMC275

92TL5933


550S440, 58CJC1541, 62RTC69,


74JOC1166, 87JOC1700, 89SC1787, 90JCS(P1)311, 91MI425, 92MI119,


, 93TL7677, 94SC321, 94TL977],


aminoiminosulfonic acids [86JOC1882,


87S777


, 88TL3183,


90SC3433],


3,5-dimethylpyrazole-1 -carboxamidine nitrate


[58CJC1541,


90JCS(P1)311,


91MI425,


94SC321],


pyrazole- 1-carboxamidine


hydrochloride [92JOC2479, 93SC3055, 93TL3389] and N, N'-bis(tert-butyloxycarbonyl)-

and N, N'-bis(benzyloxycarbonyl)thiourea [94TL977].

Historically, preparation of guanidines has been accomplished using cyanamide (4-


001)


[04CB 1681


46HCA324,


4270S46,


50CB1260,


50JOC884,


50JOC890,


50CJC718, 51JCS1252, 71JA5542].


The cyanamide methodology has usually been used


to synthesize aromatic guanidines such as phenylguanidine, dibenzoylphenylguanidine and


n-methvlnhenvliruanidine nitrate l04CR 16R11


fGurlnidine nlhatitntedp with elertrnn-





77


p-nitrophenylguanidine, a, a-diphenylguanidine, phenylbenzoylguanidine and m- and p--


nitrophenylbenzoylguanidine [50CB 1260].

been moderate to good (50--80%) but t


Reaction yields of this cyanamide process have


the reaction conditions have often been harsh


involving refluxing at high temperatures for long periods of time [50JOC884, 50JOC890,


51CJC718].


Even more harsh conditions involve fusion at 200


-260


*C [51JCS1252].


These conditions were used to prepare aliphatic guanidines in moderate yields.


Compound


4-001 has also been used to prepare guanidines from amino acids--but long reaction times

(several days) are required [71JA5542] with the products isolated as pirates.


H2N


4-001


S-Alkylthiouronium halides or salts have been used effectively to synthesize


guanidines [58CJC 1541


63JMC275,


71JA5542, 92TL5933].


More specifically


ethylthiourea hydrogen bromide (4-002)


(which requires synthesis from thiourea)


[550S440] has been used to convert glycine to guanidinoacetic acid in 80


- 90% yield.


Methylthiourea sulfate/hydrogen sulfate (4-003)


[430S345,


62RTC69,


74JOC1166,


90JCS(P1)311,


92MI119, 94SC321] has been used to generate a variety of compounds.


Compound 4-003 has been used in the synthesis of dicyanodiamide [430S345] and to

generate monosubstituted guanidines [90JCS(P1)311] (reaction time 48 h).


H2N


NH*HBr


H2N' NH*H2SO4


4-002


4-003


S/\









guanidino group.


Guanylation of the aminomethyl derivatives of azepines [94SC321] has


also been accomplished using this methodology.

Aminoiminomethanesulfonic acid (4-004) and its phenyl derivatives [86S777,

86JOC1882, 88TL3183] have been used to generate guanidines at ambient temperature


within a matter of minutes.

purified by crystallization.


Products precipitate from the reaction mixture and can be

Formamidinesulfinic acid which is used to generate the


aminoiminosulfinic acids may be used as a guanylating reagent [88TL3183].


acid derivatives are crystalline and are stable over a few weeks.


The sulfonic


Displacement of the


HSO3-


groups


takes


place


more easily


than


the alkylmercaptan anion of


kylthioureas


classical


synthetic


procedures


[88TL3183].


Ethylaminoethyliminomethanesulfonic acid (4-005) has been used in the amidination of

lysine [90SC3433] of which the amidination is known to occur regiospecifically.


SOaH


H2N


EtHN


SOaH

NEt


4-004


4-005


Literature searches thus far have revealed two pyrazole reagents for the conversion


amines to guanidines:


i) 3,5-dimethylpyrazole-1-carboxamidine nitrate (4-006)


[63JA2


86S777


, 90JCS(P1)311


91MI425


94SC32


pyrazole-1-


carboxamidine hydrochloride (4-007).


Both reagents have been used effectively with


amines and are improvements over the existing methods.


However, 4-006 requires a


strongly basic medium and/or heat when used in the formation of guanidines [86S777].









C


H2N


NH*HNO3


H2N


NH*HCI


4-006


4-007


Compound 4-006 is a convenient reagent for the synthesis of monosubstituted


guanidines [90JCS(P1)311].
room temperature (2 days) d<


Reactions are normally carried out at 40


pending on the substrate.


*C (about 4 h) or


This guanylnitrate reagent has also


been


used in


the synthesis of


analogs of


the antihypersensitive agent


guanetidine


[94SC321],


but with low isolated yields.


Products were isolated as nitrates.


A more versatile reagent is pyrazole-1-carboxamidine hydrochloride (4-007)


[92JOC2497, 93SC3055, 93TL3389].


Pyrazole 4-007 reacts with primary and secondary


amines to produce guanidine hydrochlorides in good yields, and is also a useful reagent for
peptide synthesis when standard methods for the conversion of amines to guanidines are


not practical [92JOC2497].


for short periods of time and


The gaunylpryazole 4-007 can be stored in aqueous solution


used in stoichiometric amounts at room temperature.


pyrazole by-product is soluble in ether and can be easily removed [92JOC2497].


This is a


welcomed advantage over 4-006 which requires refluxing and two equivalents of the

amine.


Protection of 4


-007 [93SC3055, 93TL3389] is known to enhance its reactivity.


, N-bis-(tert-Butyloxycarbonyl)- 1-carboxamidinepyrazole (4-008a)


N' -bis-


(benzyloxycarbonyl)-l-carboxamidinepyrazole(4-008b) have been used for mild and
efficient preparation of monosubstituted guanidines [93TL3389] and in peptide synthesis


[93SC3055].


The bis-urethane protected (Boc, Cbz) derivatives 4-008a and 4-008b










N


ZHN


4-008a
4-008b


=Boc
=Cbz


Slight modification of the guanyl reagent allows for the generation of (protected)


guanidines


which are


more soluble


in organic solvents.


Acyl-


[92TL5933]


cyanothioureas [89TL7313] have been used for the preparation of


monosubstituted


guanidines.


Normally, this


occurs as a one pot, two stage procedure.


Also, bis-protection


of the guanidine reagent with tert-butoxycarbonyl (Boc) or benzyloxycarbonyl (Cbz)


enhances


reactivity.


,N-bis(tert-B utoxycarbonyl)thiourea


(4-009)


methylisothiourea (4-010)


[87JOC1700, 92MI 119, 93TL7677, 94TL977] and N, N'


bis(benzyloxycarbonyl)thiourea (4-011) [87JOC 1700, 92MI 119, 94TL977] have been
used to synthesize protected guanidines which are easy to purify.


BocHN


NHBoc


BocN


NHBoc


CbzHN


NHCbz


4-009


4-010


4-011


Kozikowski and co-workers have used these protected guanidine reagents (4-009-

-4-011) [94TL977] to synthesize guanidines in excellent yields starting from alcohols,

while Kim and co-workers have enhanced the reactivity of highly deactivated amines and


the bis-Boc protected guanidines by treatment with HgC12 or CuCl2


[93TL7677].


usefulness of benzotriazole


(4-012)


as a synthetic


auxiliary


well





81


of benzotriazole adducts, and (ii) it's anion is an especially good leaving group which can


be displaced by various types of nucleophiles.


report a novel,


In extending this latter property we now


effective and convenient reagent for the mild and efficient conversion of


amines


to guanidines utilizing benzotriazole methodology.


Our approach


utilizes


benzotriazole- 1-carboxamidinium tosylate (4-013) to generate substituted guanidines from

amines.


H2N


NH+
NH2


TsO'
4-013


Results and Discussion


Benzotriazole-1-carboxamidinium tosylate (4


-013) was conveniently prepared in


good yield by modification of a procedure previously reported for the preparation of


pyrazole-1-carboxamidine hydrochloride (4-007) [92JOC2497]:


benzotriazole, cyanamide and p-toluenesulfonic acid (p-TsOH)


dioxane (Scheme 4-1).


molar equivalents of


were refluxed in


The amidinium tosylate 4-013 preciptated from the reaction during


reflux, and could be filtered from the reaction mixture.


Recrystallization gave pure


benzotriazole- 1-carboxamidinium tosylate (4-013) (77%) as stable, non-hygroscopic, fine

white needles.

The reaction for the formation of guanidines from benzotriazole- 1-carboxamidinium
.- 1 at-n- A A lll "\ .- ..... I C-... _--.. .-- .-.. .. __ ___- ... ..








(DIEA) at room temperature, (ii) in CH3CN or (iii) in the absence of solvent.


Product


isolation is facile as the precipitated guanidine can be filtered from the ether soluble


benzotriazole by-product when DMF is used as solvent.


When CH3CN is employed the


product precipitates during the reaction, while in the absence of solvent the product can be

isolated chromatographically (Scheme 4-2, Table 4-1).


p-TsOH


-CEN


1,4-dioxane,


reflux


| N
- N
+
H2N~ N2


TsO'


4-001


4-012


4-013


Scheme 4-1


RN, R'
+NH
H2NO-NH
TsO"


50 C


R-N,


15 mins


H2N


4-015d


NH+
NH2


DMF
DIEA
rt


R, R1
N


H2N


NH2


TsO"


TsO'


4-013


4-014a-


4-015


= n-Bu


DMF


cR, R1
b R.R1


=Me
= -(CH2)5-


RN


gR, R1


= -[(CH2)21-
= -(CH,2)s-


H2N


TsO"
4-015


cR, R1
e R.R1


= MeOCeH4


=C6H


Scheme 4-2


- C6H1








Table 4-1


Products of the Reaction of Benzotriazole-1-carboxamidinium Tosylate (4-
013) with Primary and Secondary Amines


Entry


Amine


4-014a-h


Guanidine
4-015a-h


Yield(%)a


NHI
(i) Me2NH MeNH2N2 69b


NNH2


MeO NH2


MeO


H NH2 Ts


C4HQNH


C4HgNH2


/


NH2
NHTsO
NHo'5


H2
NH2
NH2 TsO"


NH2
NH2


0 I


NH2


TsO'


(viii)


C6H13NH2 CH13NH


NH2
NH2 TsO


aReported yields for purified compounds, reaction time 4-5 h,


Reaction time 24 h, performed in the


absence of DIEA (diisopropylethylamine), reaction time 15 min in the absence of solvent, reaction time
days, performed in CH3CN in the absence of DIEA, reaction time 24 h.


-4


--4





84



Formation of the guanidines 4-015a-b, and 4-015f-h was carried out in DMF in


the presence of DIEA (Scheme 4-


Table 4-1).


In these reactions DIEA serves to


neutralize 4-013 and make it more miscible with organic solvents.


amine 4-014h


Use of the primary


and the secondary amines 4-014a and 4-014f-g afforded the desired


guanidines easily.


However, when the secondary amine, N


, N-diethylamine (4


-0141) was


used, this resulted in the formation of the tosylate salt 4-016 and not the desired guanidine


(Scheme 4-3).


This may be because N


, N-diethylamine is a sterically hindered, more basic


secondary amine.


DMF


4-013 + EtN ,H

H


4-0141


DIEA


EtN ;Et

H TsO


4-016


Scheme 4-3


4-Methoxyaniline- 1-carboxamidinium


tosylate


(4-015c)


aniline-l-


carboxamidinium tosylate (4-015e) were both prepared from 4-013 in DMF in the


absence of DIEA.


reaction.


With primary aromatic amines, the absence of DIEA does not hinder the


Guanidine 4-015e could also be synthesized in CH3CN after five days stirring


at room temperature.


Attempts were made to generate various other phenyl substituted


guanidines under the above conditions, but resulted in the recovery of unreacted starting

materials (Scheme 4-4).


4-013


R,'N'


DMF


No Reaction


4-014


*.... t ._ ...


SA -,,1


& LA A I


* | i


**
a a





85


Since previous attempts to generate n-butylamine-1-carboxamidinium tosylate (4-

015d) by the standard procedure using 4-013 in DMF with DIEA resulted either in poor


yield (34%) or isolation of the corresponding n-butylamine tosylate salt (4-017),


prepared in the absence of solvent.


it was


Guanidine 4-015d was prepared by heating 4-013


4-014d


at 50


minutes.


product


was


purified


column


chromatography.


The poor yield isolated in the standard procedure may be due to


reversible formation of the desired product, which can then decompose to starting materials

and undergo formation of the tosylate salt at a much faster rate (Scheme 4-5).


slow


4-013 +


r 4-015d


C4H9


4-014d

fast


C4H9N H3+ TsO'
4-017
Scheme 4-5


Comparisons of the existing literature methods for the preparation of guanidines

from amines suggest that the pyrazole-1-carboxamidine (4-007) [92JOC2497] approach


is superior to the other literature methods previously mentioned.


Some of the advantages


include mild reaction conditions, the ease of preparation and product isolation and the

extended shelf-life of the parent amidine.

We therefore compared benzotriazole-1 -carboxamidinium tosylate (4-013) with the


pyrazole derivative 4-007 and concluded that 4-013,


while similar in ease of preparation









from pyrazole-1-carboxamidine hydrochloride (4-007) [92JOC2497].


We now report a


yield


84%


using


4-013.


Preparation


hydrochloride


derivative of


methoxyaniline-1-carboxamidinium tosylate (4-015c)


using


pyrazole-1-carboxamidine


hydrochloride (4-007) [92JOC2497], required a reaction time of 21 h to give a yield of


58%.


Using the benzotriazole methodology, an improved yield of 68% was isolated after a


reaction time of 24 h.


The benzotriazole derivative 4-013 is more reactive than 4-007


which is


as expected,


since


benzotriazole is a better leaving group than pyrazole


[91T2683].


The hydrochloride analog of the phenylguanidine salt 4-015e was prepared


previously from aniline using 4-007 [92JOC2497],


in nitrobenzene.


but the procedure involved refluxing


The use of 4-013 afforded 4-015e in dimethylformamide or acetonitrile


after 5 days at room temperature.


Conclusions


In summary, benzotriazole methodology has been extended in the preparation of an

alternative reagent for the preparation of guanidines from primary aliphatic and aromatic


amines and secondary aliphatic and cyclic amines.


Guanidines can be conveniently


prepared and isolated in a one pot sequence as the corresponding tosylate salts.


This


eliminates the step of converting the guanidine to an isolable compound such as a pirate.


Under mild conditions,


benzotriazole- 1-carboxamidinium


tosylate


(4-013)


gives


guanidines in moderate to good yields, and offers advantages such as increase yields and

reactivity over the existing procedure employing pyrazole-1-carboxamidine hydrochloride


(4-007).


Benzotriazole-1-carboxamidinium tosylate (4-013) can be easily prepared and


purified and stored over lone periods of time.





87


Experimental


General.


Melting points were obtained using a Thomas Hoover capillary melting


point apparatus and are uncorrected.


VXR 300 (300 MHz),


1H NMR spectra were recorded either on a Varian


Gemini (300 MHz) or General Electric QE 300 (300 MHz)


spectrometer.


l3C NMR were recorded at 75 MHz on the same instruments.


Chemical


shifts (6) are reported in parts per million (ppm) downfield from tetramethylsilane (TMS)


as the internal standard.


Coupling constants (J values) are reported in Hz.


All reactions


were performed in an inert atmosphere using oven-dried glassware.


Elemental analyses


and high resolution mass spectrometry were performed on site at the analytical facility.

Benzotriazole, ether and piperidine were purchased from Fisher and used as


supplied.


Cyanamide,


DMF, also purchased from Fisher,


dimethylamine, n-butylamine,


was dried over


4A molecular sieves.


pyrrolidine, n-hexylamine and DIEA


were


purchased from Aldrich and used as supplied. Aniline (Aldrich) was distilled prior to use.


4-Methoxyaniline (Aldrich) was recrystallized from hexane prior to use.


(Fluka) was used as supplied.


Morpholine


TLC was performed on pre-coated silica gel F254 plates


which were developed using hexane:ether (70:30) and were visualized with UV light and

iodine.


Benzotriazole- 1-carboxamidinium Tosvlate (4-013).


A mixture of benzotriazole


(11.9 g, 0.1 mol),


cyanamide (4.2


g, 0.1 mol) and p-toluenesulfonic acid (19.2 g, 0.1


mol) was refluxed in 1,4-dioxane (150 mL) for 24 h.


heating.


A white precipitate formed upon


The reaction was then cooled to room temperature, diluted with Et20 (200 mL)


and stirred vigorously for several hours.


The solid was filtered under vacuum


allowed to


.









8.0 (d, 1H, J


= 8.4),


8.3 (d, 1H, J


= 8.2),


10.1 (br


s, 4H).


13C NMR


(DMSO-d6):


20.9, 112.9,


120.4,


126.7


, 128.4,


130.6,


130.7


, 138.4,


144.6,


145.8,


152.0.


Further confirmation was accomplished by single x-ray crystallography (see Appendix C).



General procedure for the formation of substituted guanidines


, N'-Dimethvlamine- 1-carboxamidinium tosvlate (4-015a).


To a mixture of


dimethylamine (40% wt. soln.


in water) (100 pL, 90 mg,


2.0 mmol),


benzotriazole-1-


carboxamidinium tosylate (666 mg,


2.0 mmol) and diisopropylethylamine (DIEA) (347


mg, 2.0 mmol) was added DMF (10 mL).


The reaction was stirred at room


temperature and monitored by TLC.


After


5 h the reaction mixture was diluted with Et20


(20 mL),


stirred and the crude precipitate collected,


washed with Et20O and


dried.


Recrystallization from EtOH afforded white prisms (356 mg, 69%),


mp 173-175 *C (lit.


[51JCS1252] mp 179


1H NMR (DMSO-d6):


= 2.3 (s,


3H),


2.9 (s,


6H),


2H, J


= 8.0),


7.3 (s,


4H),


7.5 (d, 2H, J


= 8.1).


13C NMR (DMSO-d6):


= 20.9, 37.8,


128.4, 138.4, 144.7


156.9.


Piperidine-1 -carboxamidinium tosvlate (4- 015 b).


mg, 3.0 mmol),


DIEA (


Treatment of piperidine (296


benzotriazole-1-carboxamidinium tosylate (1.0 g, 3.0 mmol) and


1 pL, 387 mg, 3.0 mmol) as described for compound 4-015a gave the crude


product after 4 h.


Crystallization from EtOH gave fine white needles (753 mg, 84%),


183-184 *C.


1H NMR


(DMSO-d6):


1.4-1


.5 (m, 6H),


2.3 (s,


3H),


3.4 (t,


4H, J


2 (d, 2H, J


= 8.4),


7.3 (s,


4H),


7.5 (d, 2H, J


= 8.2).


13C NMR (DMSO-d6):


20.8, 2


- -


46.2, 125.5. 128.3.


138.4. 144.8. 1


5. C1IH1iNtOtS requires:









4-Methoxvaniline- 1-carboxamidinium tosvlate (4-015c).


Treatment of


methoxyaniline (393 mg, 3.0 mmol) and benzotriazole-1-carboxamidinium tosylate (1.0 g,


3.0 mmol) as described for compound 4-015a gave


the crude product after 24 h.


Crystallization from MeOH/Et20 gave fine white needles (884 mg, 68%),


mp 143-144


1H NMR (DMSO-ds):


(s, 3H),


3.8 (s, 3H), 6.9 (d, 2H, J


= 4.4),


= 4.4),


7.3 (s,


4H),


5 (d, 2H, J


= 3.7),


13C NMR (DMSO-d6):


= 20.9,


114.9,


128.4,


144.6,


156.3


158.1.


(C14Hi9N304S, FAB):


(M+H)+


= 166.0910.


CgH12N3 (calcd as free base) requires


166.0980.


n-Butvlamine- 1-carboxamidinium


tosylate


(4-015d).


Benzotriazole- 1-


carboxamidinium tosylate (3.0 g, 9.0 mmol),


n-butylamine (887 pL, 657 mg, 9.0 mmol)


and DIEA (1.56 mL, 1.16 g, 9.0 mmol) were heated (50 *C) with stirring for 15 minutes.

The viscous, pale-yellow crude material was cooled to room temperature, dissolved in a


minimal amount of THF and purified by flash column chromatograghy using Et20,


THF


EtOH


consecutively


as eluents.


hygroscopic white solid obtained


upon


evaporation of the EtOH fractions


was suspended in CHC13 to precipitate the pure


hygroscopic white solid (1.4 g,


55%


mp 135 *C (decomposition).


1H NMR


(DMSO-


0.9 (t, 3H, J


= 5.4),


1.3 (septet, 2H, J


= 7.5),


1.4 (septet, 2H, J


7.1),


2.3 (s,


3H),


3.1 (q,


2H, J


= 6.4),


7.1 (d, 2H, J


7.6 (d, 2H, J


= 7.2),


NH protons not


observed.


13C NMR


(DMSO-d6):


20.8, 30.4,


40.5, 125.4,


138.3


144.3


156.8.


HR MS (C12H21N303S,


FAB)


(M+H)+


= 116.1186.


CsH13N3


(calcd as free base) requires 116.1187.





90


filtered and recrystallized from EtOH/Et20 to yield a fine white powder (417 mg, 68%),


mp 150-151 *C.


1H NMR


(DMSO-d6):


= 2.3


3H),


7.1 (d, 2H, J


7.3),


2H, J


= 8.0),


7.3 (d,


2H, J


7.4),


7.4, (t, 1H, J


7.1) 7


(d, 2H, J


= 8.2) 9.7 (s,


1H),


NH2 not observed.


13C NMR


(DMSO-d6):


= 20.9,


124.4,


126.4,


128.4,


129.7


138.4


, 144.6,


(C14H17N303S,


FAB):


(M+H)+


136.0854.


C7H10N3 (calcd as free base) requires 136.0874.


Aniline- 1-carboxamidinium tosylate (4-015e).


Treatment of benzotriazole-1-


carboxamidinium tosylate (666 mg,


0 mmol) and aniline (182 pL, 186 mg,


0 mmol) in


CH3CN as described for compound 4-015a gave the crude product after


5 days (392 mg,


64%).


HR MS (C14H17N303S,


FAB)


(M+H)+


= 136.0854.


C7H10N3 (calcd as free


base) requires 136.0874.


Morpholine-4-carboxamidinium tosvlate (4-015 f).


Treatment of morpholine (174


HL, 174 mg, 2.0 mmol),


benzotriazole-1-carboxamidinium tosylate (666 mg,


2.0 mmol)


and DIEA (347 yL, 258 mg,


2.0 mmol) in DMF (3 mL) as described for compound 4-


014a gave the crude product after 24 h.

crystalline, white powder (520 mg, 86%),


Crystallization from EtOH/Et20 gave a fine


mp 165-167 *C.


1H NMR


(DMSO-d6):


, 3H), 3.6 (t,


SJ = 4.8),


3.9 (t,


4H, J


7.4 (d, 2H, J


= 8.3),


7.8 (d &


6H Jd


8.2).


13C NMR


(DMSO-d6):


= 20.8,


65.3


128.4,


138.4,


144.7


156.4.


HR MS (C12H19N304S, FAB):


(M+H)+


130.0973.


C5H12N30 (calcd


as free base) requires 130.0981.


Pvnnrolidine-1-carboxamidinium tnsvlate (4-.01 Yl


TrePatment nf nvrrnlidina (1i









yellow needles (404 mg, 71%),


mp 185-187 "C.


1H NMR (DMSO-d6):


1.9 (t,


4H, J


= 6.6),


2.3 (s, 3H), 3.3 (t,


4H, J


= 6.6),


7.2 (d &


,6H, Jd


= 8.0),


7.5 (d,


= 8.0).


13C NMR


(DMSO-d6):


= 20.8,


24.7


46.9


, 125.4,


128.3


144.8,


154.3.


C12H 19N303S requires:


H, 6.71


14.73.


Found:


C, 50.


H, 6.70


HR MS (C12H19N304S,


FAB):


(M+H)+


= 114.1025.


CsH12N3 (calcd as free


base) requires 114.1031.


n-Hexvlamine- 1-carboxamidinium tosvlate (4- 015 h).


Treatment of n-hexylamine


(264 yL, 202 mg,


mmol) and DIEA (347 pL,


4-015a gave the crude product after 24 h.


2.0 mmol), benzotriazole-1-carboxamidinium tosylate (666 mg,


0 mmol) in DMF (3 mL) as described for compound


Crystallization from EtOHIEt20 gave fine


white, crystalline flakes (420 mg, 67%),


mp 1


1H NMR (DMSO-d6):


(t, 3H, J


= 6.6),


.2 (br


s, 6H),


1.4 (q,


2H, J


= 6.3),


(s, 3H), 3.1


2H, J


= 6.5),


7.2 (d &


7H,Jd


8.2),


7.6 (d, 2H, J


= 8.3).


13C NMR (DMSO-d6):


13.9, 20.8,


28.3


(C14H25N303S,


30.8


FAB):


40.8


(M+H)+


138.4


= 144.1431


156.8.


. C7H18N3 (calcd as free base) requires


130.1501.


N. N-Diethvlamine tosvlate salt (4- 016).


Treatment of N


, N-diethylamine (197uL,


146 mg, 2.0 mmol),


benzotriazole-1-carboxamidinium tosylate (666 mg,


0 mmol) and


DIEA (287 4L, 258 mg, 2.0 mmol)


gave the crude product after 24 h.


n DMF (5 mL) as described for compound 4-015a

Crystallization from EtOH/Et20 gave fine white,


crystalline flakes (470 mg, 82


), mp 96-98


1H NMR (DMSO-d6):


1.0 (t, 6H, J


= 7.3),


7 (a


4H.J


7.3).


7.1 (d. 2H. J


'.9L 7.4 (d. 2H J.


7.8g 8R


3 H)


. .. .


-


n









n-Butvlamine tosvlate salt (4-017).


Treatment of n-butylamine (197uL, 146 mg,


0 mmol),


benzotriazole-1-carboxamidinium tosylate (666 mg, 2.0 mmol) and DIEA (287


yL, 258 mg,


0 mmol) in DMF (5


mL) as described for compound 4-015a gave the


crude product after 24 h.


Crystallization from EtOH/Et20 gave fine white, crystalline


flakes (380 mg, 68%), mp 80-82


1H NMR (DMSO-d6):


= 0.9 (t, 6H, J


= 9.0),


(m, 2H),


.5 (m


3H),


7 (t, 2H, J


= 8.5),


7.1 (d, 2H,


= 8.5),


7.5 (d,


2H, 8.5),


3H).


13C NMR


(DMSO-d6):


13.8,


, 29.4, 39.08,


9, 128.6,


145.4.


2H,),














CHAPTER V
INVESTIGATIONS OF 4-AMINO-1,2,4-TRIAZOLE:
APPROACHES TO THE DEVELOPMENT OF A NEW ELECTROPHILIC
AMINATING AGENT & METHODOLOGY FOR THE PREPARATION OF
4-(ALKYLAMINO)- 1,2,4-TRIAZOLES



Introduction


4-Amino-1,2,4-triazole (5-001)


was


first


obtained


Curtius


Lang


[1888JPR531].


Later in 1906, Bulow and co-workers demonstrated that triazole 5-001


reacts with 1,4-dicarbonyl compounds to afford the corresponding pyrrole derivatives


[06CB2618, 06CB4106].


This reaction is characteristic for most primary amines.


Triazole


5-001 was also synthesized from the self-condensation of formhydrazide at 150-250 *C


[440S12].


The formhydrazide was made from ethyl format and hydrazine.


The amino


group of the triazole 5-001 is weakly basic [71JPR795, 89JOC731], therefore it is


alkylated and aminated only at the ring nitrogen atom [89S69].


N-Alkylaminotriazdoles


have been synthesized by the reduction of the corresponding Schiff bases with sodium

borohydride and lithium aluminium hydride [88JOC3978].


-N

INH
NH2


5-001


This chapter, which focuses upon investigations of 4-amino-l,2,4-triazole will be




Full Text
xml version 1.0 encoding UTF-8
REPORT xmlns http:www.fcla.edudlsmddaitss xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.fcla.edudlsmddaitssdaitssReport.xsd
INGEST IEID EQ1XI9ZA0_N7KX0G INGEST_TIME 2011-08-29T15:31:03Z PACKAGE AA00002056_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES



PAGE 1

678',(6 ,1 7+( &+(0,675< 2) &<&/,& $1' $&<&/,& 1,752*(1 &203281'6 %\ 526/<1 /255$,1( :+,7( $ ',66(57$7,21 35(6(17(' 72 7+( *5$'8$7( 6&+22/ 2) 7+( 81,9(56,7< 2) )/25,'$ ,1 3$57,$/ )8/),//0(17 2) 7+( 5(48,5(0(176 )25 7+( '(*5(( 2) '2&725 2) 3+,/2623+< 81, 9(56,7< 2) )/25, '$

PAGE 2

7R P\ KXVEDQG $EGXO IRU KLV ORYLQJ VXSSRUW

PAGE 3

$ &.12 :/('*(0(176 )LUVW DQG IRUHPRVW ZRXOG OLNH WR JLYH SUDLVHV WR WKH $OPLJKW\ *RG ZLWKRXW ZKRP DOO OLIH ZRXOG QRW EH SRVVLEOH 6HFRQGO\ ZRXOG OLNH WR WKDQN P\ VXSHUYLVRU 'U $ODQ 5 .DWULW]N\ IRU DOORZLQJ PH WKH RSSRUWXQLW\ WR EHFRPH D PHPEHU RI KLV UHVHDUFK JURXS ZRXOG DOVR OLNH WR H[SUHVV JUDWLWXGH IRU KLV JXLGDQFH GXULQJ P\ VWD\ KHUH ZRXOG HVSHFLDOO\ OLNH WR WKDQN KLP IRU FKDOOHQJLQJ PH IRU LW LV WKRVH FKDOOHQJHV ZKLFK KDYH SXVKHG PH WR ORRN GHHS ZLWKLQ P\VHOI DQG WR VWULYH WR EHFRPH D EHWWHU VWURQJHU FKHPLVW )RU WKH WLPH VSHQW DQG KHOSIXO VXJJHVWLRQV JLYHQ ZRXOG OLNH WR H[SUHVV VLQFHUH WKDQNV WR P\ VXSHUYLVRU\ FRPPLWWHH PHPEHUV 'U -DPHV $ 'H\UXS 'U :LOOLDP 5 'ROELHU -U 'U 9DQHLFD
PAGE 4

7$%/( 2) &217(176 SDJH $&.12:/('*(0(176 LLL $%675$&7 YL &+$37(56 *(1(5$/ ,1752'8&7,21 *HQHUDO ,QWURGXFWLRQ WR 1LWURJHQ &RPSRXQGV ,QWURGXFWLRQ ,, ),567 '(021675$7,21 2) 63(&,),& && %21' 6&,66,21 2) 7+( 3<5,',1( 5,1* 5($&7,216 2) 3,3(5,',1( 3<5,',1( $1' 620( 2)7+(,5 0(7+
PAGE 5

,9 %(1=275,$=2/( &$5%2;$0,',1,80 726
PAGE 6

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f RQH VHFRQGDU\ DOLSKDWLF DPLQH GLRFW\ODPLQHf DQG WZR WHUWLDU\ DOLSKDWLF DPLQHV 1 $GLPHWK\O RFW\ODPLQH 1 $GLPHWK\OGRGHF\ODPLQHf ZHUH HDFK KHDWHG DW r& DQG r& ZLWK b DTXHRXV IRUPLF DFLG IRU YDU\LQJ SHULRGV RI WLPH 7KH SULPDU\ DPLQHV VKRZHG WZR YL

PAGE 7

GRPLQDQW UHDFWLRQ SDWKZD\V YL] Lf M9IRUP\ODWLRQ ZLWK VXEVHTXHQW UHGXFWLRQ WR JLYH 1 PHWK\O DQG L9AGLPHWK\ODON\ODPLQHV DQG LLf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fIOXRUHQLPLQH 7KLV QRYHO LPLQH ZDV LQYHVWLJDWHG DV D SRWHQWLDO HOHFWURSKLOLF DPLQDWLQJ DJHQW %HQ]RWULD]ROO\OPHWK\ODPLQRf WULD]ROH ZDV V\QWKHVL]HG E\ WKH FRQGHQVDWLRQ RI DPLQRWULD]ROH DQG K\GUR[\PHWK\OEHQ]RWULD]ROH 7KLV DGGXFW XQGHUJRHV QXFOHRSKLOLF GLVSODFHPHQW E\ *ULJQDUG UHDJHQWV WR JHQHUDWH DON\ODPLQRf WUL D]ROHV YLO

PAGE 8

&+$37(5 *(1(5$/ ,1752'8&7,21 *HQHUDO ,QWURGXFWLRQ WR 1LWURJHQ &RPSRXQGV 1LWURJHQ LV RQH RI WKH SULQFLSDO HOHPHQWV LQ DOO OLYLQJ FUHDWXUHV 7KHUHIRUH QLWURJHQ FRQWDLQLQJ FRPSRXQGV DUH XELTXLWRXV LQ QDWXUH $ ODUJH QXPEHU RI PHGLFDOO\ DQG ELRORJLFDOO\ LPSRUWDQW FRPSRXQGV DUH 1FRPSRXQGVf§LQ SDUWLFXODU YDULRXV DPLQHV DQG DPLQR DFLGV 0DQ\ RI WKHVH FRPSRXQGV KDYH SRZHUIXO SK\VLFDO DQG SV\FKRORJLFDO HIIHFWV 1LWURJHQ FRPSRXQGV DUH DOVR LPSRUWDQW LQGXVWULDOO\ 7KH SHWURFKHPLFDO LQGXVWU\ SURYLGHV UDZ PDWHULDOV IRU OLTXLG SHWUROHXP DQG QDWXUDO JDV IHHG VWRFNV LQ WKH IRUP RI DPLQHV QLWURn FRPSRXQGV KHWHURF\FOLF 1FRPSRXQGV G\HV GUXJV HWF 'XH WR WKH LPSRUWDQFH RI QLWURJHQ WR WKH JURZWK RI SODQWV DQG DQLPDOV LW LV QRW VXUSULVLQJ WKDW QLWURJHQ FRPSRXQGV SDUWLFXODUO\ IHUWLOL]HUVf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

PAGE 9

FDQ EH XVHG WR UHPRYH WKH GHOHWHULRXV QLWURJHQ FRPSRXQGV IRXQG LQ FUXGH SHWUROHXP DQG V\QWKHWLF RLOV 1RUPDOO\ RUJDQLF FRPSRXQGV GR QRW UHDFW ZLWK ZDWHU XQGHU VWDQGDUG UHDFWLRQ FRQGLWLRQV +RZHYHU RUJDQLF PROHFXOHV ZKLFK DUH XQUHDFWLYH LQ OLTXLG ZDWHU FDQ EH VXEMHFWHG WR PDQ\ FKHPLFDO UHDFWLRQV ZKHQ WKH WHPSHUDWXUH RI ZDWHU LV UDLVHG WR r& r& &RPSRXQGV VXFK DV HWKHUV f DQG HVWHUV f XQGHUJR FOHDYDJH DQG K\GURO\VLV UHVSHFWLYHO\ ZLWK HDVH >()@ 6FKHPH f $Q DQDORJRXV SURFHVV WR WKH DERYH UHDFWLRQVf FDWDJHQHVLV WDNHV SODFH LQ QDWXUH &DWDJHQHVLV LV WKH SURFHVV E\ ZKLFK FURVVOLQNHG PDFURPROHFXODU VWUXFWXUHV VROLG SHWUROHXP NHURJHQVf DUH FRQYHUWHG LQ VRXUFH URFN LQWR OLTXLG SHWUROHXP ,Q QDWXUH FDWDJHQHVLV KDV D WLPH IUDPH RI PLOOLRQV RI \HDUV DQG RFFXUV DW WHPSHUDWXUHV OHVV WKDQ r& LQ DTXHRXV HQYLURQPHQWV DW DERXW 03D RI SUHVVXUH >6&,@ 525 KR r& 5+ +25 FOHDYDJH SURGXFWV 2 LL 5&25 KR r& 2 5&2+ 25 2 5&f +25 K\GURO\VLV SURGXFWV 6FKHPH :KHQ ZDWHU LV KHDWHG DW HOHYDWHG WHPSHUDWXUHV VLJQLILFDQW FKDQJHV LQ LWV SK\VLFDO DQG FKHPLFDO SURSHUWLHV WDNH SODFH $V WKH WHPSHUDWXUH RI ZDWHU LV LQFUHDVHG IURP WR r& WKH IROORZLQJ FKDQJHV WDNH SODFH Lf WKH GHQVLW\ RI ZDWHU GHFUHDVH IURP WR JFP >0,(@ LLf WKH GLHOHFWULF FRQVWDQW GHFUHDVHV IURP WR >-$@ LLLf WKH VROXELOLW\ SDUDPHWHU GHFUHDVHV IURP WR FDOFPf >0,@

PAGE 10

7KH SK\VLFDO FKDQJHV DOORZ ZDWHU DW r& WR EHKDYH VLPLODU WR DFHWRQH DW r& >6&,@ FUHDWLQJ DQ HQYLURQPHQW IRU LRQLF UHDFWLRQV &KDSWHU ,9 GLVFXVVHV WKH V\QWKHVLV RI EHQ]RWULD]ROHOFDUER[DPLGLQLXP WRV\ODWH DQG WKH UHODWHG DSSOLFDWLRQ RI EHQ]RWULD]ROH PHWKRGRORJ\ LQ WKH V\QWKHVLV RI JXDQLGLQHV IURP DPLQHV $ XVHIXO V\QWKHWLF DX[LOLDU\ EHQ]RWULD]ROH f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f KDV DOVR EHHQ LQYHVWLJDWHG 7KLV DPLQRWULD]ROH FDQ EH FRQGHQVHG ZLWK NHWRQHV WR JHQHUDWH WKH FRUUHVSRQGLQJ LPLQH ,Q DGGLWLRQ WKLV WULD]ROH FDQ DOVR EH FRQGHQVHG ZLWK EHQ]RWULD]ROH DQG IRUPDOGHK\GH WR JHQHUDWH WKH FRUUHVSRQGLQJ EHQ]RWULD]ROHWULD]ROH DGGXFW &KDSWHU 9, GHDOV ZLWK WKH GHULYDWL]DWLRQ RI DPLQRWULD]ROH DQG LWV DSSOLFDWLRQ LQ WKH DWWHPSWHG V\QWKHVLV RI LPLQHV DQG DON\ODPLQRfWULD]ROHV +

PAGE 11

&+$37(5 ,, ),567 '(021675$7,21 2) 63(&,),& && %21' 6&,66,21 2) 7+( 3<5,',1( 5,1* 5($&7,216 2) 3,3(5,',1( 3<5,',1( $1' 620( 2) 7+(,5 0(7+()@ ,Q RUGHU WR FRQYHUW VROLG FRDOV DQG RLO VKDOH NHURJHQV WR OLTXLGV ZKLFK FDQ EH XVHG DV V\QWKHWLF IXHOV WKHf FURVVOLQNV RI WKH DERYH PHQWLRQHG KHWHURDWRPV QHHG WR EH EURNHQ 7KLV SURFHVV RI WKH OLTXLILFDWLRQ RI FRDO QRUPDOO\ UHTXLUHV D YDULHW\ RI FDWDO\VWV >()@ 8QIRUWXQDWHO\ D VSHFLILF FDWDO\VW LV UHTXLUHG IRU WKH UHPRYDO RI D VSHFLILF KHWHURDWRP DQG FDQ EHFRPH TXLWH FRVWO\ /LTXLGV GHULYHG IURP 1FRQWDLQLQJ FRDOV RIWHQ FRQWDLQ ODUJH DPRXQWV RI 1 LPSXULWLHV >0,@ &RPSRXQGV ZKLFK FRQWDLQ QLWURJHQ DUH GHWULPHQWDO IRU WKH IROORZLQJ WKUHH UHDVRQV Lf WKH\ SRLVRQ DQG GHDFWLYDWH FDWDO\VW XVHG ODWHU LQ UHILQLQJ SURFHVVHV LLf WKH\ IRUP WR[LF QLWURJHQ R[LGHV XSRQ FRPEXVWLRQ DQG LLLf WKH\ FRQIHU LQVWDELOLW\ RQ WKH SURGXFW IXHO FDXVLQJ GLVFRORUDWLRQ DQG RWKHU GHWULPHQWDO UHDFWLRQV >()7/@ 7KH QLWURJHQFRQWDLQLQJ FRPSRXQGV IRXQG LQ SHWUROHXP RU V\QWKHWLF RLOV LQFOXGH ERWK KHWHURF\FOHV IRU H[DPSOH S\ULGLQHV DQG S\UUROHV DQG QRQKHWHURF\FOHV VXFK DV DOLSKDWLF DPLQHV :LWK 1KHWHURF\FOHV WKH QRUPDO PRGH RI UHPRYDO KDV EHHQ GHQLWURJHQDWLRQ >7/@ RU K\GURGHQLWURJHQDWLRQ >()@ +\GURGHQLWURJHQDWLRQ LQYROYHV WKH

PAGE 12

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r& b DTXHRXV IRUPLF DFLG LQGXFHV WKH K\GURJHQDWLRQ RI WKH S\ULGLQH ULQJ WR SLSHULGLQH LQ VLJQLILFDQW DPRXQWV DQG DOVR LQGXFHV WKH VFLVVLRQ RI WKH S\ULGLQH ULQJ >7/@ 2YHU WKH ODVW \HDUV PXFK HYLGHQFH KDV DFFXPXODWHG WKDW WKH FRPPRQ KHWHURF\FOHV FDQ XQGHUJR RIWHQ UHYHUVLEO\f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b DTXHRXV IRUPLF DFLG RQ SLSHULGLQH f PHWK\OSLSHULGLQH f PHWK\OSLSHULGLQH f S\ULGLQHfDQGPHWK\OS\ULGLQHf 6FKHPHf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f &RPSRXQG QXPEHUV HTXDO HDWHU WKDQ DUH XVHG IRU SRVWXODWHG LQWHUPHGLDWHV QRW GHWHFWHG E\ WKH *&06 DQDO\VHV

PAGE 13

KHWHURDURPDWLF PRGHOV RI FRPSRXQGV IRXQG LQ IXHO UHVRXUFH VWUHDPV ,Q DGGLWLRQ WR UHSRUWLQJ WKH XQLTXH EHKDYLRU RI WKHVH FRPSRXQGV XQGHU DTXDWKHUPRO\VLV FRQGLWLRQV ZH QRZ GLVFORVH WKH ILUVW H[DPSOHV RI VSHFLILF &&ERQG VFLVVLRQ LQ WKH XQDFWLYDWHG KHWHURF\FOLF V\VWHP RI S\ULGLQH DQG GHPRQVWUDWH KRZ WKH ORQJVWXGLHG LQGXVWULDOO\ LPSRUWDQW SURFHVVHV E\ ZKLFK S\ULGLQH ULQJV DUH IRUPHG IURP &c & DQG & DOGHK\GHV DUH LQ SULQFLSOH UHYHUVLEOH 6FKHPH 7KH JDV FKURPDWRJUDSKLF *&f EHKDYLRU UHWHQWLRQ WLPHVf RI DOO WKH FRPSRXQGV HPSOR\HG LQ WKLV VWXG\ VWDUWLQJ PDWHULDOV DQG SURGXFWVf DUH VXPPDUL]HG LQ 7DEOH 7DEOHV DQG FRQWDLQ WKH FRPSLOHG PDVV VSHFWUDO GDWD IRU WKH DQDO\VLV RI WKH UHVXOWV 7DEOH FRQWDLQV WKH VRXUFHV DQG SXULWLHV RI WKH VWDUWLQJ PDWHULDOV XVHG DQG KDYH EHHQ FRPSLOHG EDVHG XSRQ WKH GLUHFW FRPSDULVRQ RI WKH *& UHWHQWLRQ WLPHV DQG RI WKH PDVV VSHFWUDO 06f IUDJPHQWDWLRQ SDWWHUQV ZLWK WKRVH RI WKH DXWKHQWLF FRPSRXQGV 7DEOH FRQWDLQV FRPSRXQGV ZKLFK KDYH EHHQ FRPSDUHG ZLWK OLWHUDWXUH PDVV VSHFWUDO GDWD IRU WKH VDPH FRPSRXQG 7KRVH FRPSRXQGV IRU ZKLFK QR VXLWDEOH OLWHUDWXUH 06 GDWD ZHUH DYDLODEOH KDYH EHHQ LGHQWLILHG E\ 06 IUDJPHQWDWLRQ SDWWHUQV REWDLQHG IURP WKH DTXDWKHUPRO\VLV UXQVf DQG KDYH EHHQ FRPSLOHG LQ 7DEOH )XUWKHU H[SODQDWLRQ RI WKH 7DEOHV f§ LV JLYHQ LQ VHFWLRQ ([SHULPHQWDO $OO WKH UHVXOWV IURP WKH DTXDWKHUPRO\VHV DUH FROOHFWHG LQ 7DEOHV DQG 7KH SURGXFW \LHOGV DUH UHSUHVHQWHG DV 7KH GDWD KDV EHHQ FRPSLOHG DV H[SODLQHG LQ WKLV SDUDJUDSK DFFRUGLQJ WR WKH VHULHV RI DTXDWKHUPRO\VLV SDSHUV >()@

PAGE 14

7DEOH 6WUXFWXUH DQG ,GHQWLILFDWLRQ RI 6WDUWLQJ 0DWHULDOV DQG 3URGXFWV 1R U PLQf 6WUXFWXUH 0: (T :W %DVLV D )DFWRU E SHQWHQH 7DEOH PHWK\O SHQWHQH 7DEOH SHQW\ODPLQH 7DEOH SLSHULGLQH 7DEOH S\ULGLQH 7DEOH r A4PHWK\OSLSHULGLQH 7DEOH PHWK\OSLSHULGLQH 7DEOH PHWK\OSLSHUL GLQH 7DEOH 1 L9GLPH WK\ OSHQW\ ODPLQH 7DEOH GL PHWK\OSLSHULGLQH 7DEOH HWK\OSLSHULGLQH 7DEOH PHWK\OS\ULGLQH 7DEOH $I1GLPHWK\O PHWK\ OSHQ W\ DPLQH 7DEOH HWK\O PHWK\OSLSHULGLQH 7DEOH SURS\OSLSHULGLQH 7DEOH SURS\O PHWK\O SLSHULGLQH 7DEOH EXW\OSLSHULGLQH 7DEOH EXW\O PHWK\OSLSHULGLQH 7DEOH PHWK\OEXW\O fSLSHULGLQH 7 DEOH SHQW\OSLSHULGLQH 7DEOH SHQWHQ\OfSLSHULGLQH 7DEOH A &fIRLP \OSL SHULGLQH 7DEOH IRUP\OSLSHULGLQH 7DEOH PHWK\OSHQW\OfSLSHULGLQH 7DEOH SHQW\O PHWK\OSLSHULGLQH 7DEOH DFHW\OSLSHULGLQH 7DEOH

PAGE 15

7DEOH FRQWLQXHG 1R U PLQf 6WUXFWXUH IRUP\OPHWK\OSLSHULGLQH PHWK\OSHQW\Of PHWK\OSLSHULGLQH DPLQRSHQW\OfSL SHUL GLQH DFHW\OPHWK\OSLSHULGLQH PHWK\ODPLQRSHQW\Of PHWK\OSLSHULGLQH 0: (T :W %DVLV D )DFWRU E 7DEOH 7DEOH 7DEOH 7 DEOH 7DEOH WS PLQf 5HWHQWLRQ WLPH LQ PLQXWHV 0: PROHFXODU ZHLJKW (T :W HTXLYDOHQW ZHLJKW D ,GHQWLILFDWLRQ %DVLV VHH DSSURSULDWH WDEOHV E 5HVSRQVH )DFWRU VHH UHI >7&0@

PAGE 16

7DEOH $XWKHQWLF &RPSRXQGV 8VHG DV 6WDUWLQJ 0DWHULDOV DQG IRU WKH ,GHQWLILFDWLRQ RI 3URGXFWV &RP SRXL ,+ 0: 3XULW\ P] b UHODWLYH LQWHQVLW\f bf 5HI E VSHFWUD SHQWHQH PHWK\O SHQWHQH SHQW\ODPLQH SLSHULGLQH S\ULGLQH PHWK\OSL SHUL GLQH PHWK\O SL SHUL GLQH 1 :GLPHWK\O SHQW\ODPLQH GLPHWK\O SLSHULGLQH HWK\OSLSHULGLQH PHWK\OS\ULGQH L9M9GLPHWK\O PHWK\OSHQW\ODPLQH OPHWK\OEXW\Of SLSHULGLQH IRUP\O SL SHUL GLQH PHWK\OSHQW\O f SLSHULGLQH DFHW\OSLSHULGLQH $ $ $ $ $ $ $ 6 $ $ $ 6 6 $ 6 $ f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f >F@ f f f f f f f f f f f f f f f f WF@ f f f f f f f f f f f f f f f f f f f 0: PROHFXODU ZHLJKW D $ $OGULFK 6 V\QWKHVL]HG DXWKHQWLF FRPSRXQG VHH H[SHULPHQWDO VHFWLRQf E VSHFWUDO QXPEHUV RI WKH PDVV VSHFWUDO GDWD IRU WKH FRPSRXQGV IRXQG IURP D VHDUFK RI WKH :LOH\ 1%6 5HJLVWU\ RI 0DVV 6SHFWUDO 'DWD %DVH ): 0F/DIIHUW\ '% 6WDXIIHU 7KLV ERRN LV WKH FRPELQDWLRQ RI WKH UHYLVLRQV RI WKH IROORZLQJ WZR ERRNV DQG WKHLU GDWDEDVH YHUVLRQV 5HJLVWU\ RI 0DVV 6SHFWUD GDWD E\ ( 6WHQKDJHQ 6 $EUDKDPVVRQ DQG ): 0F/DIIHUW\ DQG (3$ 1,+ 'DWDEDVH E\ 65 +HOOHU *: 0LOQH DQG LWV WZR VXSSOHPHQWV F QR OLWHUDWXUH 06 GDWD DYDLODEOH G QRYHO FRPSRXQG

PAGE 17

7DEOH ,GHQWLILFDWLRQ RI 3LSHULGLQHV E\ &RPSDULVRQ RI 0DVV 6SHFWUDO )UDJPHQWDWLRQ ZLWK /LWHUDWXUH GDWD 1R 3LSHULGLQH 0: )UDJPHQWDWLRQ )RXQG 5HI D )UDJPHQWDWLRQ 5HSRUWHG E 6XEVWLWXHQW P] b UHO LQWHQVLW\f VSHFWUD P] b UHO LQWHQVLW\f EXW\O f f f f f f f f SHQW\O f f f f f f f f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f

PAGE 18

7DEOH ,GHQWLILFDWLRQ RI 3LSHULGLQHV IURP 0DVV 6SHFWUDO )UDJPHQWDWLRQ 3DWWHUQV 1R 3LSHULGLQH 0: )UDJPHQWDWLRQ 3DWWHUQ P] b UHO LQWHQVLW\ 6XEVWLWXHQW VWUXFWXUH RI IUDJPHQW LRQf O&fPHWK\O 0f 0+f 0(Wf f &+1f &+1f HWK\OPHWK\O SURS\O SURS\O PHWK\O EXW\OPHWK\O OSHQWHQO\Of OA&fIRUP\O 0f 0&+f &+1f f f f f f 0f 0+f 0(Wf &+1f 0f 0(Wf f f f f 0f 03Uf f f f f f 0f 0&+f f f 0fO 0+f 0&+f 0&+2f 0&+Af SHQW\OPHWK\O 0f 0&+f f f f f IRUP\OPHWK\O HWK\ OSHQW\O f 0 f 0f f 0&+f 0&+2f &+1f 0f 0&+cf 0&+1f f f f f ODPLQRSHQW\Of DFHW\O 0f 0&+ 1+f f f f f f f f 0 f 0f 0+f 0&+f 0&2&+f f PHWK\ODPL QR SHQW\2AOPHWK\O 0f f f f f f f f f 0: PROHFXODU ZHLJKW

PAGE 19

SHUFHQWDJHV RI PROHV RI VWDUWLQJ PDWHULDO DV GHVFULEHG LQ GHWDLO SUHYLRXVO\ >()@ DQG KDYH EHHQ FRUUHFWHG ZLWK UHJDUG WR WKHLU UHVSRQVH IDFWRUV >7&0@ 7DEOH GHPRQVWUDWHV WKH SHUFHQWDJHV RI WKH YDULRXV VLPSOH 1DON\OSLSHULGLQHV IRUPHG IURP S\ULGLQH DQG WKHLU PHWK\O GHULYDWLYHV VLQJO\ DQG DGPL[HG 6WUXFWXUHV DQG SURSRVHG PHFKDQLVWLF SDWKZD\V IRU WKH IRUPDWLRQ RI WKHVH SURGXFWV ZKLFK DUH MXVWLILHG ODWHU LQ WKLV FKDSWHUf DUH JLYHQ LQ 6FKHPHV f§ ,Q WKHVH UHDFWLRQ 6FKHPHV QXPEHUV JUHDWHU WKDQ DUH XVHG IRU SRVWXODWHG LQWHUPHGLDWHV QRW GHWHFWHG E\ WKH *&06 DQDO\VHV 6\QWKHVLV RI &RPSRXQGV ,Q WKH SURMHFW RXWOLQHG DERYH XQGHUWDNHQ LQ RXU ODERUDWRULHV RQ WKH DTXDWKHUPRO\VLV RI SLSHULGLQH S\ULGLQH DQG VRPH RI WKHLU PHWK\O GHULYDWLYHV LQ b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f DQG $U$AGLPHWK\OPHWK\OSHQW\ODPLQHf DQG WKUHH DON\OSLSHULGLQHV OPHWK\OEXW\OfSLSHULGLQHf OPHWK\OSHQW\OfSLSHULGLQH f DQG PHWK\OSHQW\OfSLSHULGLQH f 6FKHPH f 7KH QRYHO F\FOLF DPLQHV f DQG WKH NQRZQ F\FOLF DPLQH f ZHUH SUHSDUHG LQ UHVSHFWDEOH \LHOGV E\ WKH UHDFWLRQV RI OSLSHULGLQRPHWK\OfEHQ]RWULD]ROH f ZLWK WKH *ULJQDUG UHDJHQWV 7KH SRVVLELOLW\ RI FDOFXODWLQJ WKH UHVSRQVH IDFWRU DOORZV IRU WKH TXDQWLWDWLYH DQDO\VLV RI FRPSOH[ SURGXFW PL[WXUHV E\ *&06 HVSHFLDOO\ IRU WKRVH FDVHV ZKHUH VRPH RU DOO RI WKH SURGXFWV DUH XQDYDLODEOH

PAGE 20

, 50J%U A5 1 5 5 5 &+f 5 5 0H &RPSRXQG 5 5 5 bf \LHOG &+f 0H 0H 0H 0H &+&+&+&+ 0H 0H &+&+&+&+f&+ &+f &+&+&+f&+ &+fV &+&+&+&+f&+ &+f &+f&+&+&+ 6FKHPH

PAGE 21

RI EURPREXWDQH OEURPRPHWK\OEXWDQH DQG EURPRPHWK\OEXWDQH UHVSHFWLYHO\ 7KH WHUWLDU\ DF\FOLF DPLQHV f ZHUH SUHSDUHG E\ WKH UHDFWLRQ RI O11 GLPHWK\ODPLQRPHWK\OfEHQ]RWULD]ROHf ZLWK WKH FRUUHVSRQGLQJ *ULJQDUG UHDJHQWV RI mEXW\O EURPLGH DQG EURPRSHQWDQH UHVSHFWLYHO\ VHH VHFWLRQ ([SHULPHQWDOf O3LSHULGLQRPHWK\OfEHQ]RWULD]ROH f >-$ -&63f@ DQG $$GLPHWK\ODPLQRPHWK\OfEHQ]RWULD]ROH f >-$ -2&@ ZHUH SUHSDUHG LQ KLJK \LHOGV HPSOR\LQJ OLWHUDWXUH SURFHGXUHV 7KH EHQ]RWULD]ROH DGGXFW ZDV V\QWKHVL]HG E\ FRQGHQVDWLRQ RI EHQ]RWULD]ROH IRUPDOGHK\GH DQG SLSHULGLQH ZKLOH DGGXFW ZDV V\QWKHVL]HG E\ WKH FRQGHQVDWLRQ RI EHQ]RWULD]ROH IRUPDOGHK\GH DQG GLPHWK\ODPLQH 6FKHPH f )XUWKHU GLVFXVVLRQ RI WKH PDVV VSHFWUDO LGHQWLILFDWLRQ DQG LQWHUSUHWDWLRQ RI WKH DPLQHV LV FRYHUHG LQ WKH 'LVFXVVLRQ f ([SHULPHQWDO f DQG $SSHQGL[ 5HVXOWV 3LSHULGLQH f 2Q KHDWLQJ ZLWK DTXHRXV b +&2+ DW r& IRU K SLSHULGLQH f ZDV FRPSOHWHO\ FRQVXPHG 7DEOH f 7KH PDMRU SURGXFW ZDV IRUP\OSLSHULGLQH bf WRJHWKHU ZLWK DQ DSSUHFLDEOH DPRXQW RI PHWK\OSLSHULGLQH bf +RZHYHU HWK\O bf SURS\O bf DQG DFHW\OSLSHULGLQH bf ZHUH DOO GHWHFWHG DV PLQRU SURGXFWV DORQJ ZLWK WUDFHV RI SHQW\OSLSHULGLQH bf $IWHU K DW r& LQ b +&2+ WKH \LHOG RI IRUP\OSLSHULGLQH f ZDV URXJKO\ KDOYHG bf DQG WKH DIRUHPHQWLRQHG DON\OSLSHULGLQHV QRWLFHDEO\ SHQW\OSLSHULGLQH bf ZHUH DOO IRUPHG LQ ODUJHU DPRXQWV O0HWK\OEXW\OfSLSHULGLQH f ZDV IRUPHG LQ WUDFH DPRXQW bf ,W LV FOHDU WKDW IRUP\OSLSHULGLQH f LQLWLDOO\ IRUPHG LV ODWHU FRQYHUWHG LQWR PHWK\OSLSHULGLQH f DQG YLD GHIRUP\ODWLRQ LQWR WKH RWKHU DON\OSLSHULGLQHV

PAGE 22

7DEOH 3URGXFWV 2EWDLQHG IURP 0HWK\OSLSHULGLQH 0H3LSf 0HWK\OSLSHQGLQH 0H3LSf 3LSHULGLQH 3LSf 0HFK 7\SH $GGLWLYH VHH WH[Wf 7LPH Kf 1R 6WUXFWXUH 0H3LS 0H3LS 3LS ; \ ] SHQWHQH SHQW\ODPLQH LLLf f§ SLSHULGLQH S\ULGLQH f B PHWK\OSLSHULGLQH Lf 1 $IGLPHWK\OSHQW\ ODPLQH LLLf GLPHWK\OSLSHULGLQH Lf HWK\OSLSHULGLQH LLf 1 1GLPHWK\OPHWK\O LLLf SHQW\ODPLQH HWK\OPHWK\OSLSHUL GLQH LLf SURS\OSLSHULGLQH LLf SURS\O PHWK\O SLSHULGLQH LLf EXW\OSLSHULGLQH LLf EXW\O PHWK\OSLSHULGLQH LLf PHWK\OEXW\OfSLSHULGLQH LLf SHQW\OSLSHULGLQH LYf SHQWHQ \OfSLSHULGLQH LYf IRUP\O SLSHUL GLQH Lf SHQW\O PHWK\OSLSHULGLQH LLf DFHW\OSLSHULGLQH Lf IRUP\OPHWK\O SLSHUL GLQH Lf PHWK\OSHQW\OfPHWK\O SLSHULGLQH LLf DPLQRSHQW\ fSL SHUL GLQH LLLf DFHW\O PHWK\OSLSHULGLQH LLf PHWK\O DPL QRSHQW\O f SLSHULGLQH LLf f§ ? S\ULGLQH \ PHWK\OSHQWHQH ] SHQWHQH UHVLGXDO S\ULGLQH IURP DGGLWLYH

PAGE 23

3LSHULGLQH f SOXV SHQWHQH f 7KH VDPH UHDFWLRQ RI SLSHULGLQH ZDV FDUULHG RXW LQ WKH SUHVHQFH RI SHQWHQH f HTXLYDOHQWf LQ b +&2+ DW r& IRU K DQG JDYH WKH VDPH VODWH RI SURGXFWV DV LQ WKH DEVHQFH RI SHQWHQH LH OPHWK\O bf DQG IRUP\OSLSHULGLQH bf WRJHWKHU ZLWK WKH VDPH PLQRU SURGXFWV ,Q SDUWLFXODU QR VLJQLILFDQW LQFUHDVH LQ SHQW\OSLSHULGLQH f ZDV IRXQG LQ WKLV UXQ VXJJHVWLQJ WKDW ROHILQV DUH QRW LQWHUPHGLDWHV LQ WKHVH UHDFWLRQV 0HWKYOSLSHULGLQH f 7KLV FRPSRXQG VKRZHG D b FRQYHUVLRQ DIWHU MXVW K DW r& LQ b +&2+ 7KH PDMRU SURGXFW ZDV IRUP\OSLSHULGLQH bf 7KLV SURGXFW LV SUREDEO\ IRUPHG YLD WKH 9IRUP\ODWLRQ RI PHWK\OSLSHULGLQH ZLWK WKH VXEVHTXHQW HOLPLQDWLRQ RI D PHWK\O FDWLRQ SUREDEO\ DVVLVWHG E\ WKH IRUPDWH LRQ 2WKHU SURGXFWV LQFOXGHG SLSHULGLQH bf DQG VPDOO TXDQWLWLHV RI HWK\O bf SURS\O bf EXW\O bf DQG SHQW\OSLSHULGLQH bf ([WHQGLQJ WKH UHDFWLRQ WLPH WR K \LHOGHG D VLPLODU SURGXFW VODWH DOWKRXJK D KLJKHU FRQYHUVLRQ bf ZDV REVHUYHG 7KH PDMRU SURGXFW ZDV DJDLQ IRUP\OSLSHULGLQH bf 7KH 9DON\OSLSHULGLQHV REVHUYHG LQ WKH DERYH UHDFWLRQ r& Kf ZHUH DJDLQ VHHQ KHUH EXW LQ LQFUHDVHG DPRXQWV VHH 7DEOH f ([WHQGLQJ WKH UHDFWLRQ WLPH IXUWKHU WR K OHG WR D b FRQYHUVLRQ ZKLFK LV RQO\ VOLJKWO\ ORZHU WKDQ WKDW REVHUYHG IRU WKH K UXQ 7KH PDMRU SURGXFW KHUH LV DJDLQ IRUP\OSLSHULGLQH bf 1 $'LPHWK\OPHWK\OSHQW\ODPLQHf ZDV IRUPHG LQ WUDFH DPRXQW bf ZKLOH 1 $IGLPHWK\OSHQW\ODPLQHf ZDV REVHUYHG VOLJKWO\ KLJKHU bf +RZHYHU LW VHHPV OLNHO\ WKDW GXULQJ WKH H[WHQGHG WLPH RI WKLV UHDFWLRQ VRPH RI WKH IRUP\OSLSHULGLQH LV UHGXFHG E\ K\GULGH LRQ IURP WKH IRUPLF DFLG WR UHWXUQ WR PHWK\O SL SHUL GLQH f LQ YLHZ RI WKH LQFUHDVHG DPRXQWV RI WKH VDPH KLJKHU 1 DON\OSLSHULGLQHV ZKLFK ZHUH REVHUYHG VHH 7DEOH f 2Q KHDWLQJ DW r& IRU K ZLWK b +&2+ PHWK\OSLSHULGLQH f XQGHUZHQW D b FRQYHUVLRQ 7DEOH f $JDLQ WKHUH ZDV D VLJQLILFDQW LQFUHDVH LQ WKH IRUPDWLRQ RI 1DON\OSLSHULGLQHV ZKLFK LQFOXGHG HWK\O bf SURS\O bf EXW\O bf

PAGE 24

DQG SHQW\OSLSHULGLQH bf $I $'LPHWK\OSHQW\ODPLQHf ZDV IRUPHG LQ b $IWHU K IRUP\OSLSHULGLQH f ZDV SUHVHQW RQO\ LQ D VPDOO DPRXQW bf 0HWK\O SLSHULGLQH f 7KLV FRPSRXQG XQGHUZHQW FRPSOHWH FRQYHUVLRQ DIWHU K VHH 7DEOH f DQG WKH PDMRU SURGXFWV ZHUH GLPHWK\OSLSHULGLQH bf OIRUP\OPHWK\OSLSHULGLQH bf DQG OPHWK\ODPLQRSHQW\Of PHWK\OSLSHULGLQH bf $ WUDFH DPRXQW RI HWK\OPHWK\OSLSHULGLQH bf ZDV DOVR VHHQ $W r& IRU K LQ b +&2+ PHWK\OSLSHULGLQH f XQGHUZHQW D FRPSOHWH FRQYHUVLRQ WR JLYH GLPHWK\OSLSHULGLQH bf IRUP\OPHWK\OSLSHULGLQH bf WRJHWKHU ZLWK VPDOOHU DPRXQWV RI HWK\O bf SURS\O bf EXW\O bf DQG SHQW\O bf DQG OPHWK\OSHQW\OfPHWK\OSLSHULGLQHV bf ,W ZLOO EH GHPRQVWUDWHG WKDW WKH $DON\O JURXSV RQ WKH QLWURJHQIXQFWLRQDOLW\ DUH QRZ GHULYHG IURP WKH PHWK\OSLSHULGLQH f ULQJ 0HWK\OSLSHULGLQH f SOXV PHWK\OSHQWHQH f 7KLV UXQ ZDV FDUULHG RXW WR GHWHUPLQH ZKHWKHU RU QRW PHWK\OSHQWHQH f LV DQ LQWHUPHGLDWH LQ WKH IRUPDWLRQ RI IURP 0HWK\OSLSHULGLQH f RQ KHDWLQJ ZLWK b +&2+ DW r& IRU K LQ WKH SUHVHQFH RI RQH HTXLYDOHQW RI PHWK\OSHQWHQH f XQGHUZHQW D b FRQYHUVLRQ ZLWK WKH PDMRU SURGXFWV EHLQJ GLPHWK\OSLSHULGLQH bf DQG IRUP\OPHWK\OSLSHULGLQH bf 7KH SURGXFW VODWH IURP WKLV UXQ 7DEOH f VXJJHVWV WKDW PHWK\OSHQWHQH f GRHV QRW SOD\ D VLJQLILFDQW UROH LQ WKH JHQHUDWLRQ RI WKH SURGXFWV HVSHFLDOO\ DV PHWK\OSHQW\Of PHWK\OSLSHULGLQHf ZDV QRW VHHQ LQ LQFUHDVHG DPRXQWV 3\ULGLQH f 3\ULGLQH f RQ KHDWLQJ ZLWK b +&+ r& IRU K XQGHUZHQW D b FRQYHUVLRQ LQWR PHWK\O bf HWK\O bf SURS\O bf SHQW\O bf DQG IRUP\OSLSHULGLQH bf 7DEOH f +HDWLQJ LQ b +&+ DW r& IRU K LQFUHDVHG WKH FRQYHUVLRQ IURP

PAGE 25

7DEOH 3URGXFWV 2EWDLQHG IURP 0HWK\OS\ULGLQH 0H3\f 3\ULGLQH 3\f $GGLWLYH 7LPHK 1R 6WUXFWXUH 0HFK 7\SH VHH WH[Wf 0H3\ 3\ Z r SLSHULGLQH S\ULGLQH Or &fPHWK\O SLSHULGLQH LLf PHWK\OSL SHUL GLQH GLPHWK\OSLSHULGLQH Lf HWK\OSLSHULGLQH LLf PHWK\OS\ULGLQH HWK\O PHWK\OSLSHULGLQH LLf SURS\ OSLSHULGLQH LLf SURS\O PHWK\OSLSHULGLQH LLf EXW\OSLSHULGLQH LLf EXW\O PHWK\OSLSHULGLQH LLf PHWK\OEXW\OfSLSHULGLQH LLf SHQW\O SLSHULGLQH LYf Or &fIRUP\OSLSHULGLQH Lf IRQQ\OSLSHULGLQH Lf PHWK\OSHQW\OfSLSHULGLQH LYf f§ SHQW\O PHWK\OSLSHULGLQH LLf DFHW\OSLSHULGLQH Lf IRUP\OPHWK\OSLSHULGLQH Lf PHWK\OSHQW\OfPHWK\O SLSHULGLQH LLf DPLQRSHQW\OfSLSHULGLQH LLLf DFHW\O PHWK\OSLSHULGLQH LLf Z SLSHULGLQH r b +&&!+

PAGE 26

b WR b DQG SURGXFHG DOO WKH IRUHJRLQJ SURGXFWV LQ PXFK LQFUHDVHG TXDQWLWLHV WRJHWKHU ZLWK DFHW\OSLSHULGLQH bf OPHWK\OEXW\OfSLSHULGLQH bf DQG ODPLQRSHQW\OfSLSHULGLQH bf 2Q KHDWLQJ LQ b +A&;A+ DW r& IRU K S\ULGLQH f VKRZHG D b FRQYHUVLRQ LQWR D VLPLODU VODWH RI SURGXFWV EXW LQ LQFUHDVHG DPRXQWV SUREDEO\ IDFLOLWDWHG E\ WKH XVH RI b +&2+ VHH 7DEOH f DV VHHQ IRU WKH UXQ LQ b +&2+ DW r& IRU K 6LJQLILFDQWO\ RQO\ WKH PHWK\OSLSHULGLQH bf DQG WKH IRUP\OSLSHULGLQH bf ZHUH ODEHOOHG DQG HDFK FRQWDLQHG MXVW RQH & ODEHO 7KH IDFW WKDW HWK\O bf SURS\O bf DQG SHQW\OSLSHULGLQH bf SURGXFHG VLPXOWDQHRXVO\ KDG QR ODEHOOHG FDUERQV VKRZV FRQFOXVLYHO\ WKDW WKH HWK\O SURS\O DQG SHQW\O JURXSV LQ DQG UHVSHFWLYHO\ DUH DOO GHULYHG FRPSOHWHO\ IURP S\ULGLQH FDUERQ DWRPV DQG QRW IURP FDUERQV RI WKH IRUPLF DFLG 0HWK\OS\ULGLQH f 0HWK\OS\ULGLQHf RQ KHDWLQJ LQ b +&2+ DW r& IRU K VKRZHG D b FRQYHUVLRQ LQWR GLPHWK\O bf IRUP\OPHWK\O bf DQG OPHWK\OSHQW\OfPHWK\OSLSHULGLQH bf WRJHWKHU ZLWK VPDOOHU DPRXQWV RI HWK\O bf DQG OEXW\O PHWK\OSLSHULGLQH bf 7DEOH f (YLGHQWO\ WKH HWK\O DQG EXW\O JURXSV UHTXLUHG IRU WKH 1DON\ODWLRQ RI PHWK\OSLSHULGLQH ZHUH GHULYHG E\ IUDJPHQWDWLRQ RI PHWK\OS\ULGLQH PROHFXOHV O0HWK\OSHQW\OfSLSHULGLQH f ZDV REVHUYHG LQ WUDFH DPRXQW bf 0HWK\OS\ULGLQH f RQ KHDWLQJ LQ b +&2+ DW r& IRU K XQGHUZHQW D b FRQYHUVLRQ WR GLPHWK\OSLSHULGLQH bf OIRUP\O PHWK\OSLSHULGLQH bf DQG OPHWK\OSHQW\OfPHWK\OSLSHULGLQH bf 2WKHU SURGXFWV LQFOXGHG VPDOO DPRXQWV RI HWK\O f SURS\O f EXW\O f SHQW\O f DQG DFHW\O f PHWK\OSLSHULGLQHV

PAGE 27

0HWK\OSLSHULGLQHf SOXV S\ULGLQH f 7R XQGHUVWDQG WKH W\SHV RI LQWHUPHGLDWHV LQYROYHG LQ WKH && DQG &1 ERQG FOHDYDJHV ZH UDQ DQ DTXDWKHUPRO\VLV RI PHWK\OSLSHULGLQH f PL[HG ZLWK S\ULGLQH f PROH HTXLYDOHQWf LQ b +&2+ DW r& IRU K 7DEOH f 0HWK\OSLSHULGLQH f XQGHUZHQW D b DQG S\ULGLQH D b FRQYHUVLRQ XQGHU WKHVH FRQGLWLRQV 9DULRXV 1VXEVWLWXWHG SLSHULGLQHV DQG f ZHUH IRUPHG WRJHWKHU ZLWK WKH IROORZLQJ 9VXEVWLWXWHGPHWK\OSLSHULGLQHV GLPHWK\O bf HWK\OPHWK\O bf SURS\OPHWK\O bf OSHQW\O PHWK\O bf OPHWK\OSHQW\OfPHWK\O bf OPHWK\O DPLQRSHQW\OfPHWK\O bf DQG OIRUP\OPHWK\OSLSHULGLQH bf 0HWK\OS\ULGLQH f SOXV SLSHULGLQH f 7KLV UHDFWLRQ ZDV FDUULHG RXW LQ RUGHU WR FRPSDUH WKH UHVXOWV ZLWK WKRVH REWDLQHG IURP WKH PHWK\OSLSHULGLQH f SOXV S\ULGLQH f UXQ 0HWK\OS\ULGLQH f VKRZHG D b FRQYHUVLRQ ZLWK b +&2+ DW r& IRU K DQG WKH VDPH VODWH RI SURGXFWV ZDV VHHQ DV LQ WKH FDVH RI PHWK\OSLSHULGLQH f SOXV S\ULGLQH f 7DEOH f 7KH ORQJ OLVW RI SURGXFWV FDQ EH FODVVLILHG LQWR WZR JURXSV Lf 9VXEVWLWXWHG SLSHULGLQHV DQG f DQG LLf PHWK\O9VXEVWLWXWHG SLSHULGLQHV DQG f 1R SLSHULGLQH f RU PHWK\O SLSHULGLQH f UHGXFWLRQ SURGXFW RI PHWK\O S\ULGLQH ^`f ZDV OHIW LQ WKH UHDFWLRQ PL[WXUH ZKLFK LQGLFDWHV WKDW WKH\ ZHUH FRPSOHWHO\ FRQVXPHG LQ IXUWKHU UHDFWLRQV *HQHUDO 'LVFXVVLRQ 7KH PRVW VWULNLQJ IHDWXUH RI WKH UHVXOWV LV WKDW WKH SURGXFWV FRPSULVH D UHODWLYHO\ VPDOO QXPEHU RI VSHFLILFDOO\ 1VXEVWLWXWHG SLSHULGLQHV 7KH H[SHULPHQW XVLQJ + A&&A+ VKRZV FRQFOXVLYHO\ WKDW DSDUW IURP WKH 9PHWK\O DOO WKH RWKHU 9DON\O JURXSV DUH IRUPHG

PAGE 28

IURP WKH ULQJ FDUERQ DWRPV 7KH IDFW WKDW SLSHULGLQH f IRUPV D UDWKHU VLPLODU VODWH RI SURGXFWV WR WKDW REWDLQHG IURP S\ULGLQH f VXJJHVW WKDW IRUPLF DFLG DFWV QRW RQO\ DV D UHGXFLQJ EXW DOVR HYLGHQWO\ WRZDUG SLSHULGLQH f DV DQ R[LGL]LQJ DJHQW DOWKRXJK ZH KDYH EHHQ XQDEOH WR ILQG OLWHUDWXUH SUHFHGHQFH IRU WKLV :H EHOLHYH WKDW PRVW RI WKH SURGXFWV IRUPHG FDQ EH H[SODLQHG E\ IRXU W\SHV RI PHFKDQLVWLF URXWHV Lf &RQYHQWLRQDO UHDFWLRQV ZKHUH WKH IRUPLF DFLG LV EHKDYLQJ DV D K\GULGH LRQ GRQRU DQG DV D IRUP\ODWLQJ DJHQW LLf 5HWURYLQ\ORJRXVELVD]DDOGRO UHDFWLRQV RI SURGXFWV IRUPHG E\ WKH DGGLWLRQ RI SLSHULGLQHV WR GLK\GURS\ULGLQHV LLLf 6LPSOH ULQJRSHQLQJ RI DPLGLQH RU DPLQDO W\SH LQWHUPHGLDWHV IRUPHG E\ DGGLWLRQ RI SLSHULGLQH WR GLK\GUR RU WHWUDK\GURS\ULGLQHV IROORZHG E\ UHGXFWLRQ LYf 5LQJRSHQLQJ RI LVRPHUV RI SURGXFWV IRUPHG E\ DGGLWLRQ RI SLSHULGLQHV WR D TXDWHPL]HG S\ULGLQLXP FDWLRQ :H QRZ GLVFXVV HDFK RI WKHVH PHFKDQLVWLF SDWKZD\V LQ WXUQ Lf &RQYHQWLRQDO IRUPLF DFLG UHGXFWLRQIRUP\ODWLRQ )RUPLF DFLG UHGXFWLRQV RI TXDWHUQDU\ VDOWV RI S\ULGLQH DQG RI PHWK\OS\ULGLQLXP FDWLRQ WR WKH FRUUHVSRQGLQJ IXOO\ K\GURJHQDWHG SURGXFWV YL] SLSHULGLQH f DQG PHWK\OSLSHULGLQH f DUH ZHOO GRFXPHQWHG >=2. =2. &&& 0,@ 7KH PHFKDQLVWLF SDWKZD\ >&&& &&&@ WR WKHVH FRPSRXQGV 6FKHPH f LQYROYHV IRUPLF DFLG RU IRUPDWH DQLRQf GRQDWLQJ K\GULGH LRQ WR WKH & RI WKH S\ULGLQLXP FDWLRQ f UHVXOWLQJ LQ GLK\GURS\ULGLQH f )XUWKHU VXFFHVVLYH SURWRQDWLRQV DQG DWWDFNV RI K\GULGH LRQ DW & DQG & \LHOG SLSHULGLQHV DQG f 3LSHULGLQH f XQGHUJRHV IRUP\ODWLRQ WR IRUP\OSLSHULGLQH f ZKLFK LV UHGXFHG WR PHWK\OSLSHULGLQHf LQ WKH SUHVHQFH RI IRUPLF DFLG DV VKRZQ LQ 6FKHPH ,Q WKH VDPH PDQQHU PHWK\OSLSHULGLQH f IRUPHG IURP PHWK\OS\ULGLQH f LV FRQYHUWHG VXFFHVVLYHO\ LQWR OIRUP\OPHWK\OSLSHULGLQH f DQG GLPHWK\OSLSHULGLQH f

PAGE 29

5 5 + + 5 + 5 0H ff 5 0H &+2 &+2 &+2 f f 5 + 5 0H 6FKHPH LLf 5HWURYLQ\ORJRXVELVD]D$OGRO UHDFWLRQ URXWH 7KH $OGRO UHDFWLRQ >5@ DQG LWV UHYHUVH WKH UHWUR$OGRO UHDFWLRQ >0,@ DUH DPRQJ WKH PRVW LPSRUWDQW UHDFWLRQV LQ RUJDQLF FKHPLVWU\ 0RQRD]D$OGRO UHDFWLRQV DUH DOVR ZHOO NQRZQ >$*(f@ $OWKRXJK WKH VHOIFRQGHQVDWLRQ RI QLWULOHV 6FKHPH f LV D ZHOO NQRZQ QDPHG UHDFWLRQ 7KRUSHUHDFWLRQf >-&6@ ZH KDYH EHHQ XQDEOH WR ILQG DQ\ H[DPSOH RI WKH VLPLODU VHOIFRQGHQVDWLRQ RI LPLQHV ZKLFK ZRXOG FRQVWLWXWH D ELVD]D$OGRO UHDFWLRQ LH D WUDQVIRUPDWLRQ RI WKH W\SH SOXV 7KH UHWURELVD]D$OGRO UHDFWLRQ

PAGE 30

ZKLFK VKRXOG WKXV LQYROYH WKH IUDJPHQWDWLRQ RI D -DPLQRLPLQH f LQWR WZR LPLQHV DQG f DOVR DSSHDUV WR EH XQNQRZQ 6FKHPH f 1+ &1 5&+&1 5&+&1 5&+& &n f f f 5 DON\O DU\O 6FKHPH f f f 55 DON\O DU\O 6FKHPH $V UHJDUGV YLQ\ORJV RI WKH $OGRO UHDFWLRQ DOWKRXJK WKH UHDFWLRQV RI DOGHK\GHV DW WKH \SRVLWLRQ RI DQ D6XQVDWXUDWHG NHWRQH 6FKHPH f LV ZHOO NQRZQ >5@ ZH KDYH EHHQ XQDEOH WR ILQG DQ\ H[DPSOH ZKHQ WKLV UHDFWLRQ VWRSV DW WKH LQWHUPHGLDWH K\GUR[\ FRPSRXQG 5&+2 5&+&+ &+&25 f f 555 DON\O DU\O +2 5 2 , ,, 5&&& &&5 _/ _/ + + R 5f§& &f§& &&5 + + + + f 6FKHPH

PAGE 31

$]D DQDORJV RI YLQ\ORJRXV $OGRO UHDFWLRQV DOVR DSSHDU WR EH XQLQYHVWLJDWHG DOWKRXJK VXFK UHDFWLRQV DUH DOPRVW FHUWDLQO\ LQYROYHG LQ WKH FRPPHUFLDOO\ LPSRUWDQW SUHSDUDWLRQ RI S\ULGLQHV IURP DOLSKDWLF DOGHK\GHV DQG DPPRQLD VHH ODWHUf %DVHG RQ WKH SUHYLRXV DUJXPHQWV DP L QR \ X QVDWXUDWHG LPLQHV FRXOG EH H[SHFWHG WR XQGHUJR UHWUR YLQ\ORJRXVELVD]D$OGRO 59% $ $f UHDFWLRQV FI t 6FKHPH f b+ 5 5 1I n1 5 5 Wf,+5 / f§ L LL LL $ B 5f§& &f§&f§&f§&5 5&f§& & & &5 ,,, ,,r 5 5 5 U U + f 5 + DON\O f f 6FKHPH &RPSRXQGV RI W\SH DUH WDXWRPHUV RI EELVLPLQHV DQG WKH UHODWHG FDWLRQV ^FI f DUH FDSDEOH RI IRUPDWLRQ E\ ULQJRSHQLQJ RI WKH DGGLWLRQ SURGXFWV f RI D VHFRQGDU\ DPLQH 51+f WR D ORU f GLK\GURS\ULGLQH f VHH 6FKHPH f 7KH 59%$$ UHDFWLRQ RI WKXV FDXVHV VFLVVLRQ LQWR SURWRQDWHG DFU\ODOGHK\GH LPLQH f DQG WKH $YLQ\O GHULYDWLYH f RI WKH RULJLQDO VHFRQGDU\ DPLQH 7KLV 1 YLQ\O FRPSRXQG f LV UDSLGO\ FRQYHUWHG E\ VXFFHVVLYH + DQG +f DGGLWLRQ ERWK VXSSOLHG E\ IRUPLF DFLGf LQWR WKH FRUUHVSRQGLQJ $HWK\O GHULYDWLYH f ,Q DGGLWLRQ LQWHUPHGLDWH FDQ XQGHUJR SURWRQ ORVV DQG SURWRQ DGGLWLRQ WR JLYH WKH LVRPHULF • DPLQR\GXQVDWXUDWHG LPLQH FDWLRQ 7KH 59%$$ UHDFWLRQ RI DIIRUGV YLQ\ODPLQH DQG WKH XQVDWXUDWHG LPLQH FDWLRQ WKH ODWWHU ZKLFK LV FRQYHUWHG UDSLGO\ E\ VXFFHVVLYH DGGLWLRQV RI +f + DQG +? LQWR WKH SURS\O GHULYDWLYH RI WKH RULJLQDO VHFRQGDU\ DPLQH 7KH DFHW\O GHULYDWLYH FDQ DOVR EH IRUPHG IURP E\ K\GUDWLRQ DQG R[LGDWLRQ DQG WKLV YDULDWLRQ FRUUHVSRQGV WR WKH H[SHULPHQWDOO\ IRXQG SURGXFWV DQG

PAGE 32

&+ +1 &+ f 15 f +n + +n &+&+&+15 f + &+ KFrQU f + ++ FKFKQU f 2 &+ ; 15 f 6FKHPH 7KH IRUPDWLRQ RI HWK\O f DQG SURS\OSLSHULGLQH f IURP WKH UHDFWLRQ RI S\ULGLQH f DQG RI SLSHULGLQH ^`f ZLWK IRUPLF DFLG DUH WKXV H[SODLQHG E\ WKH WUDQVIRUPDWLRQ RI 6FKHPH 0RUHRYHU LW ZRXOG EH H[SHFWHG WKDW PHWK\OS\ULGLQH f DQG DOVR PHWK\OSLSHULGLQH ^`f ZRXOG XQGHU VLPLODU FRQGLWLRQV IRUP DON\OPHWK\OSLSHULGLQHV DV LV REVHUYHG H[SHULPHQWDOO\

PAGE 33

5 + 5 0H 6FKHPH )XUWKHU HYLGHQFH IRU WKH PHFKDQLVP SURSRVHG FDQ EH GHULYHG IURP WKH VHOHFWHG GDWD RI 7DEOHV DQG ZKLFK KDYH EHHQ DEVWUDFWHG LQWR 7DEOH 7KLV FRPSDUHV WKH

PAGE 34

7DEOH &RPSDULVRQ RI WKH 3HUFHQWDJHV RI VRPH RI WKH 1$ON\OSLSHULGLQHV IRUPHG IURP 3\ULGLQH 3\f DQG 3LSHULGLQH 3LSf DQG WKHLU 0HWK\O 'HULYDWLYHV 6LQJO\ DQG $GPL[HG LQ b +&4+ DW r& IRU K 3LSHULGLQH 3URGXFW (QWU\ 1R 6XEVWLWXHQW 2ULJLQ RI W 0H3\ 3LS 5LQJ M9DON\O 0H3\ 0H3LS 0H3LS 3\ fI3LS 3\ f HWK\O + (LWKHU f f HWK\O PHWK\O 0H (LWKHU f SURS\O + + LY SURS\O PHWK\O 0H + 9 EXW\O + 0H YL EXW\O PHWK\O 0H 0H f f 9OO SHQW\O + + f f 9OO OPHWK\O SHQW\Of + 0H L[ M9SHQW\O PHWK\O 0H + ; PHWK\O SHQW\OfPHWK\O 0H 0H [L r + +WKHU f f ;, r 0H HWKHU f f ;OOO r (LWKHU + [LY r (LWKHU 0H W + LV IURP 3\ RU 3LS 0H LV IURP 0H3\ RU 0H3LS r WRWDO IRU FRPSRXQGV OLVWHG

PAGE 35

DPRXQWV RI WKH VLPSOH L9DON\OSLSHULGLQHV IRUPHG IURP SLSHULGLQH f PHWK\OSLSHULGLQH f S\ULGLQH f DQG PHWK\O S\ULGLQH f DORQH ZLWK WKRVH IURP WKH WZR PL[HG UXQV 7DEOH GHPRQVWUDWHV YHU\ FOHDUO\ WKDW WKH SURGXFWV H[SHFWHG IURP WKH PHFKDQLVWLF URXWHV GLVFXVVHG DQG RQO\ WKH H[SHFWHG SURGXFWV DUH IRUPHG LQ WKH UXQV IURP D VLQJOH VXEVWUDWH )XUWKHUPRUH 7DEOH SURYLGHV JRRG HYLGHQFH IRU WKH PHFKDQLVP SRVWXODWHG IURP WKH QDWXUH DQG WKH SURSRUWLRQV RI WKH SURGXFWV IRUPHG LQ WKH PL[HG UXQV 7KXV ZKHQ PHWK\OSLSHULGLQH f DQG S\ULGLQH f ZHUH UHDFWHG WRJHWKHU WKH PHWK\OSLSHULGLQH f SUHGRPLQDWHO\ SURYLGHG WKH ULQJ FRPSRQHQW RI WKH SLSHULGLQHV IRUPHG FRPSDUH b WR b (QWULHV [LL DQG [L UHVSHFWLYHO\f ZKHUHDV S\ULGLQH SUHGRPLQDWHO\ SURYLGHG WKH SLSHULGLQH 9DON\O VXEVWLWXHQW FRPSDUH b WR b (QWULHV [LLL DQG [LY UHVSHFWLYHO\f &RQYHUVHO\ ZKHQ D PL[WXUH RI SLSHULGLQH f DQG PHWK\OS\ULGLQH f ZDV UHDFWHG D WRWDO RI b RI SURGXFWV IRUPHG ZDV GHULYHG IURP SLSHULGLQH f UHDFWLQJ DV WKH DPLQH +15 FRPSDUHG ZLWK b IURP WKH PHWK\OS\ULGLQHf UHDFWLQJ DV +15 $JDLQ WKH 1DON\O JURXSV RI WKH SLSHULGLQH SURGXFWV ZHUH IRUPHG b IURP WKH VWDUWLQJ SLSHULGLQH DQG b IURP WKH PHWK\OS\ULGLQH 7KLV LV LQ JRRG DJUHHPHQW ZLWK WKH PHFKDQLVP SURSRVHG LQ 6FKHPH LQ ZKLFK WKH VDWXUDWHG VHFRQGDU\ DPLQH DGGV WR D GLK\GURS\ULGLQH LQ D NH\ VWHS LLLf $GGLWLRQ WR WHWUDKYGURS\ULGLQLXP FDWLRQV $ VLPSOHU VHTXHQFH RI DGGLWLRQ RI 51+ WR D WHWUDK\GURS\ULGLQLXP ULQJ f IROORZHG E\ ULQJn RSHQLQJ DQG UHGXFWLRQ OHDGV WR DPLQHV RI W\SH 51&+f1+ DQG WKLV H[SODLQV WKH IRUPDWLRQ RI DQG 6FKHPH f LYf 5LQJ RSHQLQJ RI LVRPHUV RI SURGXFWV RI DGGLWLRQ RI SLSHULGLQHV WR TXDWHPL]HG S\ULGLQHV $GGLWLRQ RI D VHFRQGDU\ DPLQH WR D TXDWHPL]HG S\ULGLQH f ZLOO JLYH DGGLWLRQ SURGXFW VHH 6FKHPH f :H SRVWXODWH WKDW D K\GURJHQ VKLIW LQ OHDGV WR ZKLFK FDQ XQGHUJR HOHFWURF\FOLF ULQJRSHQLQJ WR 1H[W IRXU VXFFHVVLYH SURWRQDWLRQV HDFK IROORZHG E\ D K\GULGH LRQ DGGLWLRQ

PAGE 36

FRQYHUWV LQWR WKH VDWXUDWHG SURGXFW :H EHOLHYH PHFKDQLVPV RI WKHVH W\SHV WR EH LQYROYHG LQ WKH IRUPDWLRQ RI SURGXFWV DQG 6FKHPH f 0H + f 5 f + 5 + 6FKHPH

PAGE 37

6FKHPH

PAGE 38

+ f + f 5 + + f 0H + + D 0H 5 0H 5 f f f 5 + 6FKHPH

PAGE 39

&RQFOXVLRQV )RUPLF DFLG YDULRXVO\ DFWV DV D IRUP\ODWLQJ PHWK\ODWLQJ UHGXFLQJ DQG R[LGL]LQJ DJHQW ZKHQ LW UHDFWV ZLWK SLSHULGLQH S\ULGLQH DQG VRPH RI WKHLU PHWK\O GHULYDWLYHV XQGHU DTXDWKHUPRO\VLV FRQGLWLRQV ,Q VLPLODU UHDFWLRQV ERWK SLSHULGLQH DQG S\ULGLQH DUH FRQYHUWHG WR VLJQLILFDQW DPRXQWV RI DON\OSLSHULGLQHV QDPHO\ PHWK\O HWK\O SURS\O DQG SHQW\OSLSHULGLQHV O0HWK\OSHQW\OfSLSHULGLQH ZDV QRW REVHUYHG DV SURGXFW IURP WKH DTXDWKHUPRO\VHV 7KURXJK WKH XVH RI LVRWURSLF ODEHOOLQJ LW KDV EHHQ GHPRQVWUDWHG WKDW RQO\ WKH PHWK\O GHULYDWLYH RULJLQDWHG IURP IRUPLF DFLG 7KDW LV GXULQJ WKH FRXUVH RI WKH UHDFWLRQV SLSHULGLQH DQG S\ULGLQH ZHUH ERWK IRUP\ODWHG DQG WKHQ VXEVHTXHQWO\ UHGXFHG WR WKH PHWK\O GHULYDWLYHV 7KH HWK\O DQG SURS\O GHULYDWLYHV DULVH IURP WKH KHWHURF\FOLF ULQJ && ERQG ILVVLRQ E\ UHWURYLQ\ORJRXVELVD]D$OGRO UHDFWLRQV 7KHVH XQLTXH && ERQG VFLVVLRQV VKRZ IRU WKH ILUVW WLPH WKDW KHWHURF\FOLF ULQJV DUH VXVFHSWLEOH WR RSHQLQJ RWKHU WKDQ DW WKH KHWHURDWRPV 2WKHU UHDFWLRQ SDWKZD\V HOXFLGDWHG GXULQJ WKH FRXUVH RI WKLV ZRUN LQFOXGH FRQYHQWLRQDO IRUPLF DFLG UHGXFWLRQIRUP\ODWLRQ DGGLWLRQ WR WHWUDK\GURS\ULGLQLXP FDWLRQV DQG ULQJ RSHQLQJ RI LVRPHUV RI SURGXFWV IRUPHG E\ DGGLWLRQ RI SLSHULGLQHV WR D TXDWHPL]HG S\ULGLQLXP FDWLRQ ,W KDV EHHQ VKRZQ WKDW IRUPLF DFLG DW r& FRQYHUWV S\ULGLQH DQG SLSHULGLQH LQWR D ZHOO GHILQHG PL[WXUH RI VSHFLILF $DON\OSLSHULGLQHV 0HWK\OS\ULGLQH DQG PHWK\OSLSHULGLQH DUH VLPLODUO\ FRQYHUWHG LQWR WKH FRUUHVSRQGLQJ ODON\O PHWK\OSLSHULGLQHV ,W KDV EHHQ GHPRQVWUDWHG WKDW DOO WKH DON\O JURXSV H[FHSW IRU PHWK\Of DULVH IURP D VHFRQG PROHFXOH RI WKH KHWHURF\FOLF ULQJ FRPSRXQG DQG QRW IURP WKH IRUPLF DFLG 7KH IRUPDWLRQ RI DOO SURGXFWV FDQ EH UDWLRQDOL]HG E\ DGGLWLRQ RI D SLSHULGLQH PROHFXOH WR D S\ULGLQH RU GL RU WHWUDK\GURS\ULGLQH DQDORJ 0DQ\ RI WKH UHDFWLRQV SURSRVHG LQ WKH SUHVHQW ZRUN DUH WKH UHYHUVH RI WKH FRPPHUFLDOO\ LPSRUWDQW S\ULGLQH ULQJIRUPLQJ UHDFWLRQ IURP DOGHK\GHV DQG DPPRQLD DQG VKRXOG KHOS LQ EHWWHU XQGHUVWDQGLQJ RI WKH ODWWHU ,Q SULQFLSOH D YHU\ XVHIXO FRPPHUFLDO

PAGE 40

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f RU D *HQHUDO (OHFWULF 4( 0+]f VSHFWURPHWHU 105 VSHFWUD ZHUH UHFRUGHG DW 0+] RQ WKH VDPH VSHFWURPHWHUV &KHPLFDO VKLIWV DUH UHSRUWHG LQ SDUWV SHU PLOOLRQ SSPf GRZQILHOG IURP WHWUDPHWK\OVLODQH 706f XVHG DV WKH LQWHUQDO VWDQGDUG &RXSOLQJ FRQVWDQWV YDOXHVf DUH UHSRUWHG LQ +] $OO *ULJQDUG UHDFWLRQV ZHUH UXQ XQGHU DQ LQHUW DWPRVSKHUH XVLQJ RYHQ GULHG DSSDUDWXV 6ROYHQWV DQG DQK\GURXV OLTXLG UHDJHQWV ZHUH GULHG SULRU WR XVH GLHWK\O HWKHU ZDV GLVWLOOHG RYHU VRGLXP EHQ]RSKHQRQH NHW\O $QDO\WLFDO WKLQ OD\HU FKURPDWRJUDSK\ 7/&f ZDV SHUIRPHG XVLQJ SUHFRDWHG VLOLFD JHO ) SODVWLF SODWHV PP WKLFNf XVLQJ LRGLQH DV LQGLFDWRU +3LSHULGLQRPHWKY'EHQ]RWULD]ROH f ZDV SUHSDUHG E\ DSSO\LQJ WKH OLWHUDWXUH SURFHGXUH >-&63f@ %HQ]RWULD]ROH J PPROf ZDV GLVVROYHG LQ (W2+ P/f 1H[W ZDV DGGHG b DTXHRXV IRUPDOGHK\GH P/ PPROf DQG SLSHULGLQH P/ PPROf DQG WKH UHDFWLRQ ZDV VWLUUHG YLJRURXVO\ DW URRP WHPSHUDWXUH Kf 3UHFLSLWDWLRQ ZDV LQGXFHG E\ DGGLWLRQ RI +2 P/f 7KH SURGXFW REWDLQHG ZDV ZDVKHG ZLWK (W2+ P/f WR \LHOG D ZKLWH VROLG J bf ZKLFK ZDV SXUH E\ A+ 105 DQG XVHG LQ VXEVHTXHQW UHDFWLRQV 0S r& OLW>-$@ PS r&f + 105 &'&,f P +f SLSHULGLQHf TXLQWHW + f SLSHULGLQHf W

PAGE 41

+ f SLSHULGLQHf V +f &+f P +f %Wf G + f %Wf G + f %Wf & 105 &'&f O$$'LPHWKYODPLQRPHWK\OfEHQ]RWULD]ROH f ZDV SUHSDUHG DFFRUGLQJ WR WKH OLWHUDWXUH SURFHGXUH >-2&@ %HQ]RWULD]ROH J PPROf ZDV GLVVROYHG LQ (W2+ P/f 1H[W ZDV DGGHG b DTXHRXV IRUPDOGHK\GH P/ PPROf 7KH PL[WXUH ZDV VWLUUHG YLJRURXVO\ DQG FRROHG WR r& $IWHU WKH LQLWLDO SUHFLSLWDWH IRUPHG 1 $GLPHWK\ODPLQH P/ PPROf ZDV DGGHG GURSZLVH YLD DQ DGGLWLRQ IXQQHO DQG WKH UHDFWLRQ ZDV DOORZHG WR ZDUP XS WR URRP WHPSHUDWXUH Kf &U\VWDOOL]DWLRQ RI WKH FUXGH SURGXFW ZDV LQGXFHG E\ FRROLQJ WKH PL[WXUH WR r& 7KH FUXGH ZKLWH VROLG ZDV ILOWHUHG DQG ZDVKHG ZLWK (W2+ P/f 5HFU\VWDOOL]DWLRQ IURP HWKDQRO \LHOGHG ZKLWH SULVPV J bf 0S r& OLW>-$@ PS r&f 105 &'&,f V +f &+f V +f &+f P +f %Wf W + f %Wf G + f %Wf G + f %Wf & 105 &'&,f *HQHUDO SURFHGXUH IRU WKH V\QWKHVLV RI $DON\OSLSHULGLQHV O0HWKYOEXW\OfSLSHULGLQH f 0J PHWDO J PPROf ZDV VXVSHQGHG ZLWK DQ LRGLQH FKLS LQ (W P/f %URPREXWDQH J PPROf ZDV GLVVROYHG LQ (W P/f DQG DGGHG GURSZLVH WR WKH 0J PHWDO $IWHU WKH DGGLWLRQ ZDV FRPSOHWH WKH PL[WXUH ZDV KHDWHG XQGHU UHIOX[ DQG VWLUUHG IRU K 3LSHULGLQRPHWK\OfEHQ]RWULD]ROH J PPROf ZDV WKHQ DGGHG YLD D 6R[KOHW H[WUDFWRU 7KH UHDFWLRQ ZDV WKHQ VWLUUHG DQG UHIOX[HG IRU K 7KH UHDFWLRQ ZDV FRROHG DQG TXHQFKHG ZLWK D PLQLPDO DPRXQW RI ZDWHU P/f 7KH EXON RI WKH (W ZDV GHFDQWHG IURP WKH VROLG DQG WKH UHPDLQGHU ILOWHUHG WKURXJK FHOLWH 7KH (W ZDV GULHG 0J6f DQG

PAGE 42

UHPRYHG LQ YDFXR WR \LHOG D FUXGH \HOORZ RLO ZKLFK ZDV SXULILHG E\ .XJHOURKU GLVWLOODWLRQ $ FRORUOHVV RLO J bf ZDV LVRODWHG %S r& PP +J 105 &'&,f G + f &+f W + f &+f P +f &+f P +f &+ >ULQJ@f TXLQWHW + f &+ >ULQJ@f G RI G + f &+1 >DOLSKDWLF@f EU P +f &+1 >ULQJ@f & 105 &'&,f +5 06 H9 (Of P] bf f >0@ f >&+K1@&LR+L1 UHTXLUHV 0HWK\O SHQW\'SLSHULGLQH f 7KLV SURGXFW ZDV REWDLQHG DV D FUXGH \HOORZ RLO DQG ZDV SXULILHG E\ .XJHOURKU GLVWLOODWLRQ WR JLYH D FRORUOHVV RLO J bf %S & PP +J r+ 105 &'&,f G t W + f &+f TXLQWHW + f &+f P +f &+ >DOLSKDWLF@f P +f &+ >ULQJ@f TXLQWHW + f &+ >ULQJ@f P +f &+1 >DOLSKDWLF@f EU V +f &+1 >ULQJ@f & 105 &'&,f +5 06 H9 (Of P] bf f >0@ f >&+Q1@&+1 UHTXLUHV O0HWKYOSHQW\OfSLSHULGLQH f 7KLV SURGXFW ZDV REWDLQHG DV D FUXGH \HOORZ RLO DQG ZDV SXULILHG E\ .XJHOURKU GLVWLOODWLRQ WR JLYH D SDOH \HOORZ RLO J bf %S r& PP +J r+ 105 &'&,f G + f &+f TXLQWHW + f &+f P +f SLSHULGLQHf P +f SLSHULGLQHf W + f &+ >ULQJ@f EU V +f DOLSKDWLFf & 105 &'&,f +5 06 H9 (Of P] bf f >0@ f >&+Q1@ &M c+1 UHTXLUHV

PAGE 43

*HQHUDO SURFHGXUH IRU WKH V\QWKHVLV RI DF\FOLF DPLQHV $$'LPHWK\OSHQW\ODPLQHf Q%XW\O EURPLGH J PPROf ZDV GLVVROYHG LQ (W P/f DQG DGGHG GURSZLVH WR 0J PHWDO J PPROf LQ WKH SUHVHQFH RI DQ LRGLQH FKLS $IWHU WKH DGGLWLRQ ZDV FRPSOHWH WKH PL[WXUH ZDV KHDWHG XQGHU JHQWOH UHIOX[ DQG VWLUUHG IRU K $IWHU WKLV SHULRG RI WLPH 11 GLPHWK\ODPLQRPHWK\OfEHQ]RWULD]ROH J PPROf ZDV DGGHG YLD 6R[KOHW H[WUDFWRU 7KH PL[WXUH ZDV VWLUUHG DQG UHIOX[HG IRU K 7KH UHDFWLRQ ZDV FRROHG DQG TXHQFKHG ZLWK DTXHRXV 1D2+ P/f 7KH EXON RI WKH (W ZDV GHFDQWHG IURP WKH VROLG DQG WKH UHPDLQGHU ILOWHUHG WKURXJK FHOLWH GULHG 0J6&!f DQG FRQFHQWUDWHG LQ YDFXR WR JLYH D FUXGH \HOORZ RLO *& \LHOG b 7KH FUXGH SURGXFW ZDV SXULILHG E\ .XJHOURKU GLVWLOODWLRQ WR JLYH D FRORUOHVV RLO bf %S r& PP +J OLW >0,@ ES r& PP +Jf O+ 105 &'&,f W + f &+f P +f &+f V +f &+1f G + f &+1f & 105 &'&,f +5 06 H9 (Of P] bf bf >0@ f >&+ O1@ &+1 UHTXLUHV 1$'LPHWKYOPHWK\OSHQW\ODPLQH f 7KLV SURGXFW ZDV REWDLQHG FUXGH DV D \HOORZ RLO ZKLFK ZDV SXULILHG E\ .XJHOURKU GLVWLOODWLRQ WR JLYH D FRORUOHVV RLO J bf %S r& PP +J OLW>&&&@ ES r& PP +Jf r+ 105 &'&,f W + f &+ >WHUPLQDO@f G f+f &+f T + f &+Df G + f &+Ef P +f &+f P +f &+ >&+@f G RI G + f &+1f V +f &+1f & 105 &'&,f +5 06 H9 (Of P] bf f >0@ f >&+Q1@ &+L1 UHTXLUHV

PAGE 44

$TXDWKHUPRO\VLV *HQHUDO $OO VWDUWLQJ PDWHULDOV ZHUH FKHFNHG E\ *& SULRU WR XVH ZKHUH QHFHVVDU\ WKH\ ZHUH SXULILHG WR !b b $TXHRXV IRUPLF DFLG ZDV GHR[\JHQDWHG ZLWK DUJRQ IRU K SULRU WR XVH 7KH PRGHO FRPSRXQG Jf DQG WKH IRUPLF DFLG P/f ZHUH FKDUJHG LQWR D QLWURJHQ EODQNHWHG 6ZDJHORN VWDLQOHVV VWHHO ERPE SOXJ DQG FDSf ZKLFK ZDV WKHQ VHDOHG 7KH UHDFWRU ZDV WKHQ NHSW ZLWKRXW DJLWDWLRQ LQ D IOXLGL]HG VDQG EDWK PRGHO 6%6f VHW DW r& XVLQJ D 7HFKQH WHPSHUDWXUH FRQWUROOHU 7&'f IRU WKH VSHFLILHG WLPH SHULRG 7KH WHPSHUDWXUH SURILOH ZDV PHDVXUHG E\ D %DUQDQW WKHUPRFRXSOH WKHUPRPHWHU W\SH -f SODFHG LQ WKH VDQGEDWK DGMDFHQW WR WKH UHDFWLRQ YHVVHO $IWHU WKH UHDFWLRQ SHULRG WKH UHDFWRU ZDV LPPHGLDWHO\ FRROHG ZLWK D VWUHDP RI FROG DLU DQG WKHQ TXHQFKHG LQ GU\ LFH 7KH UHDFWLRQ PL[WXUH ZDV WKHQ ZRUNHG XS DV SUHYLRXVO\ GHVFULEHG >()@ DQG VXEMHFWHG WR *& DQDO\VHV RQ D +HZOHWW 3DFNDUG LQVWUXPHQW IODPH LRQL]DWLRQ GHWHFWRU >),'@f ZLWK D P FDSLOODU\ FROXPQ 63%f DQG D WHPSHUDWXUH SURJUDP RI r& PLQnO IURP r& *&06 DQDO\VHV RI DOO FRPSRXQGV ZHUH SHUIRUPHG RQ D 9DUDQ JDV FKURPDWRJUDSK DQG D )LQQLJDQ 0$7 LRQ WUDS GHWHFWRU 3URGXFW LGHQWLILFDWLRQ 7KH *& EHKDYLRU RI DOO WKH FRPSRXQGV LQ WKLV FKDSWHU VWDUWLQJ PDWHULDO DQG SURGXFWVf DUH FROODWHG LQ 7DEOH LQ WKH IRUPDW DV H[SODLQHG LQ HDUOLHU SDSHUV >()@f :LWKLQ WKH UHDFWLRQ PL[WXUHV WKH LGHQWLWLHV RI DOO WKH VWDUWLQJ PDWHULDOV DQG VRPH RI WKHLU UHDFWLRQ SURGXFWV > @ ZHUH FRQILUPHG E\ GLUHFW FRPSDULVRQV RI UHWHQWLRQ WLPHV DQG PDVV VSHFWUDO IUDJPHQWDWLRQ SDWWHUQV ZLWK WKRVH RI WKH DXWKHQWLF FRPSRXQGV XQGHU HVVHQWLDOO\ WKH VDPH PDVV VSHFWUDO RSHUDWLQJ FRQGLWLRQV 7DEOH UHFRUGV WKH PDMRU IHDWXUHV RI WKH PDVV VSHFWUD WRJHWKHU ZLWK D OLWHUDWXUH UHIHUHQFH WR WKH 06 RI WKH FRPSRXQGV ZKHUH DYDLODEOHf 7DEOH UHFRUGV WKH PDVV VSHFWUDO IUDJPHQWDWLRQ SDWWHUQV RI SURGXFWV f ZKLFK ZHUH LGHQWLILHG E\ FRPSDULVRQ ZLWK SXEOLVKHG 06 GDWD ,Q VXFK FDVHV WKH VRXUFH RI $OO DTXDWKHQQRO\VHV ZHUH FRQGXFWHG MRLQWO\ E\ 0DUXGDL %DODVXEUDPDQLDQ 5LFKDUG $ %DU FRFN DQG (OHQD 6 ,JQDWFKHQNR DW WKH 8QLYHUVLW\ RI )ORULGD

PAGE 45

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f DQG DUH UHSUHVHQWHG

PAGE 46

&+$37(5 ,,, 5($&7,21 2) 9$5,286 $/,3+$7,& $0,1(6 :,7+ )250,& $&,' 2&7 < /$ 0,1( ', 2&7()@ 'XH WR WKH GHOHWHULRXV HIIHFWV RI 1 LPSXULWLHV LWV PHQWLRQHG LQ &KDSWHU ,,f UHPDLQLQJ LQ V\QWKHWLF RLOV LW LV KLJKO\ HFRQRPLFDO WR UHPRYH WKHP HDVLO\ DQG FRVW HIIHFWLYHO\ 1RUPDO PRGHV RI SXULILFDWLRQ LQYROYH GHQLWURJHQDWLRQ DQG K\GURGHQLWURJHQDWLRQ >() 7/@ $TXDWKHUPRO\VLV WKH WKHUPDO WUDQVIRUPDWLRQ RI RUJDQLF FRPSRXQGV LQ DTXHRXV HQYLURQPHQWV KROGV SRWHQWLDO HFRQRPLF LQFHQWLYH DV DQ DOWHUQDWLYH SXULILFDWLRQ PHWKRG IRU WKH FRQYHUVLRQ DQG SXULILFDWLRQ RI IRVVLO IXHOV VXFK DV FRDOr 'HQLWURJHQDWLRQ FDQ EH D FRVWO\ SURFHVV IRU WKH UHPRYDO RI QLWURJHQ IRUP KHWHURF\FOLF QLWURJHQ FRQWDLQLQJ FRPSRXQGV GXH WR WKH ODUJH H[FHVV RI K\GURJHQ QHHGHG WR DIIRUG K\GURJHQRO\VLV RI WKH KHWHURF\FOLF ULQJ DV PHQWLRQHG LQ &KDSWHU ,,f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

PAGE 47

GLUHFWO\ 7KHUH ZRXOG EH QR QHHG IRU VLJQLILFDQW SUHK\GURJHQDWLRQ RI WKH V\VWHP $OLSKDWLF DPLQHV DUH DPRQJ WKH QLWURJHQ FRPSRXQGV IRXQG LQ SHWUROHXP RU V\QWKHWLF RLOV 2XU PDLQ REMHFWLYH ZDV WR XQFRYHU WKH JHQHUDO SDWWHUQ RI UHDFWLYLW\ XQGHU DTXDWKHUPRO\VLV FRQGLWLRQV RI VRPH FRPPRQ QDWXUDOO\ RFFXUULQJ DPLQHUHODWHG IXQFWLRQDO JURXSV /LWHUDWXUH UHSRUWV KDYH VKRZQ WKDW IRUPLF DFLG DW WHPSHUDWXUHV UDQJLQJ IURP r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b DTXHRXV IRUPLF DW r& S\ULGLQH ZDV FRQYHUWHG SUHGRPLQDQWO\ LQWR IRUP\OSLSHULGLQH DFFRPSDQLHG E\ VHYHUDO $DON\OSLSHULGLQHV DV PLQRU SURGXFWV ,Q FRQQHFWLRQ ZLWK WKH HOXFLGDWLRQ RI WKH PHFKDQLVP IRU WKH IRUPDWLRQ RI WKH 1 DON\OSLSHULGLQHV ZH KDYH DOVR VWXGLHG WKH HIIHFW RI b DTXHRXV IRUPLF DFLG RQ UHSUHVHQWDWLYH SULPDU\ >RFW\ODPLQH f GRGHF\ODPLQH f@ VHFRQGDU\ >GLORFW\ODPLQH f@ DQG WHUWLDU\ >1 $GLPHWK\OORFW\ODPLQH f 11 GLPHWK\OGRGHF\ODPLQH f@ DON\ODPLQHV 6FKHPH f $OO V\QWKHWLF ZRUN DQG PDVV VSHFWUDO LQYHVWLJDWLRQV LQWHUSUHWDWLRQV ZHUH SHUIRUPHG E\ 5ROV\Q / :KLWH DW WKH 8QLYHUVLW\ RI )ORULGD $OO DTXDWKHUPRO\VLV UHDFWLRQV ZHUH FRQGXFWHG E\ (OHQD 6 ,JQDWFKHQNR DW WKH 8QLYHUVLW\ RI )ORULGD &RPSRXQGV KDYH EHHQ QXPEHUHG VHTXHQWLDOO\ DFFRUGLQJ WR WKHLU UHWHQWLRQ WLPHV ZLWK FRPSRXQG EHDULQJ WKH ORZHVW UHWHQWLRQ WLPH VHH 7DEOH IRU D FRPSOHWH OLVWLQJf &RPSRXQG QXPEHUV HTXDO WR RU JUHDWHU WKDQ DUH XVHG IRU SRVWXODWHG LQWHUPHGLDWHV QRW GHWHFWHG E\ WKH *&06 DQDO\VHV

PAGE 48

&+1+ &+10H &+1+ &+10H &+f1+ 6FKHPH 7KH JDV FKURPDWRJUDSKLF *&f EHKDYLRU RI DOO WKH FRPSRXQGV HPSOR\HG IRU WKLV VWXG\ DQG WKH SURGXFWV DUH UHFRUGHG LQ 7DEOH 7DEOH DQG FRQWDLQ WKH FRPSLOHG PDVV VSHFWUDO GDWD IRU WKH DQDO\VLV RI UHVXOWV 7DEOH FRQWDLQV WKH VRXUFHV DQG SXULWLHV RI WKH VWDUWLQJ PDWHULDOV XVHG DQG KDYH EHHQ FRPSLOHG EDVHG XSRQ WKH GLUHFW FRPSDULVRQ RI WKH *& UHWHQWLRQ WLPHV DQG RI WKH PDVV VSHFWUDO 06f IUDJPHQWDWLRQ SDWWHUQ ZLWK WKRVH RI WKH DXWKHQWLF FRPSRXQG 7DEOH FRQWDLQV FRPSRXQGV ZKLFK KDYH EHHQ LGHQWLILHG E\ FRPSDULVRQ RI 06 SDWWHUQV ZLWK OLWHUDWXUH 06 GDWD IRU WKH VDPH FRPSRXQG 7KRVH FRPSRXQGV IRU ZKLFK QR VXLWDEOH OLWHUDWXUH 06 GDWD ZHUH DYDLODEOH KDYH EHHQ LGHQWLILHG E\ WKHLU 06 IUDJPHQWDWLRQ SDWWHUQV REWDLQHG IURP WKH DTXDWKHUPRO\VLV UXQVf DQG KDYH EHHQ FRPSLOHG LQ 7DEOH $ PRUH GHWDLOHG H[SODQDWLRQ RI 7DEOHV f§ LV JLYHQ LQ VHFWLRQ ([SHULPHQWDO 7KH UHVXOWV IURP WKH DTXDWKHUPRO\LV RI HDFK DPLQH DUH FROOHFWHG LQ 7DEOHV f§ $OO SURGXFW \LHOGV PRODU bf DUH UHSUHVHQWHG DV D SHUFHQWDJH RI PROHV DV GHVFULEHG LQ GHWDLO SUHYLRXVO\ >()@ DQG KDYH EHHQ FRUUHFWHG ZLWK UHJDUG WR WKHLU UHVSRQVH IDFWRUV >7&0@ 6WUXFWXUHV DQG SURSRVHG UHDFWLRQ SDWKZD\V IRU WKH IRUPDWLRQ RI WKHVH SURGXFWV DUH JLYHQ LQ 6FKHPHV f§ VHH VHFWLRQ 'LVFXVVLRQf ,Q WKHVH UHDFWLRQ 6FKHPHV QXPEHUV DUH XVHG IRU SRVWXODWHG LQWHUPHGLDWHV QRW GHWHFWHG E\ WKH *&06 DQDO\VHV 7KH GDWD KDV EHHQ FRPSLOHG DV H[SODLQHG LQ WKLV SDUDJUDSK DFFRUGLQJ WR WKH VHULHV RI DTXDWKHUPRO\VLV SDSHUV >()@ .QRZOHGJH RI WKH UHVSRQVH IDFWRU DOORZV TXDQWLWDWLYH DQDO\VLV RI FRPSOH[ SURGXFW *&06 HVSHFLDOO\ IRU WKRVH FDVHV ZKHUH VRPH RU DOO RI WKH SURGXFWV DUH XQDYDLODEOH WL[WXUHV E\

PAGE 49

7DEOH 6WUXFWXUH DQG ,GHQWLILFDWLRQ RI 6WDUWLQJ 0DWHULDOV DQG 3URGXFWV 1R W5PLQf &RPSRXQG 1 L9GLPHWK\O EXW\ODPLQH KH[DQRO 1 $AGLPHWK\ KH[\ODPLQH 1PHWK\OGL EXW\ODPLQH RFWDQRQH 1 GLPHWK\O HWK\O KH[\ODPLQH PHWK\O EXW\OIRUPDPLGH RFW\ODPLQH 1 GLPH WK\ RFW\ODPLQH RFWDQRO PHWK\O RFW\ODPLQH $PHWK\O RFW\ODPLQH 1 GLPHWK\O RFW\ODPLQH WULEXW\ODPLQH GRGHFHQH B GRG L9PHWK\OL9 KH[\OIRUPDPLGH K W B L f 1 1L EXW\OIRUPDPLGH $IPHWK\OGLKH[\ODPLQH $0RFW\ ,IRUPDPL GH GRGHF\ODPLQH $IPHWK\O1 RFW\OIRLPDPLGH 1 RFW\ODFHWDPLGH K B Y LQ \9PHWK\O GRGHF\ODPLQH 1 L9GLPHWK\O GRGHF\ODPLQH 1PHWK\O$A RFW\ODFHWDPLGH \9DFHW\O$I RFW\OIRUPDPLGH 1 RFW\O1 RFW\ODPLQH 0: (T: %DVLV r )DFWL 7DEOH 7DEOH 7DEOH 7DEOH $ 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH A 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH 7DEOH RUE

PAGE 50

7DEOH FRQWLQXHG W5PLQf &RPSRQ 0: (T : %DVLV )DFWRUA 1PHWK\OGL RFW\ODPLQH GLRFW\ODPLQH 1 RFW\O1 RFW\OIRUPDPLGH 1 GRGHF\OIRUPDPLGH 1PHWK\O1 GRGHF\OIRUPDPLGH :PHWK\O: GRGHF\O DFHWDPL GH L9DFHW\O1 GRGHF\OIRUPDPLGH $IPHWK\O1RFW\O RFW\ODPLQH 1 \9GL RFW\OIRUPDPLGH 1 1GL RFW\ODFHWDPLGH WULRFW\ODPLQH \9PHWK\OGL GRGHF\O DPLQH GL GRGHF\O DPLQH 7DEOH 7DEOH 7DEOH $ 7DEOH 7DEOH 7DEOH 7DEOH $ 7DEOH $ 7DEOH 7DEOH 7DEOH 7DEOH $ 7DEOH W5PLQf 5HWHQWLRQ WLPH LQ %DVLV VHH DSSURSULDWH WDEOH f,1, 0: PROHFXODU ZHLJKW (T : HTXLYDOHQW ZHLJKW D ,GHQWLILFDWLRQ H )DFWRU VHH UHI >7&0

PAGE 51

7DEOH 3URSHUWLHV RI $XWKHQWLF &RPSRXQGV XVHG DV 6WDUWLQJ 0DWHULDOV DQG IRU WKH ,GHQWLILFDWLRQ RI 3URGXFWV 1R &RPSRXQG 1 1GLPHWK\O EXW\ODPLQH $A$AGLPHWK\OOKH[\ODPLQH RFWDQRQH RFW\ODPLQH RFWDQRO 1 \9GLPHWK\O RFW\ODPLQH W W GRGHF\ODPLQH K L B W QUmX} :GLPHWK\OO GRGHF\ ODPLQH GLRFW\ODPLQH 1 GRGHF\OIRPLDPLGF WULRFW\ODPLQH 0: D 3XULW\ bf $ $ $ $ $ $ ) $ $ $ 6 $ -] b UHODWLYH LQWHQVLW\f 5HI 6SHFWUD f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f F f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f D $ $OGULFK ) )OXND (DVWPDQ .RGDN / /DQFDVWHU 6 V\QWKHVL]HG DXWKHQWLF FRPSRXQG VHH H[SHULPHQWDO VHFWLRQf E VSHFWUDO QXPEHUV RI WKH PDVV VSHFWUDO GDWD IRU WKH FRPSRXQGV IRXQG IURP D VHDUFK RI WKH :LOH\ / 063 F QR VSHFWUD DYDLODEOH

PAGE 52

7DEOH ,GHQWLILFDWLRQ RI 3URGXFWV E\ &RPSDULVRQ RI 0DVV 6SHFWUDO )UDJPHQWDWLRQ ZLWK /LWHUDWXUH 'DWD 1R &RPSRXQG 0: )UDJPHQWDWLRQ )RXQG P] b UHODWLYH LQWHQVLW\f 5HID 6SHFWUD )UDJPHQWDWLRQ 5HSRUWHG P] b UHODWLYH LQWHQVLW\@ KH[DQRO 1 M9GLPHWK\OHWK\O KH[\ODPLQH 1 1GLPHWK\ORFW\ODPLQH PHWK\O RFW\ODPLQH WULEXW\O DPLQH m 0!a_ GRG f m Lm K W B L f fm L 1 1GL EXW\OIRUPDPLGH 1 RFW\OIRUPDPLGH 1PHWK\OGL RFW\ODPLQH 1 1GL RFW\OIRUPDPLGH 1 $IGL RFW\ODFHWDPLGH GL GRGHF\ODPLQH f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f F\L D VSHFWUDO QXPEHUV RI WKH PDVV VSHFWUDO GDWD IRU WKH FRPSRXQGV IURP D VHDUFK RI WKH :LOH\ / 063

PAGE 53

7DEOH ,GHQWLILFDWLRQ RI 3URGXFWV )URP 0DVV 6SHFWUDO )UDJPHQWDWLRQ 3DWWHUQV 1R &RPSRXQGV 0: )UDJPHQWDWLRQ 3DWWHUQ >b UHODWLYH LQWHQVLW\ VWUXFWXUH RI IUDJPHQW LRQ PHWK\OGL EXW\ODPLQH PHWK\O 1 EXW\OIRUPDPLGH PHWK\O RFW\ODPLQH PHWK\O KH[\OIRUPDPLGH PHWK\O GL KH[\ODPLQH PHWK\O 1 RFW\OIRUPDPLGH 1 RFW\ODFHWDPLGH PHWK\O GRGHF\ODPLQH PHWK\O 1 RFW\ODFHWDPLGH DFHW\O RFW\OIRUPDPLGH 1 RFW\O 1 RFW\ODPLQH 1 RFW\O 1 RFW\OIRUPDPLGH PHWK\O 1 GRGHF\OIRUPDPLGH PHWK\O1 GRGHF\ODFHWDPLGH DFHW\O GRGHF\OIRUPDPLGH PHWK\O RFW\O RFW\ODPLQH PHWK\OGL GRGHF\ODPLQH 0f 0&+f 0&+Lff 0f 0+f 0&+f 0&+f 0&+&2f f 0f 0+f 0&+f 0&+Qff f 0f 0+f 0&+f 0&+f f f 0f 0+f 0&+f 0&+f f 0f 0&+f f f 0&+f 0&+Lff 0f 0&+f f f f 0&+f f 0f 0+f f f 0&+f 0&L L+ff 0f 0+f f f f 0&+f f f 0f 0+f f 0&+f 0+&2f f f 0f 0&+f 0&+f 0&+f 0&+f 0f 0+f 0&+f 0&+f ff 0f 0+f 0&+f f f f 0&L +f 0f 0+f 0&2f f f f f f 0f 0+f 0+&2f f f f 0f 0(Wf f 0&+f 0&+ f f 0f 0+f 0&L +f 0&L +f f

PAGE 54

6\QWKHVLV RI &RPSRXQGV $IWHU H[WHQVLYH PDVV VSHFWUDO LQWHUSUHWDWLRQ DQG VXEVHTXHQW LGHQWLILFDWLRQ RI DOO WKH SURGXFWVXQNQRZQV REWDLQHG IURP WKH DTXDWKHUPRO\VLV UXQV WKHUH ZHUH VHYHUDO FRPSRXQGV ZKRVH IRUPDWLRQ UHPDLQHG REVFXUH 7KHUHIRUH ILYH FRPSRXQGV ZHUH VHOHFWHG WR EH V\QWKHVL]HG 7KH\ LQFOXGHG $ORFW\ODFHWDPLGH f 1 $GLPHWK\ORFW\ODPLQH f 1 $GLPHWK\ORFW\ODPLQHf GRGHF\ODPLQH f DQG GRGHF\ODPLQH f $PLQH ZDV FKRVHQ EHFDXVH LW DSSHDUHG WR EH DQ XQOLNHO\ SURGXFW EDVHG XSRQ WKH H[SHFWHG UHDFWLRQ SDWKZD\V ZKLOH DPLQHV DQG ZHUH FKRVHQ EHFDXVH QR GLUHFW PHFKDQLVWLF SDWKZD\ IRU WKHLU IRUPDWLRQ FRXOG EH VXJJHVWHG 7KH SULPDU\ DPLQHV f ZHUH V\QWKHVL]HG WR LQYHVWLJDWH ZKHWKHU RU QRW DQLPDWLRQ RI WKH DONHQHV IRUPHG GXULQJ DTXDWKHUPRO\VLV ZDV RFFXUULQJ $O2FW\ODFHWDPLGH f ZDV V\QWKHVL]HG XVLQJ RFW\ODPLQH f DQG DFHWLF DQK\GULGH DQG ZDV LVRODWHG DV D FOHDU RLO LQ b \LHOG 6FKHPH f $QDO\VLV RI WKH 06 IUDJPHQWDWLRQ SDWWHUQ RI RXU DXWKHQWLF $ORFW\ODFHWDPLGH f VKRZV WKDW LWV SDWWHUQ LV LGHQWLFDO WR WKDW RI WKH OLWHUDWXUH VHH 7DEOH f DQG VXJJHVWV WKDW DPLGH FRXOG EH D SURGXFW IURP WKH DTXDWKHUPRO\VLV RI RFW\ODPLQH f DFHWLF DQK f f &+1+ &+1+&2&+ r& K 6FKHPH 1 $'LPHWK\ORFW\ODPLQH f ZDV V\QWKHVL]HG XVLQJ D OLWHUDWXUH PHWKRG >7/@ 7KLV PHWKRG XVHV WLWDQLXP ,9f LVRSURSR[LGH >7L2L3Uf@ DQG VRGLXP ERURK\GULGH 1D%+f IRU WKH UHGXFWLYH DPLQDWLRQ RI IRUPDOGHK\GH ZLWK RFW\ODPLQH f 2QH HTXLYDOHQW RI DPLQH DQG WZR HTXLYDOHQWV RI 7L2L3Uf DUH DOORZHG WR UHIOX[ LQ GLJO\PH 7KH FRUUHVSRQGLQJ LPLQH LV WKHQ UHGXFHG ZLWK VRGLXP ERURK\GULGH 1D%+f ,W

PAGE 55

LV WKRXJKW WKDW WKH 7L2L3Uf IXQFWLRQV DV D /HZLV DFLG FDWDO\VW DV ZHOO DV D ZDWHU VFDYHQJHU 6FKHPH f 2FW\ODPLQH f ZDV SUHSDUHG IURP WKH FRUUHVSRQGLQJ NHWRQH RFWDQRQH f XVLQJ WKH OLWHUDWXUH PHWKRG >-&63f@ 6FKHPH f +&+2fQ 7L2L3Uf GLJO\PH 1D%+&1 1 +2$F (W2+ UHIOX[ 6FKHPH 0DVV VSHFWUDO DQDO\VLV RI WKH DXWKHQWLF 1 L9GLPHWK\ORFW\ODPLQH f UHYHDOHG WKDW WKH 06 IUDJPHQWDWLRQ SDWWHUQ LV LGHQWLFDO WR WKDW RI WKH OLWHUDWXUH VHH 7DEOH f DQG VXJJHVWV WKDW DPLQH FRXOG EH D SURGXFW IURP 1 L9GLPHWK\OORFW\ODPLQH f 7KH SURSRVHG FRPSRXQG LH IURP WKH IUDJPHQWDWLRQ IRXQG LQ WKH DTXDWKHUPRO\VLV UXQVf WKH OLEUDU\ PDWFK DQG WKH V\QWKHVL]HG FRPSRXQG DUH LGHQWLFDO VHH 7DEOH f 9f9'LPHWK\ORFW\ODPLQH f ZDV DOVR V\QWKHVL]HG XVLQJ WKH DERYH OLWHUDWXUH SURFHGXUH >7/@ IURP PHWK\OKHSW\ODPLQH f 6FKHPH f ,W ZDV VXJJHVWHG WKDW WKH FRPSRXQG SURSRVHG WR EH 1 9GLPHWK\OHWK\OOKH[\ODPLQH f PD\ KDYH EHHQ ZURQJO\ LGHQWLILHG DQG WKDW LW PLJKW DFWXDOO\ EH 1 9GLPHWK\ORFW\ODPLQH f 8QIRUWXQDWHO\ WKH PDVV VSHFWUDO LQWHUSUHWDWLRQ RI WKH DXWKHQWLF FRXOG QRW SURYH WKLV K\SRWKHVLV

PAGE 56

+&+2fQ 7Lc3Uf GLJO\PH _1D%+ 6FKHPH 'RGHF\ODPLQHf DQG GRGHF\ODPLQH f ZHUH V\QWKHVL]HG IURP WKH FRUUHVSRQGLQJ DQG GRGHFDQRQH XVLQJ D OLWHUDWXUH PHWKRG >-&63f@ 6FKHPH f $V ZLWK DPLQH WKH NHWRQH LV UHGXFWLYHO\ DPLQDWHG WR WKH FRUUHVSRQGLQJ DPLQH 7KHVH SULPDU\ DPLQHV ZHUH V\QWKHVL]HG WR WHOO ZKHWKHU WKH GRGHFHQH f DQG GRGHFHQH f IRUPHG VHH VHFWLRQ 5HVXOWVf ZHUH EHLQJ FRQYHUWHG EDFN WR WKH FRUUHVSRQGLQJ DPLQHV 7KLV K\SRWKHVLV ZDV GLVSURYHQ DV QHLWKHU RI WKH DPLQHV QRU f ZHUH REVHUYHG DV SURGXFWV )XUWKHU GLVFXVVLRQ RI WKHVH DQG WKH DERYH FRPSRXQGV ZLOO EH FRYHUHG LQ WKH 'LVFXVVLRQ VHFWLRQ f 2 &+&+f&&+ 1D%+&1 1+2$F (W2+ UHIOX[ A+ &+&+f&+&+ 2 1D%+&1 &+&+f&&+&+ QK2$F (W2+ UHIOX[ Uc-+ &+&+f&+&+&+ 6FKHPH

PAGE 57

5HVXOWV 2FWYODPLQH f 7DEOH f 7KH UHDFWLRQ RI RFW\ODPLQH f ZLWK b DTXHRXV IRUPLF DFLG +&2+f DW r& IRU K VKRZHG D b FRQYHUVLRQ WR WKH PDMRU SURGXFWV $ORFW\OIRUPDPLGH bf DQG GLRFW\ODPLQH bf 2WKHU PLQRU SURGXFWV LQFOXGHG RFWDQRO bf $PHWK\O RFW\ODPLQH bf $PHWK\O$ORFW\OIRUPDPLGH bf $ORFW\ODFHWDPLGH bf $PHWK\OGLORFW\ODPLQH bf DQG $ $GLORFW\OIRUPDPLGH bf $ $'LPHWK\O RFW\ODPLQH bf $PHWK\O$RFW\OO RFW\ODPLQH bf DQG WULRFW\ODPLQH bf ZHUH IRUPHG LQ WUDFH DPRXQWV ([WHQGLQJ WKH UHDFWLRQ WLPH WR K UHVXOWHG LQ D b FRQYHUVLRQ ZLWK $ RFW\OIRUPDPLGH bf GLRFW\ODPLQH bf $$GL RFW\OIRUPDPLGH bf DQG WULRFW\ODPLQH bf DV WKH PDMRU SURGXFWV 6LPLODU PLQRU DQG WUDFH SURGXFWV ZHUH REVHUYHG DV LQ WKH K UHDFWLRQ 5HDFWLRQV DW ORZHU WHPSHUDWXUH JDYH VLJQLILFDQW IRUPDPLGH SURGXFW IRUPDWLRQ $W r& LQ b DTXHRXV +&2+ IRU K RFW\ODPLQH f XQGHUZHQW D b FRQYHUVLRQ WR SURGXFWV ZLWK $ORFW\OIRUPDPLGH bf DV WKH PDMRU SURGXFW DORQJ ZLWK $PHWK\O$ORFW\OIRUPDPLGH bf DQG $RFW\ODFHWDPLGH bf ,QFUHDVLQJ WKH UHDFWLRQ WLPH WR K JDYH D VRPHZKDW ORZHU FRQYHUVLRQ bf WR WKH PDMRU SURGXFWV $ORFW\OIRUPDPLGH bf $PHWK\O$O RFW\OIRUPDPLGH bf DQG $ORFW\ODFHWDPLGH bf $ $'LPHWK\O RFW\ODPLQH f $DFHW\O$ORFW\OIRUPDPLGH f DQG $ $GL RFW\OIRUPDPLGH f ZHUH HDFK REVHUYHG LQ OHVV WKDQ b 2FWDQRO f $ PHWK\O$ORFW\ODFHWDPLGHf DQG GLRFW\ODPLQH f ZHUH HDFK REVHUYHG LQ WUDFH DPRXQWV $ VLPLODU WUHQG LQ FRQYHUVLRQ ZDV VHHQ DIWHU K ZKHUH WKHUH ZDV DQ b SURGXFW FRQYHUVLRQ 7KH K UHDFWLRQ JDYH $ORFW\OIRUPDPLGH bf

PAGE 58

7DEOH 3URGXFWV IURP O2FW\ODPLQH f b +&2+ 7HPSr&f 7LPH Kf 1R &RPSRXQG 0: ,GHQWLILFDWLRQ n RFW\ODPLQH 7DEOH RFWDQRO 7DEOH 1PHWK\O RFW\ODPLQH 7DEOH 1 L9GLPHWK\O RFW\ODPLQH 7DEOH 1 RFW\OIRUPDPLGH 7DEOH -9PHWK\O: RFW\OIRUPDPLGH 7DEOH 1 RFW\ODFHWDPLGH 7DEOH L9PHWK\O1 RFW\ODFHWDPLGH 7DEOH 1DFHW\?1 RFW\OIRUPDPLGH 7 DEOH 1PHWK\OGL RFW\ODPLQH 7DEOH GLRFW\ODPLQH 7DEOH L9PHWK\ 1RFW\O RFW\ODPLQH 7DEOH f§ 1 1GL RFW\OIRUPDPLGH 7DEOH WULRFW\ODPLQH 7DEOH

PAGE 59

$PHWK\O$ORFW\OIRUPDPLGH bf GLRFW\ODPLQH bf DQG $ $GLORFW\OIRUPDPLGH bf DV PDMRU SURGXFWV $ VLPLODU VODWH RI PLQRU SURGXFWV DV VHHQ SUHYLRXVO\ ZDV DOVR REVHUYHG 7KH SURGXFW VODWH VXJJHVWV WKDW IRUP\ODWLRQ RI \LHOGV $ORFW\OIRUPDPLGH f ZKLFK FDQ VXEVHTXHQWO\ XQGHUJR UHGXFWLRQ WR IXUQLVK $PHWK\ORFW\ODPLQH f 6LPLODUO\ $ $GLPHWK\ORFW\ODPLQHf FDQ EH GHULYHG IURP $PHWK\O RFW\ODPLQH f EXW WKLV FRQYHUVLRQ DSSHDUV WR RFFXU LQ VPDOO DPRXQWV 'L RFW\ODPLQH f FDQ EH REWDLQHG E\ IXUWKHU UHDFWLRQ RI ZLWK RFW\ODPLQH f 5HDFWLRQ RI GLRFW\ODPLQH f ZLWK +&2+ OHDGV WR $ $GL RFW\OIRUPDPLGH f ZKLFK FDQ EH VXEVHTXHQWO\ UHGXFHG WR $PHWK\OGL RFW\ODPLQH f 7ULORFW\ODPLQH f FDQ EH REWDLQHG E\ UHDFWLRQ RI ZLWK 7KH LQFUHDVLQJ DPRXQW RI RFW\ODPLQH f UHPDLQLQJ ZLWK LQFUHDVLQJ UHDFWLRQ WLPH DQG WHPSHUDWXUH LV XQH[SHFWHG 6LQFH UHDFWLRQ DW r& K LQGLFDWHV b FRQYHUVLRQ LW DSSHDUV WKDW ZLWK LQFUHDVLQJ WLPH DQG WHPSHUDWXUH DOO WKH RFW\ODPLQH f LV FRQYHUWHG WR WKH REVHUYHG SURGXFWV VRPH RI ZKLFK UHYHUW WR VWDUWLQJ PDWHULDO 'LRFW\ODPLQH f 7DEOH f $IWHU K WKH UHDFWLRQ RI GLRFW\ODPLQH f ZLWK b DTXHRXV +&2+ DW r& VKRZHG b FRQYHUVLRQ WR RFW\ODPLQH bf RFWDQRO bf $PHWK\OGLRFW\ODPLQH bf $ $GLORFW\OIRUPDPLGH bf DQG WULORFW\ODPLQH bf $ 0HWK\ORFW\ODPLQH f $ORFW\OIRUPDPLGH f $PHWK\O$ RFW\OIRUPDPLGH f DQG $ $GLORFW\ODFHWDPLGHf ZHUH IRUPHG LQ OHVV WKDQ b 7UDFH DPRXQWV RI $ $GLPHWK\O RFW\ODPLQH f DQG $RFW\O$ RFW\OIRUPDPLGH f ZHUH REVHUYHG +HDWLQJ ZLWK b +&2+ IRU K OHG WR WKH IRUPDWLRQ RI RFW\ODPLQH bf RFWDQRO bf $PHWK\OGL RFW\ODPLQH bf $ $GLORFW\OIRUPDPLGH bf DQG WULO RFW\ODPLQH bf $0HWK\O RFW\ODPLQH f $ORFW\OIRUPDPLGH f $PHWK\O$RFW\OIRUPDPLGH f DQG 1 $GLORFW\ODFHWDPLGH f

PAGE 60

7DEOH 3URGXFWV IURP 'LRFW\ODPLQH f b +&2+ 7HPSr&f 7LPH Kf 1R &RPSRXQG 0: ,GHQWLILFDWLRQ RFW\ODPLQH 7DEOH RFWDQRO 7DEOH 9PHWK\O RFW\ODPLQH 7DEOH 1 9GL PHWK\O RFW\ODPLQH 7DEOH 1 RFW\OIRUPDPLGH 7DEOH 1PH?K\?1 RFW\OIRUPDPLGH 7DEOH -9PHWK\OL9 RFW\ODFHWDPLGH 7DEOH 9PHWK\OGL RFW\ODPLQH 7DEOH GLRFW\ODPLQH 7DEOH 1 RF W\O9RFW\O IRUP DPLGH 7DEOH L9PHWK\O1RFW\O RFW\ODPLQH 7DEOH 1 1GL RFW\O IRUP DPLGH 7DEOH 1 L9GL RFW\ODFHWDPLGH 7DEOH WULRFW\ODPLQH 7DEOH FQ 2-

PAGE 61

ZHUH HDFK REVHUYHG LQ OHVV WKDQ b 7UDFHV RI $ $GLPHWK\OORFW\ODPLQHf DQG $ORFW\O$RFW\OIRUPDPLGH f ZHUH REVHUYHG LQ b DQG b UHVSHFWLYHO\ 7KH ILUVW VWHS LQ WKH UHDFWLRQ VHTXHQFH FRXOG EH WKH FOHDYDJH RI GLORFW\ODPLQH f WR JLYH RFW\ODPLQH f 2FW\ODPLQH f WKXV REWDLQHG FRXOG IXUWKHU UHDFW WR JLYH D VLPLODU SURGXFW VODWH WR WKDW GLVFXVVHG 2QFH DJDLQ IRUPDPLGH IRUPDWLRQ ZDV GRPLQDQW DW ORZHU WHPSHUDWXUHV $W r& K UHDFWLRQ WLPH OHG WR $PHWK\OGLRFW\ODPLQH bf $ $GL RFW\OIRUPDPLGH bf DQG WULRFW\ODPLQH bf DV PDMRU SURGXFWV 7KH IROORZLQJ IRXU FRPSRXQGV ZHUH LGHQWLILHG HDFK LQ OHVV WKDQ b RFW\ODPLQH f $ $GLPHWK\O RFW\ODPLQHf $ RFW\O$RFW\OIRUPDPLGH f DQG $PHWK\O$RFW\OORFW\ODPLQH f ([WHQGLQJ WKH UHDFWLRQ WLPH WR K JDYH $ PHWK\OGLRFW\ODPLQH bf $ $GLORFW\OIRUPDPLGH bf DQG WULRFW\ODPLQH bf ZLWK DQ b FRQYHUVLRQ WR SURGXFWV ZKLOH WKH K UHDFWLRQ JDYH $PHWK\OGLRFW\ODPLQH bf $ $GLORFW\OIRUPDPLGH bf DQG WULRFW\ODPLQH bf ZLWK DQ b FRQYHUVLRQ WR SURGXFWV $JDLQ WKHUH DSSHDUV WR EH VRPH HTXLOLEULXP UHYHUVLRQ WR VWDUWLQJ PDWHULDO 7KH K UHDFWLRQ DOVR JDYH D VPDOO DPRXQW RI $ RFW\O$RFW\OIRUP DPLGH bf DQG WUDFH DPRXQWV RI RFW\ODPLQH f RFWDQRO f $ $GLPHWK\O RFW\ODPLQH f $ RFW\OIRUPDPLGH f $PHWK\O$ RFW\OIRUPDPLGH f $PHWK\O$RFW\ODFHWDPLGH f DQG $PHWK\O$RFW\ORFW\ODPLQH f 6LPLODUO\ WKH K UHDFWLRQ JDYH VPDOO DPRXQWV RI $RFW\OIRUPDPLGH bf $PHWK\OORFW\OIRUPDPLGH bf $ORFW\O$RFW\OIRUPDPLGH bf DQG $ $GLORFW\ODFHWDPLGH bf DQG WUDFHV RI RFW\ODPLQH f RFWDQRO f $ $GLPHWK\ORFW\ODPLQH f $PHWK\O$ RFW\ODFHWDPLGH f DQG $PHWK\O$RFW\ORFW\ODPLQH f

PAGE 62

1 $'LPHWKYO RFWYODPLQH f 7DEOH f $W r& LQ +&2+ IRU K 1 $GLPHWK\ORFW\ODPLQH f VKRZHG D b FRQYHUVLRQ 3URGXFWV REVHUYHG LQFOXGH RFWDQRO bf $PHWK\OGLORFW\ODPLQH bf GL RFW\ODPLQH bf DQG WULORFW\ODPLQH bf 7KH IROORZLQJ SURGXFWV ZHUH LGHQWLILHG LQ OHVVHU DPRXQWV RFWDQRQH bf RFW\ODPLQH bf $PHWK\O$0RFW\OIRUPDPLGH bf DQG 1 9GLORFW\OIRUPDPLGH bf ZLWK $PHWK\OORFW\ODFHWDPLGHf DQG $0RFW\O$RFW\ODPLQH f LQ WUDFHV $W ORZHU WHPSHUDWXUHV 1 $0LPHWK\O RFW\ODPLQH f ZDV QRW YHU\ UHDFWLYH ZLWK b DTXHRXV +&2+ $W r& IRU K D b FRQYHUVLRQ OHG WR $PHWK\O$0 RFW\OIRUPDPLGH bf DV WKH PDMRU SURGXFW 2WKHU SURGXFWV LGHQWLILHG LQFOXGH 1 $GLPHWK\OHWK\OOKH[\ODPLQH bf 1 $0LPHWK\ORFW\ODPLQH bf $PHWK\OGLRFW\ODPLQH bf DQG GLORFW\OIRUPDPLGH bf $IWHU K D b FRQYHUVLRQ OHG WR $PHWK\ORFW\ODPLQH bf DQG $PHWK\OGLRFW\ODPLQH bf $PHWK\OORFW\OIRUPDPLGH bf 1 $GLPHWK\ORFW\ODPLQH bf DQG RFW\ODPLQH bf 'RGHF\ODPLQH f 7DEOH f 'RGHF\ODPLQH f ZDV YHU\ UHDFWLYH LQ b DTXHRXV IRUPLF DFLG $ b FRQYHUVLRQ ZDV REVHUYHG DIWHU K 7KH VL[ PDMRU SURGXFWV ZHUH GRGHFDQRO bf 1 $GLPHWK\O GRGHF\ODPLQH bf $0GRGHF\OIRUPDPLGH bf $PHWK\O$n GRGHF\OIRUPDPLGH bf $PHWK\OGLGRGHF\ODPLQH bf DQG GLOGRGHF\ODPLQH bf 0LQRU SURGXFWV REVHUYHG ZHUH GRGHFDQH bf GRGHFHQH bf GRGHFDQRO bf $PHWK\O$0GRGHF\ODFHWDPLGH bf DQG $DFHW\O$0GRGHF\OIRUPDPLGH bf $IWHU K D VLJQLILFDQW QXPEHU RI PLQRU SURGXFWV ZHUH REVHUYHG DORQJ ZLWK D SURGXFW VODWH VLPLODU WR WKH DERYH

PAGE 63

7DEOH 3URGXFWV IURP 1 1'LPHWK\OORFW\ODPLQHf b +&2+ 7HPSr&f 7LPH Kf 1R &RPSRXQG 0: ,GHQWLILFDWLRQ RFWDQRQH 7DEOH f 1 \9GLPHWK\OHWK\O KH[\ODPLQH 7DEOH RFW\ODPLQH 7DEOH 1 $IGLPHWK\ORFW\ODPLQH 7DEOH RFWDQRO 7DEOH L9PHWK\ORFW\ODPLQH 7DEOH 1 9GLPHWK\ORFW\ODPLQH 7DEOH 1PH?K\O1 RFW\OIRUP DPLGH 7DEOH M9PHWK\O$A RFW\ODFHWDPLGH 7DEOH 1 RFW\OY9RFW\ODPL QH 7DEOH L9PHWK\OGLRFW\ODPLQH 7DEOH GLRFW\ODPLQH 7DEOH 1 1GL RFW\O IRUPDPLGH 7DEOH WULRFW\ODPLQH 7DEOH /Q 21

PAGE 64

7DEOH 3URGXFWV IURP 'RGHF\ODPLQH f b +&2+ 7HPSr&f 7LPH Kf 1R &RPSRXQG 0: ,GHQWLILFDWLRQ GRGHFHQH 7DEOH GRGHFDQH 7DEOH GRGHFHQH 7DEOH GRGHFHQH 7DEOH GRGHF\ODPLQH 7DEOH GRGHFDQRO 7DEOH 9PHWK\O GRGHF\ODPLQH 7DEOH 1 9GL PHWK\O GRGHF\ODPLQH 7DEOH 1 GRGHF\OIRUPDPLGH 7DEOH 9PHWK\OL9 GRGHF\OIRUPDPLGH 7DEOH 9PHWK\O9 GRGHF\ ODFHWDPLGH 7DEOH 1DFHW\O1 GRGHF\OIRUPDPLGH 7DEOH \9PHWK\OGL GRGHF\ODPLQH 7DEOH GL GRGHF\ODPLQH 7DEOH 8O A

PAGE 65

7KH PDMRU SURGXFWV ZHUH GRGHFDQRO bf 1PHWK\O$ GRGHF\OIRUPDPLGH bf $IPHWK\OGLGRGHF\ODPLQH bf DQG GLOGRGHF\ODPLQH bf $OVR PLQRU DPRXQWV RI WKUHH LVRPHUV RI GRGHFHQH f ZHUH REVHUYHG /RZHU WHPSHUDWXUH UXQV DOVR VKRZHG PRGHUDWH WR KLJK UHDFWLYLW\ $IWHU K LQ b +&2+ DW r& GRGHF\ODPLQH f VKRZHG b FRQYHUVLRQ WR $0 GRGHF\OIRUPDPLGH bf DQG D WUDFH RI GLOGRGHF\ODPLQH bf $IWHU K DW r& DQ b FRQYHUVLRQ ZDV REVHUYHG ZLWK $0GRGHF\OIRUPDPLGH bf DQG $PHWK\O$0GRGHF\OIRUPDPLGH bf DV SURGXFWV $ b FRQYHUVLRQ ZDV REVHUYHG DIWHU K ZLWK 1 $0LPHWK\OGRGHF\ODPLQH bf $0GRGHF\OIRUPDPLGH bf DQG $PHWK\O$0GRGHF\OIRUPDPLGH bf DV WKH PDMRU SURGXFWV 0LQRU SURGXFWV LGHQWLILHG ZHUH $PHWK\O$0 GRGHF\ODFHWDPLGH bf $DFHW\O$0GRGHF\OIRUPDPLGH bf 1 PHWK\OGLGRGHF\ODPLQHbf DQG GLOGRGHF\ODPLQH f 1 $'LPHWK\OOGRGHF\ODPLQHf 7DEOH f $ b FRQYHUVLRQ ZDV REVHUYHG DIWHU UHDFWLQJ 1 $GLPHWK\OGRGHF\ODPLQH f ZLWK b DTXHRXV R +&2+ IRU K DW & 7KH PDMRU SURGXFWV REVHUYHG ZHUH GRGHFDQRO bf DQG 1PHWK\OGL GRGHF\ODPLQH bf $0HWK\O$0 GRGHF\OIRUPDPLGH f GRGHFHQH f DQG GRGHFDQH f ZHUH IRUPHG LQ PLQRU DPRXQWV ([WHQGLQJ WKH UHDFWLRQ WLPH WR K OHG WR D b FRQYHUVLRQ ZLWK D VLJQLILFDQW QXPEHU RI PLQRU SURGXFWV GRGHFDQH bf $PHWK\O$0 GRGHF\ODFHWDPLGH bf DQG GLOGRGHF\ODPLQH bf 7KH PDMRU SURGXFW ZDV DJDLQ $PHWK\OGLGRGHF\ODPLQH bf 7ZR LVRPHULF GRGHFHQHV f ZHUH DOVR IRUPHG LQ WKLV UXQ LQ PLQRU DPRXQWV

PAGE 66

7DEOH 3URGXFWV IURP 1 1'LPHWK\OOGRGHF\ODPLQH f b +&2+ 7HPSr&f 7LPH Kf 1R &RPSRXQG 0: ,GHQWLILFDWLRQ GRGHFHQH 7DEOH GRGHFDQH 7DEOH GRGHFHQH 7DEOH GRGHFHQH 7DEOH GRGHFDQRO 7DEOH 1 79GLPHWK\O GRGHF\O DPLQH 7DEOH :PHWK\O: GRGHF\OIRUPDPLGH 7DEHO 9PHWK\O: GRGHF\ODFHWDPLGH 7DEOH 1PHWK\OGL GRGHF\ODPLQH 7DEOH GL GRGHF\ODPLQH 7DEOH FL Ye!

PAGE 67

L9L9'LPHWK\OGRGHF\ODPLQH f ZDV PXFK OHVV UHDFWLYH DW r& LQ +&2+ IRU K 2QO\ D b FRQYHUVLRQ ZDV REVHUYHG ZLWK GRGHFDQRO bf DQG M9PHWK\O$IOGRGHF\OIRUPDPLGH bf DV WKH PDMRU SURGXFWV 7UDFHV RI GRGHFHQH bf GRGHFDQH bf GRGHFHQH bf DQG GRGHFHQH bf ZHUH DOVR LGHQWLILHG ([WHQGLQJ WKH UHDFWLRQ WLPH WR K VKRZHG D b FRQYHUVLRQ ZLWK GRGHFDQRO bf 1PH?K\O1 GRGHF\OIRUPDPLGH bf DQG 9PHWK\OGLOGRGHF\ODPLQH bf DV WKH RQO\ SURGXFWV 7DEOH f 6LQFH D FOHDU PHFKDQLVWLF SDWKZD\ VHH 'LVFXVVLRQf FRXOG QRW EH SURSRVHG IRU WKH IRUPDWLRQ RI WKH UHDUUDQJHG SURGXFW WZR DGGLWLRQDO DTXDWKHUPRO\VHV ZHUH SHUIRUPHG WR VHH ZKHWKHU VLPLODU UHDUUDQJHG SURGXFWV ZRXOG EH IRUPHG DQG ZKHWKHU D FOHDU PHFKDQLVWLF SDWKZD\ FRXOG EH GHWHUPLQHG 7KH DPLQHV RI FKRLFH ZHUH 1 1GLPHWK\O EXW\ODPLQH f DQG 1 9GLPHWK\OOKH[\ODPLQH f 7KHVH WZR WHUWLDU\ DPLQHV ZHUH KHDWHG DW r& IRU K LQ b +&2+ VLQFH WKHVH ZHUH WKH FRQGLWLRQV XQGHU ZKLFK 1 1GLPHWK\ORFW\ODPLQHf ZDV REVHUYHG 1 9'LPHWKY,OEXWYODPPHf 7DEOH f 2Q KHDWLQJ ZLWK DTXHRXV b +&2+ DW r& IRU K L99GLPHWK\OOEXW\ODPLQH f VKRZHG D b FRQYHUVLRQ 7DEOH f 7KH WZR PDMRU SURGXFWV ZHUH 9PHWK\OGLOEXW\ODPLQH bf DQG $nPHWK\O1OEXW\OIRUPDPLGH bf 7ULOEXW\ODPLQH bf DQG 1 L9GLOEXW\OIRUPDPLGH bf ZHUH GHWHFWHG LQ PLQRU DPRXQWV 7KHUH ZDV QR GHWHFWLRQ RI DQ\ UHDUUDQJHG SURGXFW WKDW LV QR 1 9GLPHWK\OEXW\ODPLQH

PAGE 68

7DEOH 3URGXFWV IURP 1 <'LPHWK\OOEXW\ODPLQHf b +&2+ 7HPSr&f 7LPHKf 1R &RPSRXQG 0: ,GHQWLILFDWLRQ 1 9GL PHWK\OEXW\ODPLQH 7DEOH $APHWK\OGLEXW\ODPLQH 7DEOH 9PHWK\O9 EXW\OIRUPDPLGH 7DEOH WULOEXW\ODPLQH 7DEOH 1 1GL EXW\OIRUPDPLGH 7DEOH 0: PROHFXODU ZHLJKW L9L9'LPHWKYOKH[YODPLQHf 7DEOH f 1 :'LPHWK\OOKH[\ODPLQH f VKRZHG D b FRQYHUVLRQ DIWHU K DW r& LQ b DTXHRXV +&2+ 7DEOH f 7KH PDMRU SURGXFW ZDV 1PHWK\O$0KH[\OIRUPDPLGH bf 2WKHU SURGXFWV LQFOXGHG KH[DQRO bf DQG 1PHWK\OGLOKH[\ODPLQH bf 7KHUH ZDV QR GHWHFWLRQ RI DQ\ UHDUUDQJHG SURGXFWV 7DEOH 3URGXFWV IURP : 1'LPHWK\OOKH[\ODPLQH f b +&2+ 7HPSr&f 7LPHKf 1R &RPSRXQG 0: ,GHQWLILFDWLRQ KH[DQRO 7DEOH 1 9GLPHWK\OOKH[\ODPLQH 7DEOH M9PHWK\O9 KH[\O IRUP DPLGH 7DEOH 9PHWK\OGL KH[\ODPLQH 7DEOH 0: PROHFXODU ZHLJKW

PAGE 69

*HQHUDO 'LVFXVVLRQ 7KH DOLSKDWLF SULPDU\ DPLQHV VKRZHG WKH GRPLQDQW UHDFWLRQ SDWKZD\ DV 1 IRUP\ODWLRQ ZLWK VXEVHTXHQW UHGXFWLRQ WR JLYH $PHWK\O DQG 1 9GLPHWK\ODON\ODPLQHV 7KDW LV XQGHU WKH DERYH PHQWLRQHG DTXDWKHUPRO\VLV FRQGLWLRQV WKH DOLSKDWLF DPLQHV DUH LQYROYHG LQ FRQYHQWLRQDO UHDFWLRQV ZKHUH WKH IRUPLF DFLG LV EHKDYLQJ DV D K\GULGH GRQRU DQG DV D IRUP\ODWLQJ DJHQW ,Q WKH FDVH RI GRGHF\ODPLQH f LQ DGGLWLRQ WR WKH DERYH PHQWLRQHG SDWKZD\ HOLPLQDWLRQ RI 1+ DQG +10H WR WKH FRUUHVSRQGLQJ DONHQH ZDV DOVR REVHUYHG ZKLFK FRXOG WKHQ XQGHUJR LVRPHUL]DWLRQ 7KH VHFRQGDU\ DPLQH GL RFW\ODPLQH f XQGHUZHQW FRQYHQWLRQDO 9IRUP\ODWLRQ DQG VXEVHTXHQW UHGXFWLRQ WR WKH $PHWK\O GHULYDWLYH $OVR IRUPDWLRQ RI WKH PRQR DQG WUL RFW\O GHULYDWLYHV LV UHSUHVHQWDWLYH RI D FOHDYDJH SURFHVV 7KH WHUWLDU\ DPLQHV XQGHUZHQW UHGXFWLYH FOHDYDJHV WR SULPDU\ DQG VHFRQGDU\ DPLQHV ZKLFK VXEVHTXHQWO\ IROORZHG WKH UHDFWLRQ VHTXHQFHV VHHQ IRU WKH SULPDU\ DPLQHV )RUPDWLRQ RI \9ORFW\OIRUPDPLGH f DQG VXEVHTXHQW UHGXFWLRQ SURGXFWV ZDV WKH PDMRU UHDFWLRQ SDWKZD\ IRU RFW\ODPLQH f 6FKHPH f ,W LV HYLGHQW WKDW DW ORZHU WHPSHUDWXUHV WKHUH LV VLJQLILFDQW IRUPDPLGH SURGXFW IRUPDWLRQ DV ZHOO 6XEVHTXHQW UHGXFWLRQ RI WKH $IRUP\ODWLRQ SURGXFW LV VXSSRUWHG E\ WKH SUHVHQFH RI 1 PHWK\OORFW\DPLQHf DQG 1 \9GLPHWK\OORFW\ODPLQHf $PLQH b WKH UHGXFHG SURGXFW RI IRUPDPLGH XQGHUZHQW D VHFRQG IRUP\ODWLRQ WR JLYH 1 PHWK\O$ORFW\OIRUPDPLGH f 6XEVHTXHQW UHGXFWLRQ RI DPLGH OHDGV WR $ \9GLPHWK\O RFW\ODPLQH f 7ULRFW\ODPLQH f FDQ EH IRUPHG E\ WKH UHDFWLRQ RI DPLQH ZLWK GL RFW\ODPLQH f ,Q WKLV SURFHVV DPLQH XQGHUJRHV ORVV RI 11GLPHWK\ODPLQH 'LRFW\ODPLQH f LV WKH SURGXFW RI VHOI FRQGHQVDWLRQ RI RFW\ODPLQH &RQYHQWLRQDO IRUP\ODWLRQ RI DPLQH JHQHUDWHV 1 $GL RFW\OIRUPDPLGHf ZKLFK FDQ EH IXUWKHU UHGXFHG WR WKH $PHWK\O GHULYDWLYH 7KH IRUPDWLRQ RI RFWDQRO f VXJJHVWV WKH SUHVHQFH RI RFWHQH

PAGE 70

+&2R+ B +n f +&2S+ 2 2 e3 &0 R ‘ &2 RR R &2 FR &0 1 &2 RR 2 R &0 8 &0 K L &2 RR M &0 ; = 2 1 R a &2 R 2 R LR &0 ‘ &2 RR R FR ‘ &2 FR ; R R 2 R! &0 ; 2 R] &2 UA RR R / &0 &0 R R &2 FR &2 R R R &0 2 ‘ &2 FR 2 &0 R R &0 &0 6 &0 ‘ &2 A ‘ &2 RR 2 &0 R &0 R &0 R R &0 R FR &2 R FR R FR FR R &0 R FR &0 R &0 &2 R &2 R &2 &2 &2 R R &0 &2 R R R &2 ,2 R FR &2 R &2 RR R &0 RR 2 FR R R &0 RR R &0 R &2 R &2 R &2 LQ &0 R &2

PAGE 71

$O2FW\ODFHWDPLGH f PD\ KDYH EHHQ SURGXFHG XQGHU DTXDWKHUPRO\VLV FRQGLWLRQV YLD D UHDUUDQJHPHQW RI $PHWK\O$ORFW\O IRUP DPLGH f 6FKHPH f DOWKRXJK ZH KDYH EHHQ XQDEOH WR ILQG DQ H[DPSOH RI DQ DFLG SURPRWHG UHDUUDQJHPHQW RI D IRUPDPLGH WR DQ DFHWDPLGH 7KH RWKHU DFHW\O GHULYDWLYHV ZRXOG KDYH EHHQ IRUPHG IURP IXUWKHU UHDFWLRQ RI $$FHW\O$ RFW\OIRUPDPLGH f LV SURGXFHG IURP WKH $IRUP\ODWLRQ RI DFHWDPLGH 6XEVHTXHQWO\ UHGXFWLRQ RI DPLGH ZRXOG JHQHUDWH $PHWK\O$ORFW\ODFHWDPLGHf 6FKHPH f 6LPLODUO\ WKH RWKHU SULPDU\ DPLQH GRGHF\ODPLQH f JDYH 1 GRGHF\OIRUPDPLGH f DV WKH PDLQ SURGXFW XQGHU DOO UHDFWLRQ FRQGLWLRQV WKH VXEVHTXHQW UHGXFWLRQ ZDV VXSSRUWHG E\ IRUPDWLRQ RI WKH YDULRXV $PHWK\O GHULYDWLYHV ,Q FRQWUDVW WR LPSOLHG IRUPDWLRQ RI RFWHQH IRUPDWLRQ RI GRGHFHQH LV REVHUYHG DV ZHOO DV WKH DQG LVRPHU 6FKHPH f 8QGHU DTXDWKHUPRO\VLV FRQGLWLRQV GRGHF\ODPLQH f XQGHUZHQW FRQYHQWLRQDO $IRUP\ODWLRQ WR JLYH $OGRGHF\OIRUPDPLGH f 6FKHPH f 6XEVHTXHQW UHGXFWLRQ RI DPLGH JHQHUDWHV WKH $PHWK\O GHULYDWLYH /RVV RI PHWK\ODPLQH IURP UHVXOWV LQ WKH IRUPDWLRQ RI GRGHFHQH f $OWHUQDWHO\ DONHQH PD\ EH JHQHUDWHG HLWKHU E\ WKH ORVV RI DPPRQLD IURP GRGHF\ODPLQH f RU E\ WKH ORVV RI $ $GLPHWK\ODPLQH IURP $ $GLPHWK\OGRGHF\ODPLQH f ,Q WXUQ WKH DPLQH LV JHQHUDWHG IURP WKH UHGXFWLRQ RI $PHWK\O$ORFW\OIRUPDPLGH f ZKLFK LV SURGXFHG E\ WKH $IRUP\ODWLRQ RI $PHWK\O GRGHF\ODPLQHf 'RGHFHQH FDQ XQGHUJR LVRPHUL]DWLRQ WR ERWK WKH f DQG WKH f GHULYDWLYH 6FKHPH f 5HGXFWLRQ RI HLWKHU RI WKHVH DONHQHV ZRXOG OHDG WR GRGHFDQH f ,Q DGGLWLRQ ORVV RI DPPRQLD IURP GRGHF\ODPLQH f DQG D IRUPLF DFLG FDWDO\]HG UHDFWLRQ ZLWK ZDWHU JHQHUDWHG GRGHFDQRO f $ $'LPHWK\O GRGHF\ODPLQH f WKURXJK ORVV RI $ $GLPHWK\ODPLQH DQG VXEVHTXHQW FRQGHQVDWLRQ ZLWK DPLQH ZDV FRQYHUWHG WR GLGRGHF\ODPLQH f )RUP\ODWLRQ RI DPLQH OHDGV WR $PHWK\OGL GRGHF\ODPLQH f

PAGE 72

&++ 5$5 + $ + 1+ + &+ n n 1&f&+ f +&+ "+ K "+ 9&+1&f&+L9 &+ n n 1&f&+ KFRK &+1+&+2 + &+1+&+ + FKFK FK +10H + + 1+ +n + +10H &+&+ (W &+&+&+ f &+ + + &J+LJ&+(W f + &+&+ &+(W KFRK &+10Hf&+2 + &L+1+0H f +10H F+1+& A KFRK &L+f1&+ + &+f1&+2 f 8O 6FKHPH

PAGE 73

7KH DFHW\O GHULYDWLYHV PD\ EH MXVWLILHG YLD WKH DPLGH WKRXJK WKH FRUUHVSRQGLQJ $OGRGHF\ODFHWDPLGH f ZDV QRW GHWHFWHG E\ WKH *&06 DQDO\VLV 6FKHPH f $$FHW\O$OGRGHF\OIRUPDPLGH f PD\ EH H[SODLQHG YLD WKH IRUP\ODWLRQ RI ZLWK VXEVHTXHQW UHGXFWLRQ OHDGLQJ WR $PHWK\O$ GRGHF\ODFHWDPLGH f $JDLQ WKHUH LV QR OLWHUDWXUH SUHFHGHQFH IRU WKH IRUPDWLRQ RI DFHWDPLGH IURP WKH IRUPDPLGH $V H[SHFWHG GLORFW\ODPLQH f XQGHUZHQW $IRUP\ODWLRQ ,I D VLPSOH UHGXFWLRQ ZHUH WKH RQO\ SRVVLEOH UHDFWLRQ SDWKZD\ WKHQ $PHWK\OGL RFW\ODPLQH f ZRXOG EH WKH RQO\ QH[W ORJLFDO SURGXFW +RZHYHU LW LV DSSDUHQW WKDW UHGXFWLYH FOHDYDJH WDNHV SODFH RQ WKH VWDUWLQJ DPLQHf GXH WR WKH SUHVHQFH LQ WKH SURGXFW VODWH RI VLPLODU SURGXFWV WR WKRVH REWDLQHG IURP RFW\ODPLQH f 6FKHPH f )RUPDWLRQ RI $ RFW\O$RFW\OIRUPDPLGHf DQG $PHWK\O$RFW\O RFW\ODPLQH f DSSHDU WR EH IURP WKH LVRPHUL]DWLRQ RI WKH RFW\O PRLHW\ EHIRUH WKH IRUP\ODWLRQ DQG UHGXFWLRQ WDNH SODFH 7DEOH f 6LQFH WKH WHUWLDU\ DPLQH FRXOG QRW XQGHUJR $IRUP\ODWLRQ GLUHFWO\ $IRUP\O DQG VXEVHTXHQW UHGXFWLRQ SURGXFWV ZRXOG KDYH WR EH IRUPHG DIWHU UHGXFWLYH FOHDYDJH RI WKH VWDUWLQJ DPLQH 5HGXFWLYH FOHDYDJH H[SODLQV IRUPDWLRQ RI WKH DOFRKRO DQG $ PHWK\OGLDON\ODPLQH PDMRU SURGXFWV IURP ERWK $ $GLPHWK\O RFW\ODPLQH f 6FKHPH f DQG $ $GLPHWK\O GRGHF\ODPLQHf 6FKHPH f $ $'LPHWK\O RFW\ODPLQH f PD\ EH UHGXFWLYHO\ FOHDYHG WR DPLQH DQGRU DPLQH ZKLFK FDQ HDFK XQGHUJR WKH UHDFWLRQ SDWKZD\V RXWOLQHG LQ 6FKHPH $V VKRZQ LQ &KDSWHU ,, IRUPLF DFLG PD\ DFW ERWK DV D UHGXFLQJ DQG DV DQ R[LGL]LQJ DJHQW ,WV UROH DV DQ R[LGL]HU PD\ H[SODLQ WKH IRUPDWLRQ RI RFWDQRQH f $JDLQ WKH UHDUUDQJHG GHULYDWLYHV DQG 7DEOH f PD\ EH IURP WKH LVRPHUL]DWLRQ RI WKH RFW\O PRLHW\ $ $'LPHWK\OEXW\ODPLQH f XQGHUZHQW FRQYHQWLRQDO IRUP\ODWLRQ DQG VXEVHTXHQW UHGXFWLRQ WR JHQHUDWH LWV SURGXFWV 6FKHPH f $V VWDWHG SUHYLRXVO\ WKLV

PAGE 74

WHUWLDU\ DPLQH ZRXOG XQGHUJR UHGXFWLYH FOHDYDJH WR WKH SULPDU\ DPLQH EHIRUH IRUP\ODWLRQ WRRN SODFH +RZHYHU WKH FRUUHVSRQGLQJ SULPDU\ DPLQH EXW\ODPLQH f ZDV QRW GHWHFWHG E\ *&06 6WLOO $PHWK\O$OEXW\OIRUPDPLGH f GRHV VXSSRUW WKH DERYH SDWKZD\ VLQFH LWV f IRUPDWLRQ PD\ EH YLHZHG WKURXJK WKH IRUP\ODWLRQ RI WR IRUP ZKLFK ZRXOG VXEVHTXHQWO\ EH UHGXFHG WR DQG ILQDOO\ IRUP\ODWHG RQFH DJDLQ WR JLYH DPLGH /LNHZLVH 11GLO EXW\OIRUPDPLGH f LV IRUPHG YLD IRUP\ODWLRQ RI 7KH LQWHUPHGLDWH LV JHQHUDWHG IURP FRQGHQVDWLRQ RI DQG DFFRPSDQLHG E\ WKH ORVV RI 1 1 GLPHWK\ODPLQH 7UL EXW\ODPLQH f LV D VHOI FRQGHQVDWLRQ SURGXFW YLD LQWHUPHGLDWH 6LPSOH UHGXFWLRQ RI OHDGV WR 9PHWK\OGL EXW\ODPLQH f 6FKHPH f 7KH SURGXFWV IURP 9 $GLPHWK\OOKH[\ODPLQH f DUH IRUPHG VLPLODUO\ WR WKRVH RI DPLQH 6FKHPH f $V VHHQ ZLWK DPLQH IRUPDWLRQ RI 9PHWK\O 9OKH[\OIRUPDPLGH VXJJHVWV WKH SUHVHQFH RI LQWHUPHGLDWHV DQG WKRXJK WKH\ ZHUH QRW GHWHFWHG E\ WKH *&06 DQDO\VLV 9)RUP\ODWLRQ RI LQWHUPHGLDWH ZRXOG JLYH ZKLFK FRXOG XQGHUJR UHGXFWLRQ WR 6XEVHTXHQW UHGXFWLRQ RI LQWHUPHGLDWH ZRXOG JHQHUDWH IRUPDPLGH 6LQFH WKHVH LQWHUPHGLDWHV ZHUH QRW GHWHFWHG f WKLV PD\ VXJJHVW WKDW WKH\ DUH EHLQJ FRQVXPHG ZLWKLQ WKH UHDFWLRQV 90HWK\GL KH[\ODPLQH f PD\ EH H[SODLQHG VLPLODUO\ YLD IRUP\ODWLRQ DQG UHGXFWLRQ RI DQG UHVSHFWLYHO\ $V ZLWK RFW\ODPLQH f IRUPDWLRQ RI KH[DQRO f LPSOLHV WKH SUHVHQFH RI DQ DONHQH KH[HQH f 6FKHPH f

PAGE 75

&+Jf1 > FKQK f I &+10H +&2A+ >FKQKFKR f &+1+&+ f +&+ &+2 &+1&+ &+f1&+ &+f1+ f KFRK &+f1&+2 6FKHPH

PAGE 76

&+f1+ f KFRK FKQK f KFRK &+f1&+2 f + &+1+&+2 f &+10 +&2A +10H + + &+&+ &+ f + &+f1&+ FKQKFK f KFRK "KR &+1&+ FKFKFK f + &J+A&+J2+ 21 6FKHPH

PAGE 77

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f GLVSOD\HG VLJQLILFDQW DPRXQWV RI 9IRUP\ODWLRQ DQG VXEVHTXHQW UHGXFWLRQ SURGXFWV 7KLV WUHQG ZDV REVHUYHG DW r& DV ZHOO DV DW ORZHU WHPSHUDWXUHV 7KHUH ZDV DOVR VRPH VHOI FRQGHQVDWLRQ SURGXFWV GLORFW\ODPLQH f DQG WUL RFW\ODPLQH f 6\QWKHVLV RI DXWKHQWLF 9ORFW\ODFHWDPLGH f DQG LQYHVWLJDWLRQ RI LWV 06 SDWWHUQ VXJJHVW WKDW LW FRXOG EH D SODXVLEOH SURGXFW XQGHU WKH DTXDWKHUPRO\VLV FRQGLWLRQV +RZHYHU VLQFH WKH VXJJHVWHG SDWKZD\ IRU LWV IRUPDWLRQ ODFNV OLWHUDWXUH SUHFHGHQFH DQG LV DQ DQRPDO\ DPLGH PD\ EH DOWHUQDWHO\ H[SODLQHG DV DQ REVFXUH LPSXULW\ 'RGHF\ODPLQH f DOVR JDYH VLJQLILFDQW 9IRUP\ODWLRQ ,Q DGGLWLRQ IRUPDWLRQ RI DONHQHV ZDV REVHUYHG YLD WKH ORVV RI DPPRQLD DQG 1 9GLPHWK\ODPLQH 7KHVH DONHQHV ZHUH VXEMHFW WR LVRPHUL]DWLRQ 7KH DQG GRGHF\ODPLQH ZHUH QRW REVHUYHG DV SURGXFWV LQ WKH DTXDWKHUPRO\VLV UHDFWLRQV 7KXV LW FDQ EH FRQFOXGHG WKDW WKH K\SRWKHVLV RI DQLPDWLRQ RI WKH DONHQHV WR WKH FRUUHVSRQGLQJ DPLQHV LV XQIRXQGHG

PAGE 78

'LRFW\ODPLQH f DOVR JDYH $IRUP\ODWLRQ EXW LW ZDV QRW VLJQLILFDQW 7KLV VHFRQGDU\ DPLQH DOVR XQGHUZHQW UHGXFWLYH FOHDYDJH DQG VXEVHTXHQW UHGXFWLRQ ZLWK SURGXFWV VLPLODU WR WKRVH IURP RFW\ODPLQH f %RWK WHUWLDU\ DPLQHV f ZHUH DV H[SHFWHG OHVV UHDFWLYH WKDQ WKH SULPDU\ DQG VHFRQGDU\ DPLQHV 0RVW SURGXFWV ZHUH JHQHUDWHG IURP D SULPDU\ RU VHFRQGDU\ DPLQH ZKLFK ZDV SURGXFHG E\ UHGXFWLYH FOHDYDJH RI WKH FRUUHVSRQGLQJ WHUWLDU\ DPLQH $ QXPEHU RI UHDUUDQJHG SURGXFWV ZHUH LGHQWLILHG EXW PD\ ZHOO EH LQDGYHUWHQW LPSXULWLHV 7KRXJK 06 LQYHVWLJDWLRQV LQGLFDWH 1 $GLPHWK\ORFW\ODPLQHf DV D SRVVLEOH SURGXFW DTXDWKHUPRO\VLV RI 1 $GLPHWK\OOEXW\ODPLQH f DQG 11 GLPHWK\OOKH[\ODPLQH f UHYHDOHG QR UHDUUDQJHG SURGXFWV VLPLODU WR DPLQH DQG WKHUHIRUH FRXOG VKHG QR OLJKW RQ D SRVVLEOH UHDUUDQJHPHQW SDWKZD\ ,W LV YHU\ OLNHO\ WKDW WKH UHDUUDQJHG DPLQH PLJKW KDYH EHHQ DQ LPSXULW\ ,W DSSHDUV WKDW UHDUUDQJHPHQW LV QRW D QRUPDO SDWKZD\ XQGHU WKH UHDFWLRQ FRQGLWLRQV ([SHULPHQWDO r+ 105 VSHFWUD ZHUH UHFRUGHG HLWKHU RQ D *HPLQL 0+]f 9DULDQ 9;5 0+]f RU D *HQHUDO (OHFWULF 4( 0+]f VSHFWURPHWHU & 105 VSHFWUD ZHUH UHFRUGHG DW 0+] RQ WKH VDPH VSHFWURPHWHUV &KHPLFDO VKLIWV DUH UHSRUWHG LQ SDUWV SHU PLOOLRQ SSPf GRZQILHOG IURP WHWUDPHWK\OVLODQH 706f XVHG DV DQ LQWHUQDO VWDQGDUG &RXSOLQJ FRQVWDQWV YDOXHVf DUH UHSRUWHG LQ KHUW] +]f $QDO\WLFDO WKLQ OD\HU FKURPDWRJUDSK\ 7/&f ZDV SHUIRUPHG XVLQJ SUHFRDWHG VLOLFD JHO ) SODVWLF SODWHV PP WKLFNf XVLQJ LRGLQH DV DQ LQGLFDWRU WR YLVXDOL]H WKH SURGXFW FRPSRXQGV

PAGE 79

*HQHUDO SURFHGXUH IRU WKH V\QWKHVLV RI 1 9GLPHWK\ORFW\ODPLQHV 1 M9'LPHWK\O6RFW\ODPLQH f 2FW\ODPLQH HT J PPROf IRUPDOGHK\GH HT J PPROf DQG WLWDQLXP WHWUDLVRSURSR[LGH HT J PPROf ZDV UHIOX[HG LQ GLJO\PH POf DW r& $IWHU K WKH UHDFWLRQ ZDV FRROHG WR URRP WHPSHUDWXUH DQG VRGLXP ERURK\GULGH HT J PPROf ZDV DGGHG 7KH UHDFWLRQ ZDV WKHQ VWLUUHG DW URRP WHPSHUDWXUH Kf $IWHU FRROLQJ WR URRP WHPSHUDWXUH WKH UHDFWLRQ ZDV GLOXWHG ZLWK (W P/f DQG DTXHRXV DPPRQLXP K\GUR[LGH ZDV DGGHG WR SUHFLSLWDWH WKH LQRUJDQLF SURGXFW ZKLFK ZDV ILOWHUHG DQG ZDVKHG ZLWK H[FHVV (W 7KH RUJDQLF OD\HU ZDV GULHG RYHU 1D6&! DQG FRQFHQWUDWHG LQ YDFXR '\JOLPH ZDV UHPRYHG E\ GLVWLOODWLRQ LQ YDFXR $ SDOH FRORUHG RLO J bf ZDV LVRODWHG r+ 105 &'&,f W + f &+&+f W + f &+&+&+f V +f &+f P +f &+&+&+f V +f 10Hf P +f &+f & 105 &'&,f /5 06 0 P] &+1f EDVH SHDN P] &+1f 1 $'LPHWK\ORFW\ODPLQH f 7KLV SURGXFW ZDV REWDLQHG DV DQ RIIZKLWH RLO ZKLFK VROLGLILHG XSRQ FRROLQJ + 105 &'&,f W + f &+&+f G + f &+&+f V +f &+f P +f &KE&+f 6 +f 10Hf P +f &+f & 105 &'&,f /5 06 0 P] &+1f EDVH SHDN P] &+1f $02FW\ODFHWDPLGH f 2FW\ODPLQH POf ZDV GLVVROYHG LQ DFHWLF DQK\GULGH P/f DQG ZDUPHG IRU DERXW K 7KH PL[WXUH ZDV WKHQ FRROHG WR URRP WHPSHUDWXUH DQG GLOXWHG ZLWK HWKHU ZDVKHG ZLWK 0 +& DQG WKHQ b 1D2+ 7KH VROXWLRQ ZDV GULHG RYHU 0J6&! DQG FRQFHQWUDWHG LQ YDFXR $ SDOH \HOORZ RLO PJ bf ZDV LVRODWHG L+ 105 &'&,f W + f P +f W +

PAGE 80

f V +f T + f V +f & 105 &'&f /5 06 0 P] &+12f EDVH SHDN P] &+1f 1 'F[OHF\OIRUPDPLGH f 'RGHF\ODPLQH J PPROf ZDV VXVSHQGHG LQ DQ H[FHVV RI DTXHRXV IRUPLF DFLG bf J PPROf 7KH PL[WXUH ZDV UHIOX[HG LQ EHQ]HQH P/f XQGHU 'HDQ6WDUN FRQGLWLRQV IRU WKH D]HRWURSLF UHPRYDO RI ZDWHU 7KH UHDFWLRQ ZDV UHIOX[HG IRU K FRROHG WR URRP WHPSHUDWXUH DQG WKH VROYHQW UHPRYHG LQ YDFXR 7KH SDOH \HOORZ VROLG ZDV UHFU\VWDOOL]HG IURP SHWUROHXP HWKHU WR JLYH WKH WLWOH FRPSRXQG DV ZKLWH IODNHV J bf PS r&f /LW >0,@ PS r&f O+ 105 &'&f W + f V +f W + f T + f EU V +f V +f & 105 &'&f &f +5 06 P] 0 b &+12 UHTXLUHV f *HQHUDO SURFHGXUH IRU WKH V\QWKHVLV RI SULPDU\ DPLQHV 2FW\ODPLQH4f 6RGLXP F\DQRERURK\GULGH HT J PPROf ZDV VXVSHQGHG LQ DEVROXWH (W2+ P/f DQG RFWDQRQH HT J PPROf LQ DEVROXWH (W2+ POf ZDV DGGHG GURSZLVH YLD DGGLWLRQ IXQQHO $PPRQLXP DFHWDWH HT J PPROf ZDV WKHQ DGGHG DQG WKH PL[WXUH ZDV DOORZHG WR UHIOX[ DW r& $IWHU K WKH UHDFWLRQ PL[WXUH ZDV FRROHG WR URRP WHPSHUDWXUH DFLGLILHG ZLWK FRQH +& WR S+ WKHQ EDVLILHG ZLWK b 1D2+ 7KH DTXHRXV OD\HU ZDV WKHQ H[WUDFWHG ZLWK &+&, PO ;f GULHG RYHU 1D6&! DQG FRQFHQWUDWHG WR JLYH D SDOH \HOORZ YLVFRXV RLO J bf 7KH VDPSOH ZDV XVHG LQ VXEVHTXHQW UHDFWLRQV ZLWKRXW IXUWKHU SXULILFDWLRQ r+ 105 &'&,f W + f &+&+f W + f &+A&+"&+f EU V +f &+f P +f &7+&+"&+f T + f &+f G

PAGE 81

+f 1+f & 105 &'&f /5 06 0 P] &J+L1f EDVH SHDN P] &+1f 'RGHF\ODPLQH f 7KLV FRPSRXQG ZDV REWDLQHG FUXGH DV D SDOH \HOORZ YLVFRXV RLO E\ WKH SURFHGXUH RXWOLQH DERYH IRU 7KH VDPSOH ZDV WKHQ SXULILHG E\ .XJHOURKU GLVWLOODWLRQ WR SURGXFH D FRORUOHVV RLO J bf r+ 105 &'&,f W + f &+&+f W + f &)K&KEf G RI G + f &+&+f V +f &+f V +f &+f G + f &+f & 105 &'&,f &f +5 06 P] 0 b &+12 UHTXLUHV f 'RGHF\ODPLQH f 7KLV FRPSRXQG ZDV REWDLQHG FUXGH DV D SDOH \HOORZ YLVFRXV RLO E\ WKH SURFHGXUH RXWOLQH DERYH IRU 7KH VDPSOH ZDV WKHQ SXULILHG E\ .XJHOURKU GLVWLOODWLRQ WR SURGXFH D FRORUOHVV RLO J bf + 105 &'&,f P +f 1&+&+ &+&+f W + f &UWW&+Uf V +f &+f P +f &+&+"f P +f 1+f P +f &+f & 105 &'&,f +5 06 P] 0 b &+12 UHTXLUHV f $TXDWKHUPRO\VLV *HQHUDO 7KH SXULWLHV RI DOO VWDUWLQJ PDWHULDOV ZHUH FKHFNHG E\ *& SULRU WR XVH b $TXHRXV IRUPLF DFLG ZDV GHR[\JHQDWHG ZLWK DUJRQ IRU K SULRU WR XVH 7KH PRGHO FRPSRXQG Jf DQG WKH DFLG P/f ZHUH FKDUJHG LQWR D QLWURJHQ EODQNHWHG VWDLQOHVV VWHHO ERPE ZKLFK ZDV WKHQ VHDOHG 7KH UHDFWRU ZDV WKHQ NHSW ZLWKRXW DJLWDWLRQ LQ D IOXLGL]HG VDQG EDWK PRGHO 6%6f VHW DW r& DQG r& ZKHQ DSSURSULDWHf $IWHU WKH UHDFWLRQ SHULRG WKH UHDFWRU ZDV LPPHGLDWHO\ TXHQFKHG LQ D VWUHDP RI FROG DLU DQG WKHQ GU\ $OO DTXDWKHUPRO\VLV UXQV ZHUH SHUIRUPHG E\ (OHQD 6 ,JQDWFKHQNR DW WKH 8QLYHUVLW\ RI )ORULGD

PAGE 82

LFH 7KH UHDFWLRQ PL[WXUH ZDV WKHQ ZRUNHG XS DV SUHYLRXVO\ GHVFULEHG >()@ DQG VXEMHFWHG WR *& DQDO\VHV RQ D +HZOHWW 3DFNDUG LQVWUXPHQW IODPH LRQL]DWLRQ GHWHFWRU ),'f ILWWHG ZLWK D P FDSLOODU\ FROXPQ 63%f DQG DQ RYHQ WHPSHUDWXUH SURJUDP RI R R &PLQ IURP & *DV FKURPDWRJUDSKLFPDVV VSHFWUDO DQDO\VHV ZHUH REWDLQHG RQ D +HZOHWW 3DFNDUG 6HULHV ,, *DV &KURPDWRJUDSK ZLWK D +3 $ 0DVV 6HOHFWLYH 'HWHFWRU 06'f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f IUDJPHQWDWLRQ SDWWHUQV ZLWK SXEOLVKHG PDVV VSHFWUD 7DEOH f 7KH VWUXFWXUH IRU WKH UHPDLQLQJ SURGXFWV 7DEOH f > f§ f§ DQG @ ZHUH DVVLJQHG E\ FRQVLGHUDWLRQ RI WKHLU PDVV VSHFWUDO IUDJPHQWDWLRQ SDWWHUQV WRJHWKHU ZLWK WKH VWDUWLQJ PDWHULDOV UHDFWLRQ FRQGLWLRQV DQG UHDVRQDEOH PHFKDQLVWLF SDWKZD\V IRU WKHLU IRUPDWLRQ IURP WKH VWDUWLQJ PDWHULDOV 7DEOHV DQG UHFRUG WKH PDVV VSHFWUDO IUDJPHQWDWLRQ SDWWHUQ RI WKRVH FRPSRXQGV IRU ZKLFK DXWKHQWLF VDPSOHV ZHUH QRW DYDLODEOH WKH VWUXFWXUDO DVVLJQPHQWV RI WKHVH ZHUH EDVHG HLWKHU RQ WKH IUDJPHQWDWLRQ SDWWHUQ RI WKDW VDPH FRPSRXQG UHSRUWHG LQ WKH OLWHUDWXUH 7DEOH f RU GHGXFHG IURP WKH IUDJPHQWDWLRQ REVHUYHG DQG UHSRUWHG LQ GHWDLO LQ WKH DSSHQGL[ 7DEOH 6HFWLRQ f

PAGE 83

&+$37(5 ,9 %(1=275,$=2/( &$5%2;$0,',1,80726&% &% 6 +&$ -2& -2& &-& -&6 -$@ 6 DON\OWKLRXURQLXP VDOWV DQG GHULYDWLYHV >6 26 &-& 57& -0& -2& -2& 6& -&63f 0, 0, 7/ 7/ 6& 7/@ DPLQRLPLQRVXOIRQLF DFLGV >-2& 6 7/ 6&@ GLPHWK\OS\UD]ROHOFDUER[DPLGLQH QLWUDWH >&-& -&63f 0, 6&@ S\UD]ROHFDUER[DPLGLQH K\GURFKORULGH >-2& 6& 7/@ DQG 1 1 fWHWHUWEXW\OR[\FDUERQ\Of DQG 1 1 n\EHQ]\OR[\FDUERQ\OfWKLRXUHD >7/@ +LVWRULFDOO\ SUHSDUDWLRQ RI JXDQLGLQHV KDV EHHQ DFFRPSOLVKHG XVLQJ F\DQDPLGH f >&% +&$ 6 &% -2& -2& &-& -&6 -$@ 7KH F\DQDPLGH PHWKRGRORJ\ KDV XVXDOO\ EHHQ XVHG WR V\QWKHVL]H DURPDWLF JXDQLGLQHV VXFK DV SKHQ\OJXDQLGLQH GLEHQ]R\OSKHQ\OJXDQLGLQH DQG "PHWK\OSKHQ\OJXDQLGLQH QLWUDWH >&%@ *XDQLGLQHV VXEVWLWXWHG ZLWK HOHFWURQ ZLWKGUDZLQJ JURXSV KDYH DOVR EHHQ V\QWKHVL]HG WKLV ZD\ DQG LQFOXGH P DQG

PAGE 84

SQLWURSKHQ\OJXDQLGLQH D DGLSKHQ\OJXDQLGLQH SKHQ\OEHQ]R\OJXDQLGLQH DQG P DQG Sf§ QLWURSKHQ\OEHQ]R\OJXDQLGLQH >&%@ 5HDFWLRQ \LHOGV RI WKLV F\DQDPLGH SURFHVV KDYH EHHQ PRGHUDWH WR JRRG bf EXW WKH UHDFWLRQ FRQGLWLRQV KDYH RIWHQ EHHQ KDUVK LQYROYLQJ UHIOX[LQJ DW KLJK WHPSHUDWXUHV IRU ORQJ SHULRGV RI WLPH >-2& -2& &-&@ (YHQ PRUH KDUVK FRQGLWLRQV LQYROYH IXVLRQ DW r& >-&6@ 7KHVH FRQGLWLRQV ZHUH XVHG WR SUHSDUH DOLSKDWLF JXDQLGLQHV LQ PRGHUDWH \LHOGV &RPSRXQG KDV DOVR EHHQ XVHG WR SUHSDUH JXDQLGLQHV IURP DPLQR DFLGVf§EXW ORQJ UHDFWLRQ WLPHV VHYHUDO GD\Vf DUH UHTXLUHG >-$@ ZLWK WKH SURGXFWV LVRODWHG DV SLFUDWHV KQF Q 6$ON\OWKLRXURQLXP KDOLGHV RU VDOWV KDYH EHHQ XVHG HIIHFWLYHO\ WR V\QWKHVL]H JXDQLGLQHV >&-& -0& -$ 7/@ 0RUH VSHFLILFDOO\ 6 HWK\OWKLRXUHD K\GURJHQ EURPLGH f ZKLFK UHTXLUHV V\QWKHVLV IURP WKLRXUHDf >26@ KDV EHHQ XVHG WR FRQYHUW JO\FLQH WR JXDQLGLQRDFHWLF DFLG LQ b \LHOG 6 0HWK\OWKLRXUHD VXOIDWHK\GURJHQ VXOIDWH f >6 57& -2& -&63f 0, 6&@ KDV EHHQ XVHG WR JHQHUDWH D YDULHW\ RI FRPSRXQGV &RPSRXQG KDV EHHQ XVHG LQ WKH V\QWKHVLV RI GLF\DQRGLDPLGH >6@ DQG WR JHQHUDWH PRQRVXEVWLWXWHG JXDQLGLQHV >-&63f@ UHDFWLRQ WLPH Kf +1 1++%U +1 L?,++6 6 &RQYHUVLRQ RI DPLQHV WR JXDQLGLQHV LV RIWHQ FDUULHG RXW ZLWK WKHVH DON\OWKLRXURQLXP VDOWV f XQGHU EDVLF FRQGLWLRQV >-2& 0,@ EXW SURGXFWV FDQ EH GLIILFXOW WR SXULI\ GXH WR WKH SUHVHQFH RI WKH KLJKO\ SRODU EDVLF

PAGE 85

JXDQLGLQR JURXS *XDQ\ODWLRQ RI WKH DPLQRPHWK\O GHULYDWLYHV RI D]HSLQHV >6&@ KDV DOVR EHHQ DFFRPSOLVKHG XVLQJ WKLV PHWKRGRORJ\ $PLQRLPLQRPHWKDQHVXOIRQLF DFLG f DQG LWV SKHQ\O GHULYDWLYHV >6 -2& 7/@ KDYH EHHQ XVHG WR JHQHUDWH JXDQLGLQHV DW DPELHQW WHPSHUDWXUH ZLWKLQ D PDWWHU RI PLQXWHV 3URGXFWV SUHFLSLWDWH IURP WKH UHDFWLRQ PL[WXUH DQG FDQ EH SXULILHG E\ FU\VWDOOL]DWLRQ )RUPDPLGLQHVXOILQLF DFLG ZKLFK LV XVHG WR JHQHUDWH WKH DPLQRLPLQRVXOILQLF DFLGV PD\ EH XVHG DV D JXDQ\ODWLQJ UHDJHQW >7/@ 7KH VXOIRQLF DFLG GHULYDWLYHV DUH FU\VWDOOLQH DQG DUH VWDEOH RYHU D IHZ ZHHNV 'LVSODFHPHQW RI WKH +6&!f JURXSV WDNHV SODFH PRUH HDVLO\ WKDQ WKH DON\OPHUFDSWDQ DQLRQ RI WKH 6 DON\OWKLRXUHDV LQ FODVVLFDO V\QWKHWLF SURFHGXUHV >7/@ (WK\ODPLQRHWK\OLPLQRPHWKDQHVXOIRQLFDFLG f KDV EHHQ XVHG LQ WKH DPLGLQDWLRQ RI O\VLQH >6&@ RI ZKLFK WKH DPLGLQDWLRQ LV NQRZQ WR RFFXU UHJLRVSHFLILFDOO\ (W+1 1(W KQ QK /LWHUDWXUH VHDUFKHV WKXV IDU KDYH UHYHDOHG WZR S\UD]ROH UHDJHQWV IRU WKH FRQYHUVLRQ RI DPLQHV WR JXDQLGLQHV Lf GLPHWK\OS\UD]ROHOFDUER[DPLGLQH QLWUDWH f >-$ 6 -&63f 0, 6&@ DQG LLf S\UD]ROH FDUER[DPLGLQH K\GURFKORULGH f %RWK UHDJHQWV KDYH EHHQ XVHG HIIHFWLYHO\ ZLWK DPLQHV DQG DUH LPSURYHPHQWV RYHU WKH H[LVWLQJ PHWKRGV +RZHYHU UHTXLUHV D VWURQJO\ EDVLF PHGLXP DQGRU KHDW ZKHQ XVHG LQ WKH IRUPDWLRQ RI JXDQLGLQHV >6@

PAGE 86

+1 1++1 +1 n1++&, &RPSRXQG LV D FRQYHQLHQW UHDJHQW IRU WKH V\QWKHVLV RI PRQRVXEVWLWXWHG JXDQLGLQHV >-&63f@ 5HDFWLRQV DUH QRUPDOO\ FDUULHG RXW DW r& DERXW Kf RU URRP WHPSHUDWXUH GD\Vf GHSHQGLQJ RQ WKH VXEVWUDWH 7KLV JXDQ\OQLWUDWH UHDJHQW KDV DOVR EHHQ XVHG LQ WKH V\QWKHVLV RI DQDORJV RI WKH DQWLK\SHUVHQVLWLYH DJHQW JXDQHWLGLQH >6&@ EXW ZLWK ORZ LVRODWHG \LHOGV 3URGXFWV ZHUH LVRODWHG DV QLWUDWHV $ PRUH YHUVDWLOH UHDJHQW LV S\UD]OH FDUER[DPLGLQH K\GURFKORULGH f >-2& 6& 7/@ 3\UD]ROH UHDFWV ZLWK SULPDU\ DQG VHFRQGDU\ DPLQHV WR SURGXFH JXDQLGLQH K\GURFKORULGHV LQ JRRG \LHOGV DQG LV DOVR D XVHIXO UHDJHQW IRU SHSWLGH V\QWKHVLV ZKHQ VWDQGDUG PHWKRGV IRU WKH FRQYHUVLRQ RI DPLQHV WR JXDQLGLQHV DUH QRW SUDFWLFDO >-2&@ 7KH JDXQ\OSU\D]ROH FDQ EH VWRUHG LQ DTXHRXV VROXWLRQ IRU VKRUW SHULRGV RI WLPH DQG LV XVHG LQ VWRLFKLRPHWULF DPRXQWV DW URRP WHPSHUDWXUH 7KH S\UD]ROH E\SURGXFW LV VROXEOH LQ HWKHU DQG FDQ EH HDVLO\ UHPRYHG >-2&@ 7KLV LV D ZHOFRPHG DGYDQWDJH RYHU ZKLFK UHTXLUHV UHIOX[LQJ DQG WZR HTXLYDOHQWV RI WKH DPLQH 3URWHFWLRQ RI >6& 7/@ LV NQRZQ WR HQKDQFH LWV UHDFWLYLW\ 1 $LnVWHL%XW\OR[\FDUERQ\OfOFDUER[DPLGLQHS\UD]ROH Df DQG 11nELV EHQ]\OR[\FDUERQ\OfOFDUER[DPLGLQHS\UD]ROHEf KDYH EHHQ XVHG IRU PLOG DQG HIILFLHQW SUHSDUDWLRQ RI PRQRVXEVWLWXWHG JXDQLGLQHV >7/@ DQG LQ SHSWLGH V\QWKHVLV >6&@ 7KH ELVXUHWKDQH SURWHFWHG %RF &E]f GHULYDWLYHV D DQG E ZHUH IRXQG WR EH PRUH UHDFWLYH UHDJHQWV IRU WKH FRQYHUVLRQ RI DPLQHV WR JXDQLGLQHV WKDQ WKH JXDQ\O K\GURFKORULGH >7/@

PAGE 87

D = %RF E = &E] 6OLJKW PRGLILFDWLRQ RI WKH JXDQ\O UHDJHQW DOORZV IRU WKH JHQHUDWLRQ RI SURWHFWHGf JXDQLGLQHV ZKLFK DUH PRUH VROXEOH LQ RUJDQLF VROYHQWV $F\O >7/@ DQG F\DQRWKLRXUHDV >7/@ KDYH EHHQ XVHG IRU WKH SUHSDUDWLRQ RI PRQRVXEVWLWXWHG JXDQLGLQHV 1RUPDOO\ WKLV RFFXUV DV D RQH SRW WZR VWDJH SURFHGXUH $OVR ELVSURWHFWLRQ RI WKH JXDQLGLQH UHDJHQW ZLWK WHUWEXWR[\FDUERQ\O %RFf RU EHQ]\OR[\FDUERQ\O &E]f HQKDQFHV UHDFWLYLW\ 1 $WHIHUI%XWR[\FDUERQ\OfWKLRXUHD f RU 6 PHWK\OLVRWKLRXUHD f >-2& 0, 7/ 7/@ DQG 11n eVEHQ]\OR[\FDUERQ\OfWKLRXUHD f >-2& 0, 7/@ KDYH EHHQ XVHG WR V\QWKHVL]H SURWHFWHG JXDQLGLQHV ZKLFK DUH HDV\ WR SXULI\ V 6 6 [ ; $ %RF+1 1+%RF %RF1 1+%RF &E]+1 1+&E] .R]LNRZVNL DQG FRZRUNHUV KDYH XVHG WKHVH SURWHFWHG JXDQLGLQH UHDJHQWV f >7/@ WR V\QWKHVL]H JXDQLGLQHV LQ H[FHOOHQW \LHOGV VWDUWLQJ IURP DOFRKROV ZKLOH .LP DQG FRZRUNHUV KDYH HQKDQFHG WKH UHDFWLYLW\ RI KLJKO\ GHDFWLYDWHG DPLQHV DQG WKH ELV%RF SURWHFWHG JXDQLGLQHV E\ WUHDWPHQW ZLWK +J&O RU &X&O >7/@ 7KH XVHIXOQHVV RI EHQ]RWULD]ROH f DV D V\QWKHWLF DX[LOLDU\ LV ZHOO GRFXPHQWHG >7@ %HQ]RWULD]ROH f GLVSOD\V WZR H[WUHPHO\ LPSRUWDQW SURSHUWLHV GXH WR LWV PRGHUDWH DFLGLW\ S.D f Lf LW HDVLO\ XQGHUJRHV 0DQQLFKW\SH FRQGHQVDWLRQ ZLWK DQ DOGHK\GH DQG D FRPSRXQG ZLWK DQ DFWLYH K\GURJHQ WR IRUP D YDULHW\

PAGE 88

RI EHQ]RWULD]ROH DGGXFWV DQG LLf LWnV DQLRQ LV DQ HVSHFLDOO\ JRRG OHDYLQJ JURXS ZKLFK FDQ EH GLVSODFHG E\ YDULRXV W\SHV RI QXFOHRSKLOHV ,Q H[WHQGLQJ WKLV ODWWHU SURSHUW\ ZH QRZ UHSRUW D QRYHO HIIHFWLYH DQG FRQYHQLHQW UHDJHQW IRU WKH PLOG DQG HIILFLHQW FRQYHUVLRQ RI DPLQHV WR JXDQLGLQHV XWLOL]LQJ EHQ]RWULD]ROH PHWKRGRORJ\ 2XU DSSURDFK XWLOL]HV EHQ]RWULD]ROH FDUER[DPLGLQLXP WRV\ODWHf WR JHQHUDWH VXEVWLWXWHG JXDQLGLQHV IURP DPLQHV 7V2n 5HVXOWV DQG 'LVFXVVLRQ %HQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH f ZDV FRQYHQLHQWO\ SUHSDUHG LQ JRRG \LHOG E\ PRGLILFDWLRQ RI D SURFHGXUH SUHYLRXVO\ UHSRUWHG IRU WKH SUHSDUDWLRQ RI S\UD]ROHOFDUER[DPLGLQH K\GURFKORULGH f >-2&@ PRODU HTXLYDOHQWV RI EHQ]RWULD]ROH F\DQDPLGH DQG SWROXHQHVXOIRQLF DFLG S7V2+f ZHUH UHIOX[HG LQ GLR[DQH 6FKHPH f 7KH DPLGLQLXP WRV\ODWH SUHFLSWDWHG IURP WKH UHDFWLRQ GXULQJ UHIOX[ DQG FRXOG EH ILOWHUHG IURP WKH UHDFWLRQ PL[WXUH 5HFU\VWDOOL]DWLRQ JDYH SXUH EHQ]RWULD]ROHOFDUER[DPLGLQLXPWRV\ODWHf bf DV VWDEOH QRQK\JURVFRSLF ILQH ZKLWH QHHGOHV 7KH UHDFWLRQ IRU WKH IRUPDWLRQ RI JXDQLGLQHV IURP EHQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH f LV JHQHUDO IRU SULPDU\ DQG VHFRQGDU\ DPLQHV LQFOXGLQJ DURPDWLF DPLQHV 5HDFWLRQV DUH FRQYHQLHQWO\ FDUULHG RXW XVLQJ RQH PRODU HTXLYDOHQW HDFK RI DQG WKH DPLQH Lf LQ GLPHWK\OIRUPDPLGH '0)f LQ WKH SUHVHQFH RU DEVHQFH RI GLLVRSURS\OHWK\ODPLQH

PAGE 89

',($f DW URRP WHPSHUDWXUH LLf LQ &+&1 RU LLLf LQ WKH DEVHQFH RI VROYHQW 3URGXFW LVRODWLRQ LV IDFLOH DV WKH SUHFLSLWDWHG JXDQLGLQH FDQ EH ILOWHUHG IURP WKH HWKHU VROXEOH EHQ]RWULD]ROH E\SURGXFW ZKHQ '0) LV XVHG DV VROYHQW :KHQ &+&1 LV HPSOR\HG WKH SURGXFW SUHFLSLWDWHV GXULQJ WKH UHDFWLRQ ZKLOH LQ WKH DEVHQFH RI VROYHQW WKH SURGXFW FDQ EH LVRODWHG FKURPDWRJUDSKLFDOO\ 6FKHPH 7DEOH f +1& 1 S7V2+ GLR[DQH UHIOX[ 6FKHPH 7V2f Y KQAQK 7V&7 G 5 + 5 Q%X r & PLQV 7V2f DK +1 AQK 7V2f F 5 5 0H2&+ H 5 5 &+ F 5 5 0H E 5 5 &+f I 5 5 >&+f@ J55 &+f K 5 + 5 &+ 6FKHPH

PAGE 90

7DEOH 3URGXFWV RI WKH 5HDFWLRQ RI %HQ]RWULD]ROHOFDUER[DPLGLQLXP 7RV\ODWH f ZLWK 3ULPDU\ DQG 6HFRQGDU\ $PLQHV (QWU\ $PLQH DK *XDQLGLQH DK Lf 0H1+ LLf 2K LLLf 0H2 1+ LYf FKQK 9f 2QK 1_1+ 9Lf YLLf &QK YLLLf &+1+ FKQK D5HSRUWHG \LHOGV IRU SXULILHG FRPSRXQGV EUHDFWLRQ WLPH K FUHDFWLRQ WLPH K SHUIRUPHG LQ WKH DEVHQFH RI ',($ GLLVRSURS\OHWK\ODPLQHf 5HDFWLRQ WLPH PLQ LQ WKH DEVHQFH RI VROYHQW 5HDFWLRQ WLPH GD\V SHUIRUPHG LQ &+&1 LQ WKH DEVHQFH RI ',($ AUHDFWLRQ WLPH K

PAGE 91

)RUPDWLRQ RI WKH JXDQLGLQHV DE DQG IK ZDV FDUULHG RXW LQ '0) LQ WKH SUHVHQFH RI ',($ 6FKHPH 7DEOH f ,Q WKHVH UHDFWLRQV ',($ VHUYHV WR QHXWUDOL]H DQG PDNH LW PRUH PLVFLEOH ZLWK RUJDQLF VROYHQWV 8VH RI WKH SULPDU\ DPLQH + DQG WKH VHFRQGDU\ DPLQHV D DQG IJ DIIRUGHG WKH GHVLUHG JXDQLGLQHV HDVLO\ +RZHYHU ZKHQ WKH VHFRQGDU\ DPLQH 1 79GLHWK\O DPLQH Lf ZDV XVHG WKLV UHVXOWHG LQ WKH IRUPDWLRQ RI WKH WRV\ODWH VDOW DQG QRW WKH GHVLUHG JXDQLGLQH 6FKHPH f 7KLV PD\ EH EHFDXVH 1 $GLHWK\ODPLQH LV D VWHULFDOO\ KLQGHUHG PRUH EDVLF VHFRQGDU\ DPLQH '0) (8 f(W (8 (W 1 ',($ 1 + UW + 7V2n L 6FKHPH 0HWKR[\DQLOLQHOFDUER[DPLGLQLXP WRV\ODWH Ff DQG DQLOLQH FDUER[DPLGLQLXP WRV\ODWH Hf ZHUH ERWK SUHSDUHG IURP LQ '0) LQ WKH DEVHQFH RI ',($ :LWK SULPDU\ DURPDWLF DPLQHV WKH DEVHQFH RI ',($ GRHV QRW KLQGHU WKH UHDFWLRQ *XDQLGLQH H FRXOG DOVR EH V\QWKHVL]HG LQ &+&1 DIWHU ILYH GD\V VWLUULQJ DW URRP WHPSHUDWXUH $WWHPSWV ZHUH PDGH WR JHQHUDWH YDULRXV RWKHU SKHQ\O VXEVWLWXWHG JXDQLGLQHV XQGHU WKH DERYH FRQGLWLRQV EXW UHVXOWHG LQ WKH UHFRYHU\ RI XQUHDFWHG VWDUWLQJ PDWHULDOV 6FKHPH f )/ O;5 '0) Sr 1R 5HDFWLRQ 1 + M 5 + 5 S\ULGLQH N 5 + 5 1&+ 5 0H 5 &+ P 5 + 5 &+&f 6FKHPH

PAGE 92

6LQFH SUHYLRXV DWWHPSWV WR JHQHUDWH ]EXW\ODPLQHOFDUER[DPLGLQLXP WRV\ODWH Gf E\ WKH VWDQGDUG SURFHGXUH XVLQJ LQ '0) ZLWK ',($ UHVXOWHG HLWKHU LQ SRRU \LHOG bf RU LVRODWLRQ RI WKH FRUUHVSRQGLQJ QEXW\ODPLQH WRV\ODWH VDOW f LW ZDV SUHSDUHG LQ WKH DEVHQFH RI VROYHQW *XDQLGLQH G ZDV SUHSDUHG E\ KHDWLQJ DQG G DW r& IRU PLQXWHV 7KH SURGXFW ZDV SXULILHG E\ FROXPQ FKURPDWRJUDSK\ 7KH SRRU \LHOG LVRODWHG LQ WKH VWDQGDUG SURFHGXUH PD\ EH GXH WR UHYHUVLEOH IRUPDWLRQ RI WKH GHVLUHG SURGXFW ZKLFK FDQ WKHQ GHFRPSRVH WR VWDUWLQJ PDWHULDOV DQG XQGHUJR IRUPDWLRQ RI WKH WRV\ODWH VDOW DW D PXFK IDVWHU UDWH 6FKHPH f + + 1 VORZ G L &+ G IDVW I IDVW &+1+ 7V2 6FKHPH &RPSDULVRQV RI WKH H[LVWLQJ OLWHUDWXUH PHWKRGV IRU WKH SUHSDUDWLRQ RI JXDQLGLQHV IURP DPLQHV VXJJHVW WKDW WKH S\UD]ROHOFDUER[DPLGLQH f >-2&@ DSSURDFK LV VXSHULRU WR WKH RWKHU OLWHUDWXUH PHWKRGV SUHYLRXVO\ PHQWLRQHG 6RPH RI WKH DGYDQWDJHV LQFOXGH PLOG UHDFWLRQ FRQGLWLRQV WKH HDVH RI SUHSDUDWLRQ DQG SURGXFW LVRODWLRQ DQG WKH H[WHQGHG VKHOIOLIH RI WKH SDUHQW DPLGLQH :H WKHUHIRUH FRPSDUHG EHQ]RWULD]ROHOFDUER[DPLGLQLXP WRV\ODWH f ZLWK WKH S\UD]ROH GHULYDWLYH DQG FRQFOXGHG WKDW ZKLOH VLPLODU LQ HDVH RI SUHSDUDWLRQ DQG LVRODWLRQ DQG LQ VKHOIOLIH VWDELOLW\ GRHV RIIHU DGYDQWDJHV RYHU LQ WHUPV RI \LHOGV DQG LQFUHDVHG UHDFWLYLW\ 7KXV WKH K\GURFKORULGH GHULYDWLYH RI SLSHULGLQH FDUER[DPLGLQLXP WRV\ODWH Ef ZDV UHSRUWHG WR EH SUHSDUHG LQ b LVRODWHG \LHOG

PAGE 93

IURP S\UD]ROHOFDUER[DPLGLQH K\GURFKORULGH f >-2&@ :H QRZ UHSRUW D \LHOG RI b XVLQJ 3UHSDUDWLRQ RI WKH K\GURFKORULGH GHULYDWLYH RI PHWKR[\DQLOLQHOFDUER[DPLGLQLXP WRV\ODWH Ff XVLQJ S\UD]ROHOFDUER[DPLGLQH K\GURFKORULGH f >-2&@ UHTXLUHG D UHDFWLRQ WLPH RI K WR JLYH D \LHOG RI b 8VLQJ WKH EHQ]RWULD]ROH PHWKRGRORJ\ DQ LPSURYHG \LHOG RI b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f JLYHV JXDQLGLQHV LQ PRGHUDWH WR JRRG \LHOGV DQG RIIHUV DGYDQWDJHV VXFK DV LQFUHDVH \LHOGV DQG UHDFWLYLW\ RYHU WKH H[LVWLQJ SURFHGXUH HPSOR\LQJ S\UD]ROHOFDUER[DPLGLQH K\GURFKORULGH f %HQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH f FDQ EH HDVLO\ SUHSDUHG DQG SXULILHG DQG VWRUHG RYHU ORQJ SHULRGV RI WLPH

PAGE 94

([SHULPHQWDO *HQHUDO 0HOWLQJ SRLQWV ZHUH REWDLQHG XVLQJ D 7KRPDV +RRYHU FDSLOODU\ PHOWLQJ SRLQW DSSDUDWXV DQG DUH XQFRUUHFWHG 105 VSHFWUD ZHUH UHFRUGHG HLWKHU RQ D 9DUDQ 9;5 0+]f *HPLQL 0+]f RU *HQHUDO (OHFWULF 4( 0+]f VSHFWURPHWHU & 105 ZHUH UHFRUGHG DW 0+] RQ WKH VDPH LQVWUXPHQWV &KHPLFDO VKLIWV f DUH UHSRUWHG LQ SDUWV SHU PLOOLRQ SSPf GRZQILHOG IURP WHWUDPHWK\OVLODQH 706f DV WKH LQWHUQDO VWDQGDUG &RXSOLQJ FRQVWDQWV YDOXHVf DUH UHSRUWHG LQ +] $OO UHDFWLRQV ZHUH SHUIRUPHG LQ DQ LQHUW DWPRVSKHUH XVLQJ RYHQGULHG JODVVZDUH (OHPHQWDO DQDO\VHV DQG KLJK UHVROXWLRQ PDVV VSHFWURPHWU\ ZHUH SHUIRUPHG RQ VLWH DW WKH DQDO\WLFDO IDFLOLW\ %HQ]RWULD]ROH HWKHU DQG SLSHULGLQH ZHUH SXUFKDVHG IURP )LVKHU DQG XVHG DV VXSSOLHG '0) DOVR SXUFKDVHG IURP )LVKHU ZDV GULHG RYHU ƒ PROHFXODU VLHYHV &\DQDPLGH GLPHWK\O DPLQH QEXW\ODPLQH S\UUROLGLQH QKH[\ODPLQH DQG ',($ ZHUH SXUFKDVHG IURP $OGULFK DQG XVHG DV VXSSOLHG $QLOLQH $OGULFKf ZDV GLVWLOOHG SULRU WR XVH 0HWKR[\DQLOLQH $OGULFKf ZDV UHFU\VWDOOL]HG IURP KH[DQH SULRU WR XVH 0RUSKROLQH )OXNDf ZDV XVHG DV VXSSOLHG 7/& ZDV SHUIRUPHG RQ SUHFRDWHG VLOLFD JHO ) SODWHV ZKLFK ZHUH GHYHORSHG XVLQJ KH[DQHHWKHU f DQG ZHUH YLVXDOL]HG ZLWK 89 OLJKW DQG LRGLQH %HQ]RWULD]ROH FDUER[DPLGLQLXP 7RV\ODWH f $ PL[WXUH RI EHQ]RWULD]ROH J PROf F\DQDPLGH J PROf DQG SWROXHQHVXOIRQLF DFLG J PROf ZDV UHIOX[HG LQ GLR[DQH P/f IRU K $ ZKLWH SUHFLSLWDWH IRUPHG XSRQ KHDWLQJ 7KH UHDFWLRQ ZDV WKHQ FRROHG WR URRP WHPSHUDWXUH GLOXWHG ZLWK (2 P/f DQG VWLUUHG YLJRURXVO\ IRU VHYHUDO KRXUV 7KH VROLG ZDV ILOWHUHG XQGHU YDFXXP DOORZHG WR DLU GU\ WKHQ UHFU\VWDOOL]HG IURP EHQ]HQH(W2+ f DQG GULHG LQ YDFXR )LQH ZKLWH QHHGOHV J bf ZHUH LVRODWHG PS r& O+ 105 '062Gf V +f G + f G + f W + f W + f

PAGE 95

G + f G + f EU V +f & 105 '062Gf )XUWKHU FRQILUPDWLRQ ZDV DFFRPSOLVKHG E\ VLQJOH [UD\ FU\VWDOORJUDSK\ VHH $SSHQGL[ &f *HQHUDO SURFHGXUH IRU WKH IRUPDWLRQ RI VXEVWLWXWHG JXDQLGLQHV 1 $n'LPHWK\ODPLQHFDUER[DPLGLQLXP WRV\ODWH Df 7R D PL[WXUH RI GLPHWK\ODPLQH b ZW VROQ LQ ZDWHUf SL/ PJ PPROf EHQ]RWULD]ROH FDUER[DPLGLQLXP WRV\ODWH PJ PPROf DQG GLLVRSURS\OHWK\ODPLQH ',($f SL/ PJ PPROf ZDV DGGHG '0) P/f 7KH UHDFWLRQ ZDV VWLUUHG DW URRP WHPSHUDWXUH DQG PRQLWRUHG E\ 7/& $IWHU K WKH UHDFWLRQ PL[WXUH ZDV GLOXWHG ZLWK (W P/f VWLUUHG DQG WKH FUXGH SUHFLSLWDWH FROOHFWHG ZDVKHG ZLWK (W DQG GULHG 5HFU\VWDOOL]DWLRQ IURP (W2+ DIIRUGHG ZKLWH SULVPV PJ bf PS r& OLW >-&6@ PS r&f -+ 105 '062Gf V +f V +f G + f V +f G + f & 105 '062Gf 3LSHULGLQHFDUER[DPLGLQLXP WRV\ODWH Ef 7UHDWPHQW RI SLSHULGLQH MD/ PJ PPROf EHQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH J PPROf DQG ',($ SL/ PJ PPROf DV GHVFULEHG IRU FRPSRXQG D JDYH WKH FUXGH SURGXFW DIWHU K &U\VWDOOL]DWLRQ IURP (W2+ JDYH ILQH ZKLWH QHHGOHV PJ bf PS r& 105 '062Gf P +f V +f W + f G + f V +f G + f & 105 '062GHf &+126 UHTXLUHV & + 1 )RXQG & + 1

PAGE 96

0HWKR[\DQLOLQHOFDUER[DPLGLQLXP WRV\ODWH Ff 7UHDWPHQW RI PHWKR[\DQLOLQH PJ PPROf DQG EHQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH J PPROf DV GHVFULEHG IRU FRPSRXQG D JDYH WKH FUXGH SURGXFW DIWHU K &U\VWDOOL]DWLRQ IURP 0H+(W JDYH ILQH ZKLWH QHHGOHV PJ bf PS r& r+ 105 '062Gf V +f V +f G + f G + f V +f G + f V +f & 105 '062Gf +5 06 &+126 )$%f 0+f &+1 FDOHG DV IUHH EDVHf UHTXLUHV L%XW\ODPLQHOFDUER[DPLGLQLXP WRV\ODWH Gf %HQ]RWULD]ROH FDUER[DPLGLQLXP WRV\ODWH J PPROf QEXW\ODPLQH / PJ PPROf DQG ',($ P/ J PPROf ZHUH KHDWHG r&f ZLWK VWLUULQJ IRU PLQXWHV 7KH YLVFRXV SDOH\HOORZ FUXGH PDWHULDO ZDV FRROHG WR URRP WHPSHUDWXUH GLVVROYHG LQ D PLQLPDO DPRXQW RI 7+) DQG SXULILHG E\ IODVK FROXPQ FKURPDWRJUDJK\ XVLQJ %2 7+) DQG (W2+ FRQVHFXWLYHO\ DV HOXHQWV 7KH K\JURVFRSLF ZKLWH VROLG REWDLQHG XSRQ HYDSRUDWLRQ RI WKH (W2+ IUDFWLRQV ZDV VXVSHQGHG LQ &+&, WR SUHFLSLWDWH WKH SXUH K\JURVFRSLF ZKLWH VROLG J bf PS r& GHFRPSRVLWLRQf + 105 '062 Gf W + f VHSWHW + f VHSWHW + f V +f T + f G + f G + f 1+ SURWRQV QRW REVHUYHG & 105 '062Gf +5 06 &+126 )$%f 0+f &+1 FDOHG DV IUHH EDVHf UHTXLUHV $QLOLQHFDUER[DPLGLQLXP WRV\ODWH Hf %HQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH PJ PPROf DQG DQLOLQH cD/ PJ PPROf ZHUH VXVSHQGHG LQ &+&1 P/f DQG VWLUUHG DW URRP WHPSHUDWXUH IRU GD\V 7KH FUXGH SUHFLSLWDWH ZDV

PAGE 97

ILOWHUHG DQG UHFU\VWDOOL]HG IURP (W+(W WR \LHOG D ILQH ZKLWH SRZGHU PJ bf PS r& O+ 105 '062Gf V +f G + f G + f G + f W + f G + f V +f 1+ QRW REVHUYHG & 105 '062Gf +5 06 &+126 )$%f 0+f &+1 FDOHG DV IUHH EDVHf UHTXLUHV $QLOLQHFDUER[DPLGLQLXP WRV\ODWH Hf 7UHDWPHQW RI EHQ]RWULD]ROH FDUER[DPLGLQLXP WRV\ODWH PJ PPROf DQG DQLOLQH / PJ PPROf LQ &+&1 DV GHVFULEHG IRU FRPSRXQG D JDYH WKH FUXGH SURGXFW DIWHU GD\V PJ bf +5 06 &+126 )$%f 0+f &+1 FDOHG DV IUHH EDVHf UHTXLUHV 0RUSKROLQHFDUER[DPLGLPXP WRV\ODWH If 7UHDWPHQW RI PRUSKROLQH SL/ PJ PPROf EHQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH PJ PPROf DQG ',($ SL/ PJ PPROf LQ '0) P/f DV GHVFULEHG IRU FRPSRXQG D JDYH WKH FUXGH SURGXFW DIWHU K &U\VWDOOL]DWLRQ IURP (W2+(W JDYH D ILQH FU\VWDOOLQH ZKLWH SRZGHU PJ bf PS r& -+ 105 '062Gf V +f W + f W + f G + f G t V +-G f & 105 '062Gf +5 06 &L+L16 )$%f 0+f &+L1 FDOHG DV IUHH EDVHf UHTXLUHV 3\UUROLGLQH FDUER[DPLGLQLXP WRV\ODWH Jf 7UHDWPHQW RI S\UUROLGLQH SL/ PJ PPROf EHQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH PJ PPROf DQG ',($ SW/ PJ PPROf LQ '0) P/f DV GHVFULEHG IRU FRPSRXQG D JDYH WKH FUXGH SURGXFW DIWHU K &U\VWDOOL]DWLRQ IURP (W2+(W4 JDYH ILQH SDOH

PAGE 98

\HOORZ QHHGOHV PJ bf PS r& O+ 105 '062GHf W + f V +f W + f G t V + -G f G + f & 105 '062Gf &+1266 UHTXLUHV & + 1 )RXQG & + 1 +5 06 &+126 )$%f 0+f &+1 FDOHG DV IUHH EDVHf UHTXLUHV Q+H[\ODPLQH FDUER[DPLGLQLXP WRV\ODWH Kf 7UHDWPHQW RI QKH[\ODPLQH SL/ PJ PPROf EHQ]RWULD]ROHOFDUER[DPLGLQLXP WRV\ODWH PJ PPROf DQG ',($ SL/ PJ PPROf LQ '0) P/f DV GHVFULEHG IRU FRPSRXQG D JDYH WKH FUXGH SURGXFW DIWHU K &U\VWDOOL]DWLRQ IURP (W2+(W JDYH ILQH ZKLWH FU\VWDOOLQH IODNHV PJ bf PS r& r+ 105 '062Gf W + f EU V +f T + f V +f T + f G t V + -G f G + f & 105 '062Gf +5 06 &+146 )$%f 0+f &+1 FDOHG DV IUHH EDVHf UHTXLUHV 1 $'LHWK\ODPLQH WRV\ODWH VDOW f 7UHDWPHQW RI 1 $GLHWK\ODPLQH X/ PJ PPROf EHQ]RWULD]ROH FDUER[DPLGLQLXP WRV\ODWH PJ PPROf DQG ',($ SL/ PJ PPROf LQ '0) P/f DV GHVFULEHG IRU FRPSRXQG D JDYH WKH FUXGH SURGXFW DIWHU K &U\VWDOOL]DWLRQ IURP (W2+(W JDYH ILQH ZKLWH FU\VWDOOLQH %DNHV PJ bf PS r& r+ 105 '062Gf W + f V +f T + f G + f G + f V +f &105 '062Gf

PAGE 99

Q%XW\O DPLQH WRV\ODWH VDOW f 7UHDWPHQW RI ]EXW\ODPLQH X/ PJ PPROf EHQ]RWULD]ROHOFDUER[DPLGLQLXP WRV\ODWH PJ PPROf DQG ',($ SW/ PJ PPROf LQ '0) P/f DV GHVFULEHG IRU FRPSRXQG D JDYH WKH FUXGH SURGXFW DIWHU K &U\VWDOOL]DWLRQ IURP (W2+(W JDYH ILQH ZKLWH FU\VWDOOLQH IODNHV PJ bf PS r& r+ 105 '062Gf W + f P +f P +f V +f W + f G + f G + f V +f & 105 '062Gf

PAGE 100

&+$37(5 9 ,1 9(67, *$7,216 2) $ 0, 1275, $=2/( $3352$&+(6 72 7+( '(9(/230(17 2) $ 1(: (/(&7523+,/,& $0,1$7,1* $*(17 t 0(7+2'2/2*< )25 7+( 35(3$5$7,21 2) $/.-35@ /DWHU LQ %XORZ DQG FRZRUNHUV GHPRQVWUDWHG WKDW WULD]ROH UHDFWV ZLWK GLFDUERQ\O FRPSRXQGV WR DIIRUG WKH FRUUHVSRQGLQJ S\UUROH GHULYDWLYHV >&%&%@ 7KLV UHDFWLRQ LV FKDUDFWHULVWLF IRU PRVW SULPDU\ DPLQHV 7ULD]ROH ZDV DOVR V\QWKHVL]HG IURP WKH VHOIFRQGHQVDWLRQ RI IRUPK\GUD]LGH DW r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

PAGE 101

DQG WKH VHFRQG SDUW ZLOO IRFXV XSRQ WKH V\QWKHVLV RI WKH EHQ]RWULD]ROH DGGXFW RI 7KH JHQHUDWLRQ RI $VXEVWLWXWHG LPLQHV IURP SULPDU\ DPLQHV DQG DOGHK\GHV RU NHWRQHV 6FKHPH f SOD\V DQ LPSRUWDQW UROH LQ WKH V\QWKHVLV RI D]DDURPDWLF FRPSRXQGV >0,@ DQG WKH ELRV\QWKHVLV RI DPLQR DFLGV >0,@ 5 R n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f KDV EHHQ XVHG WR SURPRWH WKH IRUPDWLRQ RI NHWLPLQHV IURP VXEVWLWXWHG F\FORKH[DQRQHV >-2&@ DQG WKH DGGLWLRQ RI D]LULGLQH WR NHWRQHV >-2&@ $ PRODU HTXLYDOHQW RI m%X6Q&O KDV EHHQ XVHG IRU WKH VDPH SXUSRVH >6&@ 6LPLODUO\ =Q&O KDV EHHQ VKRZQ WR FDWDO\]H WKH SUHSDUDWLRQ RI NHWLPLQHV IURP NHWRQHV DQG 1 $WHWULPHWK\OVLO\OfDPLQHV >%6)@ 2WKHU LQGLUHFW URXWHV WR NHWLPLQHV 6FKHPH f LQFOXGH WKH UHDFWLRQV RI NHWRQHV ZLWK LPLQRSKRVSKRUDQHV (TXDWLRQ f >$*(f@ RI $GLPHWK\ODON\ODOXPLQRLPLQHV ZLWK SULPDU\ DPLQHV (TXDWLRQ f >/$@ DQG RI DLPLQRSKRVSKRQLXP PHWK\OLGHV ZLWK DOGHK\GHV (TXDWLRQ f >6@ $OVR (LVFK DQG FRZRUNHUV KDYH GHYHORSHG ELV GLFKORURDOXPLQXPfSKHQ\OLPLGH DV D KLJKO\ VHOHFWLYH LPLQDWLQJ DJHQW IRU DOGHK\GHV NHWRQHV DQG DFLG FKORULGHV (TXDWLRQ f >-2&@

PAGE 102

)R& A& AAfAf14+ &+f32 S T 5 DG 5 + &+ 5 & 14+ f 5 5 & 1$,5 5r1+ KQDLU A& 15 ff 15f &H+V-D3&+ 5 5 &+2 UFK "UI + 5 1 5 &+f32 f U 51$,(f 2nF 5 5 5 & 15 f ( (W RU &O 5 DON\O 5 DON\O RU + 6FKHPH 7KH GHYHORSPHQW RI HOHFWURSKLOLF DQLPDWLRQ KDV PDGH LW SRVVLEOH WR WUDQVIHU DPLQR RU VXEVWLWXWHG DPLQR JURXSV IURP YDULRXV DPLQDWLQJ DJHQWV WR YDULRXV QXFOHRSKLOHV 6FKHPH f 7KH PRVW LQWHUHVWLQJ DQG LPSRUWDQW VWUXFWXUDO IHDWXUH RI HOHFWURSKLOLF DPLQDWLQJ DJHQWV RI WKH W\SH 5LA1= LV WKH DWWDFKPHQW RI D JRRG OHDYLQJ JURXS WR WKH 15A JURXS 7KH OHDYLQJ JURXS = LV GLVSODFHG E\ D QXFOHRSKLOH GXULQJ WKH DPLQDWLRQ SURFHVV 1X 551= 1X155 =f 6FKHPH

PAGE 103

7KH HOHFWURSKLOLF DPLQDWLRQ RI RUJDQRPHWDOOLF UHDJHQWV FRQVWLWXWHV DQ H[DPSOH RI fXPSROXQJf PHWKRGRORJ\ IRU WKH GLUHFW IRUPDWLRQ RI &1 ERQGV $ GHWDLOHG UHYLHZ E\ (UGLN DQG FRZRUNHUV GHVFULEHV WKH HOHFWURSKLOLF DPLQDWLQJ DJHQWV FRPPRQO\ XVHG IRU FDUEDQLRQV >&59@ 7KH ILUVW SDUW RI WKLV SURMHFW IRFXVHV RQ WKH GHYHORSPHQW RI D SRWHQWLDOO\ QHZ HOHFWURSKLOLF DPLQDWLQJ UHDJHQW $OWQD]RO\OfIOXRUHQLPLQH f ZKLFK VKRXOG UHTXLUH RQH PROH RI QXFOHRSKLOH DQG VLPSOH K\GURO\VLV WR IUHH WKH GHVLUHG DPLQH ,Q WKLV FDVH WKH WULD]ROH JURXS VKRXOG EH D SRWHQWLDOO\ JRRG OHDYLQJ JURXS ZKLFK VKRXOG EH HDVLO\ GLVSODFHG E\ QXFOHRSKLOHV 7KHVH IHDWXUHV ZRXOG PDNH DQ DWWUDFWLYH VRXUFH RI 1+ $O 7ULD]RO\OfIOXRUHQLPLQH f ZRXOG WKHUHIRUH FRPSOLPHQW DQG LPSURYH XSRQ FRPPRQO\ XVHG HOHFWURSKLOLF DPLQDWLQJ UHDJHQWV VXFK DV GLIHUWEXW\OfD]RGLFDUER[\ODWH f >+&$ -$ -$ -$@ FKORUROQLWURVRF\FORKH[DQH f >7/@ DQG WULV\O D]LGH f >-$ 7/@ 6FKHPH f 3UHYLRXVO\ WKH DERYH UHDJHQWV KDYH EHHQ DSSOLHG WR WKH DV\PPHWULF HOHFWURSKLOLF DPLQDWLRQ RI NHWRQH HQRODWHV 7KHVH UHDJHQWV JHQHUDOO\ UHTXLUH K\GURJHQRO\VLV IRU WKH UHOHDVH RI WKH SURWHFWHG SULPDU\ DPLQH JURXS DIWHU UHDFWLRQ ZLWK D FDUERQ QXFOHRSKLOH

PAGE 104

1&W%X ,, W%X&A&n 1 6FKHPH 7 ULV\O 1 ,Q DGGLWLRQ DPL QRWULD]ROH PD\ EH GHULYDWL]HG E\ UHDFWLRQ ZLWK YDULRXV FRPSRXQGV 7KH V\QWKHVLV RI VXEVWLWXWHG DPLQRWULD]ROHV LV ZHOO GRFXPHQWHG ZLWKLQ WKH OLWHUDWXUH $ IHZ H[DPSOHV DUH QRWHG EHORZ 6\QWKHVLV RI FRPSRXQGV VXFK DV KDYH EHHQ REWDLQHG IURP DPLQRWULD]ROH f DQG DU\OLVRWKLRF\DQDWHV >-+&@ 6FKHPH f $$ PL QR WULD]ROHV KDYH EHHQ V\QWKHVL]HG E\ WKH R[LGDWLRQ RI DU\OLGHQHK\GUD]LGLQHV >%&-@ 6FKHPH f 11 1 6 ? [ 1 &1 + $U 6 ? 1 + 1+ 1 + 9 1 6FKHPH +11 P& nA3K 1 +1 n$U +J2 (W2+ 11 3Kf§L `f§ 3K 1 +1Q $U 6FKHPH 0RUH VSHFLILFDOO\ DON\O DPL QRfAWULD]ROHV KDYH EHHQ V\QWKHVL]HG IURP WKH PHWK\O SWROXHQHVXOIRQDWHV RI FDWLRQ D DQG WKH HWK\O DQDORJXH E 6FKHPH f >-35@

PAGE 105

11 &+55 1 1+ D5 5 + E5 + 5 &+ 11 1 1+&+55 6FKHPH $ VHFRQG DQG PRUH FRQYHQLHQW PHWKRG IRU WKH V\QWKHVLV RI DON\ODPLQRf WULD]ROHV LV WKH UHGXFWLRQ RI LPLQHV >0,@ 7KH UHDFWLRQ RI DPLQRWULD]ROH f ZLWK DSSURSULDWH DOGHK\GHV RU NHWRQHV JLYHV WKH FRUUHVSRQGLQJ LPLQHV f ZKLFK FDQ EH UHGXFHG E\ /$,+ DQG 1D%+ WR JLYH WKH FRUUHVSRQGLQJ DON\ODPLQRf WULD]ROHV 6FKHPH f 11 11 2 UFU 1 1D%+ 1 1+ 5 1 ?O & RU /L$,+ 5 11 1 1+&+55 6FKHPH .DWULW]N\ DQG /DXUHQ]R >-2&@ XVHG WKH DERYH PHWKRGRORJ\ WR V\QWKHVL]H DON\ODPLQRfWULD]ROHV ZKLFK ZHUH XVHG LQ WKH V\QWKHVLV RI DON\ODPLQRQLWUREHQ]HQHV E\ YLFDULRXV QXFOHRSKLOLF DPLQDWLRQ ,W KDV EHHQ H[WHQVLYHO\ GRFXPHQWHG WKDW SULPDU\ DQG VHFRQGDU\ DPLQHV FDQ EH FRQGHQVHG ZLWK EHQ]RWULD]ROH WR JHQHUDWH D KRVW RI EHQ]RWULD]ROH DGGXFWV 7KHUH LV DOVR DPSOH GRFXPHQWDWLRQ WKDW YDULRXV GHULYDWLYHV FDQ EH V\QWKHVL]HG E\ H[SORLWLQJ WKH OHDYLQJ JURXS DELOLW\ RI EHQ]RWULD]ROH >7@ 7KLV VHFRQG SDUW RI WKLV FKDSWHU GHDOV ZLWK WKH

PAGE 106

V\QWKHVLV RI DON\ODPLQRfOWULD]ROHV XVLQJ DPLQRWULD]ROH f DQG EHQ]RWULD]ROH PHWKRGRORJ\ 7KH WULD]ROHEHQ]RWULD]ROH DGGXFW EHQ]RWULD]ROO \OPHWK\ODPLQRfWULD]ROH f FRXOG EH UHDFWHG ZLWK YDULRXV *ULJQDUG UHDJHQWV WR SURYLGH DON\ODPLQRf WULD]ROHV 8VLQJ EHQ]RWULD]ROH PHWKRGRORJ\ ZRXOG RIIHU PLOG FRQGLWLRQV IRU WKH V\QWKHVLV RI DON\ODPLQRfWULD]ROHV +19 A%W 5HVXOWV DQG 'LVFXVVLRQ 6\QWKHVLV RI FRPSRXQGV DQG VXEVHTXHQW UHDFWLRQV RI WKH HOHFWURSKLOLF DPLQDWLRQ ZLOO EH GLVFXVVHG LQ WKLV )LUVW SDUW RI WKH UHVXOWV 7KH VHFRQG SDUW RI WKH UHVXOWV VHFWLRQ ZLOO IRFXV XSRQ WKH V\QWKHVLV DQG VXEVHTXHQW UHDFWLRQV GHDOLQJ ZLWK WKH SUHSDUDWLRQ DON\ODPLQRfWULD]ROHV $O7ULD]RO\OfIOXRUHQLPLQH f ZDV VXFFHVVIXOO\ SUHSDUHG E\ DSSO\LQJ D OLWHUDWXUH SURFHGXUH >-2&@ XVHG WR V\QWKHVL]H DURPDWLF IOXRUHQLPLQHV $PLQRWULD]ROH f IOXRUHQRQH f DQG ERURQ WULIOXRULGH HWKHUDWH ZHUH UHIOX[HG LQ &+&, 6FKHPH f $IWHU K UHPRYDO RI WKH VROYHQW LQ YDFXR \LHOGHG WKH FUXGH SURGXFW ZKLFK ZDV UHFU\VWDOOL]HG IURP HWKDQRO )LQH \HOORZ QHHGOHV J bf ZHUH LVRODWHG PS r& GHFRPSRVLWLRQf 7KH SURGXFW ZDV FRQILUPHG E\ + DQG & 105 VSHFWURVFRS\ ORZ UHVROXWLRQ /5f DQG KLJK UHVROXWLRQ +5f PDVV VSHFWURPHWU\ DQG LQIUDUHG ,5f VSHFWURVFRS\ 7KH LPLQR FDUERQ ZDV REVHUYHG DW SSP LQ WKH & 105 7KH PROHFXODU LRQ ZDV GLVSOD\HG DW P] LQ WKH /5 PDVV VSHFWUXP DQG WKH 0 DW P]

PAGE 107

LQ WKH +5 PDVV VSHFWUXP 7KH & 1 ERQG ZDV REVHUYHG DW FPn LQ WKH ,5 VSHFWUXP 6FKHPH 3UHOLPLQDU\ VROXELOLW\ WHVWV LQGLFDWHG WKDW QHLWKHU HWKHU (Wf QRU WHWUDK\GURIXUDQ 7+)f ZDV D VXLWDEOH VROYHQW IRU WKH HOHFWURSKLOLF DQLPDWLRQ UHDFWLRQV RI LPLQH 7KXV WKH LQLWLDO UHDFWLRQV ZHUH SHUIRUPHG E\ GLVVROYLQJ DGGHG YLD D 6R[KOHW H[WUDFWRUf LQ UHIOX[LQJ WROXHQH ZLWK DGGLWLRQ RI WKH SUHIRUPHG *ULJQDUG LQ DQK\GURXV 52 7KH ILUVW UHDFWLRQ LQYHVWLJDWHG ZDV WKDW RI WRO\OPDJQHVLXQ EURPLGH Df DQG LPLQH 6FKHPH f 7KLQ OD\HU FKURPDWRJUDSK\ RI WKH FUXGH UHDFWLRQ PL[WXUH LQGLFDWHG WKDW D UHDFWLRQ KDG WDNHQ SODFH EXW WKH\ ZHUH DW OHDVW ILYH SURGXFW VSRWV HOXWLQJ WRJHWKHU $IWHU DTXHRXV ZRUNXS XVLQJ 0 +& DQG b 1D2+f D FUXGH 105 DQDO\VLV FRQILUPHG D FRPSOH[ PL[WXUH RI SURGXFWV &ROXPQ FKURPDWRJUDSKLF VHSDUDWLRQ OHG WR WKH LVRODWLRQ RI WKUHH RI WKH ILYH SURGXFW VSRWV 0H&+0J%U &+0H WROXHQH UHIOX[ K D D 6FKHPH

PAGE 108

7KH XSSHUPRVW VSRW 5I f KDV EHHQ LGHQWLILHG DV WKH GLPHU E\SURGXFW RI D 7KH VWUXFWXUH RI ZDV FRQILUPHG E\ r+ 105 DQG /5 PDVV VSHFWURPHWU\ ,Q WKH r+ 105 VSHFWUXP D + VLQJOHW LQGLFDWHV WKH PHWK\O JURXS :LWKLQ WKH DURPDWLF UHJLRQ UDQJLQJ IURP WR SSP WZR + GRXEOHWV LQGLFDWH WKH WZR VHWV RI &+V RI WKH SDUDVXEVWLWXWHG SKHQ\O ULQJ ,Q WKLV FDVH WKH VLPSOLFLW\ RI WKH VSHFWUXP VXJJHVWHG WKDW WKH RWKHU KDOI RI WKH PROHFXOH PXVW EH LGHQWLFDO ZLWK WKDW LQGLFDWHG DQG KHQFH WKH LGHQWLILFDWLRQ RI WKH GLPHU 7KH PROHFXODU LRQ ZDV REVHUYHG DW P] 7KH QH[W ORZHU VSRW 5I f ZKLFK DOLJQV ZLWK WKH VWDUWLQJ LPLQH ZDV LGHQWLILHG DV IOXRUHQRQH f E\ 105 7KH FKDUDFWHULVWLF WULSOHW GRXEOHW GRXEOHW SDWWHUQ ZDV LGHQWLFDO WR WKDW RI DQ DXWKHQWLF VDPSOH RI IOXRUHQRQH 7KH NHWRQH FDUERQ\O ZDV FOHDUO\ HYLGHQW DW SSP LQ & 105 VSHFWUXP 7KH SUHVHQFH RI IOXRUHQRQH DV D SURGXFW FRXOG LQGLFDWH RQH RI WKH IROORZLQJ Df WKH VWDUWLQJ LPLQH ZDV LPSXUH Ef WKH UHDFWLRQ ZDV FRQWDPLQDWHG E\ ZDWHU ZKLFK K\GURO\]HG WKH VWDUWLQJ PDWHULDO RU Ff XQGHU WKH UHIOX[LQJ FRQGLWLRQV LQ WROXHQH PROHFXODU R[\JHQ ZDV UHVSRQVLEOH IRU VRPH SHFXOLDU UHDFWLRQV 7KH WKLUG VSRW 5I f ZDV WKRXJKW WR EHf WKH GHVLUHG SURGXFW D 6FKHPH f $ SDOH \HOORZ RLO ZDV LVRODWHG LQ b \LHOG + 105 GLVSOD\V D VSHFWUXP VXSSRUWLYH RI VWUXFWXUH D $ + VLQJOHW DW SSP LQGLFDWHV WKH PHWK\O JURXS RI WKH SKHQ\O ULQJ 7ZR + GRXEOHWV LQ WKH DURPDWLF UHJLRQ RQH DW DQG WKH RWKHU DW SSP LQGLFDWH WKH WZR VHWV RI &+V RI WKH SDUDVXEVWLWXWHG SKHQ\O ULQJ ZKLOH D PXOWLSOHW DOVR ZLWKLQ WKH DURPDWLF UHJLRQ UHJLVWHUV WKH + RI WKH IOXRUHQ\O PRLHW\ 7KH & VSHFWUXP DOVR VXSSRUWV LGHQWLILFDWLRQ RI LPLQH D KRZHYHU WKH WK FDUERQ SHDN WKH LPLQH FDUERQ IDLOHG WR EH REVHUYHG H[SHFWHG DURXQG SSPf HYHQ DIWHU D ORQJ

PAGE 109

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f UHYHDOHG D PROHFXODU LRQ RI P] WKUHH PDVV XQLWV KLJKHU WKDQ WKDW RI WKH H[SHFWHG LPLQH P] f 7KH HYHQ PROHFXODU LRQ UXOHG RXW WKH SUHVHQFH RI D VLQJOH QLWURJHQ EXW GLG QRW H[FOXGH WKH SRVVLELOLW\ RI DQ HYHQ PXOWLSOH RI QLWURJHQV 7KHUHIRUH WKH FRPSRXQG LVRODWHG IURP 6FKHPH ZDV LGHQWLILHG DV WKH DOFRKRO P] f DQG QRW WKH LPLQH D RU LWV UHGXFHG SURGXFW D P] &+0H D P] :LWK LQGLFDWLRQ RI DQ DOFRKRO f DQG QRW WKH LPLQH f LW DSSHDUV WKDW WKH SURGXFWV RI WKH UHDFWLRQ DUH JHQHUDWHG IURP WKH UHDFWLRQ RI WKH QXFOHRSKLOH ZLWK IOXRUHQRQH DQG QRW IURP WKH LPLQH 7KH SXULW\ RI WKH VWDUWLQJ PDWHULDO ZDV FKHFNHG WR HQVXUH WKDW WKHUH ZDV QR IOXRUHQRQH SUHVHQW &+1 DQDO\VLV ZDV QRW H[DFW &+1 UHTXLUHV & + 1 IRXQG & + 1 f EXW LQGLFDWHG WKDW WKH VWDUWLQJ PDWHULDO EHLQJ XVHG WR EH WKH LPLQH +5 06 DQDO\VLV UHYHDOHG DQ 0 RI P] IRU DQ HOHPHQWDO FRPSRVLWLRQ RI &+1 7KH 0 LV RQH PDVV XQLW

PAGE 110

KLJKHU WKDQ WKDW RI LPLQH &+1f )URP WKH UHDFWLRQ SURGXFWV LW DSSHDUHG WKDW PROHFXODU R[\JHQ ZDV HQWHULQJ LQWR WKH UHDFWLRQ 7KLV FRXOG KDYH EHHQ FRPLQJ IURP WKH LQKRXVH QLWURJHQ XVHG LQ WKH UHDFWLRQ +2 ZDV UXOHG RXW DV FRQWDPLQDQW VLQFH WKH *ULJQDUG ZDV VWLOO DFWLYH )RUPDWLRQ RI WKH LPLQH D HYHQ LQ SRRU \LHOG ZRXOG YDOLGDWH WKH WKHRU\ WKDW PD\ EH XVHG DV DQ HOHFWURSKLOLF DPLQDWLQJ DJHQW UHTXLULQJ RQH HTXLYDOHQW RI QXFOHRSKLOHf 7KH SRRU \LHOG ZDV VSHFXODWHG WR EH GXH WR D FRPELQDWLRQ RI WKH IROORZLQJ IDFWRUV Lf 7KH VORZ IRUPLQJ *ULJQDUG D PD\ QRW KDYH EHHQ IXOO\ DFWLYH WKHUHIRUH RQH IXOO HTXLYDOHQW PD\ QRW KDYH EHHQ XVHG LLf ,W LV NQRZQ IURP OLWHUDWXUH UHSRUWV >-$@ WKDW WKH \LHOGV RI DPLQHV LQ WKH UHDFWLRQV RI 6FKLII EDVHV LPLQHVf ZLWK *ULJQDUGV DUH OHVV WKDQ b ZKHQ D UDWLR RI 50J;6FKLII EDVH LV HPSOR\HG DOWKRXJK TXDQWLWDWLYH \LHOGV PD\ EH REWDLQHG ZKHQ UDWLRV DUH HPSOR\HG 7KLV VXJJHVWV WKDW RQO\ KDOI RI WKH DYDLODEOH 5 JURXSV DUH XWLOL]HG LQ WKH DGGLWLRQ RI D *ULJQDUG UHDJHQW DFURVV WKH & 1 GRXEOH ERQG RI WKH 6FKLII EDVH LPLQHf LLLf 7KH UHDFWLRQ PD\ KDYH SURFHHGHG WR FRQVLGHUDEOH H[WHQW EXW LQDGHTXDWH WHFKQLTXH IRU LVRODWLRQ RI WKH FORVH HOXWLQJ VSRWV RU GHFRPSRVLWLRQ RQ WKH FROXPQ PD\ OHDG WR SRRU LVRODWHG \LHOGV ,Q DQ DWWHPSW WR SURYH RU GLVSURYH IDFWRUV Lf DQG LLf WKH UHDFWLRQ 6FKHPH f ZDV UHSHDWHG XVLQJ HT RI *ULJQDUG UHDJHQW ,W ZDV H[SHFWHG WKDW WKH H[FHVV RI QXFOHRSKLOH ZRXOG LPSURYH WKH DPRXQW RI GHVLUHG SURGXFW IRUPHG 8QIRUWXQDWHO\ QRQH RI WKH GHVLUHG SURGXFW ZDV GHWHFWHG $QDO\VLV RI WKH UHDFWLRQ PL[WXUH E\ 06 UHYHDOHG WKUHH PDLQ SURGXFWV Lf 5W PLQV P] bf LLf 5W PLQV P] bf LLLf 5W PLQV P] bf

PAGE 111

7KH SHDN DW 5W PLQV ZDV GHWHUPLQHG WR EH WKH GLPHU DV PHQWLRQHG SUHYLRXVO\f 7KH VLJQLILFDQW DPRXQW bf RI GLPHU SUHVHQW LQGLFDWHG WKDW WKH *ULJQDUG SUHSDUHG ZDV QRW ZHOO IRUPHG %DVHG XSRQ WKH UHDFWDQWV DQG UHDFWLRQ FRQGLWLRQV WKH SHDNV DW 5W DQG PLQV ZHUH GHWHUPLQHG WR FRPSRXQGV D DQG UHVSHFWLYHO\ &RPSRXQG D LQGLFDWHV WZR PDVV XQLWV KLJKHU P] f WKDQ WKH H[SHFWHG LPLQH D VXJJHVWLQJ WKH UHGXFHG VWUXFWXUH LQGLFDWHG 7KH RGG PROHFXODU LRQ VXJJHVWHG WKH SUHVHQFH RI D VLQJOH QLWURJHQ RU DQ RGG QXPEHU RI QLWURJHQV &RPSRXQGV ZLWK LWV PDVV DW P] VXJJHVWHG WKH DEVHQFH RI QLWURJHQ RU WKH SUHVHQFH RI DQ HYHQ QXPEHU RI QLWURJHQV DQG ZDV GHWHUPLQHG WR EH WKH VXEVWLWXWHG IOXRUHQRQH $QRWKHU DWWHPSW RI WKH UHDFWLRQ LQGLFDWHG WKH DERYH SURGXFWV WR EH IRUPHG LQ b Df DQG b f E\ *&06 &+0H &+0H RU r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

PAGE 112

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f WKH GHVLUHG LPLQH D ZKLFK ZDV QRW WKH PDMRU SURGXFW DQG LLf IOXRUHQRQH f+IOXRUHQDPLQH f 7KH FRPSRQHQW LGHQWLILHG DV LPLQH D ZDV REVHUYHG DV D VKDUS SHDN DW 5W PLQV ZLWK WKH PROHFXODU LRQ DV EDVH SHDN DW P] 7KH RWKHU FRPSRQHQW KDG D UHWHQWLRQ WLPH 5W PLQVf FRUUHVSRQGLQJ WR IOXRUHQRQH f EXW KDG D ZHDN 0 DW P] ZLWK EDVH SHDN 0 DW P] 7KH 0 P] f FRXOG EH LQWHUSUHWHG DV WKH 0 RI IOXRUHQRQH 'XH WR WKH ODFN RI VXFFHVV ZLWK FROXPQ FKURPDWRJUDSK\ D WHGLRXV VHSDUDWLRQ ZDV DWWHPSWHG XVLQJ SUHSDUDWLYH 7/& 7KHUH ZDV VRPH VHSDUDWLRQ RI WKH GHVLUHG SURGXFW D LQ YHU\ SRRU \LHOG $ VPDOO DPRXQW RI GDUN \HOORZ FU\VWDOV ZHUH UHFRYHUHG WKH VHFRQG EDQG IRUP WKH VROYHQW IURQWf $QDO\VLV E\ 105 IXUWKHU FRQILUPHG WKH D]RSKLOLF GHVLUHG SURGXFW D VHH ([SHULPHQWDOf r+ 105 UHYHDOHG D FRPSOH[ VSOLWWLQJ SDWWHUQ UHSUHVHQWDWLYH RI WZHOYH

PAGE 113

DURPDWLF SURWRQV ZKLOH WKH & VSHFWUXP GLVSOD\HG WZHOYH FDUERQV 7KH PRVW GHVKLHOGHG FDUERQ ZDV REVHUYHG DW SSP DQG ZDV LQWHUSUHWHG DV WKH LPLQH FDUERQ 8QIRUWXQDWHO\ WKHUH ZDV QRW HQRXJK PDWHULDO UHFRYHUHG IURP WKH VHSDUDWLRQ WR WHOO GHILQLWLYHO\ EHWZHHQ DQG E\ 105 2WKHU ORZHU VSRWV ZHUH UHFRYHUHG DV D FRPSOH[ PL[WXUH ZKLFK WKH 105 LQGLFDWHG WR EH PRVWO\ DURPDWLF P] 7KH UHDFWLRQ XQGHU DUJRQ JDV ZDV DOVR TXHQFKHG ZLWK 0H2+ 6FKHPH f *&06 DQDO\VLV LQGLFDWHG b RI WKH GHVLUHG D]RSKLOLF SURGXFW D 5W PLQV P] f b RI DQ XQNQRZQ 5W PLQV P] EDVH SHDN P] f DQG b RI P] LGHQWLILHG DV +IOXRUHQLPLQH f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r+ 105 VXSSRUWHG LGHQWLILFDWLRQ RI +IOXRUHQLPH f $ + WULSOHW ZDV REVHUYHG DW SSP DQG WZR + GRXEOHWV ZHUH REVHUYHG DW DQG SSP $GGLWLRQDO VHSDUDWLRQ RI WKHVH FORVH UXQQLQJ VSRWV E\ +3/& ZDV IXWLOH

PAGE 114

PW] 3UHYLRXV ZRUN E\ .DW]HQHOOHQERJHQ DQG FRZRUNHUV >-2&@ LQGLFDWHV WKDW ZLWK IOXRUHQLPLQHV FDUERSKLOLF DQG D]RSKLKF DWWDFN DUH FRPSHWLQJ UHDFWLRQV :LWK Q EXW\OOLWKLXP Q%X/LfDV WKH QXFOHRSKLOH ZKHQ WKH QLWURJHQ VXEVWLWXHQW LQ WKH LPLQH LV DOLSKDWLF H[FOXVLYH D]RSKLOLF DWWDFN RFFXUV ,Q FRQWUDVW ZKHQ WKH QLWURJHQ VXEVWLWXHQW LQ WKH LPLQH LV DURPDWLF WKH DPRXQW RI D]RSKLOLF DWWDFN GHFUHDVHV DV ORZ DV bf DQG WKH DPRXQW RI FDUERSKLOLF DWWDFN EHFRPHV VLJQLILFDQW 6XFK PD\ EH WKH FDVH ZLWK LPLQH ZKHUH WKH WULD]ROH ULQJ LV DQ DURPDWLF PRLHW\ 7KH VHFRQG HOHFWURSKLOLF DQLPDWLRQ UHDFWLRQ ZDV SHUIRUPHG ZLWK EHQ]\OPDJQHVLXP FKORULGH Ef 6FKHPH f &ROXPQ FKURPDWRJUDSKLF VHSDUDWLRQ OHG WR WKH LVRODWLRQ RI b RI SURGXFW 7KH FRPSRXQG KDV EHHQ LGHQWLILHG DV E EDVHG XSRQ LWV + 105 VSHFWUXP ZKLFK GLVSOD\V D WRWDO RI + RI ZKLFK DUH REVHUYHG LQ WKH DURPDWLF UHJLRQ SSPf 7KH GHVLUHG LPLQH E KDV EHHQ UXOHG RXW EHFDXVH LW ZRXOG GLVSOD\ D WRWDO RI + ZLWKLQ WKH VDPH UHJLRQ 7KH WZR DGGLWLRQDO SURWRQV REVHUYHG LQ WKH DURPDWLF UHJLRQ PD\ EH DQ 1+ JURXS ,Q WKH + 105 VSHFWUXP WKH PHWK\OHQH + VLQJOHW LV REVHUYHG DW SSP 6WUXFWXUH D KDV DOVR EHHQ H[FOXGHG EHFDXVH LW ZRXOG GLVSOD\ D + VLQJOHW EHWZHHQ DQG SSP ZKLFK ZDV QRW REVHUYHG 7KH & 105 VKRZV D SURPLQHQW SHDN DERXW SSP ZKLFK PD\ LQGLFDWH D &1 FDUERQ ZKLOH WKH PHWK\OHQH FDUERQ LV FOHDUO\ YLVLEOH DW SSP

PAGE 115

[&+3K 3K&+0J&, WROXHQH UHIOX[ E E &+3K &+3K  D P] E 6FKHPH ,Q DQ HIIRUW WR JHQHUDWH WKH GHVLUHG SURGXFW WKH UHDFWLRQ ZDV UHSHDWHG XVLQJ HT RI *ULJQDUG $V ZLWK WRO\OPDJQHVLXP EURPLGH WKHUH ZDV D PL[WXUH RI ILYH SURGXFW VSRWV HOXWLQJ WRJHWKHU 7KH VHFRQG DQG WKLUG VSRWV UDQ WRJHWKHU DQG QR GHILQLWLYH LGHQWLILFDWLRQ FRXOG EH PDGH 7KH ILUVW VSRW 5I f LVRODWHG LQ b ZDV GHWHUPLQHG WR EH WKH GLPHU E\SURGXFW RI WKH *ULJQDUG E $ VKDUS + VLQJOHW DW SSP LQGLFDWHV WKH PHWK\OHQH SURWRQV ZKLOH D PXOWLSOHW LV REVHUYHG LQ WKH DURPDWLF UHJLRQ VXJJHVWLQJ D PRQRVXEVWLWXWHG EHQ]HQH ,Q WKH & 105 WKH PHWK\OHQH FDUERQ LV REVHUYHG DW SSP ZLWK ILYH DURPDWLF FDUERQV UDQJLQJ IURP WKURXJK SSP *&06 DQDO\VLV LQGLFDWLQJ D PROHFXODU LRQ RI P] OHG XV WR WKH ELEHQ]\O VWUXFWXUH VLQFH WKH EHQ]HQH ULQJ DQG WKH PHWK\OHQH JURXS LGHQWLILHG IURP WKH 105 DFFRXQWV IRU RQO\ KDOI WKH PDVV P] f ,VRODWLRQ RI WKLV GLPHU LQGLFDWHV WKDW WKH *ULJQDUG UHDJHQW ZDV QRW IXOO\ DFWLYH

PAGE 116

6SRW IRXU 5I f D VLQJOH VSRW E\ 7/& SURYHG WR EH D PL[WXUH RI WZR FRPSRQHQWV E\ *&06 )XUWKHU LQYHVWLJDWLRQ E\ 105 VXSSRUWHG WZR FRPSRXQGV ZKLFK ZHUH GHWHUPLQHG WR EH WKH GHVLUHG D]RSKLOLF SURGXFW E DQG LWV UHGXFHG GHULYDWLYH D 6FKHPH f ,Q WKH SURWRQ 105 WKH PHWK\OHQH SURWRQV ZHUH REVHUYHG DW SSP DV D VKDUS + VLQJOHW +RZHYHU LW ZDV HYLGHQW WKH GHVLUHG SURGXFW ZDV QRW WKH RQO\ SURGXFW SUHVHQW $ + GRXEOHW RI VLQJOHWV ZDV REVHUYHG DERXW SSP VXJJHVWLQJ D &+f DQG WKH FRPSOH[ DURPDWLF UHJLRQ LQWHJUDWHG + LQVWHDG RI + 7KH FDUERQ VSHFWUXP DOVR VXSSRUWHG WZR FRPSRXQGV EXW ZLWK D FDUERQ FOHDUO\ YLVLEOH DW SSP LQWHUSUHWHG DV WKH LPLQR FDUERQ )XUWKHU DQDO\VLV E\ *&06 FRQILUPHG ZKDW ZDV LQGLFDWHG E\ WKH 105 7KHUH ZDV D PL[WXUH RI WZR FRPSRQHQWV LQ D UDWLR RI 7KH PDMRU FRPSRQHQW ZDV WKH GHVLUHG LPLQHE ZLWK D PROHFXODU LRQ RI P] 5W PLQVf DQG WKH PLQRU FRPSRQHQW ZDV GHWHUPLQHG WR EH WKH UHGXFHG GHULYDWLYH Df DW WZR PDVV XQLWV KLJKHU P] 5W PLQVf 6SRW ILYH 5I f ZDV LQWHUSUHWHG WR EH P] f E\ 105 EXW WKH *&06 UHYHDOHG P] 5W PLQVf ZKLFK PD\ EH WKH DOFRKRO SURGXFW 7KH & 105 GLVSOD\HG WZHOYH GLIIHUHQW FDUERQV ,Q FRPSOLDQFH ZLWK WKH *&06 WKH FDUERQ SHDN DW SSP LV PRUH VXJJHVWLYH RI D FDUERQ ERQGHG WR DQ R[\JHQ DQG GHVKLHOGHG E\ DQ DURPDWLF V\VWHP 7KLV SURGXFW IURP WKH UHDFWLRQ RI WKH *ULJQDUG ZLWK IOXRUHQRQH VXJJHVWV WKH SUHVHQFH RI IOXRUHQRQH f DV D UHDFWDQW P] P]

PAGE 117

7KH ORQH DWWHPSW WR JHQHUDWH WKH GRGHF\OLPLQH F ZDV XQVXFFHVVIXO LQ IRUPLQJ WKH GHVLUHG SURGXFW 6FKHPH f 2QFH DJDLQ XVLQJ WKH VWDUWLQJ LPLQH DGGHG YLD D 6R[KOHW H[WUDFWRUf UHIOX[HG LQ WROXHQH DQG WKH *ULJQDUG HTf IRUPHG LQ (W WKH UHDFWLRQ ZDV DOORZHG WR UHDFW IRU K 7KH UHDFWLRQ PL[WXUH IRUPHG D EHDXWLIXO RUDQJHUHG FRORU 4XHQFKLQJ ZLWK 0H2+ SURGXFHG D VWURQJHU UHG FRORU &RQFHQWUDWLRQ RI WKH UHDFWLRQ PL[WXUH OHG WR SUHFLSLWDWLRQ RI D EULJKW RUDQJH VROLG r+ 105 DQDO\VLV RI WKH VROLG OHG WR VWUDQJH UHVXOWV 7KH VROLG RQO\ SDUWLDOO\ VROXEOH LQ &'&, GLVSOD\V D ZHOO UHVROYHG DOLSKDWLF UHJLRQ ZLWK D + PXOWLSOHW DW SSP DQG D EURDG VLQJOHW DW SSP } +f VXJJHVWLQJ WKH SUHVHQFH RI WKH GRGHF\O FKDLQ +RZHYHU ZKHQ REWDLQHG LQ '062G D ZHOO UHVROYHG DURPDWLF UHJLRQ ZDV GLVSOD\HG LQGLFDWLQJ WULD]ROH &+V DQG SSPf DQG D KLJKO\ DURPDWLF SURGXFW ,Q WKLV FDVH WKH DOLSKDWLF UHJLRQ DSSHDUV DV D VHULHV RI EURDG VLQJOHWV +5 06 DQDO\VLV RI WKH UHG VROLG UHYHDOHG WKH 0O DW P] ZLWK DQ HOHPHQWDO FRPSRVLWLRQ RI &+1 7KLV IRUPXOD LQGLFDWHG LV RQH XQLW KLJKHU WKDQ WKH VWUXFWXUH SURSRVHG IRU FRPSRXQG &+1f VHH 6FKHPH f 7KH SUHVHQFH RI IRXU QLWURJHQV VXJJHVWHG WKDW WKH WULD]ROH JURXS ZDV VWLOO LQ SODFH 7KH EDVH SHDN ZDV REVHUYHG DW P] &+1f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f 7KHUH ZDV QR

PAGE 118

,OO LQFRUSRUDWLRQ RI D + PHWK\O VLQJOHW DERXW SSP DQG D VKDUS + VLQJOHW DW SSP ZDV D FOHDU LQGLFDWLRQ IRU WKH SUHVHQFH RI WKH WULD]ROH PRLHW\ 7KH & 105 LQGLFDWHG RQO\ DURPDWLF FDUERQV RI WKH VWDUWLQJ LPLQH VHH (VSHULPHQWDOf $ 1 WROXHQH 91 &f+AAA & A UHIOX[ K 1 LL &L+ & RU D P] 6FKHPH n n E 0H0J%U WROXHQH UHIOX[ K G G 6FKHPH 6WLOO LQYHVWLJDWLQJ WKH SDWWHUQ RI UHDFWLYLW\ IRU WKH DOLSKDWLF QXFOHRSKLOHV Q EXW\OPDJQHVLXP EURPLGH ZDV XVHG 7KH r+ 105 REWDLQHG LQ '062GJf RI WKH UHGLVK VROLG LVRODWHG VXJJHVWHG D KLJKO\ DURPDWLF SURGXFW 6XUSULVLQJO\ D + VLQJOHW DW SSP LQGLFDWHG WKH SUHVHQFH RI WULD]ROH &+V ZKLOH D + VLQJOHW DERXW SSP VXJJHVWHG WKH PHWK\O RI WKH DOLSKDWLF JURXS +5 06 RI WKH UHGLVK VROLG LVRODWHG GLVSOD\HG DQ 0 RI P] &+1f QRW WKH GHVLUHG LPLQH H P] &+1f QRU WKH DGGLWLRQ SURGXFW P] &+1f 6FKHPH f

PAGE 119

&+0J%U H WROXHQH UHIOX[ K H P] 1 1 b? RU D P] E 6FKHPH %DVHG XSRQ .DW]HQHOOHQERJHQnV ILQGLQJV >-2&@ WKH UHDFWLRQ ZDV FRQGXFWHG ZLWK L%X/L HTf :H ZDQWHG WR LQYHVWLJDWH WKH HIIHFW RI WKH PHWDO FDWLRQ RQ WKH SURGXFW IRUPDWLRQ LQ WKH UHDFWLRQ :LWK m%X/L DQG IOXRUHQLPLQHV 15f WKH PDMRU SURGXFW WHQGV WR EH IURP D]RSKLOLF DGGLWLRQ ZKHQ 5 LV DOLSKDWLF DQG FDUERSKLOLF ZKHQ 5 LV DURPDWLF >-2&@ &UXGH 105 VXJJHVWHG WKDW DOO WKH VWDUWLQJ LPLQH ZDV FRQVXPHG +RZHYHU *&06 GLG QRW LQGLFDWH WKH H[SHFWHG SURGXFW H EXW LQVWHDG D FRPSOH[ PL[WXUH RI SURGXFWV SDUWLFXODUO\ WKH GLVXEVWLWXWHG SURGXFW ZLWK P] 7KDW LV PDQ\ RWKHU SURGXFWV GLVSOD\HG D PROHFXODU LRQ RI P] ZLWK YDU\LQJ EDVH SHDNV ([FHVV RI WKH QXFOHRSKLOH DFFRXQWV IRU WKH ELV DGGLWLRQ SURGXFW 6FKHPH f :LWK WKH SURPLVLQJ UHVXOWV IURP WKH H[FHVV QXFOHRSKLOH WKH UHDFWLRQ ZDV UHSHDWHG ZLWK D VLQJOH HTXLYDOHQW RI Q%X/L 6LQFH H[FHVV Q%X/L OHG WR ELV DGGLWLRQ WKHQ D VLQJOH HTXLYDOHQW VKRXOG RIIHU PRQR DGGLWLRQ DQG KHOS GHWHUPLQH ZKHWKHU D]RSKLOLF RU FDUERSKLOLF DWWDFN ZDV GRPLQDQW 8QIRUWXQDWHO\ DIWHU K *&06 VXJJHVWHG YDULRXV FDUERSKLOLF DGGLWLRQ SURGXFWV P] f IOXRUHQRQH P] f f DQG IOXRUHQLPLQH P] f f VHH SUHYLRXVf EXW QRQH RI WKH GHVLUHG LPLQH SURGXFW H 7KH

PAGE 120

UHDFWLRQ ZDV WKHQ DOORZHG WR UHIOX[ IXUWKHU DQG *&06 DQDO\VLV DIWHU K LQGLFDWHG WKH VDPH VHULHV RI FDUERSKLOLF SURGXFWV DQG RQO\ D WUDFH RI WKH GHVLUHG LPLQH SURGXFW bf D P] 6FKHPH Q%X/L WROXHQH UHIOX[ &+nQ[&+ :LWK WKH VXUSULVLQJ DQG XQH[SHFWHG UHVXOWV IURP WKH DERYH HOHFWURSKLOLF DPLQDWLRQ UHDFWLRQV ZH FRQFOXGHG WKH HOHFWURSKLOLF DPLQDWLRQ LQYHVWLJDWLRQV DQG IRFXVHG WKHQ XSRQ WKH GHULYDWL]DWLRQ RI DPLQRWULD]ROH f XVLQJ EHQ]RWULD]ROH PHWKRGRORJ\ ,W VKRXOG EH QRWHG KHUH WKDW WKH GDWD UHSRUWHG LV SUHOLPLQDU\ WKHUHIRUH WKH \LHOGV DQG SURFHGXUHV UHSRUWHG KDYH QRW EHHQ RSWLPL]HG +RZHYHU WKH UHVXOWV DUH H[WUHPHO\ SURPLVLQJ $IWHU D QXPEHU RI SUHYLRXV XQVXFFHVVIXO DWWHPSWV EHQ]RWULD]ROO \OPHWK\ODPLQRfWULD]ROH f ZDV HYHQWXDOO\ V\QWKHVL]HG E\ UHIOX[LQJ DPLQR WULD]ROH f DQG K\GUR[\PHWK\OHQHEHQ]RWULD]ROH f LQ (W2+ 6FKHPH f 7KH UHDFWLRQ DSSHDUV WR EH D VORZ RQH VLQFH RQO\ b \LHOG RI SURGXFW LV LVRODWHG DIWHU WZR GD\V RI UHIOX[LQJ bf 6FKHPH

PAGE 121

7KH SURGXFW ZDV FRQILUPHG E\ r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f WULD]ROHV $OO SURGXFWV ZHUH FRQILUPHG E\ 105 DQG +5 06 7RO\OPHWK\ODPLQRfWULD]ROH Df ZDV V\QWKHVL]HG IURP EHQ]RWULD]ROOPHWK\ODPLQRfOWULD]ROHf DQG WRO\OPDJQHVLXP EURPLGH Df $OGULFKf 6FKHPH f 5HPRYDO RI WKH EHQ]RWULD]ROH E\SURGXFW LV QRUPDOO\ GRQH E\ ZDVKLQJ WKH RUJDQLF OD\HU ZLWK DTXHRXV 1D2+ KRZHYHU ERWK WKH WULD]ROH SURGXFW DQG WKH EHQ]RWULD]ROH E\SURGXFW PD\ EH UHPRYHG WKLV ZD\ DQG FROXPQ FKURPDWRJUDSK\ ZDV XVHG DV WKH PHWKRG RI SXULILFDWLRQ -+ DQG & 105 FRQILUPHG WKH GHVLUHG GHULYDWLYH D r+ 105 GLVSOD\V WKH PHWK\O SURWRQV RI WKH DU\O JURXS D + VLQJOHW DW WKHLU FKDUDFWHULVWLF SSP ZKLOH WKH PHWK\OHQH SURWRQV DUH VHHQ DV D + VLQJOHW DW SSP 7KH SKHQ\O &+V DUH VHHQ DV D SDLU RI GRXEOHWV UDQJLQJ IURP WR SSP ZKLOH WKH WULD]ROH &+V DUH REVHUYHG DW SSP ,Q WKH & 105 WKH PHWK\O FDUERQ LV VHHQ DW SSP WKH PHWK\OHQH FDUERQ DW SSP DQG WKH WULD]ROH &+V DW SSP UHVSHFWLYHO\ +5 06 GLVSOD\V WKH PROHFXODU LRQ DW P] ZLWK DQ HOHPHQWDO FRPSRVLWLRQ RI &+1 7KH EDVH SHDN ZDV REVHUYHG DW P] &+f DQG VXSSRUWV WKH ORVV RI WKH DPLQR WULD]ROH PRLHW\

PAGE 122

1 1 ? 7+) UHIOX[ 11 O? 1 50J; Z K A -! 1 +1 A%W +1A5 DHK D H (QWU\ 5 ; (D RI 50H; b \LHOG Lf D WRO\O %U LLf E L3U &O LLLf F W%X &O LYf G 0H &O FUXGHf Yf H Q%X %U FUXGHf 6FKHPH 0HWK\OOSURS\ODPLQRfWULD]ROH E ZDV V\QWKHVL]HG XVLQJ DQG LVRSURS\O PDJQHVLXP FKORULGH If $OGULFKf6FKHPH f 7KH LVRODWHG \LHOG DIWHU FROXPQ FKURPDWRJUDSK\ ZDV RQO\ b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fOWULD]ROH F ZDV DWWHPSWHG XVLQJ DQGIEXW\OPDJQHVLXP FKORULGH Jf $OGULFKf DFFRUGLQJ WR WKH SUHYLRXVO\ PHQWLRQHG SURFHGXUH 7KH LVRODWHG \LHOG DIWHU FROXPQ FKURPDWRJUDSK\ ZDV b 7KH SURWRQ 105 GLVSOD\V GRXEOH SHDNV ZKLFK PD\ VXJJHVW D PL[WXUH RI FRPSRXQGV 7KH -+ 105 LQGLFDWHV LQGLFDWHV D GRXEOHW DW SSP ZKLFK ZDV H[SHFWHG WR DSSHDU DV D VLQJOHW IRU WKH WEXW\O SURWRQV $OVR WKH & 105 LQGLFDWHV D FRUUHVSRQGLQJ

PAGE 123

VHW RI FDUERQV DW SSP DQG SSP ZKLFK VHHPV WR LQGLFDWH WZR EXW\O JURXSV RU QRQHTXLYDOHQW PHWK\OV RI RQH W%X JURXS 7KHUH DUH DOVR WZR SHDNV LQ WKH UHJLRQ ZKLFK ZDV H[SHFWHG WR LQGLFDWH D VLQJOH SHDN IRU WKH WULD]ROH &+V +5 06 DQDO\VLV RI WKH LVRODWHG FRPSRXQG UHYHDOHG D PL[WXUH EXW WKH PDMRU FRPSRXQG GLVSOD\V LWV PROHFXODU LRQ DW P] &+1f ZKLFK ZRXOG VXJJHVW WKH GHVLUHG FRPSRXQG F ZLWK D VLQJOH W%X JURXS (WK\ODPLQRfWULD]ROH Gf ZDV V\QWKHVL]HG XVLQJ DQG PHWK\OPDJQHVLXP FKORULGH Kf $OGULFKf VHH 6FKHPH f 3XULILFDWLRQ ZDV DWWHPSWHG E\ ZDVKLQJ ZLWK 1D2+ bf VLQFH WKH \LHOGV LVRODWHG IURP FROXPQ VHSDUDWLRQ ZHUH TXLWH ORZ 8QIRUWXQDWHO\ DIWHU LVRODWLQJ b FUXGH \LHOG ZDVKLQJ ZLWK 1D2+ UHVXOWHG LQ DERXW PJ RI SXUH SURGXFW -+ DQG & 105 FRQILUP WULD]ROH G ZKLFK DJUHHV ZHOO ZLWK WKDW UHSRUWHG LQ WKH OLWHUDWXUH >-2&@ 7KH PHWK\O + VLQJOHW ZDV REVHUYHG DW SSP VDPH IRU WKH OLWHUDWXUHf ZKLOH WKH PHWK\OHQH + TXLQWHW ZDV REVHUYHG DW SSP D + TXDUWHW IRU WKH OLWHUDWXUHf 7KH WULD]ROH + VLQJOHW REVHUYHG DW SSP DUH IRXQG DW SSP LQ WKH OLWHUDWXUH 7KH WULD]ROH FDUERQV ZHUH REVHUYHG DW SSP LQ WKH & 105 3HQW\ODPLQRfOWULD]ROH Hf ZDV V\QWKHVL]HG XVLQJ DQG Q EXW\OPDJQHVLXP EURPLGH Hf V\QWKHVL]HGf VHH 6FKHPH f $V ZLWK G SXULILFDWLRQ RI WKLV FRPSRXQG ZDV DWWHPSWHG YLD ZDVKLQJ ZLWK DTXHRXV 1D2+ $Q LVRODWHG \LHOG RI b VWLOO VKRZHG WUDFHV RI WKH EHQ]RWULD]ROH E\SURGXFW +RZHYHU r+ DQG & 105 FRQILUP WKH IRUPDWLRQ RI WULD]ROH H r+ 105 GLVSOD\V WKH PHWK\O SURWRQV DW SSP DV D WULSOHW ZKLOH WKH PHWK\OHQH HQYHORSH +f LV REVHUYHG DV D PXOWLSOHWDW SSP DQG WKH PHWK\OHQH SURWRQV DOSKD WR WKH 1+ DUH VHHQ DW SSP DV D WULSOHW $OVR ERWK WKH 1+ DQG WKH WULD]ROH SURWRQV DUH VHHQ DV VLQJOHWV DW SSP DQG SSP UHVSHFWLYHO\ 0HWK\O DPL QRf WULD]ROH If FDQQRW EH REWDLQHG YLD QXFOHRSKLOLF GLVSODFHPHQW RI EHQ]RWULD]ROH E\ D *ULJQDUG UHDJHQW WKHUHIRUH UHGXFWLRQ ZLWK 1D%+ ZDV

PAGE 124

DWWHPSWHG 6FKHPH f &UXGH r+ DQG & 105 LQGLFDWHG WKH GHVLUHG SURGXFW I ZKLFK FRUUHODWHV ZHOO WR WKDW UHSRUWHG LQ WKH OLWHUDWXUH >-2&@ 7KH PHWK\O + VLQJOHW DQG WKH WULD]ROH + VLQJOHW ZHUH REVHUYHG DW DQG SSP UHVSHFWLYHO\ LQ WKH + 105 7KH PHWK\O DQG WULD]ROH FDUERQV ZHUH GLVSOD\HG DW SSP DQG SSP UHVSHFWLYHO\ LQ WKH & 105 11 1 (W2+ UHIOX[ 1D%+ +1 %W 11 1 +1 &+ I 6FKHPH &RQFOXVLRQV L9O7ULD]RO\OfIOXRUHQLPLQHf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

PAGE 125

QXFOHRSKLOLF SURGXFWV +RZHYHU VZLWFKLQJ WR 7+) DQG $U GLG QRW GHFUHDVH WKH QXPEHU RU WKH FRPSOH[LW\ RI SURGXFWV IRUPHG :LWK DURPDWLF *ULJQDUGV LW DSSHDUV WKDW D]RSKLOLF DQG FDUERSKLOLF DWWDFN DUH FRPSHWLQJ UHDFWLRQV :KHQ D]RSKLOLF DWWDFN RFFXUV RQ WKH LPLQH 1f VXEVHTXHQW UHGXFWLRQ SRVVLEO\ E\ WKH *ULJQDUG UHDJHQWf RI WKH FRUUHVSRQGLQJ LPLQH PD\ H[SODLQ IRUPDWLRQ RI WKH IOXRUHQ\O DPLQH 2Q WKH RWKHU KDQG LW ZDV WKRXJKW WKDW ZKHQ FDUERSKLOLF DWWDFN RFFXUUHG ERWK WKH LPLQH 1 DQG WKH WULD]ROH JURXS DUH UHPRYHG EXW WKRVH SURGXFWV ZLWKRXW 1 PD\ EH IURP WKH UHDFWLRQ RI IOXRUHQRQH :LWK DOLSKDWLF *ULJQDUGV VSHFLILFDOO\ GRGHF\OPDJQHVLXP EURPLGH +5 06 FRQILUPV WKDW DWWDFN LV RFFXUULQJ ZLWK UHWHQWLRQ RI WKH LPLQH 1 DQG WKH WULD]ROH V\VWHP &RPPHUFLDO *ULJQDUGV ZHUH XVHG DQG VLPLODU UHVXOWV ZHUH REWDLQHG DV ZKHQ V\QWKHVL]HG QXFOHRSKLOHV ZHUH XVHG 6LQFH WKH GHVLUHG SURGXFWV ZHUH QRW IRUPHG LQ VLJQLILFDQW DPRXQWV QXPHURXV DWWHPSWV KDYH EHHQ PDGH WR LVRODWH DQG FKDUDFWHUL]H WKRVH SURGXFWV ZKLFK ZHUH 7KHVH DWWHPSWV KDYH EHHQ ZLWKRXW PXFK VXFFHVV ([FHVV HTXLYDOHQWV RI QXFOHRSKLOH OHDG WR WKH IRUPDWLRQ RI GLIIHUHQW SURGXFWV DQG QRW DQ LQFUHDVH LQ WKH DPRXQW RI GHVLUHG SURGXFW IRUPHG *&06 KDV EHHQ XVHG IRU WKH HOXFLGDWLRQ DQG FRQILUPDWLRQ RI PDQ\ RI WKH DERYH UHVXOWV ,W VKRXOG EH QRWHG WKDW WKLV PHWKRG LV QRW D XVHIXO V\QWKHWLF SURFHGXUH )RU WKH VHFRQG SDUW RI WKLV FKDSWHU EHQ]RWULD]ROH PHWKRGRORJ\ KDV EHHQ IRUPXODWHG IRU WKH V\QWKHVLV RI DON\O DPL QRfWULD]ROHV %HQ]RWULD]ROO\OPHWK\ODPLQRf WULD]ROH f ZDV V\QWKHVL]HG LQ b LVRODWHG \LHOG 7KH QXFOHRSKLOLF GLVSODFHPHQW ZLWK YDULRXV *ULJQDUGV KDYH UHVXOWHG LQ TXLWH SRVLWLYH WKRXJK SUHOLPLQDU\ UHVXOWV 7RO\OPHWK\ODPLQRfWULD]ROH Df DQG PHWK\OOSURS\ODPLQRf WULD]ROH Ef KDYH EHHQ V\QWKHVL]HG LQ b DQG b UHVSHFWLYHO\ 7KH FRPSRXQG LVRODWHG DV GLPHWK\OSURS\ODPLQRfWULD]ROH Ff ZDV YHULILHG E\ *&06 DV FRQWDLQLQJ D VLQJOH WEXW\O JURXS (WK\ODPLQRfWULD]ROH Gf DQG SHQW\ODPLQRfWULD]ROH Hf ZHUH SXULILHG E\ DTXHRXV ZDVKLQJV

PAGE 126

DQG OHG WR ORZHU \LHOGV WKDQ ZLWK FROXPQ 0HWK\ODPLQRfWULD]ROH f ZDV LVRODWHG DV WKH FUXGH PDWHULDO ([SHULPHQWDO *HQHUDO 0HOWLQJ SRLQWV ZHUH REWDLQHG XVLQJ D 7KRPDV +RRYHU FDSLOODU\ PHOWLQJ SRLQW DSSDUDWXV DQG DUH XQFRUUHFWHG + 105 VSHFWUD ZHUH UHFRUGHG HLWKHU RQ D 9DUDQ 9;5 0+]f *HPLQL 0+]f RU *HQHUDO (OHFWULF 4( 0+]f VSHFWURPHWHU & 105 ZHUH UHFRUGHG DW 0+] RQ WKH VDPH LQVWUXPHQWV &KHPLFDO VKLIWV f DUH UHSRUWHG LQ SDUWV SHU PLOOLRQ SSPf GRZQILHOG IURP WHWUDPHWK\OVLODQH 706f DV WKH LQWHUQDO VWDQGDUG &RXSOLQJ FRQVWDQWV YDOXHVf DUH UHSRUWHG LQ +] 5HDFWLRQV ZHUH SHUIRUPHG LQ DQ LQHUW DWPRVSKHUH XQGHU DUJRQ RU QLWURJHQ JDV XVLQJ RYHQGULHG JODVVZDUH 6ROXWLRQV DQG DQK\GURXV OLTXLG UHDJHQWV ZHUH GULHG SULRU WR XVH GLHWK\O HWKHU (Wf WHWUDK\GURIXUDQ 7+)f DQG WROXHQH ZHUH GLVWLOOHG RYHU VRGLXP EHQ]RSKHQRQH NHW\O $QDO\WLFDO WKLQ OD\HU FKURPDWRJUDSK\ HOXHQW KH[DQHVHWKHUf ZDV SHUIRUPHG XVLQJ SUHFRDWHG VLOLFD JHO ) SODVWLF SODWHV PP WKLFN XVLQJ LRGLQH DV DQ LQGLFDWRU 3UHSDUDWLYH 7/& ZDV SHUIRUPHG RQ VLPLODU JODVV SODWHV (OHPHQWDO DQDO\VHV DQG KLJK UHVROXWLRQ PDVV VSHFWURPHWU\ ZHUH SHUIRUPHG RQ VLWH DW WKH DQDO\WLFDO IDFLOLW\ /RZ UHVROXWLRQ PDVV VSHFWURPHWU\ ZHUH SHUIRUPHG RQ D +HZOHWW 3DFNDUG 6HULHV ,, *DV &KURPDWRJUDSK 6HULHV 0DVV 6HOHFWLYH 'HWHFWRU 9/7QD]ROYOfIOXRUHQLPLQH f )OXRUHQRQH J PROf DPLQRWULD]ROH J PROf DQG ERURQ WULIOXRULGH HWKHUDWH POf ZDV UHIOX[HG LQ FKORURIRUP P/f IRU K $IWHU FRROLQJ WR URRP WHPSHUDWXUH WKH FKORURIRUP ZDV UHPRYHG LQ YDFXR WR \LHOG D \HOORZ RLO ZKLFK ZDV SUHFLSLWDWHG E\ DGGLQJ D VPDOO DPRXQW RI HWKDQRO 7KH FUXGH VROLG ZDV UHFU\VWDOOL]HG IURP (W (W2+ f )LQH \HOORZ QHHGOHV ZHUH LVRODWHG J bf PS r& GHFRPSRVLWLRQf A 105 &'&,f G +

PAGE 127

f W + f W + f W + f P +f G + f V +f WULD]ROHf & 105 &'&f WULD]ROHf & 1f ,5 b 7f YOFPf & 1f /5 06 0 EDVH SHDN 0WULD]ROHf +5 06 &L+LL1f0O FDOHG IRXQG &+1 UHTXLUHV & + 1 )RXQG & + 1 90HWKYOSKHQYOfIOXRUHQLPLQH Df 9O7ULD]RO\OfIOXRUHQLPLQH J PPROf ZDV VXVSHQGHG DW URRP WHPSHUDWXUHf LQ IUHVKO\ GLVWLOOHG 7+) P/f XQWLO GLVVROYHG XQGHU D VWHDG\ VWUHDP RI 1 7RO\OPDJQHVLXP EURPLGH $OGULFKf HT 0f ZDV DGGHG GURSZLVH YLD V\ULQJH $IWHU K WKH UHDFWLRQ ZDV TXHQFKHG ZLWK 0H2+ DQG FRQFHQWUDWHG LQ YDFXR 7KH PDWHULDO ZDV SXULILHG E\ SUHSDUDWLYH 7/& KH[(W f WKH WLWOH FRPSRXQG ZDV UHFRYHUHG DV GDUN \HOORZ FU\VWDOV PJ bf PS r& /LW >-2&@ r&f O+ 105 &'&,f V +f &+f G + f IOXRUHQ\Of G + f SWRO\Of W + f IOXRUHQ\Of G + f IOXRUHQ\Of T + f IOXRUHQ\Of W + f IORXUHQ\Of G + f SWRO\Of G + f IOXRUHQ\Of & 105 &'&,f /5 06 &+1f 0 P] )OXRUHQRQH f 7KH WLWOH FRPSRXQG ZDV UHFRYHUHG DV D E\SURGXFW IURP WKH UHDFWLRQ IRU WKH IRUPDWLRQ RI D + 105 &'&,f W + f G + f G + f & 105 &'&,f & 4f /5 06 &L+f 0 P]

PAGE 128

n'LPHWK\OELSKHQ\O f 7KH WLWOH FRPSRXQG ZDV UHFRYHUHG DV D E\n SURGXFW IURP WKH UHDFWLRQ IRU WKH IRUPDWLRQ RI D + 105 &'&,f V +f G + f G + f & 105 &'&,f /5 06 &+f 0 P] +\GUR[YWRO\OIOXRUHQH f 7KH WLWOH FRPSRXQG ZDV UHFRYHUHG DV D E\n SURGXFW IURP WKH UHDFWLRQ IRU WKH IRUPDWLRQ RI D ZKHQ WKH UHDFWLRQ ZDV SHUIRUPHG LQ WROXHQHf O+ 105 &'&,f V +f G + f P +f G + f 2+ ZDV QRW REVHUYHG & 105 &'&,f &f /5 06 &R+Lf 0 P] )OXRUHQLPLQH f 7KH WLWOH FRPSRXQG ZDV UHFRYHUHG DV D E\SURGXFW IURP WKH UHDFWLRQ IRU WKH IRUPDWLRQ RI D 105 &'&,f W + f G + f G + f /5 06 &+1f 0 P] 0L[WXUH RI \9EHQ]\OIOXRUHQLPLQH Ef DQG EHQ]\ODPLQRIOXRUHQH Df 9O7ULD]RO\OfIOXRUHQLPLQH J PPROf DGGHG YLD D 6R[KOHW H[WUDFWRU ZDV UHIOX[HG LQ WROXHQH IUHVKO\ GLVWLOOHGf %HQ]\OPDJQHVLXP FKORULGH HT P/ 0 ^V\QWKHVL]HG`f ZDV DGGHG YLD V\ULQJH $IWHU K WKH UHDFWLRQ ZDV FRROHG WR URRP WHPSHUDWXUH DQG SRXUHG RQWR FROG 1O/M&K P/f DQG H[WUDFWHG ZLWK (W P/f 7KH RUJDQLF OD\HU ZDV GULHG RYHU 1D6&! DQG FRQFHQWUDWHG LQ YDFXR 7KH WLWOH FRPSRXQGV ZHUH LVRODWHG DV D PL[WXUH DIWHU FROXPQ FKURPDWRJUDSK\ DV D \HOORZ RLO PJ bf r+ 105&'&f G RI V + f V +f &+f G + f P +f T G t W + f W + f G RI G + f & 105 &'&,f

PAGE 129

/5 06 0 &+1 PDMRUf P] 0 &+1 PLQRUf P] EDVH SHDN P] 3K&+f $PLQREHQ]\OIOXRUHQH Ef 7KH WLWOH FRPSRXQG ZDV UHFRYHUHG DV DQ RLO DV D E\SURGXFW IURP WKH UHDFWLRQ IRU WKH IRUPDWLRQ RI E r+ 105 &'&,f V +f VHULHV RI P +f G RI G + f G RI G + f & 105 &'&,f /5 06 &+1f 0 P] %LEHQ]\O f 7KH WLWOH FRPSRXQG ZDV UHFRYHUHG DV DQ RLO DV D E\SURGXFW IURP WKH UHDFWLRQ IRU WKH IRUPDWLRQ RI E A 105 &'&,f • V +f P +f & 105 &'&,f /5 06 &+f 0 P] +\GUR[YEHQ]\OIOXRUHQH f 7KH WLWOH FRPSRXQG ZDV UHFRYHUHG DV D \HOORZ VROLG PS r&f E\SURGXFW IURP WKH UHDFWLRQ IRU WKH IRUPDWLRQ RI E O+ 105&'&f V +f VHULHV RI P +f G + f & 105 &'&,f /5 06 &+L2f0 P] 'RGHF\ODPLQR1WULD]RO \Of IO XRUHQH Df 1 7ULD]RO \OfIOXRUHQLPLQH J PPROf DGGHG YLD D 6R[KOHW H[WUDFWRU ZDV UHIOX[HG LQ WROXHQH IUHVKO\ GLVWLOOHGf 'RGHF\OPDJQHVLXP EURPLGH SUHSDUHG IURP PJ 0J J PPRO GRGHF\OEURPLGH LQ (W ^ PO`f ZDV DGGHG YLD V\ULQJH $IWHU K WKH UHDFWLRQ ZDV

PAGE 130

TXHQFKHG ZLWK 0H2+ DQG FRQFHQWUDWHG LQ YDFXR 2UDQJH \HOORZ FU\VWDOV J bf ZHUH LVRODWHG r+ 105&'&f P +f EU V r +f P +f VHULHV RI P +f V +f V +f +5 06 &+1f 0 FDOHG P] IRXQG P] EDVH SHDN P] &+1f 0 WULD]ROHf %HQ]RWULD]RO \OPHWK\ODPLQRfWULD]ROH f $PLQRWULD]ROH J PROf DQG K\GUR[\PHWK\OHQHEHQ]RWULD]ROH J PROf ZHUH UHIOX[HG LQ (W2+ POf $IWHU K WKH UHDFWLRQ ZDV VWRSSHG QRW FRPSOHWHf FRROHG WR URRP WHPSHUDWXUH DQG WKH VROYHQW UHPRYHG LQ YDFXR 7KH UHVXOWLQJ ZKLWH VROLG ZDV ZDVKHG ZLWK H[FHVV PHWK\OHQH FKORULGH XQWLO 7/& &+&O(W2$F f UHYHDOHG QR PRUH XQUHDFWHG K\GUR[\PHWK\OHQHEHQ]RWULD]ROH $ ZKLWH IODN\ VROLG ZDV REWDLQHG J bf PS r& A 105 &'&,f G + f &+f W + %Wf W + f %Wf G + f %Wf G + f V +f WULD]ROHf & 105 &'&,f &+f WULD]ROHf &+1 UHTXLUHV & + 1 )RXQG & + 1 *HQHUDO SURFHGXUH IRU WKH SUHSDUDWLRQ RI DON\ODPLQRf WULD]ROHV 7ROYOPHWK\ODPLQRfWULD]ROH Df %HQ]RWULD]RO \OPHWK\ODPLQRfOWULD]ROH J PPROf ZDV UHIOX[HG LQ 7+) P/f XQWLO GLVVROYHG 7RO\OPDJQHVLXP EURPLGH $OGULFK 0f HT PPRO P/f ZDV DGGHG GURSZLVH YLD V\ULQJH $IWHU UHIOX[LQJ IRU K WKH UHDFWLRQ ZDV FRROHG WR URRP WHPSHUDWXUH GLOXWHG ZLWK HWK\O DFHWDWH P/f DQG TXHQFKHG ZLWK ZDWHU 7KH DTXHRXV OD\HU ZDV DGMXVWHG WR S+ DQG H[WUDFWHG ZLWK HWK\O DFHWDWH ; P/f 7KH RUJDQLF OD\HUV ZHUH FRPELQHG DQG GULHG RYHU 1D6&! DQG FRQFHQWUDWHG LQ YDFXR 7KH FUXGH PDWHULDO ZDV FROXPQ FKURPDWRJUDSKHG VLOLFD XVLQJ &+&, (W2$F(W2+f $ OLJKW

PAGE 131

FRORUHG RLO PJ bf ZDV LVRODWHG r+ 105 &'&f V +f &+f V +f &+f G RI G t V + f WRO\O &+V t 1+f V +f WULD]ROH &+Vf & 105 &'&,f &+f &+f WULD]ROHf +5 06 &LR+L1f 0 FDOHG P] IRXQG P] EDVH SHDN P] &+f 0 WULD]ROH PRLHW\f 0HWK\OSURS\ODPLQRfWULD]ROH Ef 7KH WLWOH FRPSRXQG ZDV V\QWKHVL]HG DV D WKLFN RLO PJ bf IURP EHQ]RWULD]ROO\OPHWK\ODPLQRf WULD]ROH J PPROf LVRSURS\O PDJQHVLXP FKORULGH $OGULFK 0f HT PPRO P/f XVLQJ WKH DERYH SURFHGXUH IRU D r+ 105 &'&,f G + f &+f VHSWHW + f &+0Hf G + f &+f V +f 1+f V +f WULD]ROH &+Vf & 105 &'&,f &+f &+f &+f WULD]ROHf +5 06 &+L1f 0 FDOHG P] IRXQG P] EDVH SHDN P] &+1f 0 SURS\Of 'LPHWK\OSURS\ODPLQRfWULD]ROH Ff 7KH WLWOH FRPSRXQG ZDV V\QWKHVL]HG DV D WKLFN RLO PJ bf IURP EHQ]RWULD]ROO\OPHWK\ODPLQRf WULD]ROH J PPROf LVRSURS\OPDJQHVLXP FKORULGH $OGULFK 0f HT PPRO P/f XVLQJ WKH DERYH SURFHGXUH IRU D r+ 105 &'&,f V +f &+f G + f &+f W + f 1+f V +f WULD]ROH &+Vf & 105 &'&,f ^W%Xf &f &+f WULD]ROHf +5 06 &+1f 0 FDOHG P] IRXQG P] EDVH SHDN P] &+1f 0 %Xf (WK\ODPLQRfOWULD]ROH Gf 7KH WLWOH FRPSRXQG ZDV V\QWKHVL]HG b FUXGH \LHOGf IURP EHQ]RWULD]ROO\OPHWK\ODPLQRf WULD]ROH PJ PPROf PHWK\OPDJQHVLXP FKORULGH $OGULFK 0f HT PPRO P/f XVLQJ WKH

PAGE 132

DERYH SURFHGXUH IRU D 7KH WLWOH FRPSRXQG ZDV SXULILHG E\ ZDVKLQJ ZLWK bf 1D2+ WR JLYH RIIZKLWH FU\VWDOV PJ bf PS r& /LW PS >-2&@ r&f A 105 &'&f W + f &+f TXLQWHW + f &+f W + f 1+ V +f WULD]ROH &+Vf & 105 &'&f &+f &+f WULD]ROHf 3HQW\ODPLQRfWULD]ROH Hf 7KH WLWOH FRPSRXQG ZDV REWDLQHG FUXGH b \HOORZ RLOf IURP EHQ]RWULD]ROO\OPHWK\ODPLQRf WULD]ROH PJ PPROf PHWK\OPDJQHVLXP FKORULGH V\QWKHVL]HG 0f HT PPRO P/f XVLQJ WKH DERYH SURFHGXUH IRU G + 105 &'&f W + f &+f P +f &+f W + f &+1+f EU V +f 1+ V +f WULD]ROH &+Vf & 105 &'&f &+f &+f &+f &+f &+1+f WULD]ROHf 0HWK\ODPLQRfWULD]ROH If %HQ]RWULD]ROO\OPHWK\ODPLQRf WULD]ROH J PPROf ZDV UHIOX[HG LQ (W2+ ZLWK VRGLXP ERURK\GULGH HT PJ PPROf $IWHU K WKH UHDFWLRQ ZDV FRROHG WR URRP WHPSHUDWXUH TXHQFKHG ZLWK 1DA2M DQG H[WUDFWHG ZLWK (W 7KH RUJDQLF OD\HU ZDV GULHG RYHU 1D6&! DQG FRQFHQWUDWHG LQ YDFXR $ SDOH \HOORZ RLO PJ bf ZDV LVRODWHG VPDOO WUDFHV RI %Wf + 105 &'&f V +f &+f V +f WULD]ROH &+Vf & 105 &'&f &+f WULD]ROHf

PAGE 133

$33(1',; $ 0$66 63(&75$/ )5$*0(17$7,21 3$77(516 2) 3,3(5,',1( 352'8&76 ,QWHUSUHWDWLRQ RI PDVV VSHFWUDO IUDJPHQWDWLRQV &RPSRXQGV LGHQWLILHG LQ &KDSWHU ,, IRU ZKLFK QR SXEOLVKHG 06 GDWD ZDV DYDLODEOH DUH UHSUHVHQWHG EHORZ 7KH SURGXFWV ZHUH DVVLJQHG VWUXFWXUHV EDVHG XSRQ WKHLU 06 IUDJPHQWDWLRQ SDWWHUQV DORQJ ZLWK FRQVLGHUDWLRQ RI WKH UHDFWLRQ FRQGLWLRQV VWDUWLQJ PDWHULDOV DQG D UHDVRQDEOH PHFKDQLVWLF SDWKZD\ IRU WKHLU IRUPDWLRQ IURP WKH VWDUWLQJ PDWHULDOV VHH 7DEOH f 7KH DXWKHQWLF FRPSRXQGV DQG f V\QWKHVL]HG DUH DOVR UHSUHVHQWHG ,Q WKH IROORZLQJ IUDJPHQWDWLRQ VFKHPHV IUDJPHQW LRQV GHWHFWHG E\ *&06 DQDO\VHV DUH UHSUHVHQW E\ WKHLU PDVV XQLWV P]f )UDJPHQWDWLRQ RI 9+&fPHWK\OSLSHQGLQH f 6FKHPH $Of &f0HWK\OSLSHULGLQHf 6FKHPH $Of KDV WKH VDPH UHWHQWLRQ WLPH DV PHWK\OSLSHULGLQH f DQG LWV PROHFXODU LRQ DSSHDUV DW P] bf >UL UHODWLYH LQWHQVLW\@ 7KH IUDJPHQWDWLRQ SDWWHUQ 6FKHPH $Of LV LGHQWLFDO WR WKDW RI H[FHSW WKDW IUDJPHQWV VWLOO FRQWDLQLQJ WKH H[RF\FOLF FDUERQ VKRZV SHDNV DW PDVV XQLW KLJKHU WKDQ WKRVH IRU /RVV RI D K\GURJHQ UDGLFDO IURP WKH PROHFXODU LRQ OHDGV WR WKH EDVH SHDN DW P] 7KH VXEVHTXHQW IUDJPHQWDWLRQ VKRZQ LQ 6FKHPH $O LV EDVHG RQ WKDW JLYHQ LQ UHIHUHQFH >%0, %0, 0,@ H[FHSW WKHUH LV QR GRFXPHQWDWLRQ IRU WKH LRQ DW P]

PAGE 134

6FKHPH $ )UDJPHQWDWLRQ RI 1 $GLPHWK\OSHQW\ODPLQH f 6FKHPH $f $$'LPHWK\OSHQW\ODPLQH f 6FKHPH $f ZKLFK ZDV SUHYLRXVO\ V\QWKHVL]HG E\ 6ZDQQ 0,f VKRZV LWV PDMRU IUDJPHQWDWLRQ LQ WKH PDVV VSHFWURPHWHU DV DQ DFOHDYDJH FOHDYDJH RI WKH FDUERQFDUERQ ERQG DGMDFHQW WR WKH QLWURJHQ DWRPf WR JLYH LWV EDVH SHDN DW P] ZLWK WKH VXEVHTXHQW ORVV RI DQ mEXW\O UDGLFDO 7KH UHPRYDO RI DQ HOHFWURQ IURP WKH ORQH SDLU RQ WKH QLWURJHQ LV WKH WULJJHU IRU VLPSOH DFOHDYDJH DQG UHVXOWV LQ WKH IRUPDWLRQ RI DQ DON\O UDGLFDO >%0,@ 7KLV LRQ FDQ IXUWKHU IUDJPHQW WR WKH LRQ RI P] 7KH 0O IUDJPHQW DW P] LV RQO\ RI ZHDN LQWHQVLW\ bf 7KH LRQ DW P] LV D UHVXOW RI D \FOHDYDJH ZLWK WKH VXEVHTXHQW HOLPLQDWLRQ RI DQ HWK\O UDGLFDO RU ORVV RI HWK\OHQH IURP WKH 0O LRQ 6XUSULVLQJO\ WKH LQWHQVLW\ IRU WKH IUDJPHQW UHVXOWLQJ IURP SFOHDYDJH ZDV WRR ZHDN WR EH REVHUYHG /RVV RI WKH & QHXWUDO JLYHV WKH LRQ DW P] ZKLFK WKHQ ORVHV D K\GURJHQ UDGLFDO WR JLYH WKH LRQ DW P]

PAGE 135

9 &+J &+ &+ 1 &+ P] bf &+ KF Q FK P] bf P] bf + &+ I P] bf &F+ n n &+ Y +n 1 &+ bf &+ 6FKHPH $ )UDJPHQWDWLRQ RI 1 $UGLPHWK\OPHWKYOSHQW\ODPLQHf 6FKHPH $f 7KH PDMRU IUDJPHQWDWLRQ RI $ $GLPHWK\OPHWK\OSHQW\ODPLQH f 6FKHPH $f SUHYLRXVO\ V\QWKHVL]HG E\ /XNHV DQG 3OLPO >&&&@f LV DQ DFOHDYDJH WR JLYH WKH LRQ FRUUHVSRQGLQJ WR WKH EDVH SHDN DW P] ZLWK WKH VLPXOWDQHRXV HOLPLQDWLRQ RI D VHFSHQW\O UDGLFDO $V VHHQ ZLWK DOO WHUWLDU\ DPLQHV DQG SUHYLRXVO\ IRU $$ GLPHWK\SHQW\ODPLQH f WKH ODUJHVW DON\O JURXS LV ORVW SUHIHUHQWLDOO\ >%0,@ 7KH LRQ DW P] bf LV SUREDEO\ IRUPHG WKURXJK \FOHDYDJH ZLWK WKH FRQFRPLWDQW HOLPLQDWLRQ RI DQ HWK\O UDGLFDO 7KH LRQ DW P] LV D UHVXOW RI WKH ORVV RI D PHWK\O UDGLFDO DQG D QHXWUDO & IUDJPHQW IURP WKH PROHFXODU LRQ ZKLOH WKH LRQ DW P] UHVXOWHG IURP ORVV RI PHWKDQH

PAGE 136

&+ Y &+ 1 &+ P] P] bf I &+&+f&+&+ &+ &+ &+ &+ &+ P] bf KF Q FK &+ 1 &+ P] bf P] bf 6FKHPH $ )UDJPHQWDWLRQ RI SURS\OSLSHULGLQH f 6FKHPH $f 3URS\OSLSHULGLQH f 6FKHPH $f VKRZHG LWV PROHFXODU LRQ DW P] bf DQG DQ DFOHDYDJH JDYH WKH EDVH SHDN DW P] bf ZLWK WKH FRQFRPLWDQW HOLPLQDWLRQ RI DQ HWK\O UDGLFDO 7KLV LV FRQVLVWHQW ZLWK WKH IUDJPHQWDWLRQ SDWWHUQ RI WKH RWKHU DON\OSLSHULGLQHV VHH 7DEOH t 06 GDWD IRU PHWK\O HWK\O EXW\O DQG SHQW\OSLSHULGLQHf ZKLFK DOO XQGHUJR DFOHDYDJH RI WKH 9DON\O JURXS WR JLYH WKH VDPH EDVH SHDN DW P] >%0,@ 7KH IUDJPHQWV DW P] DQG DUH GHULYHG IURP IXUWKHU IUDJPHQWDWLRQV RI WKH SLSHULGLQH ULQJ DQG DUH DJDLQ VLPLODU WR WKH EHKDYLRU RI WKH DON\OSLSHULGLQHV >%0,@ ,Q FRQWUDVW LWV SURS\OSLSHULGLQH LVRPHU ORVHV D SURS\O UDGLFDO WR JLYH WKH EDVH SHDN DW P] >%0,@

PAGE 137

I 3U KF Q FK P] bf 6FKHPH $ O$ON\OPHWK\OSLSHULGLQHV DQG f DUH HDVLO\ LGHQWLILHG IURP WKHLU IUDJPHQWDWLRQ SDWWHUQV ZKLFK DUH VLPLODU WR WKRVH RI WKH FRUUHVSRQGLQJ DON\OSLSHULGLQHV DQG f 7KH GLVWLQJXLVKLQJ IDFWRU LV WKDW WKH PROHFXODU LRQV DQG PDQ\ RI WKH IUDJPHQWDWLRQV RI WKH DON\OPHWK\OSLSHULGLQHV GLIIHU IURP WKRVH RI WKH DON\OSLSHULGLQHV E\ PDVV XQLWV (DFK DON\OPHWK\OSLSHULGLQH VKRZHG LWV EDVH SHDN DW P] ZKLFK LV DOVR PDVV XQLWV KLJKHU WKDQ WKDW IRU WKH DON\OSLSHULGLQHV P] f 7KLV DJDLQ FRQIRUPV ZLWK WKH IUDJPHQWDWLRQ SDWWHUQV RI DON\OSLSHULGLQHV LQ ZKLFK WKH DON\O JURXSV XQGHUJR D FOHDYDJH WR JHQHUDWH WKH EDVH SHDN >%0,@ >VHH 7DEOH 06 GDWD IRU GLPHWK\OSLSHULGLQH f@ &RPPRQ IUDJPHQWV DW P] DQG FRQILUP WKH SUHVHQFH RI WKH SLSHULGLQH PRLHW\ DQG IXUWKHU VXSSRUW WKH DVVLJQHG VWUXFWXUHV )UDJPHQWDWLRQ RI OHWK\OPHWK\OSLSHULGLQH f 6FKHPH $f O(WK\OPHWK\OSLSHULGLQHf 6FKHPH $f VKRZHG WKH EDVH SHDN DW P] 7KLV LV FRQVLVWHQW ZLWK WKH IUDJPHQWDWLRQ SDWWHUQ RI DON\OSLSHULGLQHV LQ ZKLFK WKH

PAGE 138

DON\O JURXSV QRUPDOO\ XQGHUJR DFOHDYDJH WR SURGXFH WKH EDVH SHDN >%0,@ >VHH 7DEOH 06 IRU GLPHWK\O SLSHULGLQH f@ 7KH IUDJPHQWV DW P] DQG DUH D UHVXOW RI UHWUR'LHOV$OGHU UHDFWLRQV >%0,-$@ ZKLFK FRQILUP WKH SUHVHQFH RI WKH SLSHULGLQH PRLHW\ DQG VXSSRUWV WKH DVVLJQHG VWUXFWXUH 6FKHPH $ )UDJPHQWDWLRQ RI SURSYOPHWKYOSLSHULGLQH f 6FKHPH $f O3URS\OPHWK\OSLSHULGLQH f 6FKHPH $f LV HDVLO\ LGHQWLILHG IURP LWV IUDJPHQWDWLRQ SDWWHUQ ZKLFK LV VLPLODU WR WKDW RI SURS\OSLSHULGLQH RXU FRPSRXQG 6FKHPH $ DERYHf 7KH PROHFXODU LRQ DW P] LV QRZ PDVV XQLWV KLJKHU WKDQ WKDW RI SURS\OSLSHULGLQH &RPSRXQG VKRZHG LWV EDVH SHDN DW P] 7KH RWKHU IUDJPHQWV DW P] bf DQG bf FRQILUP WKH SUHVHQFH RI WKH SLSHULGLQH PRLHW\ DQG IXUWKHU VXSSRUW WKH DVVLJQHG VWUXFWXUH

PAGE 139

+& 1f§&+ + P] bf &+ 1 FK P] bf 6FKHPH $ )UDJPHQWDWLRQ RI EXW\OPHWK\O SLSHULGLQH f 6FKHPH $f O%XW\OPHWK\OSLSHULGLQH f 6FKHPH $f VKRZHG LWV PROHFXODU LRQ DW P] bf 2QFH DJDLQ WKH EDVH SHDN DSSHDUHG DW P] DV VHHQ SUHYLRXVO\ IRU FRPSRXQGV DQG VHH 6FKHPHV $ t $f 2WKHU IUDJPHQWV DW P] bf DQG bf DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\ )UDJPHQWDWLRQ RI OSHQW\OPHWK\OSLSHULGLQH f 6FKHPH $f 3HQW\OPHWK\OSLSHULGLQH f 6FKHPH $f GLVSOD\V LWV PROHFXODU LRQ DW P] bf DQG LWV EDVH SHDN DW P] DV D UHVXOW RI WKH ORVV RI WKH VHFRQGDU\ DON\O UDGLFDO &RPSRXQG ZDV REWDLQHG IURP WKH PHWK\SLSHULGLQH UXQ DQG WKH PDVV GLIIHUHQFH EHWZHHQ SURGXFWV DQG LV XQLWV 7KLV UHVXOW FOHDUO\ VXJJHVWV WKDW LV D ODON\OPHWK\OSLSHULGLQH 7KH EDVH SHDN DW P] VXSSRUWV WKH IUDJPHQWDWLRQ RI DON\OSLSHULGLQHV LQ ZKLFK WKH DON\O JURXS XQGHUJRHV DFOHDYDJH >% 0,@ $V VHHQ SUHYLRXVO\ IUDJPHQWV RI P] DQG DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\

PAGE 140

L + P] bf +& 1&+ + P] bf U 0H P] bf 6FKHPH $ P] bf P] bf 6FKHPH $

PAGE 141

)UDJPHQWDWLRQ RI OPHWKYOSHQWYOfPHWK\OSLSHULGLQH f 6FKHPH $f O0HWK\OSHQW\OfPHWK\OSLSHULGLQH f 6FKHPH $f LV REWDLQHG RQO\ IURP WKH PHWK\OS\ULGLQH UXQ ,W GLVSOD\V LWV PROHFXODU LRQ DW P] bf 7KH EDVH SHDN DSSHDUV DW P] bf DV D UHVXOW RI DFOHDYDJH RI WKH DON\O FKDLQ 7KLV VXJJHVWV WKDW SURGXFW VKRXOG EH D DON\OPHWK\OSLSHULGLQH )UDJPHQWV DW P] DQG DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\ DV VHHQ SUHYLRXVO\ 3URGXFW GLIIHUV IURP LWV PROHFXODU LRQ DW P] E\ PDVV XQLWV %DVHG RQ WKH SURSRVHG PHFKDQLVP IRU WKH IRUPDWLRQ RI SURGXFW IURP WKH VWDUWLQJ PDWHULDO PHWK\OS\ULGLQH ZH VXJJHVW WKDW WKH DON\O XQLW DWWDFKHG WR WKH QLWURJHQ LV SUREDEO\ D PHWK\OSHQW\O JURXS P] &+&+&+f&+&+ P] bf +& 1f§FK + P] bf L &R+ n n UHWUR 'LHOV$OGHU &+ FK P] bf FK KF Q FK P] bf 6FKHPH $

PAGE 142

)UDJPHQWDWLRQ RI OPHWKYOEXW\OfSLSHULGLQH f 6FKHPH $f 7KH QRYHO FRPSRXQG OPHWK\OEXW\OfSLSHULGLQHf 6FKHPH $f VKRZV D PROHFXODU LRQ DW P] bf DQG XQGHUJRHV DQ DFOHDYDJH WR JLYH LWV EDVH SHDN DW P] bf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fIRUP\OSLSHULGLQH f 6FKHPH $O f O&f)RUP\OSLSHULGLQH f 6FKHPH $OOf KDV WKH VDPH UHWHQWLRQ WLPH DV IRUP\OSLSHULGLQH f DQG D IUDJPHQWDWLRQ SDWWHUQ ZKLFK LV LGHQWLFDO WR WKDW RI H[FHSW WKDW WKH IUDJPHQWV FRQWDLQLQJ WKH &+2 JURXS DUH PDVV XQLW KLJKHU 7KXV LW VKRZV LWV PROHFXODU LRQ DW P] DV WKH EDVH SHDN /RVV RI D K\GURJHQ DWRP IURP WKH PROHFXODU LRQ JLYHV WKH LRQ DW P] bf 7KH IUDJPHQWDWLRQ SDWWHUQ ZDV FRPSDUHG ZLWK WKH XQODEHOHG IRUP\OSLSHULGLQH 7KH IUDJPHQW LRQ DW P] bf LV GXH WR WKH ORVV RI D &+2 UDGLFDO IURP WKH PROHFXODU LRQ )XUWKHU IUDJPHQWDWLRQ JHQHUDWHV WKH LRQV DW P] bf DQG bf ZKLFK DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\ DV VKRZQ SUHYLRXVO\ IRU WKH RWKHU VXEVWLWXWHG SLSHULGLQHV

PAGE 143

P] bf P] bf $OGHU +& 1 &+ P] bf 6FKHPH $

PAGE 144

? FKR I &+2 O &+2 P] bf P] nbf &+ &R+ 1 L + KF Q FK P] bf P] bf &+ KF Qf§ &+2 &+2 P] bf P] bf 6FKHPH $ )UDJPHQWDWLRQ RI OPHWKYOSHQW\OfSLSHULGLQH f 6FKHPH $f O0HWK\OSHQW\OfSLSHULGLQHf 6FKHPH $f D QRYHO F\FOLF DPLQH VKRZV D PROHFXODU LRQ DW P] bf DQG WKLV UHDGLO\ XQGHUJRHV DQ DFOHDYDJH ZLWK WKH FRQFRPLWDQW HOLPLQDWLRQ RI D PHWK\OEXW\O VHFRQGDU\ UDGLFDO WR JLYH WKH EDVH SHDN DW P] bf 7KH EDVH SHDN WKHQ XQGHUJRHV D UHWUR'LHOV$OGHU UHDFWLRQ WR JLYH WKH LRQV DW P] DQG DV VHHQ SUHYLRXVO\ >%0,@ 7KH LRQ DW P] bf DULVHV DV D UHVXOW RI WKH HOLPLQDWLRQ RI D PHWK\OSHQW\O UDGLFDO ZLWK D VXEVHTXHQW K\GURJHQ UHDUUDQJHPHQW 7KLV LRQ SUREDEO\ XQGHUJRHV D UHWUR'LHOV$OGHU UHDFWLRQ WR JLYH WKH LRQ DW P] bf

PAGE 145

&+&+&+f&+&+ P] bf P] bf P] bf $ UHWUR 'LHOV$OGHU 7 + P] bf bf FK UHWUR 'LHOV $OGHU < FK P] 9 bf &+ KF Q &+ PA bf 6FKHPH $ )UDJPHQWDWLRQ RI OIRUPYOPHWK\OSLSHULGLQH f 6FKHPH $f O)RUP\OPHWK\OSLSHULGLQHf 6FKHPH $f GLVSOD\V LWV PROHFXODU LRQ DW P] bf DQG WKH EDVH SHDN DW P] 0f 7KH PROHFXODU LRQ ORVHV + DQG &+2 UDGLFDOV WR JLYH IUDJPHQW LRQV DW P] bf DQG DW P] bf UHVSHFWLYHO\ /RVV RI D PHWK\O UDGLFDO IURP WKH PROHFXODU LRQ SRVVLEO\ E\ WKH SDWKZD\ VKRZQ JLYHV WKH IUDJPHQW LRQ DW P] bf 2WKHU IUDJPHQWV DW P] bf bf DQG bf DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\ E\ WKH URXWHV LQGLFDWHG >0,@

PAGE 146

0H + KU &+2 P] bf 4 2+&n ;+ bf &+2 QQI] bf W &+2 ‘&+ + bf P] bf + bf W &+ ZLWK UHDUUDQJHPHQW &R+ n KF Q FK bf + P] bf 6FKHPH $ )UDJPHQWDWLRQ RI ODPLQRSHQWYOfSLSHULGLQHf 6FKHPH $f O$PLQRSHQW\OfSLSHULGLQHf 6FKHPH $f VKRZV LWV PROHFXODU LRQ DW P] bf /RVV RI WKH DPLQRSHQW\O UDGLFDO IURP WKH PROHFXODU LRQ JLYHV WKH EDVH SHDN DW P] 7KLV VXJJHVWV WKDW FRPSRXQG LV DQ $VXEVWLWXWHG SLSHULGLQH ZLWK DQ DPLQRSHQW\O JURXS DV WKH $VXEVWLWXHQW )XUWKHU IUDJPHQWV DW P] bf DQG bf DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\ 7RJHWKHU ZLWK WKDW DW P] bf WKH\ VXSSRUW WKH DVVLJQHG VWUXFWXUH RI

PAGE 147

&+&+f1+ + P] bf &+&+f1+ &+ &+ P] bf P] bf I UHWUR 'LHOV $OGHU +& 1 P] b P] bf P] bf 6FKHPH $ )UDJPHQWDWLRQ RI ODFHWYOPHWK\OSLSHULGLQHf 6FKHPH $f O$FHW\OPHWK\OSLSHULGLQH f 6FKHPH $f VKRZV LWV PROHFXODU LRQ DW P] bf DQG WKH EDVH SHDN DW P] 0Of /RVV RI D PHWK\O UDGLFDO DQG RI DQ DFHW\O UDGLFDO >%0,@ IURP WKH PROHFXODU LRQ JLYH WKH IUDJPHQW LRQV DW P] bf DQG bf UHVSHFWLYHO\ )XUWKHU IUDJPHQWDWLRQ JHQHUDWHV WKH LRQV DW P] bf bf DQG bf ZKLFK DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\ )UDJPHQWDWLRQ RI OPHWK\ODPLQRSHQW\OfSLSHULGLQH f 6FKHPH $f O0HWK\ODPLQRSHQW\OfSLSHULGLQHf 6FKHPH $f VKRZV LWV PROHFXODU LRQ DW P] bf 7KH PROHFXODU LRQ ORVHV WKH DPLQRSHQW\O UDGLFDO WR JLYH WKH EDVH SHDN DW P] 7KH GLIIHUHQFHV LQ WKH PDVV SHDNV RI PHWK\OS\ULGLQH RU

PAGE 148

PHWK\O SL SHUL GLQH VWDUWLQJ PDWHULDOf DQG SURGXFW f VXJJHVWV WKDW LW LV DQ $DON\ODWHG SLSHULGLQH 7KH 9DON\O VXEVWLWXHQW LV DVVLJQHG WKH PHWK\OSHQW\ODPLQH VWUXFWXUH EDVHG ODUJHO\ RQ WKH SURSRVHG PHFKDQLVP RI IRUPDWLRQ 7KH RWKHU IUDJPHQWV DW P] bf bf DQG bf DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\ DQG DUH LQ JRRG DJUHHPHQW ZLWK WKH L9VXEVWLWXWHGPHWK\O SLSHULGLQH VWUXFWXUH DVVLJQHG 6FKHPH $f U ? 0H 0H P] "bf &2&+ &2&+ 0R f + I 0H 0H &2&+J &2&+ &+2& +2&&+R P] bf P] bf P] bf KF Q FK &•f&+M 0H + P] bf n P] bf P] bf 6FKHPH $

PAGE 149

P] bf 6FKHPH $ )UDJPHQWDWLRQ RI OSHQWHQO\OfSLSHULGLQH f 6FKHPH $f O3HQWHQO\OfSLSHULGLQH f 6FKHPH $f VKRZV LWV PROHFXODU LRQ DW P] bf 7KH PROHFXODU LRQ ORVHV WKH DONHQ\O UDGLFDO WR JLYH WKH EDVH SHDN DW P] 7KH GLIIHUHQFHV LQ WKH PDVV SHDNV RI SHQW\OSLSHULGLQH f DQG SURGXFW VXJJHVWV WKDW LW LV DQ XQVDWXUDWHG 9DON\ODWHG SLSHULGLQH 7KH LRQ DW P] bf DULVHV IURP ORVV RI WKH HQWLUH DON\O FKDLQ 7KH RWKHU IUDJPHQWV DW P] bf DQG bf DUH GHULYHG IURP WKH SLSHULGLQH PRLHW\ DQG DUH LQ JRRG DJUHHPHQW ZLWK WKH OSHQWHQO \OfSLSHULGLQH VWUXFWXUH DVVLJQHG

PAGE 150

KF Q FK P] bf &+&+&+ &+ $ &R+ UHWUR 'LHOV$OGHU n n < &+ P] R\ P] bf bf &+&+f&+ &+ + P] bf 6FKHPH $ &2 R

PAGE 151

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f ,Q WKH IROORZLQJ IUDJPHQWDWLRQ VFKHPHV IUDJPHQW LRQV GHWHFWHG E\ *&06 DQDO\VHV DUH UHSUHVHQWHG E\ PDVV XQLWV P]f )UDJPHQWDWLRQ RI $PHWKYORFW\ODPLQHf 6FKHPH %Of $0HWK\ORFW\ODPLQH f 6FKHPH %Of GLVSOD\V LWV PROHFXODU LRQ DW P] bf &OHDYDJH RI D SHQW\O UDGLFDO JHQHUDWHV WKH EDVH DW P] bf )URP WKH EDVH SHDN ORVV RI HWK\OHQH OHDGV WR WKH LRQ DW P] bf ZKLOH ORVV RI SURSDQH JLYHV WKH LRQ DW P] bf 2WKHU IUDJPHQWV IURP WKH PROHFXODU LRQ ZHUH P] bf WKURXJK K\GURJHQ UDGLFDO ORVV DQG P] bf YLD ORVV RI SHQWHQH

PAGE 152

&+\Bf§+ P] bf ALL &+\B+ FK &+ P] bf &+\+ P] bf +& 1+ P] bf P] bf 6FKHPH %O )UDJPHQWDWLRQ RI $PHWK\O$ORFW\O IRUP DPLGH f 6FKHPH %f $n0HWK\O$ORFW\OIRUPDPLGH f 6FKHPH %f GLVSOD\V D ZHDN PROHFXODU LRQ DW P] bf D&OHDYDJH RI D KHSW\O UDGLFDO ZLWK VXEVHTXHQW K\GURJHQ PLJUDWLRQ JHQHUDWHV WKH EDVH SHDN DW P] bf /RVV RI KHSWHQH IURP WKH PROHFXODU LRQ JLYHV WKH LRQ P] bf ZKLFK FRXOG ORVH &2 WR IRUP WKH LRQ DW P] bf &OHDYDJH RI D PHWK\O UDGLFDO IURP WKH PROHFXODU LRQ JDYH WKH LVRF\DQDWH LRQ DW P] bf )URP WKLV LVRF\DQDWH LRQ DFOHDYDJH RI RFWHQH JHQHUDWHV WKH LRQ DW P] bf D FKDUDFWHULVWLF SHDN RI IRUPDPLGHV >%0,@ $OWHUQDWLYHO\ WKH LRQ DW P] FRXOG HOLPLQDWH &2 WR JLYH WKH LRQ DW P] bf ZKLFK FRXOG WKHQ HOLPLQDWH HWK\OHQH WR JLYH WKH LRQ DW P] bf 7KH 0O LRQ DW P] ZDV REVHUYHG ZLWK D PRGHUDWH LQWHQVLW\ bf /RVV RI &2 IURP WKLV LVRF\DQDWH LRQ JDYH WKH LRQ DW P] bf (OLPLQDWLRQ RI &2 IURP WKH

PAGE 153

PROHFXODU LRQ JLYHV WKH LRQ DW P] bf )URP WKLV LRQ ORVV RI HWK\OHQH JDYH WKH LRQ DW P] bf ZKLFK FRXOG DOVR ORVH HWK\OHQH WR JLYH WKH LRQ DW P] bf )URP WKLV LRQ P] f K\GURJHQ UDGLFDO ORVV JDYH WKH LRQ DW P] bf ZKLFK FRXOG ORVH HWK\OHQH WR IRUP WKH LRQ DW P] bf 6FKHPH %f )UDJPHQWDWLRQ RI $0RFW\ODFHWDPLGH f 6FKHPH %f L9O2FW\ODFHWDPLGH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf PRGHUDWH LQWHQVLW\ QRUPDO IRU DFHWDPLGHVf 1RUPDOO\ VHFRQGDU\ DPLGHV DUH FKDUDFWHUL]HG E\ GRXEOH D DQG &1 FOHDYDJH ZLWK K\GURJHQ UHDUUDQJHPHQW >%0,@ +RZHYHU LQ WKH DEVHQFH RI DVXEVWLWXWLRQ DGMDFHQW WR WKH 1 LRQV RI PDVV DUH IRUPHG E\ D VLPLODU IUDJPHQWDWLRQ >%0,@ 6XFK LV WKH FDVH ZLWK IRUPDWLRQ RI WKH EDVH SHDN IRU 9RFW\ODFHWDPLGH D&OHDYDJH RI D KHSW\O UDGLFDO FRXOG SURGXFH DQ LQWHUPHGLDWH LRQ ZKLFK XSRQ HOLPLQDWLRQ RI &+ & ZRXOG OHDG WR WKH EDVH SHDN DW P] bf /RVV RI D PHWK\O UDGLFDO IURP WKH PROHFXODU LRQ JDYH WKH DON\O LVRF\DQDWH LRQ DW P] bf 7KLV LVRF\DQDWH LRQ FRXOG WKHQ ORVH &2 WR IRUP WKH LRQ DW P] bf )URP WKLV LRQ DW P] ORVV RI HWK\OHQH JHQHUDWHG WKH LRQ DW P] bf 7KH PROHFXODU LRQ FRXOG DOVR ORVH D KHSW\O UDGLFDO WR IRUP WKH DF\O LRQ DW P] bf ZKLFK FRXOG ORVH &2 WR JHQHUDWH WKH LRQ DW P] bf ,Q FRQWUDVW ORVV RI WKH KHSWHQH IURP WKH PROHFXODU LRQ JHQHUDWHV WKH LRQ DW P] bf ZKLFK FRXOG IXUWKHU ORVH &2 WR IRUP WKH LRQ DW P] bf /RVV RI &2 IURP WKH PROHFXODU LRQ OHDGV WKH LRQ DW P] DW D ZHDN LQWHQVLW\ bf 6FKHPH %f

PAGE 154

KQ F R PW] bf F++ &+ PW] bf &+ fA+ &+D1TK PW] bf &+ A f+ &+1 &+ PW] bf + &2 &D+ n 0 &+I&+2 L &+ PW] bf &+ 0H PI] bf &+J1 &+ + PW] bf &+1 F R $ PW] bf &2 W + FKFK QK PW] bf &+ P] bf &R+ n n &2 &+&+f§17 + PW] bf + L &+ PW] bf FKFK e+ &+I?L &+ + P] bf PW] bf 6FKHPH %

PAGE 155

&+1+&2&+ &2 +&+ P] bf &R+ n n &+&+R1 + &2&+ &+ n n FKQK P] bf &+ &+J& P] bf &+ 9 n &+ W 1+&2&+J P] bf &2 &+! “+&+ P] bf +L" n+f§&+J &+&2 FKQK +OL &+ P] bf & &+1+&2&+ P] bf P] bf &2 &2 &+1+&+ P] bf &+&+ 1+ P] bf &+ FKFK QK P] bf 6FKHPH %

PAGE 156

)UDJPHQWDWLRQ RI L9PHWKYOOGRGHFYODPLQH f 6FKHPH %f 0HWK\O GRGHF\ODPLQH f 6FKHPH %f VKRZV LWV PROHFXODU LRQ DW P] bf D&OHDYDJH >%0,@ RI DQ XQGHF\O UDGLFDO SURYLGHV WKH EDVH SHDN DW P] bf /RVV RI D K\GURJHQ UDGLFDO IURP WKH PROHFXODU LRQ FDQ JHQHUDWH WKH LRQ DW P] bf /RVV RI DQ HWK\OHQH PROHFXOH IURP WKLV LRQ DW P] JLYHV ULVH WR WKH LRQ DW P] bf )UDJPHQWDWLRQ E\ ORVV RI D GRGHF\O UDGLFDO IURP WKH PROHFXODU LRQ JHQHUDWHV WKH LRQ DW P] bf /RVV RI DQ QGHF\O UDGLFDO IURP WKH PROHFXODU LRQ IRUPV WKH LRQ DW P] bf /RVV RI D PHWK\O UDGLFDO IURP WKH PROHFXODU LRQ IRUPV WKH LRQ DW P] bf &+&+ UWn+ &+ + AAA &+ P] bf I + &+ KQ FK P] bf &L+1f§&+ f P] bf &Q+ n F+ 1 + P] bf + &+ + &L +&+f§1f§&+ P] bf &R+&+ 1&+ + P] bf &R+ n n W + &+&+ 1&+ P] bf 6FKHPH %

PAGE 157

)UDJPHQWDWLRQ RI L9PHWKYOL9RFWYODFHWDPLGH f 6FKHPH %f 90HWK\O9 RFW\ODFHWDPLGH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf D&OHDYDJH ZLWK HOLPLQDWLRQ RI D KHSW\O UDGLFDO JHQHUDWHG WKH EDVH SHDN DW P] bf )URP WKH EDVH SHDN ORVV RI &2 UHVXOWV LQ WKH LRQ DW P] bf +\GURJHQ UDGLFDO ORVV IURP WKH PROHFXODU LRQ JDYH WKH 0O DW P] bf /RVV RI &2 IURP WKLV LRQ FRXOG JHQHUDWH WKH LRQ DW P] bf ZKLFK FRXOG VXEVHTXHQWO\ XQGHUJR VHTXHQWLDO ORVV RI HWK\OHQH PXOWLSOHV RI PDVV XQLWVf WR JHQHUDWH WKH LRQV DW P] bf DQG P] bf DV GHVFULEHG SUHYLRXVO\ 6LPLODUO\ ORVV RI &2 IURP WKH PROHFXODU LRQ JHQHUDWHV WKH LRQ DW DW P] bf ZKLFK WKURXJK HWK\OHQH ORVV FRXOG JHQHUDWH WKH IROORZLQJ VHULHV RI LRQV P] bf bf DQG bf )URP WKH LRQ DW P] ORVV RI DQ HWK\O UDGLFDO JLYHV WKH LRQ DW P] bf 7KH PROHFXODU LRQ FRXOG DOWHUQDWLYHO\ ORVH D PHWK\O UDGLFDO WR IRUP WKH LRQ DW P] bf ZKLFK DV GHVFULEHG SUHYLRXVO\ FRXOG XQGHUJR ORVV RI &2 DQG HWK\OHQH WR IRUP WKH LRQV DW P] bf DQG bf 7KH REVHUYDWLRQ RI WKH LRQ DW P] bf >% 0,@ VXSSRUWV WKH DFHWDPLGH VWUXFWXUH SURSRVHG )UDJPHQWDWLRQ RI 9DFHWYO9ORFW\OIRUPDPLGH f 6FKHPH %f $$FHW\O$ORFW\O IRUPDPLGHf 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf 7ZR PDMRU IUDJPHQWDWLRQ SDWKZD\V KDYH EHHQ QRWHG )LUVWO\ ORVV RI D K\GURJHQ UDGLFDO JHQHUDWHV WKH LRQ DW P] bf ZKLFK FDQ ORVH &2 WR \LHOG WKH EDVH SHDN DW P] bf 7KH EDVH SHDN FDQ IUDJPHQW E\ ORVV RI &2 WR \LHOG WKH LRQ DW P] bf IROORZHG E\ VHTXHQWLDO ORVV RI HWK\OHQH WR JHQHUDWH WKH LRQV DW P] bf bf bf DQG bf /RVV RI PROHFXODU K\GURJHQ IURP WKH LRQ DW P] PD\ OHDG WR WKH LRQ DW P] bf

PAGE 158

&+1&2&+ &+ &+ FK 1 &+ &+1&2&+ &+ PI] bf &2 FKQFK &+ P] bf &R+ n n &H+L1&+ &+ P] bf &R+ n n &+J1&+ &+ P] bf P] bf W f &+ FKQFRFK 9 n &+ &+ PI] bf &2 &+1&+ L &+ PI] bf FK FKQFK &+ PI] bf FK FKQFK &+ P] bf &2 IMM FRFK &+ PI] bf &+ FKQ F R &+ P] bf &+ FKFR I &2 &+ 1+ PI] bf &+&+ 1+&+ P] bf &+ FKFK QKFK P] bf F+ FKQFK &+ PI] bf &+ 6M + &R+ n n &+ P] bf 6FKHPH %

PAGE 159

7KH RWKHU OLNHO\ PDMRU IUDJPHQWDWLRQ SDWKZD\ LQYROYHV LQLWLDO ORVV RI D PHWK\O UDGLFDO IURP WKH PROHFXODU LRQ WR \LHOG WKH LRQ DW P] bf IROORZHG E\ VHTXHQWLDO ORVV RI WZR PROHFXOHV RI &2 WR JHQHUDWH LRQV DW P] bf DQG bf UHVSHFWLYHO\ )XUWKHU IUDJPHQWDWLRQ IURP P] E\ VHTXHQWLDO ORVV RI HWK\OHQH FDQ JHQHUDWH WKH LRQV REVHUYHG DW P] bf bf DQG bf $OWHUQDWLYHO\ WKH LRQ DW P] PD\ EH IRUPHG WKURXJK ORVV RI DQ DFHW\O UDGLFDO IURP WKH PROHFXODU LRQ 6FKHPH %f )UDJPHQWDWLRQ RI $0RHWYO$RFW\ODPLQH f 6FKHPH %f $02FW\O$RFW\ODPLQH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf &OHDYDJH RI D KH[\O UDGLFDO JHQHUDWHV WKH EDVH SHDN DW P] bf )URP WKH EDVH SHDN ORVV RI HWK\OHQH OHDGV WR WKH LRQ DW P] bf 5DGLFDO ORVVHV IURP WKH PROHFXODU LRQ LQFOXGH PHWK\O UDGLFDO ORVV WR JLYH WKH LRQ DW P] bf DQG ORVV RI D KHSW\O UDGLFDO OHDGV WR WKH LRQ DW P] bf )URP WKH LRQ DW P] ORVV RI KHSWHQH JHQHUDWHV WKH LRQ DW P] bf 6LPLODUO\ ORVV RI KHSWHQH IURP WKH PROHFXODU LRQ YLD D UHDUUDQJHPHQWf OHDGV WR WKH LRQ DW P] bf IURP ZKLFK ORVV RI KHSWDQH FDQ OHDG WR WKH LRQ DW P] bf $OVR ORVV RI KH[HQH IURP WKH PROHFXODU LRQ OHDGV WR WKH LRQ DW P] bf

PAGE 160

r fM&FK FmKQFKR P] bf + &2&+J &m+“ & &2 &2&+J FKFK 1+ P] bf P] bf &2&+J &+ W &2 9 + &A&+ gn&+2 P] bf &+ n n &+2 FKQ F R &+ &+ 1+ P] bf &2 P] bf 9 &R+ n n 9 &+ n n FK AK P] bf +& 1+ P] bf fQV &+ 1+ "+ &+&+ 1+ P] bf P] bf 9 FK FK 9 + &+&+ UYM+ P] bf &+ FKFK LVA P] bf FK FKFK LMA P] bf P] bf 6FKHPH %

PAGE 161

P] bf &F+ n n &+&+ 1+ P] bf FK &+&+ “+ ‘I P] bf &+ + &Y+ P] bf + L FKQ &+ P] bf &W+ n n P] bf &W+ n n I &+ FKQ FK bf bf &+1U+ bf 6FKHPH % )UDJPHQWDWLRQ RI $LORFW\OM96RFW\OIRUPDPLGH f 6FKHPH %f $AO2FW\O\9RFW\OIRUPDPLGH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf D&OHDYDJH RI D KHSW\O UDGLFDO JHQHUDWHV WKH EDVH SHDN DW P] bf

PAGE 162

)URP WKLV LRQ P] f ORVV RI &2 OHDGV WR WKH LRQ DW P] bf $ VXEVHTXHQW ORVV RI SHQWHQH IRUPV WKH LRQ DW P] bf 7KH 0 LRQ P] f ZDV REVHUYHG DW D YHU\ ORZ LQWHQVLW\ bf /RVV RI DQ RFWHQH PROHFXOH IURP WKH 0 LRQ JHQHUDWHG WKH LRQ DW P] bf DQG VXEVHTXHQW ORVV RI DQRWKHU RFWHQH PROHFXOH UHVXOWV LQ WKH LRQ DW P] bf $Q DOWHUQDWLYH DFOHDYDJH RI KHSWHQH IURP WKH PROHFXODU LRQ JLYHV WKH LRQ DW P] bf DQG VXEVHTXHQW ORVV RI &2 UHVXOWV LQ WKH PLQRU LRQ DW P] bf 6FKHPH %f P] bf &R+ n n 9 + P] bf &R+ W n KQ F R P] bf W FK.7 &+2 P] bf &+ n n P] bf + P] bf &R+ n n A P] LOO P] bf &+ QF+ + P] bf &+ 6FKHPH %

PAGE 163

)UDJPHQWDWLRQ RI 9PHWK\O79 GRGHF\OIRUPDPLGH f 6FKHPH %f $I0HWK\O1OGRGHF\OIRUPDPLGH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf ,QLWLDO ORVV RI D K\GURJHQ UDGLFDO JHQHUDWHV WKH LRQ DW P] bf IURP ZKLFK ORVV RI &2 FDQ DOORZ IRUPDWLRQ RI WKH LRQ DW P] bf 7KH LRQ FRUUHVSRQGLQJ WR P] FDQ IUDJPHQW E\ VHTXHQWLDO ORVV RI HWK\OHQH PROHFXOHV WR \LHOG WKH SHDNV REVHUYHG DW P] bf bf bf bf DQG bf UHVSHFWLYHO\ D&OHDYDJH WR \LHOG WKH XQGHF\O UDGLFDO JHQHUDWHV WKH EDVH SHDN DW P] bf /RVV RI &2 IURP WKH EDVH SHDN JLYHV WKH LRQ DW P] bf IURP ZKLFK WKH LRQ DW P] bf FRXOG EH H[SODLQHG E\ ORVV RI PHWKDQH 5DGLFDO FOHDYDJH RI WKH 9PHWK\O ERQG JHQHUDWHV LRQ DW P] bf 6HTXHQWLDO ORVV RI &2 DQG HWK\OHQH JHQHUDWHV WKH VHULHV RI LRQV GLIIHULQJ E\ PDVV XQLWV bf bf bf DQG bf )UDJPHQWDWLRQ RI $/PHWKYO9GRGHFYODFHWDPLGH f 6FKHPH %f 10HWK\O$0GRGHF\ODFHWDPLGH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf D&OHDYDJH RI DQ XQGHF\O UDGLFDO JHQHUDWHV WKH EDVH SHDN DW P] f ZKLFK PD\ ORVH &2 WR JLYH WKH LRQ DW P] bf )URP WKLV LRQ P] f ORVV RI HWK\OHQH DQG PHWKDQH JHQHUDWHV WKH LRQV DW P] bf DQG P] bf UHVSHFWLYHO\ 7KH PROHFXODU LRQ FDQ ORVH D K\GURJHQ UDGLFDO WR IRUP WKH 0 LRQ DW P] bf IURP ZKLFK ORVV RI &2 OHDGV WR WKH LRQ DW P] bf &RQVHFXWLYH ORVV RI HWK\OHQH PROHFXOHV JHQHUDWHV WKH IROORZLQJ VHULHV RI LRQ P] bf bf bf bf bf DQG bf 6LPLODUO\ ORVV RI &2 IURP WKH PROHFXODU LRQ OHDGV WR WKH LRQ DW P] bf IURP ZKLFK ORVV RI PXOWLSOHV RI PDVV XQLWV HWK\OHQH PROHFXOHVf JHQHUDWHV WKH VHULHV RI LRQV LQGLFDWHG

PAGE 164

&+&+f&+ n 1 &+ &+2 &+&+f&+ n Y&+ _?7 n&+2 + P] &+ &+&+f&+ 1+&+2 P] bf &2 &+&+f&+ &+&+f&+ 1+ P] bf &R+ W &+&+f&+ 1+ P] bf &+ &+&+f&+ 1+ P] bf &+ &+&+f&+ 1+ P] bf A&+ KAQnFKR P] bf &2 KF rA P] bf &+ +&HH“+ P] bf &+&+f&+ “A P] bf &2 &+&+ “nA+ P] bf A&+ FKFKfFK QK P] bf FK &+&+f&+ f§&+ + P] bf &R+ r n &+R &+&+f&+ 1U+ P] bf FK A&+R FKFKfFK QK P] bf L FK FK &+&+f&+ Q P] bf ;+ + 6FKHPH %

PAGE 165

W &+1&2&+ KQ FK P] bf $ &Q+ n n +& 1&2&+ &2 &R+ n n & 1&+ &+ &+ &+ P] bf + P] bf P] bf & +&+ 1f§&2&+ &+ P] bf &2 &+ n &+ 1 &+ &+ P] bf &R+ n n &R+ A &+ 1 &+ &+ P] bf &R+ n n &W+ n n &+ 1 &+ &+ &R+ &+1&+ L KF Q FK P] bf &+ &+ P] bf FKFKQFK &+ 1&+ + &+ P] bf P] bf &+ &+ f &+&+1&+ &+&+ M&+ AL L M &+ &+ P] bf P] bf $ &+ &+ &J+X&+R1&+ &+&+ IMA P] bf  &+ $ &+ P] bf FKFK Q &+ P] bf P] bf ‘FK f&+R &+&+f§ P] bf 6FKHPH %

PAGE 166

)UDJPHQWDWLRQ RI 1DFHW\O$OGRGHF\OIRUPDPLGH f 6FKHPH %O f $$FHW\O$OGRGHF\OIRUPDPLGH f 6FKHPH %OOf GLVSOD\V LWV PROHFXODU LRQ DW P] bf 7ZR PDMRU IUDJPHQWDWLRQ SDWKZD\V KDYH EHHQ QRWHG ILUVWO\ ORVV RI D K\GURJHQ UDGLFDO JHQHUDWHV WKH LRQ DW P] bf ZKLFK FDQ ORVH &2 WR \LHOG WKH EDVH SHDN DW P] bf 7KH EDVH SHDN FDQ IUDJPHQW E\ ORVV RI &2 WR \LHOG WKH LRQ DW P] bf IROORZHG E\ VHTXHQWLDO ORVV RI HWK\OHQH WR JHQHUDWH WKH LRQV DW P] bf bf bf bf bf DQG bf 7KH RWKHU OLNHO\ PDMRU IUDJPHQWDWLRQ SDWKZD\ LQYROYHV LQLWLDO ORVV RI D PHWK\O UDGLFDO IURP WKH EDVH SHDN WR \LHOG WKH LRQ DW P] bf IROORZHG E\ VHTXHQWLDO ORVV RI WZR PROHFXOHV RI &2 WR JHQHUDWH LRQV DW P] bf DQG bf UHVSHFWLYHO\ )XUWKHU IUDJPHQWDWLRQ IURP P] E\ VHTXHQWLDO ORVV RI HWK\OHQH FDQ JHQHUDWH WKH LRQV REVHUYHG DW P] bf bf bf bf DQG bf )UDJPHQWDWLRQ RI $PHWK\O$RFWYOORFW\ODPLQH f 6FKHPH %f $0HWK\O$RFW\O9ORFW\ODQLLQH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf 5DGLFDO FOHDYDJH FRQVWLWXWHG PRVW RI WKH SDWKZD\V IRU WKH VXEVHTXHQW LRQV IRUPHG IURP WKH PROHFXODU LRQ D&OHDYDJH RI D SHQW\O UDGLFDO OHG WR WKH EDVH SHDN DW P] bf &OHDYDJH RI D PHWK\O UDGLFDO IURP WKH PROHFXODU LRQ JHQHUDWHG WKH LRQ DW P] bf ZKLFK FRXOG WKHQ ORVH HWK\OHQH WR IRUP WKH LRQ DW P] bf $OVR FOHDYDJH RI DQ RFW\O UDGLFDO OHDGV WR WKH LRQ DW P] bf ZKLOH FOHDYDJH RI D EXW\O UDGLFDO OHG WR WKH LRQ DW P] bf &OHDYDJH RI DQ HWK\O UDGLFDO IURP WKH PROHFXODU LRQ JHQHUDWHV WKH SHDN DW P] bf 7KH LRQV DW P] DQG P] WKH EDVH SHDNf FRXOG XQGHUJR IXUWKHU IUDJPHQWDWLRQ WKURXJK ORVV RI HWK\OHQH PROHFXOHV PXOWLSOHV RI PDVV XQLWVf WR JHQHUDWH WKH LRQ SDWKZD\V LQGLFDWHG DV GHVFULEHG DERYH IRU WKH RWKHU ORQJ FKDLQf DOLSKDWLF FRPSRXQGV

PAGE 167

-+2 &L+1 &2&+R rA&+2 &A1n&2&+ bf &+ &+1f§F 2 &+2 bf &2 &+&+f&+ IWI+r &+&+f&+ 1&+2 &2&+ P bf + bf &2 W &+&+f&+ + P] bf &&+ &2 &+&+f&+ A+ P] bf + &2 7 I FK FKFK rn+ P] &+&+f&+ bf + &+ &+&+f&+ “+ P] bf + FK &+ &+&+f&+ QA P] bf 8+ FK bf W &+ + + &+&+f&+ “&+ P] bf + FK &+&+f&+ 1 P] bf FK &+&+f&+ “&+ P] bf + M&+ &+ Pe bf bf P] bf FK &+ IY-+ bf 6FKHPH %

PAGE 168

+1 &+ &T+ +M& &+&+ P] bf n n &T+ n r WI&+ &F+ n FKLFK +& FKFK P] bf +&f§&+ P] bf &R+ &R+ L n n +1 &+ +&&+&+ P] bf &R+ + n n P] bf +1 &+ +&&+&+ P] bf &+ FKQFK +&+ &+1&+ P] bf LL KFFKFK P] bf &+ &+L&+ W &+ +&+ P] bf &+ +1 &+ +&&+ FKQK +4f§&f§&+ P] bf &+ &+J1&+ &+ +&+ P] bf P] bf &+1+ K4 FFK P] bf 6FKHPH %

PAGE 169

)UDJPHQWDWLRQ RI 79PHWK\OGLOGRGHF\ODPLQH f 6FKHPH %f 10HWK\OGLOGRGHF\ODPLQH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf /RVV RI DQ XQGHF\O UDGLFDO JHQHUDWHV WKH EDVH SHDN DW P] bf 7KUHH RWKHU SRVVLEOH IUDJPHQWDWLRQ SDWKZD\V KDYH EHHQ QRWHG )LUVWO\ WKH PROHFXODU LRQ FDQ ORVH DQ XQGHFHQH PROHFXOH WR \LHOG WKH LRQ DW P] bf ZKLFK FDQ IXUWKHU ORVH D PHWK\O UDGLFDO WR JHQHUDWH WKH LRQ DW P] bf 6HFRQGO\ D PHWK\O UDGLFDO FDQ EH ORVW ZLWK VXEVHTXHQW K\GURJHQ UHDUUDQJHPHQW WR \LHOG WKH LRQ RI YHU\ ZHDN LQWHQVLW\ DW P] bf ,Q DGGLWLRQ WKH PROHFXODU LRQ FDQ ORVH D K\GURJHQ UDGLFDO WR JHQHUDWH WKH LRQ DW P] bf &AfA &+ P] bf &+ &L+1 &+&+f&+ F + P] bf I &L+ 1&+ &+ P] bf +r &AfA &+ P] bf &+&+f&+ &+ &R+ n n &+ “&+ P] bf &+ AA 1 &+ + P] bf 6FKHPH %

PAGE 170

)UDJPHQWDWLRQ RI L9PHWKYOGLOEXWYODPLQHf 6FKHPH %f 90HWK\OGLEXW\ODPLQH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf 7KH EDVH SHDN P] f PD\ EH IRUPHG YLD WZR SRVVLEOH SDWKZD\V Lf ORVV RI D SURS\O UDGLFDO FRXSOHG ZLWK ORVV RI SURSHQH RU LLf ORVV RI D SURS\O UDGLFDO WR JHQHUDWH WKH LRQ DW P] bf ZKLFK ZRXOG HYHQWXDOO\ ORVH SURSHQH /RVV RI PHWKDQH IURP WKH EDVH SHDN ZRXOG OHDG WR WKH LRQ DW P] f &+f10H r f rFK &+f10H P] bf &+ r&+ &+Jf§UcM &+ FK P] bf &+ P] bf &+ UVM &+ P] bf 6FKHPH % )UDJPHQWDWLRQ RI $APHWK\O$AOEXW\OIRUPDPLGH f 6FKHPH %f L90HWK\O9OEXW\OIRUPDPLGHf 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf /RVV RI D SURS\O UDGLFDO OHDGV WR WKH IRUPDPLGH LRQ DW P] bf )XUWKHU ORVV RI &2 IURP WKLV LRQ JLYHV WKH EDVH SHDN DW P] 7KH PROHFXODU LRQ XQGHUZHQW ORVV RI SURSHQH WR JHQHUDWH WKH LRQ DW P] bf DQG ORVV RI D K\GURJHQ UDGLFDO WR JHQHUDWH WKH LRQ DW P] bf

PAGE 171

FKQFKR FK W &+J1&+2 &+ rFK P] bf I + &+J6 &+ 1&+2 &+ PI] bf FK.FKR &+ P] bf &+ P] bf &2 &+ cc+ &+ PI] bf I + &+ IYM &+ bf 6FKHPH % )UDJPHQWDWLRQ RI 9PHWK\O9 KH[\OIRUPDPLGH f 6FKHPH %f 90HWK\/9 KH[\OIRUPDPLGH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf /RVV RI D SURS\O UDGLFDO WKH EDVH SHDN DW P] bf )XUWKHU ORVV RI &2 IURP WKH EDVH SHDNV JLYHV WKH LRQ DW P] bf 7KH LRQ DW P] FRXOG DOVR ORVH PROHFXODU K\GURJHQ WR JHQHUDWH WKH LRQ DW P] bf 7KH PROHFXODU LRQ XQGHUZHQW ORVV RI SHQWHQH WR JHQHUDWH WKH LRQ DW P] bf /RVV RI D K\GURJHQ UDGLFDO IURP WKH PROHFXODU LRQ JHQHUDWHG WKH 0+ LRQ DW P] bf )UDJPHQWDWLRQ RI 9PHWK\OGLOKH[\ODPLQH f 6FKHPH %f M90HWK\OGL KH[\ODPLQH f 6FKHPH %f GLVSOD\V LWV PROHFXODU LRQ DW P] bf /RVV RI D SHQW\O UDGLFDO SURYLGHG WKH EDVH SHDN DW P] 7KH EDVH SHDN FRXOG WKHQ ORVH SHQWHQH WR IRUP WKH LRQ DW P] bf ZKLFK WKURXJK ORVV RI PROHFXODU K\GURJHQ FRXOG OHDG WR WKH LRQ DW P] bf 7KH 0+ P] f ZDV REVHUYHG ZLWK D ORZ LQWHQVLW\ bf

PAGE 172

W &+1&+2 &+ P] bf A + FKQ F &+ P] bf &+ -&+2 &+ P] bf &2 &+ &+2 &+ P] bf 6FKHPH % &+f10H &+f10H P] bf f&J+Q F+1 &+ &F+ n n I + &+f1 &+ P] bf &+ P] bf &+ UMLf§+ FK bf &+ “ &+ P] bf &+I_M &+ &+ Pt bf K &+ 6c &+ P] bf 6FKHPH %

PAGE 173

$33(1',; & ;5$< &5<67$/ 6758&785( 2) %(1=275,$=2/( &$5%2;$0,',1,80726
PAGE 174

)LJXUH &O 3HUVSHFWLYH YLHZ RI WKH FU\VWDO VWUXFWXUH RI EHQ]RWULD]ROHFDUER[DPLGLQLXP WRV\ODWH f

PAGE 175

;UD\ FU\VWDO VWUXFWXUH RI fF &U\VWDO GDWD &+126 FRORUOHVV SODWH [ [ PP RUWKRUKRPELF 3EFD D f E f F f ƒ 9 f ƒ 7 r& 'F J FP = )f 'DWD FROOHFWLRQ VWUXFWXUH VROXWLRQ DQG UHILQHPHQW $OO PHDVXUHPHQWV ZHUH PDGH ZLWK D 1LFROHW 3V GLIIUDFWRPHWHU XVLQJ JUDSKLWH PRQRFKURPDWL]HG 0R .D ; ƒf UDGLDWLRQ 7KURXJKRXW WKH GDWD FROOHFWLRQ WR VFDQV LD[ rf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f ZLWK Z >RA)Tf@ 7KH SDUDPHWHUV ZHUH UHILQHG WR Z5 IRU DOO XQLTXH PHDVXUHG UHIOHFWLRQV 7KH ILQDO FRQYHQWLRQDO 5 YDOXH ZDV IRU UHIOHFWLRQV ZLWK ) R)f )LQDO GLIIHUHQFH PDS IHDWXUHV ZHUH DOO H ƒn )LQDO QRQK\GURJHQ DWRP FRRUGLQDWHV DUH JLYHQ LQ 7DEOH &O )XOO WDEOHV RI DWRP FRRUGLQDWHV WKHUPDO SDUDPHWHUV ERQG OHQJWKV ERQG DQJOHV DQG VWUXFWXUH IDFWRUV KDYH EHHQ GHSRVLWHG ZLWK WKH &DPEULGJH &U\VWDOORJUDSKLF 'DWD %DVH & 'DWD REWDLQHG E\ 'U 3HWHU 6WHHO IRU D FU\VWDO VXEPLWWHG E\ WKH ZULWHU

PAGE 176

7DEOH &O $WRP FRRUGLQDWHV [ f DQG HTXLYDOHQW LVRWURSLF GLVSODFHPHQW SDUDPHWHUV ƒ [ f IRU $WRP ; \ ] 8HT 1Of f f f f 1f f f f f 1f f f f f &$f f f f f &f f f f f &f f f f f &f f f f f &f f f f f &$f f f f f &Of f f f f 1OOf f f f f 1f f f f f &Onf f f f f &nf f f f f &nf f f f f &nf f f f f &nf f f f f &nf f f f f 6Of f f f f f f f f f f f f f f f f f f f &f f f f f

PAGE 177

5()(5(1&(6 7KH UHIHUHQFH FLWDWLRQ V\VWHP HPSOR\HG WKURXJKRXW WKLV GLVVHUWDWLRQ LV WKDW IURP &RPSUHKHQVLYH +HWHURF\FOLF &KHPLVWU\ YRO ,f 3HUJDPRQ 3UHVV 2[IRUG 7KH VHULHV LV HGLWHG E\ $ODQ 5 .DWULW]N\ )56 DQG &KDUOHV 5 5HHV )56 (DFK WLPH D UHIHUHQFH LV FLWHG D QXPEHU DQG OHWWHU FRGH DSSHDUV LQ EUDFNHWV IRU H[DPSOH >$%&@ 7KH ILUVW WZR GLJLWV GHQRWH WKH \HDU LQ XQLWV RI WHQ IRXU GLJLWV DSSHDU IRU \HDUV QRW IURP WKH WK FHQWXU\f WKH OHWWHU FRGH LV DQ DEEUHYLDWLRQ IRU WKH MRXUQDO RU ERRN FLWHG DQG WKH ODVW GLJLWVf UHSUHVHQWVf WKH SDJH QXPEHU $GGLWLRQDO QRWHV WR WKH V\VWHP DUH DV IROORZV Lf 7KH UHIHUHQFHV DUH OLVWHG FRQVHFXWLYHO\ E\ \HDU DOSKDEHWLFDO E\ WKH MRXUQDO FRGH DQG WKHQ E\ SDJH QXPEHU LLf (DFK UHIHUHQFH FRGH LV IROORZHG E\ WKH FRQYHQWLRQDO OLWHUDWXUH FLWDWLRQ FRPSOHWH ZLWK WKH QDPHV RI WKH DXWKRUV LLLf -RXUQDOV ZKLFK DUH SXEOLVKHG LQ PRUH WKDQ RQH SDUW RU PRUH WKDW RQH YROXPH SHU \HDU DUH FLWHG ZLWK WKH DSSURSULDWH SDUW RU YROXPH LYf 3DWHQWV DUH FLWHG ZLWK DSSURSULDWHG WKUHH OHWWHU FRGHV WR GHQRWH FRXQWU\ RI RULJLQ Yf %RRNV ZKLFK DUH IUHTXHQWO\ FLWHG DUH SUHFHGHG E\ WKH OHWWHU % YLf %RRNV DQG MRXUQDOV ZKLFK DUH OHVV FRPPRQO\ XVHG FRGHG n0,n IRU PLVFHOODQHRXV

PAGE 178

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

PAGE 179

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

PAGE 180

>&59@ /D\HU 5 : &KHP 5HY >-$@ 6KRUW + %LHUPDFKHU 8 'XQQXJDQ $ /HWK 7 $P &KHP 6RF >-0&@ 6KRUW + %LHUPDFKHU 8 'XQQLJDQ $ /HWK 7 0HG &KHP >0,@ %XG]LNLHZLF] + 'MHUDVVL & :LOOLDPV + ,QWHUSUHWDWLRQ RI 0DVV 6SHFWUD RI 2UJDQLF &RPSRXQGVf +ROGHQ'D\ ,QF 6DQ )UDQFLVFR S >&&&@ &HUYLQND .UL] 2 &ROOHFW &]HFK &KHP &RPPXQ >&KHP $EVWU @ >&/,@ &HUYLQND 2 &KHP /LVW\ >&KHP $EVWU @ >-$@ 'XIILHOG $ 0 %XG]LNLHZLF] + :LOOLDPV + 'MHUDVVL & $P &KHP 6RF >$*(f@ *DPEDU\DQ 1 3 5RNKOLQ ( 0 =HUIPDQ < 9 &KLQ%6)@ 'XIIDXW 1 'XSLQ 5 %XOO 6RF &KLP )U >0,@ %HFNHU + 2 %RHWWFKHU + 5RHWKOLQJ 7 7LPSH +:LVV = 7HFK +RFKVK &KHP &DUO 6FKRUOHPPHU /HXQD0HUVHEXUJ >0,@ 6DXQGHUV 5 $ :LOOLDPV $ ( $GYDQFHV LQ 0DVV 6SHFWURPHWU\f (G 0HDG : /f (OVHYLHU 3XEOLVKLQJ &R $PVWHUGDP YRO S >-2&@ :HLQJDUWHQ + &KXSS 5 :KLWH : $ 2UJ &KHP >%0,@ %XG]LNLHZLF] + 'MHUDVVL & :LOOLDPV + 0DVV 6SHFWURPHWU\ RI 2UJDQLF &RPSRXQGVf +ROGHQ'D\ ,QF6DQ )UDQFLVFR S

PAGE 181

>%0,@ 6HH >%0,@ S >%0,@ 6HH >%0,@ S >%0,@ 6HH >%0,@ S >%0,@ 6HH >%0,@ S >$*(f@ :LWWLJ 5HLII + $QJHZ &KHP ,QW (G (QJO >25 @ 1LHOVHQ $ 7 +RXOLKDQ : LQ 2UJDQLF5HDFWLRQVf 9RO (GV $GDPV 5 %ODWW $ + %RHNHOKHLGH 9 &DLUQV 7 / &UDP +RXVH + 2f -RKQ :LOH\ DQG 6RQV 1HZ -35@ %HFNHU + 2 7LPSH +3UDNW &KHP >0,@ &DOFXODWHG IURP WKH VSHFLILF LQWHUQDO HQHUJ\ YDSRUL]DWLRQ LQ6WHDP 7DEOHVf .HHQDQ + .H\HV ) +LOO 3 0RRUH :LOH\,QWHUVFLHQFH 1HZ -2& @ .XR 6 & 'DO\ : + 2UJ &KHP >/$@ %RJGDQRYLF .RQVWDQWLQRYLF 6 -XVWXV /LHELJV $QQ &KHP >-$@ 5RZOH\ / *UHHQOHDI $ / .HQ\RQ / $P &KHP 6RF >-35@ %XNHU + 2 +HLPEXUJHU 7LPSH +3UDNW &KHP >%0,@ 3RUWHU 1 %DOGDV 0DVV 6SHFWURPHWU\ RI +HUWHURF\FOLF &RPSRXQGVf :LOH\,QWHUVFLHQFH 1HZ %0,@ 6HH >%0,@ S >%0,@ 6HH >%0,@ S

PAGE 182

>0,@ -RXOH ( $ 6PLWK ) f+HWHURF\FOLF &KHPLVWU\ QG HG9DQ 1RVWUDQG 5HLQKROG 1HZ -2&@ 0DHKU + /HDFK 0 2UJ &KHP >%&-@ 7DNDKDVKL 07DQ + )XNXVKLPD 6@ 0,(@ &5& +DQGERRN RI &KHPLVWU\ DQG 3K\VLFVf HG &5& 3UHVV %RFD 5DWRQ )/ S( >6&@ 6WHLQ & 'HMHVR % 3RPPLHU & 6\Q &RPP >-&63f@ 6DVDNL 7 2KQR 0 ,WR ( &KHP 6RF 3HUNLQ 7UDQV >0,@ +HUUPDQQ 0 6RPHUYLOOH 5 / HGV f$PLQR $FLGV %LRV\QWKHVLV DQG *HQHWLF 5HJXODWLRQf $GGLVRQ:HVOH\ 3XEOLVKLQJ &R 0DVVDFKXVHWWV >0,@ 1HZPDQ 6 $6KDOH 2LO 8SJUDGLQJ t 5HILQLQJf %XWWHUZRUWK 3XEOLVKHUV %RVWRQ >%0,@ 3RUWHU 4 1 0DVV 6SHFWURPHWU\ RI +HWHURF\FOLF &RPSRXQGV :LOH\,QWHUVFLHQFH 1HZ %0,@ 6HH >0,@ S >+&$@ 2SSRO]HU : 0RUHWWL 5 +HOY &KLP $FWD >-$@ *HQQDUL & &RORPER /LQR %HUWRORQL $P &KHP 6RF >-$@ (YDQV $ %ULWWRQ 7 & (OOPDQ $ 'RURZ 5 / 'HOODULD ) $P &KHP 6RF

PAGE 183

>-$@ 7ULPEOH / $ 9HGHUDV & $P &KHP 6RF >-2&@ (LVFK 6DQFKH] 5 2UJ &KHP >-2&@ 0DU\DQRII & $ 6WDQ]LRQH 5 & 3ODPSLQ 1 0LOOV ( 2UJ &KHP >6@ 0LOOHU $ ( %LVFKRII 6\QWKHVLV >-&63f@ .DWULW]N\ $ 5 5DFKZDO 6 5DFKZDO % &KHP 6RF 3HUNLQ 7UDQV >-2&@ %HUJHURQ 5 0F0DQLV 6 2UJ &KHP >-2&@ .DWULW]N\ $ 5 /DXUHQ]R 6 2UJ &KHP >7/@ .LP /LQ <7 0RVKHU + 6 7HWUDKHGURQ /HWW >&59@ (UGLN ( $\ 0 &KHP 5HY >-+&@ 'UHLNRP % $ 8QJHU 3 +HWHURF\FOLF &KHP >-2& @ $VWOHIRUG % $ *RH / .HD\ 6YULYHQ ( ) 2UJ&KHP >-2&@ 'DL : 6ULQLYDVDQ 5 .DW]HQHOOHQERJHQ $ 2UJ &KHP >0,@ 7KHEWDUDQRQWK & 7KHEWDUDQRQWK < LQ 7KH &KHPLVWU\ RI (QRQHV (GV 3DWDL 6 5DSSRSRUW =f -RKQ :LOH\ t 6RQV 1HZ 6@ 0RULQD 3 $UJXH] $ 9HODVFR 0 9LOODOJRUGR -0 6\QWKHVLV

PAGE 184

>6&@ %DQIL % %HQHGLQL ) &DVDQRYD 3HUHJR 5 7RPD / 6\QWK &RPPXQ >7&0@ 0XVXPDUUD 3LVDQR .DWULW]N\ $ 5 /DSXFKD $ 5 /X[HP ) 0XUXJDQ 5 6LVNLQ 0 %URQV 7HWUDKHGURQ &RPS 0HWKRG >$;@ 6KHOGULFN 0 $FWD &U\VWDOORJU 6HFW $ >()@ 6LVNLQ 0 %URQV 9DXJKQ 6 1 .DWULW]N\ $ 5 %DODVXEUDPDQLDQ 0 (QHUJU\ )XHOV >()@ .DWULW]N\ $ 5 /DSXFKD $ 5 0XUXJDQ 5 /X[HP ) 6LVNLQ 0 %URQV (QHUJU\ )XHOV >-$@ (YDQV $ %ULWWRQ 7 & (OOPDQ $ 'RURZ 5 / $P &KHP 6RF >-&63f@ %ULPEOH 0 $ 5RZDQ ' &KHP 6RF 3HUNLQ 7UDQV >6&@ $U]HQR + % %LQJHQKHLPHU : 0RUJDQV -U 6\QWK &RPPXQ >7/@ 2SSRO]HU :7DPXUD 2 7HWUDKHGURQ /HWW >0,@ 7LDQ = 5RHVNH 5 : ,QW 3HSWLGH 3URWHLQ 5HV >6&,@ 6LVNLQ 0 .DWULW]N\ $ 5 6FLHQFH >7@ .DWULW]N\ $ 5 5DFKZDO 6 +LWFKLQJV 7HWUDKHGURQ >()@ $ 5 .DWULW]N\ $ 5 /DSXFKD $ 5 6LVNLQ 0 (QHUJ\ )XHOV >()@ .DWULW]N\ $ 5 /X[HP ) 0XUXJDQ 5 *UHHQKLOO 9 6LVNLQ 0 (QHUJ\ )XHOV

PAGE 185

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

PAGE 186

%,2*5$3+,&$/ 6.(7&+ 5RVO\Q / 3DUULVf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

PAGE 187

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

PAGE 188

, FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ 8 9DQHLFD
PAGE 189

/' X-6 81,9(56,7< 2) )/25,'$