Citation
Preparation of polymers via Manninch reaction

Material Information

Title:
Preparation of polymers via Manninch reaction
Creator:
Hong, Seok Heui, 1952-
Publication Date:
Language:
English
Physical Description:
x, 113 leaves : ill. ; 28 cm.

Subjects

Subjects / Keywords:
Amines ( jstor )
Ethers ( jstor )
Flasks ( jstor )
Hydroxides ( jstor )
Piperazines ( jstor )
Polymerization ( jstor )
Polymers ( jstor )
Protons ( jstor )
Sodium ( jstor )
Solvents ( jstor )
Amines ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Polymers and polymerization ( lcsh )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1985.
Bibliography:
Bibliography: leaves 110-112.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Seok Heui Hong.

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:
000869514 ( ALEPH )
14399175 ( OCLC )
AEG6551 ( NOTIS )
AA00004877_00001 ( sobekcm )

Downloads

This item has the following downloads:


Full Text













PREPARATION OF POLYMERS
VIA MANNICH REACTION






BY






SEOK HEUI HONG -


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


1985




PREPARATION OF POLYMERS
VIA MANNICH REACTION
BY
SEOK HEUI HONG
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
1985


To my family, for their love,
patience and encouragement


ACKNOWLEDGMENTS
I wish to extend my sincere appreciation to Dr. George B. Butler
for his help, advice and expertise during my program of research. I
would also like to thank the members of my supervisory committee.
Colleagues, members of the polymer research group, are
appreciated for the friendly atmosphere they provided. I also thank
Ms. Cindy Zimmerman for her skillful typing of this manuscript.
Finally, I would like to thank Mr. S.H. Yoon and Mr. M. Mura for
their help.
Financial support for this work from the Department of
Chemistry, Graduate School, International Minerals and Chemical
Corporation, Allied Chemical Company and National Institute of Health
is gratefully acknowledged.
i i i


TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS iii
LIST OF TABLES vi
LIST OF FIGURES vii
ABSTRACT ix
CHAPTERS
I INTRODUCTION 1
The Use of Amines 3
Ni troal kanes 5
Polymeric Mannich Bases 7
Proposal of Research 8
II EXPERIMENTAL 13
General 13
Reagents and Solvents 14
Synthesis of Nitroalcohols 15
Synthesis of Model Compounds 20
Reactions Utilizing Chain-Stopping Reagents 32
Synthesis of Polymers 33
Reduction of Model Compounds 39
Reduction of Polymers 41
Methyl a ti on 43
Miscellaneous Reactions 46
IIIRESULTS AND DISCUSSION 52
Model Compounds 56
Model Compounds with 2-Nitropropane as
Chain-Stopping Reagent 62
Model Compounds with N-(8-hydroxyethyl)
Piperazine 71
Studies with Nitromethane 80
Model Compounds from Bis-secondary Amines 81
Polymers 88
IV


Reduction of Model Compounds 94
Reduction of Polymers 99
Methylation 103
Mannich Reaction on Nitroethane 105
Urethanes and Polyurethanes 106
Summary and Conclusion 109
REFERENCES 110
BIOGRAPHICAL SKETCH 113
v


LIST OF TABLES
Table Page
1 Reaction of 2-nitropropane with NMPD and formaldehyde 57
2 Reaction of (18) with DMPA 58
3 Reaction of N-methyiethanolamine and compound (18) 59
vn


LIST OF FIGURES
Figure Page
1 1H NMR spectrum of the model compound (21) in CDCI3 60
1 O
2 Completely decoupled C NMR spectrum of compound
(21) in CDCI3 61
3 NMR spectrum of compound (13) in CDCI3 63
1 O
4 Completely decoupled C NMR spectrum of compound
(13) in CDC13 64
5 NMR spectra (in CDCI3) of the model compounds
utilizing 2-nitropropane as chain-stopping reagent 66
6 Plot of the number of repeating limits vs. reactant
feed ratio 68
7 NMR spectrum of compound (30) in CDC13 69
8 Completely decoupled ^C NMR spectrum of compound
(30) in CDCI3 70
9 NMR spectrum of compound (24) in CDC13 72
10 Completely decoupled 13C NMR spectrum of the compound
(24) in CDCI3 73
11 13C NMR spectra of compound (26) in DMS0-d6:
(1) completely decoupled; (2) off-resonance 75
12 Selected time dependent NMR spectra of the reaction of
NHEP with compound (19) in 0MS0-d6 at RT 73
13 Plot of the consumption of NEPD vs. reaction time 79
14 1H NMR spectra of compound (15) in DMSO-do:
(1) without D2O, (2) 1 drop of D2O was added 82
15 ^C NMR spectra of compound (15) in DMS0-d6:
(1) completely decoupled; (2) off-resonance 83
VI 1


16 NMR spectrum of compound (31) in CDC13 85
17 13C NMR spectra of compound (31) in 00013:
(1) completely decoupled; (2) off-resonance 86
18 33C NMR spectra of compound (32) in 00013:
(1) completely decoupled, (2) INEPT (CH, CH3 pos.,
CH2 neg., C, solvent suppressed) 87
19 13C NMR spectra of polymer (35) in 00013:
(1) completely decoupled; (2) off-resonance 89
20 13C NMR spectra of polymer (36) in 00013:
(1) completely decoupled, (2) INEPT (CH, CH3 pos.,
CH2 neg., C, solvent suppressed) 91
21 IR spectra of (1) compound (27), and (2) compound
(39) (reduced by NaBH4 and Pd/C) 96
22 IR spectra of (1) compound (27), and (2) compound
(39) (reduced by H2/Raney Ni) 97
23 13C NMR spectra of compound (39) in CDCI3:
(1) completely decoupled; (2) off-resonance 98
24 IR spectra of (1) polymer (35), and (2) polymer (40) 100
25 IR spectra of (1) polymer (36), and (2) polymer (41) 101
26 IR spectra of (1) polymer (37), and (2) polymer (42) 102
27 13C NMR spectra (INEPT: CH3, CH pos., CH2 neg.;
C, solvent suppressed) of compounds (40) and (43),
respecti vely 104
vi i i


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
PREPARATION OF POLYMERS
VIA MANNICH REACTION
BY
SEOK HEUI HONG
May, 1985
Chairman: Dr. George B. Butler
Major Department: Chemistry
In order to achieve the objective of this research, which was to
utilize the Mannich reaction to synthesize new water-soluble
polymers, several model compounds were studied. The reaction of N,N-
dimethyl-l,3-propanediamine with formaldehyde and 2-nitropropane was
carried out, and the best result was obtained utilizing the methylol
derivative of 2-nitropropane at a lower temperature with a base
catalyst. The reactions of other amines, i.e., N-methylethanolamine
and piperazine, with formaldehyde and 2-nitropropane were undertaken
with similar results. Some bis-secondary amines, i.e., N,N'-
dime thy1ethylenediamine (DMEA), N,N'-dimethyl-2-butene-1,4-diamine
(DMBA) and N,N-dimethylhexamethylenediamine (DMHA), were also
studied. In an attempt to provide a better understanding of the
polymerization, model compounds with controlled molecular weights
were studied utilizing chain-stopper components.
IX


Polymers of the desired structure were obtained from reactions
of the methylol derivative of nitroethane with bis-secondary amines,
including DMEA, DMBA, and DMHA. Alternatively, N,N,N',N'-
tetramethyl-2-methyl-2-nitro-l,3-propanediamine was reacted with
DMEA, DMBA and DMHA to yield polymers of the same structure. These
polymers containing nitro groups were reduced by hydrogen gas in the
presence of Raney nickel to afford the corresponding amine-containing
polymers. Upon treatment with formic acid and formaldehyde, the
polymers underwent methylation to afford the corresponding
polyamines. Since the polymers prepared were of relatively low
molecular weight, an attempt was made to prepare high molecular
weight polymers utilizing nitroethane. However, the Mannich reaction
of nitroethene with formaldehyde and dimethylamine yielded a dark
brown tar-like material which was not identifiable. The model
compound prepared from nitroethane, formaldehyde and N-(3-
hydroxyethylJpiperazine was reacted with methylenedi-_p-phenylene-
diisocyanate to afford the corresponding polyurethane, which has the
intrinsic viscosity of 0.194 dl/g in DMSO at 30C. Similarly, the
same model compound was reacted with hexamethylenediisocyanate to
yield the corresponding polyurethane.
x


CHAPTER I
INTRODUCTION
The Mannich reaction is defined as the condensation of ammonia
or a primary or secondary amine with formaldehyde and a compound
containing at least one hydrogen atom of pronounced reactivity. The
first observation of this type was made by Tollens, who isolated the
tertiary amine from ammonium chloride, formaldehyde and
1 O
acetophenone. However, the detailed study of the reaction was
initiated in 1912 by Mannich who observed that antipyrine (1),
formaldehyde and ammonium chloride reacted to form a tertiary
amine. Thus, the reaction has become known generally as the
CH
3
N CCH
3
+ 3 HCHO + NH4C1
C CH
II
0
(1)
N CCH
3
CC CH
2
N-HCl
II
0
3
1


2
Mannich reaction, and is recognized as one of the classical reactions
of organic chemistry. This reaction has been widely used in
synthesis and was the subject of many reviews.^
The mechanism of the Mannich reaction has been well
investigated, and a comprehensive review covering up to 1968 has been
published.'7 Only a few of the main points will be discussed here.
The Mannich reaction leads to products of the type (6), bearing a
substituted methylene group connecting the substrate residue with
R-H + HCHO + H<
2
(6)
an amino group. The condensation reaction occurs in 2 steps. First,
the amine reacts with formaldehyde to give condensation product
2^3t^4 (Step I), which then attacks the substrate R-H (Step II).
Even though this is believed to be the main route of the reaction,


3
some successful reactions between hydroxymethyl derivatives (5) and
alkylamines to give Mannich bases (6) are known.
The reactive species in acidic medium is the iminium ion (2),
derived principally from methylene-bis-amine (4) and secondarily from
hydroxymethylamine (3). In basic medium, the reactant is postulated
to be hydroxymethylamine (3) or, more probably, methylene-bis-amine
(4). The existence of cation (2) in aqueous solutions of amine and
formaldehyde has been demonstrated by polarographic methods; the
maximum concentration of (2) was reported to occur at pH 10-11.
The Use of Amines
The choice of the amine used in the reaction is important. It
is known that primary amines can react at both amine H-atoms, and
therefore it is difficult to obtain secondary Mannich bases free from
tertiary derivatives. However, use of the sterically hindered amine
(7), or similar amines containing bulky groups (t-butyl, di- or tri-
arylmethyl), can prevena substitution reaction involving the second
amine H-atom of (7). The bulky alkyl groups can subsequently be
removed by hydrolysis to give the N-unsubstituted aminoketone (9),
which is not directly obtainable from ammonia and formaldehyde,9


4
It is also known that use of the oxalate derivatives of the primary
amines instead of the corresponding hydrochlorides makes the
O IQ
synthesis of secondary Mannich bases in high yields possible.
The use of secondary bifunctional amines such as piperazine
leads to symmetric Mannich bases, in which both of the amino groups
have reacted. Attempts to restrict the reaction to only one amine
function or hydrolysis of the Mannich products obtained from
piperazines invariably leads to the formation of disubstituted
piperazines (10).^
/^\
R-H + HCHO + HN NH
V /
. / \
-> RCH^ N CH2R
(10)
The Mannich reaction of bis-(2-chloroethyl)amine can give a
1 ?
bicyclic salt as by-product. Two molecules of the amine thus
condense with one molecule of formaldehyde to give (11), which shows
cytostatic properties as do halgena ted derivatives of similar
13,14
structure.


/ \
Cl '"V-? c'
+
HCHO > Cl
(11)
Nitroalkanes
Henry was the first to show that Mannich type reactions will
occur with nitroalkanes.^,16 established that N-hydroxymethyl-
piperidine condensed with nitromethane and nitroethane to yield,
respectively, 2-nitro-l,3-dipiperidinopropane (12a) and 2-methyl-2-
nitro-1,3-dipi peridinopropane (12b).
2 Qch2oh + ch2rno2 > o2h--(ch2Q )2
(12)
(12a), R = H
(12b), R = CH3
Later, Senkus successfully carried out reactions using methyl amine,
isopropylamine, 1-butylamine, 2-butylamine, benzylamine, 1-
phenylethylamine, 2-amino-l-butanol, and 2-amino-2-inethyl-1-propanol
as monoalkylamine components; and nitroethane, 1- and 2-nitropropane,
and 2-nitrobutane as nitro components.^ He showed that the products
could be obtained either by allowing the amine to react with
formaldehyde and thereafter adding the nitroalkane, or by first


5
generating the methylol derivative of the nitroalkane, which was then
treated with the amine.
R
, I
R NHCHo0H + HC-N0o
I
R
R
> R'NHCHoCN0o + Ho0
\
R
R
2R'NHCH20H + RCH2N02 > R'NHCH2CCH2NHR' + H20
N02
al ternatively,
R
, I
R NH0 + H0CHo-C-N0
I
R
R R
2R*NH0 + H0CHo-C-CHo0H > RNHCH0C-CHNHR' + Ho0
2 2 | 2 ^ 21 2 2
N02 no2
Johnson extended the work of Senkus to various aliphatic
I O
secondary amines. He also carried out these reactions by two
different methods: (A) reaction of the amines, formaldehyde and
nitroparaffin; and (B) reaction of the amine with the nitro alcohol
or nitro diol. Although the same end-products resulted in either
case, the latter reaction was slower. It is also shown that
unsubstituted piperazine and 3,5-dimethylpiperazine gave the
corresponding bis condensation products (13).^


7
HN
/~\
NH + 2 HCHO
n-ch2-cch3
(13)
Polymeric Mannich Bases
Even though the Mannich reaction has been widely investigated
mechanically and used extensively in synthesis of small molecules, it
has been used only in a very limited manner in synthesis of
macromolecules. Apparently, the first application to synthesis of
macromolecules was by Bruson and Butler, who condensed 2,4,5-
trinitrotoluene with formaldehyde and ammonia to yield explosive
plastics. This was followed by Butler and Benjamin who condensed
phenols with formaldehyde and primary or secondary amines to
synthesize ion-exchange resins.23 Later, Tsuchida and Tomono
Op
condensed pyrrole, formaldehyde and amines to yield polymers.
Tomono, Hasegawa and Tsuchida extended the earlier work to include
other active hydrogen compounds as well.23 McDonald and Beaver later
published some of the details of modification of polyacrylamide by
use of the Mannich reaction. Recently, Andreani and coworkers
reported a synthetic route to tertiary amino polymers, namely the
polycondensation of bis(6-dialkylaminoketone)s, i.e. bis(Mannich
pc
bases) with bis-secondary amines to yield poly(S-aminoketone)s.


8
Angeloni and co-workers extended this work to aromatic Mannich bases
I I
such as 4,4 -bis(0-dimethylaminopropionyl)diphenyl or 4,4 -bis(S-
dimethylaminopropionyl)di-phenylether.^^7 Ghedini and coworkers
also extended this work to phenolic Mannich bases such as 2,6-bis(di-
OQ
methyl ami nomethyl)-4-methyl phenol.
Proposal of Research
It is the objective of the research to utilize the Mannich
reaction between formaldehyde, selected amines and the nitroparaffins
as the active hydrogen compounds to synthesize amine-containing
and/or quaternary ammonium containing polymers. The reactions
anticipated to occur are as follows:


9
n RCH2N2 + 2n HCHO + n R NH2
CH0-C-CH0-N-
2 I 2
N0o
+ 2n H20
Reduction,
R
I
R
I
CH,-C-CH,-N
I
NH0
Methyl a ti on
>
R
R
CH?-C-CH?-N-
I
N(CH )
J n
Quaternization
> CH0-C CH0N
21 2 i
L +N(CH3)3 CH3 J n
R = CH3 or C2H5
Nitroethane, as well as 1-nitropropane, can be utilized as the active
hydrogen compound. Both nitroparaffins should result in polymers of
high charge density. The resulting polymers from nitroethane and 1-
nitropropane would have an equivalent weight with respect to
quaternary ammonium centers (chloride form) of 114.5 and 121.5,
respectively.
It is well recognized that the effectiveness of cationic
polymers in the flocculation and coagulation applications is a direct


10
function of the charge density on the polymer. Thus, it would be
predicted that the qua termzed polymer derived from polyethyleneamine
would be most effective having an eq. wt. of 107.5 (chloride form):
However, such a polymer has been shown to be relatively unstable due
to the proximity of the positive charges. An alternative polymer of
high charge density is poly(vinyltrimethylammonium chloride) of eq.
wt. of 121.5:
CH-CH
21
- +N(CH o) o
Cl J J
However, this polymer is difficult to synthesize and its cost would
be high. The most widely used cationic polymer in the flocculation
area of application is perhaps poly(diallyldimethylammoniurn chloride)
of eq. wt. 161.5:
or
CH,
CH,
N
H3

11
Again, this polymer is made from a fairly expensive monomer and has
relatively high equivalent weight per charge.
Considerable versatility is envisioned in the above system. For
example, use of either 2-nitro-propane or a secondary amine would
produce polymers with molecular weight control, as both of these
reactants would function as chain-stoppers:
CH9C CH~ N
2| 2 i
+N(CH3)3
CH
3 J
CH.
CH0
C N(CH3)3
ch3
2-nitropropane as chain-stopper
1 +
N -
I
CH.
CH9 N CH0-
2 i 2
+N(ch3}3
CH
f+
N CH.
Secondary amine as chain-stopper
Use of nitromethane or ammonia would result in crosslinked
polymers. Thus, it is apparent that a wide variety of products are
possible from the proposed reactions.
The problem anticipated is the known requirement of considerably
high molecular weights for effective flocculation and coagulation
character!-sties in cationic polymers. The reaction proposed, the
Mannich reaction, for polymer synthesis can be classified as an
example of condensation polymerization or step-growth polymeriza
tion. And such processes are known to require (A) relatively pure


12
reactants; and (B) rigidly controlled stoichiometry in order to
attain high molecular weights. Thus one of the major objectives of
the research is to attain the necessary stoichiometric control to
lead to the desired degrees of polymerization.


CHAPTER II
EXPERIMENTAL
General
Melting points, given in degrees Celsius, were determined on a
Thomas-Hoover Capillary Melting Point Apparatus and are reported
uncorrected. Pressures are expressed in millimeters of mercury (mm
Hg). Elemental analyses were performed by either Atlantic Microlabs,
Inc., Atlanta, Georgia, or Department of Chemistry, University of
Florida, Gainesville, Florida.
Proton nuclear magnetic resonance (NMR) spectra (60 MHz) were
recorded on a Varian EM360L instrument. Carbon-13 NMR (25 MHz) and
100 MHz proton NMR spectra were recorded on a Jeol-JNM-FX-100
spectrometer. Chemical shifts are expressed in parts per million
(ppm) on the <$ scale downfield from te tramethylsi lane (TMS) or sodium
2,2-dimethyl-2-silapentane-5-sulfonate (DSS) unless otherwise
indicated. In cases where no internal reference was added, spectra
were calibrated via a characteristic signal of the deuterated solvent
used. The solvent used and calibration information are given in
parentheses for each spectrum reported. Multiplicities of proton and
off-resonance decoupled carbon resonances are designated as singlet
(s), doublet (d), triplet (t), quartet (q) or multiplet (m).
13


14
Infrared (IR) spectra were recorded on a Perkin-Elmer 281
spectrophotometer. Absorbances are expressed in wavenumbers (cm--*-)
using the 1601 cm-3 line of standard. Solid samples were run as a
KBr pellet; liquid samples were analyzed neat as a thin film between
NaCl plates. Absorption bands are assigned the classifications weak
(w), medium (m), strong (s), broad (br) and shoulder (sh).
Molecular weights of polymers were determined by vapor pressure
osmometry (VPO) on a WESCAN model 233 Molecular Weight Apparatus.
Benzil was used as a calibration standard. Intrinsic viscosities
were measured with Ubbelohde viscometer (dilution viscometer).
Reagents and Solvents
Reagents were obtained from Aldrich Chemical Co., Eastman Kodak
Co., Fischer Scientific Co. or Mal 1inckrodt, Inc., unless otherwise
noted. Deutrated solvents were purchased from Merck & Co., Inc., and
Aldrich Co.
All solvents used for general applications were of Reagent grade
or ACS grade quality. For special applications, solvents were
purified as needed by following procedures reported in the
1iterature.3^ Thus, dimethylsulfoxide (DMSO) and N.N-dirnethyl -
formamide (DMF) were allowed to stand over potassium hydroxide
pellets and distilled from calcium oxide under reduced pressure;
ethanol-free chloroform (CHCI3) was obtained by extraction of reagent
grade CHC13 with concentrated H2SO4 and water, followed by
distillation from phosphorus pentoxide (P^q).


15
Synthesis of Nitroalcohols
2-Nitroethanol (14)
The procedure reported by Burmistrou and Bashinova31 was
modified as follows. Nitromethane (610 g, 10 moles) and para
formaldehyde (30.0 g, 1 mole) were placed into a 2,000 ml three
necked round-bottomed flask fitted with a thermometer and a reflux
condenser. The mixture was heated in an oil bath to 105-110C and
potassium carbonate (0.64 g, 0.1% of the reaction mixture) was added
in 10 portions. Each successive portion of catalyst (K2C03) was
added after vigorous boiling of the mixture ceased. During the
additions, the color (cloudiness) of the mixture disappeared
slowly. When the paraformaldehyde was completely dissolved to yield
a clear solution, the mixture was held for 30 minutes at the same
temperature, cooled, filtered to separate the catalyst, and
neutralized with 4 drops of concentrated H2S0^. The light yellow
filtrate was distilled under reduced pressure to remove excess
nitromethane (30-34C at 30-60 mm Hg, then held at 5-7 mm Hg for 30
min.). The yellow residue was transferred to a 100 ml. round-
bottomed flask and distilled under vacuum (59-63C at .25 mm Hg) to
yield 52 g (57.1%) of crystal clear liquid, n^4 1.4434 [literature
value 1.4438].32
XH (CDC13,TMS): 6 4.14 (m,2H), 4.54 (m,2H).
2-Nitro-1,3-propanediol (15)
Procedure A: The following procedure was modified from the
procedure of Den Otter.33 Paraformaldehyde (38 g, 1.265 mole),
nitromethane (22.5 g, 0.369 mole) and 10 drops of 33% aqueous


16
potassium hydroxide were heated with 350 ml of methanol under reflux
in an oil bath. The 2-(hydroxymethyl)-2-nitrol-1,3-propanediol (16),
formed during the reaction, was not isolated, but used in the
dissolved condition. A solution of sodium (10.5 g, 0.457 mole) in
150 ml of methanol was added dropwise to the solution, which was
stirred and cooled in an ice bath. During this addition, a
precipitate of the sodium derivative of 2-nitro-1,3-propanediol (17)
began to separate and this separation was complete after the flask
had stood overnight in a refrigerator. The filtered and dried sodium
derivative of 2-nitro-1,3-propanediol (60 g) was mixed in 300 ml of
ether and added in 5 equal portions to a solution of 40 g of
salicylic acid in 250 ml of ether, which was brought to reflux.
After 3 hours of reflux, the mixture was cooled, the sodium
salicylate filtered off and the ether evaporated. The resulting oil
was added to a hot mixture of 1:1.7 ethylacetate and chloroform to
yield a clear yellow solution, which was placed in a refrigerator
overnight to yield white crystals. The filtered crystals were
recrystal 1ized from a 1:1.7 ethylacetate and chloroform mixture to
yield needle-like white crystals (33 g, 73.9% yield), m.p. 53C
[literature m.p. 54C].33
Sodium derivative of 2-nitro-1,3-propanediol (17)
(D20,DSS): 6 4.37 (S,2H), 3.31 (S,4H).
2-nitro-1,3-propanediol (15)
(DMS0-d6,TMS): 6 3.72 (m,4H), 4.66 (m,lH), 5.27 (t,2H).
13C (DMS0-d6> 39.5): <5 59.555, 91.917.


17
IR (KBr): 3380 (s.br), 2950 (m), 2900 (m), 1550 (s), 1460 (s),
1360 (s,sh), 1330 (s), 1245 (m), 1210 (m), 1075 (s,sh), 1010 (s), 975
(w), 915 (w,sh), 865 (m), 770 (w) cm--*-.
Analysis, calculated for C3H7N04: C, 29.75; H, 5.83; N, 11.57.
Found: C, 29.83; H, 5.84; N, 11.55.
Procedure B: A mixture of nitromethane (12.108 g, 0.2 mole) and
calcium hydroxide (0.065 g) was placed in a 250 ml round-bottomed
flask equipped with a stirrer and a condenser, and cooled in an
external ice bath. After cooling, 32.465 g of formalin solution (37%
w/w aqueous, 0.4 mole) was added slowly from a dropping funnel.
After the addition was complete, the solution was stirred at room
temperature for 66 hours. Carbon dioxide in the form of dry-ice was
added in excess and the calcium carbonate was filtered. The filtrate
was evaporated at 90C under reduced pressure to yield a molten, dark
brown, viscous oil, which upon cooling, solidified. The resulting
solid was recrystallized from a 1:1.7 ethylacetate-chloroform mixture
to yield a white crystalline product (18.3 g, 60.6%) which turned out
to be 2-(hydroxymethy1)-2-nitro-l,3-propanediol (16).
:H (acetone-d6,TMS): 6 4.05 (d,6H), 4.33 (t,3H).
2-Methyl-2-nitro-l-propanol (18)
The following procedure was modified from the procedure of
Vandervilt and Hass.^ To a 500 ml three-necked round-bottomed flask
equipped with a mechanical stirrer and thermometer was added 44.5 g
(0.499 mole) of freshly distilled 2-nitropropane and 0.125 g of
calcium hydroxide. The mixture was cooled in an external ice bath to
0-5C, after which 41 g (0.505 mole) of formalin solution (37% w/w


18
aqueous) was added dropwise from the dropping funnel. After the
addition was complete, the solution was stirred at room temperature
for 43 hours. Carbon dioxide in the form of dry-ice was added in
excess and the calcium carbonate precipitate was removed by
filtration. The precipitate was washed with 10 ml of water, and the
combined filtrate and washings were evaporated at 90C under reduced
pressure. The remaining molten product, which solidified upon
cooling, was recrystallized from 1:10 butanol-benzene to yield 54.5 g
(91.5%) of white crystalline product, m.p. 88-89C [literature m.p.
89.5-90C].34
NMR (CDC13,TMS): 6 1.58 (s,6H), 2.86 (s,lH), 3.84 (s,2H).
13C NMR (CDC13,77.0): 6 22.73, 68.13, 88.72.
IR (KBr): 3440 (s,br), 3000 (m), 2940 (m), 2880 (m), 1545 (s),
1465 (m), 1410 (w), 1400 (w), 1375 (m), 1350 (m,sh), 1150 (w), 1067
(m,sh), 990 (w), 860 (w,sh), 820 (w), 730 (w) cm-3.
2-Methyl-2-nitro-1,3-propanediol (19)
By use of the same procedure as reported for the previous
compound on preparation of this compound was accomplished by adding
slowly 160 g (2 mole) of formalin solution (37% w/w aqueous) to a
mixture of 75 g (1 mole) of nitroethane and 0.25 g of calcium
hydroxide. After stirring for 43 hours at room temperature, and a
slight excess of carbon dioxide had been added, the white precipitate
which formed was filtered and washed. The filtrate and washings were
combined and evaporated at 90C under reduced pressure to yield
molten product, which upon cooling, solidified. The crude product
was recrystallized from 1:10 butanol-benzene to yield 113 g (83.1%)


19
of white crystalline product, m.p. 153-155C [literature m.p. 149-
150C].34
XH NMR (CDC13,TMS): 6 1.52 (s,3H), 2.46 (t,2H), 4.07 (d,4H).
13C NMR (C0C13, 77.0): 6 16.93, 64.02, 93.11.
IR (KBr): 3300 (s,br), 3000 (m), 2960 (m), 2390 (m), 2100 (w),
1540 (s), 1470 (m), 1440 (m), 1410 (m), 1370 (m), 1360 (m,sh), 1305
(m), 1240 (m), 1215 (w), 1180 (m), 1130 (m), 1080 (m), 1035 (s), 985
(m), 950 (m), 905 (m), 870 (m), 835 (m), 745 (m), 740 (m,sh), 675
(m,br) cm-1.
2-Ethyl-2-nitro-1,3-propanediol (20)
Preparation of this compound was achieved as previously
described by adding 160 g (2 mole) formalin solution (37% w/w
aqueous) to a mixture of 89 g (1 mole) of 1-nitro-propane and 0.25 g
of calcium hydroxide. The recrystallization yielded white
crystalline product (126 g, 84.5%), m.p. 55-56.5C [literature m.p.
56C].34
3H NMR (CDC13,TMS): 6 0.90 (t,3H), 1.90 (q,2H), 3.04 (s,2H),
4.11 (m,4H).
13C NMR (CDC13,77.0): 6 7.650, 25.777, 63.743, 94.253.
IR (KBr): 3400 (s,br), 2980 (m), 2890 (m), 1540 (s), 1425 (m),
1360 (m), 1310 (w), 1250 (w,sh), 1190 (w), 1065 (s,sh), 975 (m), 905
(w), 860 (m), 815 (m), 785 (m), 720 (w), 640 (w) cm-1.


20
Synthesis of Model Compounds
N-(2-Hydroxyethyl)-N-methyl-(2-methyl-2-nitro-l-propyl)
amine (21)
Procedure A: In a 100 ml round-bottomed flask were placed 5.955
g (0.0500 mole) of 2-methyl-2-nitro-l-propanol (18) in 20 ml of
freshly distilled THF and 4 A molecular sieves, and 3.756 g (0.0500
mole) of N-methylethanolamine in 10 ml of THF was added slowly by
means of a dropping funnel. After the addition was complete, the
reaction was stirred for 72 hours, with fresh molecular sieves (4 A)
added every 12 hours. The molecular sieves were filtered, and the
solvent was evaporated under reduced pressure to yield a yellow oil,
4.88 g (55.4%).
Procedure B: The same procedure was used with the exception of
addition of triethylamine (1 ml) to the reaction mixture. Thus, the
reaction of (18) (5.957 g, 0.05 mole) and N-methyl-ethanolamine
(3.757 g, 0.05 mole) afforded yellow oil (5.86 g, 66.5%).
Procedure C: The reaction mixture (alcohol, amine and catalyst
NEt3) in was stirred and refluxed for 20 hours and cooled to room
temperature. The solvent was removed by evaporation under reduced
pressure to yield a yellow oil (5.95 g, 76.5%).
Analysis, calculated for C7H15N2O3; C, 47.71; H, 9.15; N, 15.90.
Found: C, 47.72; H, 9.11; N, 15.78.
1H NMR (C0C13,TMS): 6 1.57 (s,6H), 2.27 (s,3H), 2.54 (s,lH),
2.62 (t,2H), 2.88 (s,2H), 3.53 (t,2H).
13C NMR (CDC13,77.0): 23.24, 43.13, 58.63, 60.77, 66.18,
88.26.


21
IR (KBr): 3400 (s,br), 2980 (s), 2945 (s), 2370 (s), 2800 (m),
1770 (w), 1640 (w), 1530 (s), 1455 (s), 1400 (s), 1370 (s), 1345
(s,sh), 1280 (w), 1220 (w), 1185 (w), 1160 (w), 1120 (m), 1065 (s),
1035 (s,sh), 980 (w), 945 (w), 900 (w), 855 (m,sh), 815 (w), 790 (w)
cnf-*-.
2-Ethy 1 -2-n i tro-l,3-bis(2-hydroxyethyl-N-methyl )amino
propane (22)
The solution of 3.756 g (0.0500 mole) of N-methylethanolamine
and 3.729 g (0.025 mole) of 2-ethyl-2-nitro-l,3-propanediol (21) with
4 A molecular sieves in 70 ml THF was stirred for 60 hours at room
temperature. The molecular sieves were filtered out and the filtrate
was evaporated under reduced pressure to yield a yellow oil (4.76 g,
72.4%).
NMR (CDC13,TMS): 6 0.94 (t,3H), 1.89 (q,2H), 2.30 (s,3H),
2.42 (s,3H), 2.91 (t,4H), 3.23 (s,4H), 3.57 (t,4H), 4.21 (s,2H).
N,N-Dimethyl-N' ,N'-bis(2-methyl-2-nitro-l-propyl )-l,3-
propanediamine (23)
Procedure A: To a solution of N,N-dimethyl-l,3-propanediamine
(DMPA) (5.109 g, 0.050 mole) in 20 ml of 1,4-dioxane was added
formalin solution (8.303 g, 37% w/w aqueous, 0.100 mole). A
catalytic amount (~0.1 g) of hydrochloric acid was added and
stirred. To this mixture, 2-nitropropane (9.091 g, 0.102 mole) was
added and stirring was continued for 50 hours at 60C. The reaction
mixture was cooled, neutralized with 1 g of NaOH and extracted with
3x30 ml of methylene chloride. The combined organic phase was dried
over MgSO^ overnight, filtered and evaporated to yield a yellow oil
(7.55 g, 49.7%).


22
Procedure B: To a solution of 2-nitropropane (4.546 g, 0.051
mole) in 20 ml of 1,4-dioxane at 0-5C (in an external ice bath) was
added formalin solution (4.015 g, 37% w/w aqueous, 0.0495 mole) and
potassium carbonate (0.235 g). The ice bath was removed and the
mixture was stirred at room temperature for 45 hours. Then N,N-
dimethyl-l,3-propanediamine (2.555 g, 0.025 mole) in 10 ml of
1,4-dioxane was added. The reaction mixture was brought to reflux
and extracted with 3x40 ml of ether. The combined organic phase was
dried over MgSO^ overnight, filtered and evaporated to yield yellow
oil (1.87 g, 24.6%).
Procedure C: To an ice-cooled 250 ml round-bottomed flask
containing 2-nitro-2-methyl-propanol (11.91 g, 0.1 mole) in 25 ml of
water was slowly added N,N-dimethyl-l,3-propanediamine (5.109 g,
0.050 mole) in 20 ml of 1,4-dioxane. After the addition was
complete, the solution was stirred at 0-5C for 1 hour, then at 60-
70C for 18 hours. This was extracted with 3x30 ml of methylene
chloride, and the combined organic phase was dried over MgS04,
filtered and evaporated to yield a yellow oil (7.73 g, 50.9% yield).
Analysis, calculated for C^i^gN^O^: C, 51.31; H, 9.21; N,
18.42. Found: C, 51.18; H, 9.13; N, 18.52.
XH NMR (CDC13,TMS): 6 1.55 (s,12H), 2.15 (m,2H), 2.19 (s,6H),
2.6 (m,4H), 3.08 (m,4H).
13C NMR (CDC13*77.0): 6 22.41, 24.22, 45.08, 52.68, 57.02,
63.89, 88.45.
IR (Neat): 3350 (m,br), 2995 (s), 2950 (s), 2870 (s), 2830 (s),
2790 (s), 1540 (s), 1470 (s), 1400 (m), 1375 (s), 1350 (s), 1285


23
(m,br), 1200 (w), 1160 (m,sh), 1080 (m), 1040 (m), 1025 (m), 990 (w),
950 (w), 910 (w), 860 (s), 820 (m,sh), 750 (w,br), 650 (w) cm'1.
N,Ml-Bis(2-methy1-2-nitro-l-propy1)piperazine (13)
In a 100 ml 3-necked round-bottomed flask equipped with a
dropping funnel charged with 1,4-dioxane, a stirrer and a Dean-Stark
trap were placed 2-nitropropane (1.72 g, 0.02 mole), formalin
solution (1.62 g, 37% w/w aqueous, 0.02 mole) and piperazine (0.86 g,
O.01 mole) in 20 ml of 1,4-dioxane. A catalytic amount (~0.5 ml) of
sodium hydroxide solution (10% w/v, aqueous) was added and the
reaction mixture was brought to reflux. The solvent was added from
the dropping funnel to keep the volume constant. When the boiling
point of the azeotropic mixture reached 100C, addition of solvent
was stopped and the volume of the reaction mixture was reduced to
~V2 of the original volume. Petroleum ether was added to this
reaction mixture and the upper layer was decanted. The resulting oil
was crystallized from acetone to yield a yellowish white powder (1.98
g, 71.2% yield).
Analysis, calculated for C12Hi4N404: C, 50.00; H, 8.33; N,
19.44. Found; C, 49.78; H, 8.90; N, 19.32.
XH NMR (CDC13,TMS): 5 1.54 (s,12H), 2.47 (s,8H), 2.83 (s,4H).
13C NMR (CDC13,77.0): 6 24.072, 55.117, 65.669, 88.648.
IR (KBr): 2940 (m,sh), 2860 (w,sh), 2800 (m,sh), 2740 (w,sh),
1700 (w), 1560 (s), 1455 (m), 1400 (m), 1370 (m,sh), 1340 (s), 1320
(s), 1285 (w), 1235 (w), 1190 (w), 1155 (s), 1115 (m), 1015 (m), 990
(w), 945 (w,sh), 890 (w), 855 (h), 830 (m,sh), 640 (w) cm"1.


24
2-Methyl-2-nitro-l,3-bis
N'-(8-hydroxy-ethyl)-N-
piperazino
propane (24]
Procedure A: To a formalin solution (3.28 g, 0.0404 mole) were
added nitroethane (1.501 g, 0.0200 mole) and N-(e-hydroxyethyl)-
piperazine (5.208 g, 0.0400 mole). Sodium hydroxide solution (5% w/v
aqueous, 1 ml) was added to this mixture. Upon addition, an
exothermic reaction occurred immediately and a white precipitate
formed, which was not soluble in 1,4-dioxane. Petroleum ether was
added to this mixture, and the solid was filtered and dried to yield
white crystals (5.34 g, 74.4% yield) which were recrystallized in
acetone, m.p. 118-120C.
Procedure B: In a 100 ml round-bottomed flask was placed a
solution of N-(8-hydroxyethyl)piperazine (5.209 g, 0.04 mole) in 20
ml of 1,4-dioxane with sodium hydroxide solution (5% w/v aqueous, 1
ml). To this solution was slowly added a mixture of formalin
solution (37% w/w aqueous, 3.28 g, 0.04 mole) and nitroethane (1.502
g, 0.02 mole) in 10 ml of 1,4-dioxane. This reaction mixture was
brought to reflux for 2 hours, then the solvent was distilled until
the volume of the remainder became ~25 ml. Upon cooling, a yellowish
white precipitate formed after which petroleum ether (~50 ml) was
added with stirring; the precipitate which formed was filtered and
dried under reduced pressure to yield 5.94 g (82.7% yield) of
yellowish white crystals. Recrystallization from acetone gave white
crystals of mp 118-120C.
Analysis, calculated for Cig^NgO^: C, 53.46; H, 9.25; N,
19.48. Found: C, 52.96; H, 9.34; N, 19.01.


25
:H NMR (CDC13,TMS): 5 1.59 (s,3H), 2.51 (s,20H), 2.78 (d of
d,4H), 3.59 (t,4H).
13C NMR (COCI3*77.0): 6 19.32, 53.0, 55.02, 57.68, 59.11,
63.45, 92.52.
IR (Kbr): 3320 (s,Br), 2950 (s,sh), 2910 (m), 2905 (m), 2885
(m), 2805 (s,sh), 2700 (m), 1530 (s), 1460 (m), 1420 (w), 1400 (m),
1380 (m), 1360 (m), 1340 (m), 1330 (s,sh), 1280 (in), 1225 (w), 1160
(s), 1120 (m), 1100 (m,sh), 1060 (m,sh), 1050 (m), 1040 (m), 1010
(s), 990 (w), 965 (w), 930 (w), 920 (w), 870 (w), 860 (m), 840 (w),
830 (w,sh), 770 (w,sh) cm--*-.
2-Ethyl-2-nitro-l,3-bis{N'-(g-hydroxyethy1)-N-
piperazinyljpropane (25)
This material was prepared by the methods reported for compound
(24).
Procedure A: To a solution of N-(8-hydroxyethyl)piperazine
(5.208 g, 0.04 mole) in 20 ml of 1,4-dioxane was added a mixture for
formalin solution (37% w/w aqueous, 3.28 g, 0.04 mole) and 1-
nitropropane (1.782 g, 0.02 mole) in 10 ml of 1,4-dioxane. Sodium
hydroxide solution (5% w/v aqueous, 1 ml) was added and the mixture
was refluxed for 2 hours. The azeotropic mixture of 1,4-dioxane and
H2O was distilled until the volume of the remaining solution became
25 ml. The resulting dark brown oil was crystallized from acetone to
yield a white flaky solid (3.9 g, 69.9% yield) which turned out to be
methylenebis[ii1-(8-hydroxyethyl )]-N-piperazine (26). The filtrate
was evaporated to yield a brown oil (1.03 g, 13.8% yield) which was
crystallized from acetone. The yellowish white crystals obtained
were the desired product, m.p. 98-101C.


26
Procedure B: A solution of N-(0-hydroxyethyl)piperazine (5.226
g, 0.0041 mole) in 10 ml of THF was slowly added to a solution of 2-
ethyl-2-nitro-1,3-propanediol (2.984 g, 0.02 mole) with NEt-j (0.82 g)
in 10 ml of THF. The reaction mixture was refluxed for 23 hrs and
cooled to room temperature. The solvent was removed under reduced
pressure to yield a yellow oil which was dried over molecular sieves
(4 A) for 20 hours at ~0C. During this time, white crystals formed
which were filtered and dried (2.611 g, 35.2% yield).
lH NMR (CDC13,TMS): 5 0.86 (t,3H), 2.02 (q,2H), 2.49 (s,20H),
2.87 (s,4H), 3.60 (t,4H).
13C NMR (DMS0-d6,39.5): 6 7.97, 24.19, 51.05, 53.17, 54.24,
58.39, 60.14, 94.87.
IR (KBr): 3300 (s,br), 2960 (s), 2940 (s), 2880 (s), 2820
(s,sh), 1700 (w), 1530 (s), 1460 (s), 1445 (m), 1420 (w), 1390 (m),
1365 (m), 1345 (s), 1330 (s), 1305 (s,sh), 1280 (m,sh), 1230 (w),
1205 (w), 1190 (w), 1160 (s), 1140 (m), 1120 (m,sh), 1090 (m,sh),
1050 (m), 1040 (s), 1005 (s), 990 (w), 930 (m,sh), 890 (w), 880 (w),
860 (m), 830 (m), 810 (w), 770 (m), 720 (w), 700 (w,br), 660 (w), 630
(w) cm"-*-.
Methy1ene-bis{N-(e-hydroxyethyl)-N-piperazine} (26)
A formalin solution (37% aqueous, 0.8116 g, 0.01 mole) was added
to a solution of N-(g-hydroxyethyl)piperazine (2.604 g, 0.02 mole) in
10 ml of 1,4-dioxane. A sodium hydroxide solution (10% w/v aqueous,
2 ml) was added to this mixture followed by an additional 10 ml of
1,4-dioxane. This reaction mixture was refluxed for 3 hours, then
cooled to room temperature. Petroleum ether was added and the upper


27
layer was decanted. The resulting yellow oil was crystallized from
cold acetone to yield white flaky crystals (2.4 g, 88.2% yield), m.p.
134-135.5C.
Analysis, calculated for C13H23N4O2: C, 57.32; H, 10.36; N,
20.57.
Found: C, 57.06; H, 10.33; N, 20.48.
(CDC13, TMS): <$ 2.52 (s,20H), 2.93 (s,2H), 3.63 (t,4H).
13C (CDC13,77.0): 6 51.32, 52.88, 57.75, 59.50, 80.70.
IR (KBr): 3300 (s,Br), 2960 (s), 2940 (s), 2820 (s.sh), 1580
(w), 1510 (w), 1460 (m.sh), 1420 (m), 1370 (m), 1350 (s), 1320
(m,sh), 1290 (m,sh), 1270 (m), 1190 (m), 1170 (s,sh), 1140 (m), 1080
(m), 1060 (m), 1010 (m,sh), 930 (m,sh), 880 (w), 815 (m,sh), 770 (w)
cm-3.
2-Methyl-2-nitro-l,3-dipiperidinopropane (12b)
In a 500 ml round-bottomed flask equipped with a condenser was
placed a solution of 2-methyl-2-nitro-1,3-propanediol (40.439 g,
0.299 mole) in 250 ml of THF. A solution of piperidine (50.980 g,
0.599 mole) in 50 ml of THF was added, and the mixture was stirred
for 36 hours at room temperature, followed by evaporation of the
solvent. The resulting light yellow, viscous oil was crystallized in
cold methanol to yield white crystals (68.7 g, 85.3% yield).
Analysis, calculated for C14H27N3O2: C, 62.42; H, 10.10; N,
15.60. Found: C, 62.48; H, 10.13; N, 15.60.
lH NMR (CDC13,TMS): 6 1.43 (m,12H), 1.57 (s,3H), 2.40 (m,8H),
2.73 (m,4H).


28
13C NMR (CCl3,77.0): 6 18.96, 23.88, 26.24, 56.53, 64.47,
93.06.
IR (KBr): 2930 (s), 2840 (m), 2730 (m,sh), 2340 (w), 1540 (s),
1440 (m,sh), 1380 (w), 1330 (m), 1295 (w), 1270 (w), 1150 (m), 1100
(m), 1090 (m), 1045 (m.sh), 1035 (m), 995 (m), 940 (w), 850 (m,sh),
880 (w), 790 (w), 775 (w) cm'1.
2-Methy1-2-nitro-l,3-bis(dimethylamino)propane (27)
The following procedure was adopted from Johnson.13 In a 500 ml
Erlenmeyer flask was placed a mixture of 2-methyl-2-nitro-1,3-
propanediol (19) (67.56 g, 0.5 mole) and dimethylamine (40% aqueous,
112.73 g, 1 mole) and left in the refrigerator for 20 hours. A
reaction took place and phase separation occurred, the top layer
being solid. Ethyl ether (200 ml) was added and the aqueous phase
was separated, and washed with 50 ml of ether. The combined ether
layer was dried over K2CO3, filtered and evaporated to yield a yellow
liquid (81.6 g, 86.2% yield) which later solidified, m.p. 30-31C
[literature m.p. 32C].
XH NMR (CDC13,TMS): 6 1.61 (s,3H), 2.22 (s,12H), 2.74 (m,4H).
13C (COCI3,77.0): 6 18.91, 47.49, 65.33, 92.53.
IR (Neat): 2940 (s), 2860 (m), 2795 (s,sh), 1525 (s,sh), 1450
(s), 1390 (w), 1370 (m), 1325 (s,sh), 1280 (m), 1150 (s,sh), 1090
(m), 1040 (m,sh), 1005 (s), 920 (w,sh), 850 (m), 810 (w), 790 (w),
650 (w) cm-1.
2-Ethyl-2-nitro-N,N'-bis(2-methyl-2-propano-
1-propyl)amine (2T
This material was prepared as described earlier for the case of
(27) by allowing 2-ethyl-2-nitro-1,3-propanediol (20) (74.58 g, 0.05


29
mole) and dimethylamine (40% w/w aqueous, 112.74 g, 1 mole) to react
overnight in a refrigerator. A reaction took place and a non-aqueous
phase separated. The aqueous phase was extracted with 3x30 ml of
ethyl ether and the combined organic phase was dried over K2CO3,
filtered and evaporated to yield a greenish yellow oil (83.4 g, 82.2%
yield). An attempt at further purification by vacuum distillation
failed due to the decomposition of the compound.
lH NMR (CDC13,TMS): 6 0.89 (t,3H), 2.07 (q,2H), 2.21 (s,12H),
2.74 (s,4H).
13C NMR (CDC13,77.0): 6 8.11, 24.43, 47.19, 61.29, 95.05.
IR (Neat): 2980 (m), 2950 (m), 2860 (m,sh), 2825 (m), 2780 (s),
1535 (s), 1460 (s,sh), 1385 (w), 1340 (m,sh), 1270 (w), 1150 (w),
1100 (w), 1040 (m,sh), 870 (w), 850 (w), 835 (w), 795 (w) cm-1.
N,Nl-Dimethyl-N,N'-bis(2-methy1-2-nitro-l-propyl)-
ethylenediamine (29)
In a 100 ml round-bottomed flask equipped with a condenser was
placed a solution of N,N'-dimethylethylenediamine (3.717 g, 0.0422
mole), 2-nitropropane (7.521 g, 0.0844 mole) and formalin solution
(37% w/w aqueous, 6.845 g, 0.0844 mole) in 50 ml of 1,4-dioxane. A
catalytic amount of potassium hydroxide (33% aqueous, 1 ml) was
added, and the reaction mixture was heated to reflux for 2 hours.
The solvent (azeotropic mixture of 1,4-dioxane and water) was
distilled with constant addition of fresh 1,4-dioxane until the
boiling point of the azeotropic mixture reached 100C. The resulting
viscous, yellow liquid crystallized upon cooling. This crude product
was dissolved in 125 ml of ethyl ether, washed with 3x30 ml of water,


30
dried over K2CO3 overnight, filtered and evaporated to yield white
crystals (6.8 g, 55.6% yield), m.p. 63-64.5C.
Analysis calculated for Ci2^26^4^4: C, 49.63; H, 9.03; N,
19.30. Found: C, 49.67; H, 9.04; N, 19.22.
:H NMR (CDC13,TMS): <5 1.55 (s,12H), 2.28 (s,6H), 2.47 (s,4H),
2.84 (s,4H).
13C NMR (CDC13,77.0): 6 23.88, 44.36, 57.93, 67.08, 88.91.
IR (KBr): 2980 (s,sh), 2860 (rn), 2820 (s,sh), 1530 (s), 1470
(m), 1455 (m), 1435 (m), 1400 (m), 1375 (rn.sh). 1340 (s,sh), 1260
(m), 1240 (w), 1200 (m.sh), 1160 (w), 1100 (m,sh), 1040 (s), 1020
(m), 730 (w), 980 (w), 945 (w), 860 (m), 850 (m), 820 (w,sh) cm-1.
N,N1-Dimethyl-N,N1-bis(2-methyl-2-nitro-l-propyl)-2-
butene-1,4-diamine (30)
In a 250 ml round-bottomed flask equipped with a condenser was
placed a solution of N,N-dimethyl-2-butene-l,4-diamine (3.342 g,
O.0293 mole) in 100 ml of 1,4-dioxane. Formalin solution (37% w/w
aqueous, 5.227 g, 0.0644 mole), 2-nitropropane (5.655 g, 0.0635 mole)
and potassium hydroxide (33% w/w aqueous, 3 ml) were added and the
reaction mixture was brought to reflux for 2 hours followed by
distillation of the azeotropic mixture of 1,4-dioxane and water with
constant addition of fresh dioxane. When the temperature of the
outcoming vapor reached 100C, the addition of dioxane was stopped,
and the distillation was stopped when the residual reaction mixture
became cloudy. Ethyl ether (150 ml) was added, the solid portion was
filtered, and the filtrate was evaporated to yield a viscous yellow
oil (7.88 g, 85.1% yield). Storage overnight in a refrigerator


31
resulted in a yellow-white solid which was recrystal 1ized from
methanol to yield white crystals, m.p. 62-53C.
Analysis, calculated for C14H23N4O4: C, 53.14; H, 8.92; N,
17.71. Found: C, 53.23; H, 8.95; N, 17.68.
lH NMR (CDC13,TMS): 6 1.55 (s,12H), 2.25 (s,6H), 2.85 (s,4H),
3.03 (m,4H), 5.52 (m,2H).
13C NMR (CDC13,77.0): 5 24.20, 44.15, 61.35, 65.33, 88.85,
130.41.
IR (KBr): 2980 (s,sh), 2960 (m), 2920 (m,sh), 2860 (m,sh), 2940
(m), 2780 (s,sh), 1530 (s,sh), 1450 (s,sh), 1410 (w), 1395 (m), 1380
(m), 1370 (s), 1340 (s,sh), 1310 (m), 1255 (w.sh), 1210 (w), 1195
(w), 1165 (w), 1120 (m,sh), 1080 (w), 1040 (s), 1015 (w), 985 (s),
975 (m), 970 (m), 910 (w), 855 (s), 815 (w), 730 (w), 670 (w) cm'1.
N,N1-Dimethyl-N,N1-bis(2-methyl-2-nitro-l-propyl)-
hexamethylenediamine (31)
This compound was prepared by the procedure previously described
for the case of (30). N,N'-Dimethyl-hexamethylenediamine (1.561 g,
O.0108 mole), formalin solution (37% aqueous, 1.926 g, 0.0237 mole)
and 2-nitropropane (1.939 g, 0.0218 mole) were allowed to react in
the presence of potassium hydroxide (33% aqueous, 1 ml) to afford
yellow oil (2.14 g, 57.2% yield).
Analysis, calculated for 0-1^^404: C, 55.46; H, 9.89; N,
16.17. Found: C, 55.52; H, 9.91; N, 16.23.
NMR (C0C13,TMS): 6 1.30 (s,8H), 1.58 (s,12H), 2.26 (s,6H),
2.42 (m,4H), 2.83 (s,4H).
13C NMR (CDC13,77.0): 6 23.97, 26.78, 27.33, 43.74, 59.70,
66.57, 88.77.


32
IR (KBr): 2990 (m), 2940 (s), 2860 (s), 2790 (s,sh), 1680 (w),
1640 (w), 1540 (s), 1460 (s,sh), 1400 (m), 1370 (m), 1345 (m), 1320
(m), 1240 (m), 1120 (m), 1050 (m,sh), 940 (w), 910 (w), 860 (m), 820
(w), 800 (w,sh), 730 (w,sh) cm-1.
Reactions Utilizing Chain-Stopping Reagents
General Procedure A: In a round-bottomed 3-necked flask
equipped with a Dean-Stark trap and a dropping funnel charged with
fresh 1,4-dioxane was placed the mixture of the starting materials,
i.e., amine component, formalin solution and nitroalkane in 1,4-
dioxane. A catalytic amount of sodium hydroxide was added and the
azeotropic mixture of 1,4-dioxane and water was distilled off with
constant addition of fresh 1,4-dioxane. When the temperature of the
outcoming vapor reached 100C, the addition was stopped and the
volume of the residual mixture was reduced to half of the original
volume by continuous distillation. Petroleum ether was added to the
reaction mixture and the upper layer was decanted. The resulting oil
was crystallized from acetone or methanol. The feed ratio of the
starting materials and reaction conditions are described in Chapter
III, p. 62.
General procedure B: In a round bottom flask equipped with a
condensor was placed the mixture of the methylol derivative of the
nitroalkane and the amine in THF. A catalytic amount of
triethylamine and 4 A molecular sieves were added. The reaction
mixture was refluxed for 10-15 hours, cooled and filtered. The
filtrate was evaporated to yield a yellow oil, which was crystallized


33
from acetone or methanol. The feed ratio of the starting materials
and reaction conditions are described in Chapter III, p. 62.
Synthesis of Polymers
Polymerization of 2-methyl-2-nitro-1,3-propanediol (19)
with N,N-dimethyl-l,3-propanediamine (32)
In a 100 ml ice-cooled round-bottomed flask was placed a
solution of 2-methyl-2-nitro-1,3-propanediol (19) (13.512 g, 0.10
mole) in 30 ml of 1,4-dioxane. To this, freshly distilled N,N-
dimethyl-1,3-propanediol (10.218 g, 0.10 mole) 30 ml of H20 and HC1
(6N,lml) was added. After the addition was complete, the reaction
mixture was stirred for 1 hour at 0-5C, followed by 16 hours at
70C. The reaction mixture was cooled, made basic with sodium
hydroxide (pH 10~11), and extracted with 3x50 ml of methylene
chloride. The combined organic phase was dried over K2CO3, filtered
and evaporated under reduced pressure to yield a dark brown, viscous
oil (14.23 g, 70.7% yield).
NMR (C0C13,TMS): 5 3.7 (s,4H), 2.75 (m,4H), 2.22 (s,6H), 1.6
(m,2H), 1.56 (s,3H).
13C NMR (C0C13,77.0): 5 24.44, 25.17, 45.10, 51.78, 56.90,
58.02, 58.85, 85.80.
IR (Neat): 2940 (s), 2880 (m), 2850 (s), 2810 (s), 2760 (s),
1540 (s), 1450 (s), 1380 (m,sh), 1340 (m), 1320 (w,sh), 1250 (m,sh),
1210 (m), 1150 (w,sh), 1120 (s,sh), 1080 (m), 1040 (m,sh), 965 (w),
910 (w), 880 (m), 870 (s), 840 (m), 730 (w,sh), 705 (w) cm'1.


34
Polymerization of (20) with N,N-dimethyl-l,3-propanediarnine (33)
This material was prepared by the same procedure described for
(32). Thus, 14.915 g (0.10 mole) of (20) was reacted with 10.213 g
(0.10 mole) of N,N-dimethyl-1,3-propanediol to yield a dark brown oil
(13.75 g, 63.8% yield).
h NMR (CDC13,TMS): 6 3.7 (s,4H), 2.7 (m,4H), 2.25 (s,6H), 1.75
(m,4H), 0.85 (t,3H).
13C NMR (CDC13,77.0): <5 7.09, 24.50, 30.83, 45.06, 51.88,
56.90, 57.84, 87.21.
IR (Neat): 2980 (s), 2940 (s), 2880 (in), 2860 (m), 2820 (s),
2770 (s,sh), 1540 (s), 1460 (s,sh), 1375 (m,sh), 1360 (m), 1345 (m),
1325 (m,sh), 1270 (m,sh), 1215 (m), 1155 (w), 1110 (m,sh), 1040
(m,sh), 1015 (w), 970 (w,Br), 920 (w), 890 (w), 845 (m), 810 (w), 780
(w), 750 (w), 720 (w) cm-1.
Polmerization of (19) with N,N1-dimethylethylenediamine (34)
In a 100 ml round-bottomed flask equipped with a condenser was
added a solution of (19) (8.665 g, 0.0641 mole) in 20 ml of THF and
N,N*-dimethylethylenediamine (5.653 g, 0.0641 mole). To this
solution were added a catalytic amount of NEt3 (1 ml) and 4 A
molecular sieves. The reaction mixture was brought to reflux for 20
hours, cooled and filtered. The filtrate was evaporated under
reduced pressure to yield a brown, viscous oil (9.73 g, 81.0% yield).
Analysis, calculated for CgHjjN-^: C, 51.33; H, 9.09; N,
22.45. Found: C, 50.45; H, 9.02; N, 22.39.
lH NMR (CDC13,TMS): 1.49 (s,3H), 2.41 (s,6H), 2.58 (s,4H),
3.09 (m,4H).


35
13C NMR (COCI3,77.0): 624.46, 48.10, 60.53, 65.01, 90.70.
IR (Neat): 3370 (m,br), 2980 (m), 2940 (m), 2870 (m), 2820 (m),
2800 (m), 2780 (m,sh), 1670 (m), 1645 (m), 1635 (m), 1535 (s), 1455
(s), 1395 (m), 1345 (m.sh), 1290 (m), 1270 (w), 1225 (w), 1165 (w),
1130 (w,Br), 1085 (m), 1040 (ra.sh), 955 (w), 945 (w), 855 (m), 830
(w) cm .
Polymerization of (19) with DMBA (35)
The procedure employed for the polymer (34) was followed; thus,
compound (19) (13.860 g, 0.1026 mole) was allowed to react with DMBA
(11.714 g, 0.1026 mole) in the presence of NEt3 (3 ml) and molecular
sieves (4 A). The resulting yellow solid (14.68 g, 67.12 yield) was
dissolved in THF and reprecipitated in methanol to yield a white
powder.
Analysis, calculated for Cioh19n32: C, 56.31; H, 8.98; N,
19.70. Found: C, 54.99; H, 8.84; N, 19.04.
XH NMR (CDC13,TMS): 6 1.50 (s,3H), 2.21 (s,6H), 3.0 (m,3H),
5.53 (s,2H).
13C NMR (C0C13,77.0): 6 19.06, 44.15, 61.45, 63.26, 93.13,
130.37.
IR (KBr): 2940 (m,sh), 2840 (m,sh), 2780 (s), 1530 (s), 1450
(s), 1335 (m.sh), 1120 (w,sh), 1070 (w,br), 1020 (s), 975 (m,sh), 855
(m,sh) cm-*.
Polymerization of (19) with DMHA (36)
The procedure employed for the polymer (34) was followed; thus,
compound (19) (5.157 g, 0.0332 mole) was allowed to react with DMHA


36
(5.516 g, 0.0382 mole) in THF in the presence of NEt3 and 4 A
molecular sieves to yield a brown oil (6.43 g, 69.1% yield).
Analysis, calculated for Ci2^25^32: 59.23; H, 10.36; N,
17.27. Found: C, 57.62; H, 9.83; N, 17.36.
XH NMR (C0C13,TMS): 6 1.33 (s,8H), 1.59 (s,3H), 2.24 (s,6H),
2.43 (s,4H), 2.81 (m,4H).
13C NMR (CDC13,77.0):6 18.86, 26.95, 27.29, 43.86, 59.89, 64.57,
93.33.
IR (Neat): 2940 (s,sh), 2850 (s), 2790 (s), 1535 (s,sh), 1450
(s,sh), 1420 (w), 1390 (m,sh), 1340 (m.sh), 1240 (w,br), 1120 (w),
1050 (m,br), 1020 (m), 940 (w), 850 (m,sh), 730 (w) cm"1.
Polymerization of (27) with OMEA (34)
Procedure A: The following procedure was modified from the
method reported by Angeloni and coworkers.25,27 ¡n a ^qo ml 3 necked
round-bottomed flask equipped with a stirrer, a condenser and a gas
inlet tube was placed a solution of compound (27) (8.057 g, 0.0426
mole) and DMEA (3.753 g, 0.0426 mole) in 70 ml of 95% ethanol.
Nitrogen gas was bubbled through the solution for 120 hours at room
temperature with constant stirring. During this period, the color of
the solution changed from yellow to dark brown. The solvent was
evaporated under reduced pressure to afford a dark brown, viscous oil
(6.07 g, 76.2% yield), which was identical with the polymer obtained
from the compound (19) and DMEA.
Procedure B: Procedure A was modified as follows: compound
(27) (7.408 g, 0.0391 mole) and DMEA (3.455 g, 0.0392 mole) were
dissolved in 50 ml of DMS0, and placed in a 100 ml round-bottomed


38
Polymerization of (27) with piperazine (37)
Procedure A: In a 250 ml 3-necked round-bottomed flask equipped
with a condenser, a stirrer and a gas inlet tube was placed a
solution of compound (27) (11.11 g, 0.0587 mole) and piperazine (5.06
g, 0.0587 mole) in 100 ml of 95% ethanol. This reaction mixture was
stirred for 60 hours at room temperature followed by 24 hours at 50-
60C, with continuous flow of ^ gas. During the reaction time, a
white precipitate formed. After the reaction mixture was cooled, the
solid, which is insoluble in most of the common organic solvents, was
collected (7.58 g, 69.7% yield).
Procedure B: In a 100 ml 3-necked round-bottomed flask equipped
with a condenser, stirrer and a gas inlet tube was placed a solution
of compound (27) (7.641 g, 0.0404 mole) and piperazine (3.480 g,
0.0404 mole) in 75 ml of DMS0. The reaction mixture was stirred for
60 hours at 70C with a continuous flow of N2 gas. The reaction
mixture, which became a dark brown liquid and a yellow precipitate,
was poured into 400 ml of cold methanol. The solid was filtered,
washed with cold methanol and dried in a vacuum oven to yield an off-
white powder (5.49 g, 73.4% yield).
Analysis, calculated for C8H15^2: C, 51.87; H, 8.16, N,
22.69. Found: C, 54.98; H, 9.04; N, 24.66.
IR (KBr): 2940 (m), 2870 (m), 2800 (s,sh), 1530 (s), 1460
(s,sh), 1400 (w), 1375 (m), 1330 (s,sh), 1280 (m), 1150 (m,sh), 1100
(m), 1070 (w), 1040 (w), 1010 (s), 925 (w), 855 (m,sh), 815 (w), 650
(w) cm--*-.


39
Reduction of Model Compounds
Reduction of compound (12b) (38)
Procedure A: The procedure reported by Parham and Ramp35 was
employed as follows: In a 100 ml 3-necked round-bottomed flask
equipped with a dropping funnel and a condenser was placed an etheral
solution of lithium aluminum hydride (4 g). A solution of compound
(12b) (8.87 g, 0.0329 mole) in 50 ml of absolute ether was added
dropwise from the dropping funnel under N2 atmosphere, and the
reaction mixture was heated at reflux for 1 hour after the addition
was complete. Water was added dropwise until the excess LiAlH^ was
decomposed, and the solution was made alkaline. The attempt to
distill the amine with steam failed. Extraction with ether yielded
an unidentifiable mixture.
Procedure 3: In a 1000 ml Erlenmeyer flask was placed a
solution of sodium borohydride (5 g) in 250 ml methanol with
stirring. A solution of compound (12b) (1.68 g, 0.00624 mole) in 40
ml of chloroform was added dropwise after the addition of (a cata
lytic amount of) palladium on charcoal. When the bubbling had
ceased, additional sodium borohydride was added. This process was
repeated several times. After the addition was complete, the
reaction mixture was stirred for 1 hour at room temperature followed
by the addition of hydrochloric acid (1 N aqueous). When the reac
tion mixture became acidic on to pH paper, the solid (charcoal) was
filtered. The filtrate was condensed under reduced pressure to yield
a light yellow liquid. To this solution, sodium carbonate was added
until the formation of CO2 bubbles ceased (pH ~8). The resulting


40
solution was extracted with 3x100 ml of methylenechloride and the
combined organic phase was dried over K2CO3, filtered and dried to
afford a pale yellow oil (1.04 g, 69.6% yield).
Procedure C: In a 250 ml pressure bomb was placed a suspension
of compound (12b) (4.23 g, 0.0157 mole) in 100 ml of DMF with Raney
Ni (3 g). The bomb was charged with hydrogen gas (400 psi) and
released 3 times before being charged upto 800 psi. The reaction
mixture was stirred for 4 hours at 60C (pressure rose to 840 psi),
then 3 hours at room temperature. The catalyst (Raney Ni) was
filtered and the filtrate was evaporated under reduced pressure at
50C to yield a yellow oil (3.14 g, 83.5% yield).
Analysis, calculated for C14H29N3: C, 70.24; H, 12.21; N,
17.55. Found: C, 70.14; H, 12.25; N, 17.51.
NMR (CDC13,TMS): 6 0.96 (s,3H), 1.43 (s,8H), 1.55 (s,4H),
2.14 (s,4H), 2.48 (m,8H).
13C NMR (CDCl3,77.0): 6 23.93, 25.05, 26.41, 54.97, 57.31,
67.35.
IR (Neat): 3350 (m.br.sh), 2935 (s), 2850 (s), 2780 (s,sh),
1570 (w), 1555 (w,sh), 1450 (m,sh), 1440 (m), 1380 (m), 1365 (m),
1345 (w), 1320 (m,sh), 1310 (m), 1300 (m), 1270 (w), 1260 (w), 1155
(m), 1110 (s,sh), 1055 (m,sh), 1035 (m), 1000 (m), 945 (w,sh), 890
(w,sh), 860 (m), 790 (m,sh), 770 (w) cm-1.
Reduction of compound (28) (39)
In a 450 ml parr bomb equipped with a stirrer was placed a
solution of compound (28) (21.307 g, 0.105 mole) in 200 ml of
methanol with Raney Ni (5 g). The reaction mixture was flushed with
hydrogen gas for 2 hours before the pressure of the bomb was set at


41
1000 psi. The reactor was heated to 50C for 2 hours, cooled and
filtered. The filtrate was evaporated to yield a yellow oil (8.37 g,
68.72 yield) which turned out not to be the desired product but
l-(N,N-dimethylamino)-2-butylamine (39).
Analysis, calculated for CgH^g^: C, 62.01; H, 13.88; N,
24.11 Found: C, 62.11; H, 13.76; N, 24.18.
XH NMR (CDC13,TMS): 6 0.96 (t,3H), 1.42 (q,2H), 2.21 (s,6H),
2.80 (m,1H), 3.50 (d,2H).
13C NMR (CDC13,77.0): 6 10.23 (q), 28.41 (t), 45.57 (q), 49.71
(d), 66.57 (t).
IR (Neat): 3350 (s,br), 3280 (s,br), 2960 (s), 2940 (s), 2880
(s), 2860 (s), 2820 (s) 2770 (s,sh), 1660 (w), 1640 (w), 1600 (m,br),
1460 (m,sh), 1380 (w,sh), 1300 (w,br), 1265 (w), 1150 (w), 1100 (w),
1040 (m,sh), 975 (w), 910 (w), 850 (w), 780 (w) cm-1.
Reduction of Polymers
Reduction of Polymer (35) (40)
Procedure (C) previously described for model compound (27) was
employed. Thus, polymer (35) (8.20 g, 0.0438 mole) in methanol was
placed in a Parr bomb with a catalytic amount (~2 g) of Raney nickel
and the bomb was charged with hydrogen upto 800 psi. The closed
system was heated to 70C for 15 hours to afford a brown oil (5.88 g,
85.42).
Analysis, calculated for C8H19N3: C, 61:10; H, 12.18; N,
26.72. Found: C, 60.07; H, 11.54; N, 26.10.
NMR (DMS0-d6,TMS): 6 0.87 (s), 2.23 (s), 2.44 (s), 3.16
(s,br), 3.44 (m).


42
13C NMR (DMS0-d6,39.5): 6 26.68, 48.76, 52.37, 60.46, 71.47.
IR (Neat): 3400 (s,br), 2950 (s), 2860 (s), 2820 (s), 1650
(m,br), 1600 (w,br), 1460 (m), 1380 (m), 1330 (w), 1300 (w), 1280
(m.sh), 1200 (w), 1170 (w), 1130 (m), 1090 (s), 1060 (m), 1040 (m),
960 (w,sh), 940 (w), 920 (w), 890 (w), 810 (m,br) cm"1.
Reduction of Polymer (36) (41)
Procedure A: Procedure (B) described previously for model
compound (27) was employed. Thus, polymer (36) (1.68 g, 0.0079 mole)
was reduced with NaBH^CN in the presence of a catalytic amount of
palladium-charcoal to yield a light yellow oil (1.16 g, 80.3%).
Analysis, calculated for C, 65.52; H, 11.55; N,
22.93. Found: C, 61.83; H, 10.75; N, 21.71
Procedure 3: Procedure (C) previously described for compound
(27) was applied. In a Parr bomb was placed a solution of polymer
(36) (2.017 g, 0.00946 mole) in 100 ml of DMF with a catalytic amount
of Raney nickel. The bomb was charged with hydrogen gas to 800 psi,
and heated to 50C for 2 hours followed by 60C for 6 hours. The
reaction mixture was then stirred overnight at room temperature and
the catalyst was filtered. The resulting liquid was evaporated under
reduced pressure at 50C to afford a light brown oil (1.46 g, 84.3%).
Analysis, calculated for Cig^l^: C, 65.52; H, 11.55; N,
22.93. Found: C, 64.21; H, 11.34; N, 22.20.
XH NMR (CDC13,TMS): 6 1.00 (s), 1.5 (m), 2.2 (s), 2.95 (m,br),
5.55 (s,br).
13C NMR (CDC13,77.0): 6 25.66, 45.27, 55.12, 60.87, 67.59,
130.37.


43
IR (Neat): 3340 (m,br), 3000 (s), 2920 (s), 2860 (s), 1700 (w),
1570 (s), 1490 (s), 1400 (m,br), 1380 (w,br), 1150 (m), 1070 (m,br),
1005 (m), 385 (m.br), 790 (w), 750 (w) cm"1.
Reduction of Polymer (37) (42)
Procedure (C) previously described for compound (27) was
applied. In a Parr bomb was placed a solution of polymer (37) (1.46
g, 0.006 mole) in 100 ml of 2-ethoxyethanol with a catalytic amount
of Raney nickel. The bomb was charged with hydrogen gas upto 800
psi, and heated to 60C for 15 hours. The reaction mixture was
filtered and the filtrate was evaporated under reduced pressure to
yield a light yellow oil (1.1 g, 85.9%).
Analysis, calculated for C-^2^27N3* 67*55; H, 12.76; N,
19.69. Found: C, 66.16; H, 12.25; N, 19.02.
1H NMR (CDC13,TMS): 6 1.00 (s), 1.32 (s), 2.20 (s), 2.68
(s,br), 3.6 (m).
13C NMR (DMS0-d6,39.5): 6 26.83, 27.12, 45.15, 60.26, 65.52,
71.76.
IR (Neat): 3300 (m.br), 2940 (s.sh), 2860 (s), 2790 (s), 1675
(w), 1580 (w,br), 1460 (m), 1380 (m), 1350 (w), 1310 (w.br), 1270
(w,br), 1230 (w), 1120 (m.sh), 1070 (m,br), 890 (w), 850 (w,br), 730
(w) cm-1.
Methyl a ti on
Methylation of Polymer (41) (43)
Procedure A: The procedure reported by Pine and Sanchez3^ was
modified as follows: In a 50 ml round-bottomed flask was placed


44
polymer (96) (2.31 g, 0.0179 mole), and the flask was cooled in an
external ice bath. To this, formic acid (88% w/w aqueous, 3.6 g,
0.075 mole) was slowly added followed by formalin solution (37% w/w
aqueous, 5.1 g, 0.063 mole). The flask was equipped with a magnetic
stirrer and a condenser and placed in an 80C constant temperature
bath for 26 hours. The mixture was cooled and 10 ml of 6 N HC1 was
added. This was then extracted with 3x20 ml of ethyl ether, and the
combined ether extracts were washed with 10 ml of H20 and dried over
K2CO3 overnight. Evaporation of ether gave a white solid (0.23 g).
The aqueous layer was made basic with sodium hydroxide (50% w/v
aqueous) and extracted with 3x20 ml of methylene chloride. The
combined organic layer was washed with 10 ml of ^0, and dried over
K2CO3. Filtration and subsequent evaporation yielded a light brown,
clear, viscous oil (1.52 g, 45.9% yield).
Procedure B: The method previously reported by Borch and
coworkers37,33 was applied. To a stirred solution of polymer (95)
(2.31 g, 0.0179 mole) and formaldehyde (37% w/w aqueous, 11 ml, 0.136
mole) in 40 ml of acetonitrile was added sodium cyanoborohydride
(NaBl^CH). Glacial acetic acid was added until the reaction mixture
showed the pH of 6. Stirring was continued for 10 hours and the
mixture was poured into 200 ml of ether. The resulting mixture was
washed with 4x75 ml of K0H solution (2 N) and 1x60 ml of saturated
NaCl solution. The combined K0H wash was backwashed with 100 ml of
ether. The combined ether layer was dried over K2CO3 overnight and
evaporated to yield a light brown clear, viscous oil (1.72 g, 51.9%).


45
Analysis, calculated for C-^gH23N3: C, 64.31; H, 12.51; N,
22.68. Found: C, 63.55; H, 12.18; N, 22.07.
XH NMR (COCI3,TMS): 5 0.91 (s), 2.04 (s), 2.28 (s), 2.33 (s),
2.65 (m).
13C NMR (CDC13,77.0): 6 16.67, 36.94, 46.98, 59.12, 64.04,
93.01.
IR (Neat): 3320 (m,br), 2940 (s,sh), 2840 (s,sh), 2300 (s,sh),
1660 (m), 1450 (s), 1370 (m), 1350 (w), 1325 (w), 1280 (m), 1270
(m,sh), 1235 (w), 1195 (w), 1170 (w), 1145 (m), 1130 (m), 1090
(s,sh), 1060 (m), 1040 (m), 1010 (w), 975 (w), 960 (w), 940 (w), 905
(w), 890 (m), 810 (w,br), 750 (w) cm--1-.
Methylation of Polymer (42) (44)
Procedure (A) used for the methylation' of polymer (41) was
employed. Thus, polymer (41) (1.01 g, 0.0055 mole) was reacted with
formic acid (88$ aqueous, 1.5 g, 0.029 mole) and formaldehyde (37%
aqueous, 2.5 g, 0.031 mole) to yield a brown oil (0.57 g, 49.0%).
Analysis, calculated for C, 69.19; H, 11.92; N,
19.88. Found: C, 66.55; H, 10.89; N, 19.72.
1H NMR (CDC13,TMS): 5 1.02 (s), 2.21 (s), 2.42 (s), 2.90 (m),
5.65 (m).
13C NMR (CDC13,77.0): 6 18.33, 44.79, 45.13, 45.47, 61.56,
66.43, 93.53, 138.71.
IR (Neat): 3340 (w,br), 2940 (s,sh), 2850 (s), 2810 (s), 2735
(s), 1675 (w), 1645 (w), 1600 (w,br), 1540 (w), 1450 (s), 1360 (m),
1300 (w,br), 1260 (w), 1230 (w), 1170 (w), 1120 (m), 1095 (m), 1040
(s,sh), 1010 (m), 970 (m), 840 (w,sh), 770 (w) cm-1.


46
Miscellaneous Reactions
Nitroethylene (Nitroethene) (45)
The following procedure was modified from the previously
reported procedure.39,40 A mixture of phthalic anhydride (99.0 g,
.66 mole) and 2-nitroethanol (45) (49.9 g, .548 mole) was placed in a
200 ml round bottom flask equipped with a fractionating column and
distillation head. The oil bath was heated to 140-150C and pressure
was reduced to 70-30 mmHg. After the mixture became homogeneous, the
oil bath temperature was raised to 175-180C until distillation
ceased. The distillate was dried over CaCl2 yielding a pale yellow
oil (35.8 g, 0.49 mole, 89% yield).
XH NMR (CDC13,TMS): 5 5.93 (d,lH), 6.64 (d.lH), 7.21 (d. of
d,lH).
13C NMR (CDC13*77.0): 6 122.2, 144.9.
Reaction of Nitroethene (45) with Formaldehyde and Diethylamine
The method reported by Tsuchida and Tomono was followed. In a
100 ml 3-necked round-bottomed flask fitted with a magnetic stirrer,
a thermometer, a reflux condenser and a dropping funnel was placed a
suspension of nitroethene (1.229 g, 0.0168 mole) in 15 ml of
methanol. Alternatively, diethylamine (1.231 g, 0.0168 mole) was
dissolved in 10 ml of methanol and then formalin solution (37% w/w
aqueous, 1.366 g, 0.0168 mole) was added with cooling. To this
mixture, 1.718 g (0.0168 mole) of acetic anhydride was added. The
thus prepared amine-formal in solution was added dropwise to the
nitroethene suspension at 0C. The reaction mixture turned reddish
brown and yielded unidentifiable tar.


47
Reaction of Nitroethene with Formaldehyde and Dimethylamine
Hydrochloride
The method of Tsuchida and Tomono22 was employed. Thus, the
amine-formal in solution was prepared by adding formalin solution (37?
w/w aqueous, 1.334 g, 0.0164 mole) to dimethylamine hydrochloride
(1.344 g, 0.0165 mole) in 15 ml of DMF. This solution was added
slowly to the previously prepared nitroethene solution (1.200 g,
0.0164 mole) in 20 ml of DMF, and the reaction mixture was stirred
for 2 hours at 70C. The resulting dark brown solution was
neutralized with sodium carbonate to yield dark brown tar.
Polymerization of Nitroethene (45) (46)
Freshly distilled THF was attached to a high vacuum line,
degassed twice and transferred to a polymerization tube. Nitroethene
was distilled with CaCl2 in the receiving flask and attached to the
line, degassed twice and transferred to the polymerization tube. The
previously purified pyridine (catalyst) was transferred to the
polymerization tube at -78C. Polymerization was carried out in a
constant temperature bath (-73C) for 1 hour. The tube was opened
and the contents precipitated into 1 N HC1 solution. The yellow
solid was collected, dissolved in DMF and reprecipitated in water.
The solid was again collected and dried in a vacuum oven (30C)
overnight to afford an off-white powder.
Analysis, calculated for C2H3NO2: C, 32.83; H, 4.13; N,
19.17. Found: C, 32.92; H, 4.22; N, 19.10.
13C NMR (DMS0-d6,39.5):6 35.5, 81.1.
Intrinsic viscosity (DMF,25C): [n] = 0.306 dl/g.


48
IR (KBr): 3000 (w), 2970 (w), 2890 (w), 1550 (s,sh), 1430 (m),
1330 (w), 1360 (m,sh), 1310 (w), 1230 (w), 1050 (w,br), 845 (m), 720
(w), 690 (w) cm"1.
Reaction of Compound (24) with Methyl Isocyanate (MI) (47)
In a 100 ml round-bottomed flask was placed a solution of
compound (24) (0.895 g, 0.00249 mole) in 20 ml of MF. A solution of
methyl isocyanate (MI) (1 ml, 0.017 mole) in 15 ml of DMF and a
catalytic amount of tin octoate (TO) (5 drops) were added dropwise
over a 10 minute period. After the addition was complete, which was
done under a nitrogen atmosphere, the reaction mixture was stirred
for 10 hours at room temperature. Additional MI (1 ml, 0.017 mole)
was added and stirring was continued for 10 hours at room
temperature. Evaporation of soluent gave a light brown, viscous
liquid (0.63 g, 53.4% yield).
:H NMR (DMS0-d6,TMS): 6 1.49 (s,3H), 2.36 (s,20H), 2.48 (s,4H),
2.64 (d,6H), 2.92 (m,4H), 3.97 (t,4H), 7.93 (s,2H).
13C NMR (DMS0-d6,39.5): 6 16.75, 30.73, 53.05, 54.51, 56.56,
61.04, 62.91, 92.53, 156.62.
IR (Neat): 3340 (m.br.sh), 2950 (m,sh), 2320 (in), 1680 (s,sh),
1530 (s,sh), 1460 (m), 1420 (m), 1380 (m), 1315 (m), 1260 (rn), 1215
(m), 1160 (m,br), 1095 (m), 1080 (m,sh), 1010 (w), 945 (w), 865 (w),
775 (w), 760 (w), 670 (w) cm"1.
Reaction of Compound (24) with Phenyl Isocyanate (PI) (48)
Procedure A: To a solution of compound (24) (1.797 g, 0.005
mole) and a catalytic amount (0.02 g) of freshly sublimed 1,4-
diazabicyclo(2,2,2)octane (DABC0) in 25 ml of anhydrous DMF was added


49
a solution of phenyl isocyanate (PI) (1.192 g, 0.010 mole) in 20 ml
of anhydrous DMF. After the addition, which was carried out under
nitrogen, was complete, the mixture was stirred for 24 hours at 60-
70C under nitrogen. The reaction mixture was cooled to room
temperature and poured into ice-water to yield a white precipitate,
which was dried in a vacuum desiccator for 40 hours (2.36 g,
79.0%). The resulting solid was recrystallized from toluene to yield
a white powder.
Procedure B: The procedure described in (A) was used except the
catalyst, tin octoate (TO) (5 drops) was used instead of DA8C0. The
white powder (2.71 g, 90.7%), which was obtained, was identical with
the compound obtained from procedure (A).
Analysis, calculated for C3oH43N76: c> 60-28i H> 7-25 N
16.41. Found: C, 59.56; H, 73.9; N, 15.30.
lH NMR (CDC13,TMS): 6 1.56 (s,3H), 2.4 (m,22H), 4.28 (t,4H),
7.1 (m,12H).
13C NMR (CDC13,77.0): 6 19.40 (q), 53.51 (t), 54.82 (t), 56.92
(t), 62.04 (t), 63.45 (t), 92.55 (s), 118.72 (d), 123.45 (d), 129.05
(d), 137.87 (s), 153.42 (s).
IR (KBr): 3630 (w), 3550 (w,br), 3330 (m,br), 3200 (w), 3140
(w), 3060 (w,sh), 3005 (w), 2950 (m), 2880 (w), 2320 (m), 1705
(s.sh), 1650 (w), 1600 (s), 1540 (s,sh), 1500 (m), 1460 (in), 1440
(s), 1405 (w), 1380 (w), 1360 (w), 1320 (s,sh), 1250 (s.sh), 1130
(w), 1155 (m), 1130 (w), 1085 (m,sh), 1060 (m), 1010 (m,sh), 940 (w),
900 (w), 850 (w,br), 755 (m,sh), 720 (w), 690 (m) cm"1-


50
Polymerization of Compound (24) with Hexarnethylene
Diisocyanate (HMJI) (49)
To a solution of HMDI (2.152 g, 0.0128 mole) in 15 ml of
anhydrous OMF were added a solution of compound (24) (4.599 g, 0.0128
mole) in 25 ml of anhydrous DMF and 10 drops of catalyst (TO). After
the addition, which was carried out under nitrogen, was complete, the
mixture was stirred under nitrogen at 40-45C for 60 hours. During
this period, the reaction mixture turned cloudy. The resulting
yellow, cloudy liquid was poured into ice-water to afford a white
solid (6.1 g, 92%), which was extracted with ether overnight and then
dried under reduced pressure.
NMR (DMS0-d6,TMS): 6 1.27 (s), 1.52 (s), 2.36 (s), 2.89 (s),
3.90 (s), 4.32 (s).
13C NMR (DMS0-d6,39.5): 5 18.59, 26.15, 29.46, 30.09, 53.15,
54.56, 56.75, 60.99, 67.13, 92.62, 136.19.
IR (KBr): 3340 (s,br), 2940 (s), 2860 (s), 2820 (m), 1720
(s,sh), 1650 (s,sh), 1580 (s), 1560 (s), 1540 (s), 1520 (s,sh), 1480
(m), 1460 (m,sh), 1380 (w), 1340 (m,sh), 1250 (s,br), 1160 (m,br),
1010 (m,sh), 930 (w), 860 (w), 775 (w), 730 (w) cm"1.
Polymerization of Compound (24) with Methylenedi-p-
phenylenediisocyanate (MDI) (50)
The same method previously described for the case of (49) was
applied. Thus, compound (24) (1.799 g, 0.005 mole) and MDI (1.251 g,
0.005 mole) were allowed to react in the presence of a catalyst (TO)
for 40 hours at 45C under nitrogen. The resulting white solid (2.6
g, 85.3%) decomposed at 180C.


51
Analysis, calculated for C31H43N75: C, 61.06; H, 7.11; N,
16.08. Found: C, 59.08; H, 7.38; N, 15.24.
lH NMR (DMS0-d6,T,MS): 6 1.51 (s), 2.33 (s), 3.4 (s,br), 4.16
(s), 7.2 (m), 8.5 (s), 9.5 (s).
13C NMR (DMS0-d6,39.5): 6 18.59, 53.03, 54.49, 56.46, 61.29,
62.75, 92.51, 118.32, 128.85, 134.84, 137.62, 152.54, 153.41.
IR (KBr): 3320 (m,br,sh), 3120 (w), 3040 (w), 2950 (m), 2820
(m,sh), 1700 (s,br), 1600 (s), 1540 (s), 1520 (s), 1420 (s), 1310
(s), 1230 (s,sh), 1115 (w), 1070 (m), 1020 (m,sh), 920 (w), 860 (w),
815 (m), 770 (m) cm-'*.
[n] (DMS0,30C) = 0.1944 dl/g.
Polymerization of Compound (26) with MDI (51)
The procedure described for compound (49) was employed. Thus,
compound (24) (1.608 g, 0.0059 mole) and MDI (1.477 g, 0.0059 mole)
were allowed to react in the presence of TO under nitrogen for 68
hours at 40-45C. The resulting white powder (2.2 g, 71.3%) was
extracted with ether overnight and dried under reduced pressure.
lH NMR (DMS0-d6,TMS): 6 2.4 (s), 3.45 (m), 3.8 (s), 4.2 (s,br),
7.3 (m), 8.5 (d), 9.6 (s).
IR (KBr): 3320 (s,br), 3040 (w), 2960 (m), 2820 (m), 1720 (w),
1650 (s), 1600 (s), 1520 (s,sh), 1460 (w), 1415 (m), 1310 (m), 1240
(m,br), 1150 (w), 1120 (w), 1060 (w), 1020 (w), 1000 (m), 925 (w),
860 (w), 820 (m), 770 (m) cm-*-.


CHAPTER III
RESULTS AND DISCUSSION
As indicated in the INTRODUCTION, the major objective of this
research was the preparation of new polymers containing amino groups
utilizing the Mannich reaction of nitroalkanes with formaldehyde and
a primary or a bis-secondary amine. Since this polymerization can be
classified as a step-growth polymerization, the rigorous requirements
for the successful synthesis of high polymers were expected.In
a step-growth polymerization, it is necessary to allow the reaction
to proceed to a very high degree of conversion or, in other words, to
a product that contains a very small number of functional groups.
Carothers derived a simple equation relating the degree of
polymerization to the extent of the reaction.If there are NQ
number of monomer AA and NQ number of monomer BB molecules at the
start of the polymerization (equation 1), and at a given stage of the
reaction when there are 2 N molecules of any size remaining, the
total number of functional groups of either type which have reacted
N A ''"mA + N B B -> A ~~A E B A ~^A ^ B ~~B (1)
OO X
is (Nq-N). At that point the reaction conversion, P, is given by the
ratio of the reacted number of molecules to the original number of
molecules (equation 2),
52


53
P = (Nq-N)/No (2)
which can be rewritten as equation (3).
N = Nq(1-P) (3)
The average number of repeating units in all molecules at that stage
in the polymerization, Xn, is the original number of molecules
divided by the remaining number of molecules (equation 4).
X
n
N
o
N
(4)
Combining these two equations gives an expression for Xn, the number
average degree of polymerization, in terms of reaction conversion, P
(equation 5).
X = 0 ^ (5
n Nq(1-P) 1-P 10
According to this limiting equation, a reaction of 95% conversion
would give a polymer with only 20 repeating units in the average
chain.
Furthermore, the step-growth polymerization requires that an
equal concentration of reactive functional groups be maintained
throughout the reaction to produce a high polymer. This means that
not only must the reaction be initiated with stoichiometric reactant
ratios, but the system must also be free from side reactions that


54
selectively consume either functional group and thereby destroy the
equality of the functional group concentrations.^ This also means
that both reactants are free from impurities that might affect the
concentrations of either function group. Flory derived a similar
equation for the case in which there is an excess of one of the
monomers in an AA and BB polymerization reaction.33 Let NQ A and
N0>b 1)6 ^e respective number of monomers AA and BB, and their
ratio be r. This gives the total monomer concentration NQ in terms
of and r (equation 6).
or
N = 4(N + N D)
o 2 o,A o,B
N = N ()
o 2 o,A r
(6)
Since the functional groups A and B react with each other on a 1:1
basis, at a given stage of the polymerization the number of AA
monomer reacted, should be equal to the number of BB monomers
reacted, NQ. Thus the fraction of B groups that have reacted is rp
as shown by equation (3).
= P
o,A
o,B o,B
r'N,
o,A
= r P
(7)
(3)


55
The total number of molecules present, N, is half of the number of
the functional groups, which must be equal to the sum of the numbers
of the unreacted A and B groups.
Afunctional groups (l-P)N0^+( 1_rP^0>B
(9)
Since N0>b = Nq A/r, equation (9) can be easily converted into (10).
N
f-g
C 2 (1-P)+
(10)
Therefore,
f-g
" N0,A(1-P
(11)
As discussed previously, the number average degree of polymerization,
Xn, is given by the ratio of the total number of molecules and the
original number of molecules (equation 4). Combining equations (4),
(6) and (11) gives Xn in terms of conversion, P, and reactant ratio,
r (equation 12).
*n 2r(l-P)+l-r (12)
This equation can be reduced to equation (5) when r is equal to 1.
In the case when the monomer BB is in 10% excess, i.e., r = 0.9,
and the conversion is quantitative, i.e., P = 1, the average molecule
would have Xn of 19. In the case when the monomer BB has 2% of
unreactive impurity, i.e., r = 0.98, and the conversion is 95%, the


56
average chain would have only 16.8 repeating units, compared to 20
when there is no impurity.
With this information in mind, the synthesis of model compounds
was initiated since the starting materials chosen are commercially
available.
Model Compounds
In order to obtain model compounds whose structures could be
correlated with those of analogous polymers, a series of model
reactions was carried out. The model compounds were characterized by
IR, 3H and 13C NMR and elemental analysis.
A series of reactions between 2-nitropropane, formaldehyde and
N,N-dimethyl-l,3-propanediamine (DMPA) was carried out to yield model
compound (23). The IR spectrum of this compound contains absorption
bands at 1550 cm-3 and 1450 cm-3, characteristic of the nitro
group. The 3H NMR of this compound showed a peak at 1.52 ppm which
HNH
CH.
(CHJ0 + 2 HCHO + 2 ChL-CH
|2 3 3 |
N
H3c/ XcH3
NO,
cat.
>
CH,
CH.
h3c-c -ch2-n ch2-cch3
N0 (CHJ.
2 | 2 3
N
H3c/ XcH3
NO,
(23)


57
was assigned to the four methyl groups 3 to the nitro group. The
peak at 2.18 ppm was assigned to the inethyl groups attached to the
nitrogen atom. In order to determine the reaction conditions which
would afford the highest conversion, several different reaction
conditions were studied. The results are shown in Table 1.
Table 1. Reaction of 2-nitropropane with NMPD and formaldehyde.
Solvent
Temp.
T ime
Cat.
% Yield
Dioxane/H20
60C
50 hrs
HC1
50
Dioxane
60C
24
HC1
50
room temp.
20
Dioxane
75-80C
15
h2so4
45
Dioxane
room temp.
45
K?C0
25
reflux*
16
Dioxande
room temp.
45
KoCOo
40
70C
16
* Boiling Point of 1,4-dioxane = 101C.
The higher temperature was less favorable than a lower temperature
(60-8C) and the catalyst, being acidic or basic, did not
drastically alter the degree of conversion of the reaction. The poor
yield can be attributed to the lack of exact stoichiometry arising
from the formaldehyde concentration as well as the complexity of the
system. To reduce the complexity of the system, thereby reducing the


58
possible weighing error and exact stoichiometry, the methylol
derivative of 2-nitro-propane was utilized. Compound (18)
CH, CH.,
i I j
CH., CH + HCHO > CH,-CCH~0H
I I
N02 no2
(18)
which is an adduct of 2-nitropropane and formaldehyde was obtained in
almost quantitative yield. This then was reacted with DMPA to afford
the same product (23) in much improved yield. Results are shown in
HNH
(13) I (23)
I
N
XcH3
(DMPA)
Table 2. Reaction of (18) with DMPA.
Solvent
Temp.
T i me
Cat.
% Yield
Dioxane/H20
7DC
18 hrs
-
50
Dioxane/H20
70C
22
Ha OH
70
THF
reflux3
24
N(CH2CH3)3
90
THFb
room temp.
70
n(ch2ch3)3
85
* Boiling Point of THF = 66C.
b 4 A molecular sieves were added.


59
Table 2. The presence of a catalytic amount of base increased the
conversion while the longer time had little impact.
The ethanolamine derivative, i.e., N-methylethanolamine, was
reacted with compound (18) to afford the 1:1 adduct, N-(2-
hydroxyethyl)-N-methyl-(2-methyl-2-nitro-l-propyl)amine (21), in good
yield. The and 13C NMR spectra and the assignment of the peaks
are shown in Figures 1 and 2. The IR spectrum shows typical nitro
peaks at 1530 and 1370 cm--*-. The yield of this reaction ranged from
60% to 77%. The reaction conditions and yields are shown in Taole 3.
CH-
hnch2ch2oh
CH.
CH,-C-CH0OH
3 2
N0
CH0 CH0
. I I
> CH-,-C-CH0-N-CH0CH0OH
0 |
no2
(21)
Table 3.
Reaction of N-
me thylethanolamine
and compound
(18).
Solvent
Temp.
Time
Cat.
% Yield
THF
66Ca
20 hrs
NEt3
77
THFb
room temp
72
NEt3
67
THFb
room temp
72
-
60
Reflux
b Molecular sieves (4 A)
were added.


60
e
~i i i 1 1 1
5.0 4.0 3.0 2.0 1.0 0.0 ppm
Fig. 1. NMR spectrum of compound (21) in CDC13*


61
CH- CH.. -
, I 3 i 3^-t
a b I el ^
HO-CHCH_-N-CHC-CH-,
22 d 2| 3
NO-
CDCl-
V- k.
1 I 1 T 1 1 r
100
80
60
40
20
0 ppm
Completely decoupled 13C NMR spectrum of compound (21)
in CDCI3.
Fig. 2.


0
N-methylethanolamine was reacted with the methylol derivative of
nitroethane, i.e., 2-methyl-2-nitro-l,3-propanediol (19) to afford
2:1 adduct (22) in good yield (72.4%). Since the given % yield is
the separated yield, actual conversion should be higher.
CH- CH. CH- CH0 CH_
3 | 3 | 3 | 3 | 3
HN-CH-CH-OH + HOCH-C-CH-OH > H0CHCHoNCHoCCHoNCHoCHo0H
\ 2 2 2 j 2 2 2
N02 N02
(22)
Model Compounds with 2-Nitropropane as Chain-Stopping Reagent
Piperazine, a bis-secondary amine, was reacted with formaldehyde
and 2-nitropropane to form the 1:2 adduct, compound (13). The NMR
spectrum showed three singlets of methyl groups, methylene groups and
piperazine-methylene groups at 1.54, 2.47 and 2.83 ppm, respectively
(Fig. 3). The NMR spectrum is shown in Figure 4 with its peak
assignment. Both piperazine and 1-nitropropane are difunctional
compounds and thus will react to form a polymer in the presence of
formaldehyde, while 2-nitropropane is a mono-functional compound and
thus will stop the chain propagation. Assuming that the reactivity
of 2-nitropropane proton is equal to those of 1-nitropropane protons,


63
a
Fig. 3. NMR spectrum of compound (13) in CDCI3.


64
Fig. 4. Completely decoupled NMR spectrum of compound (13)
in CDC13.


65
ChL
I 3
2CH-.CH + 2 HCHO
J|
NO
/ \
+ HN NH
CH-,-C-CH0-N N-CH0-C-CH
3 | 2 \ / 2 |
N02 no2
(13)
a series of model compounds was synthesized. The repeating units of
these model compounds should come from the reaction of 1-nitropropane,
CH.
/ \
n CH3CH2CH2N02 + (n+1) HN NH + (2n+2) HCHO + 2 CH3CH
NO,
->
ch3
CH,C-CH0/ \
3I 2 w
NO,
CH.
CH,
CH0C-CHN N'
2I 2
1_ no2
CH.
CHCCH^
2| 3
n NO
n = 1, 5, 20 and 100
with 2-nitropropane serving as a chain-stopping reagent. By varying
the ratio of reactants, one can theoretically control the length of
the chain, or in other words, the number of the repeating units. As
shown in Figure 5, the 1H spectra of these compounds can be utilized
to determine the actual number of the repeating units from the
integration of the different methyl peaks. The triplet at 0.97 ppm


66
b
Fig. 5. *H NMR spectra (in CDCI3) of the model compounds utilizing
2-nitropropane as chain-stopping reagent.


67
represents the methyl group of the repeating units while the singlet
at 1.54 ppm represents the methyl groups at the end of the
molecule. From the integration of these two peaks of each spectrum,
the ratios of 4:1, 5:6, 1:4 and 1:9 were obtained for the theoretical
degrees of polymerization of 1, 5, 20 and 100, respectively. In
other words, the actual degrees of polymerization of these compounds
were 1, 5, 16 and 36, respectively, as shown in Figure 6. Similarly,
another bis-secondary amine, i.e., N,N'-dimethylethylenediamine was
reacted with formaldehyde and 1-, and 2-nitropropane to yield the
corresponding model compounds. When n=0, i.e., 1-nitropropane was
CH.
CH.
CH.
I 3 I 3 I 3
n CH3CH2CH2N02 + (n+1) HNCH2CH2NH + (2n+2) HCHO + 2CH3CH
NO,
?H3
CH0 CHq CH.
. ii r
> CH3CCH2NCH2CH2N |-CH0CCH,NCH0CH,N
NO,
CH0 CH
| 2 | 3
CH.
2| 2
L NO,
r 2
CH.
CH0COL
2| 3
NO,
n = 0, 1 and 20.
not used, the white powder of N,N'-dimethyl-N,N'-bis(2-methyl-2-
nitro-l-propyl)ethylenediamine (30) was obtained. The ^H NMR and ^C
NMR spectra are shown in Figures 7 and 8, with peak assignment. In
the other two cases, a similar result was obtained when same method
of analysis was applied to their NMR spectra. The ratios of the
methyl peak at 0.97 ppm and 1.55 ppm are 4:1 and 3:11 for the


68
Fig. 6. Plot of the number of repeating limits vs. reactant feed
ra ti o.


69
a
Fig. 7. *H NMR spectrum of compound (30) in CDC13.


70
a
Fig. 8. Completely decoupled 13C NMR spectrum of compound (30)
in CDC13.


71
theoretical chain length of 1 and 20, respectively. In other words,
the calculated chain length of 1 and 15 is obtained for these
compounds. The result shows that (A): the reactivity of the protons
of 1-nitropropane is less than that of 2-nitropropane, thus the
propagation stops before all the presenting 1-nitropropane is
consumed, and more probably (B): the reaction conversion is not
100%; therefore the growth of the chain stops before all the
reactants are consumed.
Model Compounds with N-(8-Hydroxyethyl)piperazine
Nitroethane was reacted with formaldehyde and N-(8-
hydroxyethyl)piperazine (NHEP) to afford 1:2 adduct (24). The IR
spectrum of this compound shows the characteristic peaks of the nitro
group at 1530 and 1330 cm--*-. The *H NMR spectrum, as shown in Figure
9, shows a singlet at 1.59 ppm which is assigned to the methyl
protons. The other singlet at 2.51 ppm is from the methylene
CH3CH2N02 + 2 HCH0 + 2 HN INC^C^OH
cm
^ H0CH-CH-N I
2 2 \ /
no2
(24)
protons of the piperazine ring while the triplet at 3.59 ppm is from
the methylene protons of the substituted ethanol moiety. The 13C NMR
spectrum and the peak assignment are shown in Figure 10.
A similar result was expected when l-nitropropane was reacted
with formaldehyde and NHEP. The white solid which separated first


72
TMS
Fig. 9. 'H NMR spectrium of compound (24) in CDC^.


73
100 80 60 40
20
0 ppm
Completely decoupled 13C NMR spectrum of compound (24)
in CDC13.
Fig. 10.


74
from the reaction mixture turned out to be compound (26) instead of
compound (25). The IR spectrium of this compound does not include
the characteristic peaks of the nitro group, and the *H NMR spectrum
does not have the typical triplet, characteristic of methyl protons
of the ethyl group. The spectrum of this compound shows that
there is neither primary nor quaternary carbon. This was confirmed
/ \
CH3CH2CH2N02 + 2 HCHO + 2 HN NCH2CH20H
CHq
C / \ I 3
HOCH0CH0N NCH0CCH N ,NCHoCHo0H
2 2 \ f 2| \ / 2 2
NO,
(25)
/ \
H0CH2CH2N NCH2N NCH2CH20H
(26)
by the off-resonance spectrum, as shown in Figure 11. Compound
(25) was separated from the reaction mixture afterwards in low
yield. Compound (26) is a condensation product of formaldehyde and
NHEP, and a similar reaction is known to occur between formaldehyde
and piperidine.in order to avoid the formation of the unwanted
product (26), the preformed methylol derivative of 1-nitropropane
(20) was reacted with NHEP. In this case, there is no free
formaldehyde, and therefore little condensation between formaldehyde
and NHEP was expected. However, both (26) and (25) were separated
from the rection mixture despite the fact that the yield of (25) was


75
DMSO
160 140 120
I liIII
100 30
vJ1* '> i'^** 'i M
(2)
0 ppn
Fig. 11. 13C NMR spectra of compound (26) in DMSO-d: (1)
completely decoupled; (2) off-resonance.


76
higher than in the previous reaction. The presence of this
condensation product (26) indicates that the methylol derivative of
1-nitropropane is actually in equilibrium with formaldehyde and 1-
nitropropane and thus presents the chance of condensation between
CH0H CH0H
1 N I
CH_CHoC-N0o CHoCHoC-N0o + HCHO
3 21 2 > 2 21 2
CH20H h
/ \
HOCH0CH0N NH + HCHO
2 2 V /
. / \
-> hoch9ch9n n ch9oh
2 2 \ / 2
/\
HN NCH0CH0OH
\ / 2 2
's
N
/ \ / \
H0CHoCHoN NCHN NCHoCHo0H
2 2 \ / 2 N / 2 2
(26)
formaldehyde and NHEP. For compound (25), the IR, '''H and NMR
spectra confirm the structure by the characteristic peaks of 1530 and
1330 cm-i for the nitro group, a triplet characteristic of the methyl
protons of the ethyl group, and a peak for the primary carbon at 7.97
ppm and another at 94.87 ppm for a quaternary carbon, respectively.
In order to determine which reaction conditions result in higher
conversion, a series of the condensation between NHEP and compound
(19) was followed by NMR. Since the chemical shift of the methylene


//
CH
3
H0CHoCHoN
/ \
,NH + HCH rru qh
Na0D/D20
(24)
2 2
THF-dB
or
DMS0-d6
(19)
protons adjacent to oxygen remained virtually unchanged, the triplet
corresponding to these protons was used as reference. As shown in
Figure 12, the relative intensity of the peak corresponding to the
methylene protons next to NH decreased as the reaction proceeded.
The result is shown in Figure 13. The reaction was not affected much
by the solvent since there is not much difference in conversion
between the solvents, THF and DMSO. The highest conversion was
observed at 60C rather than at 100C, probably due to the reversible
reaction.
Since NHEP can be used as a chain-stopping reagent, a series of
model compounds from nitroethane, formaldehyde, piperazine and NHEP
was preparated. When a feed ratio of piperazine to NHEP was 5:2 so


78
Fig. 12. Selected time dependent *H NMR spectra of the reaction of
NHEP with compound (19) in DMS0-d6 at RT.


100
o
o
-I I
100 200
1
300
i
400
I
500
O THF-d8, RT
A DMSO-d6, RT
DMSO-d6, 60 C
O DMSO-d6, 100 C
O


I l I
600 700 800
Time ( minute )


_J 1
900 1000
Fig. 13. Plot of the consumption of NEPD vs. reaction time


ou
that the expected degree of polymerization was 5, a white precipitate
formed during the reaction. This solid was not soluble in most of
the common organic solvents, i.e., acetone, toluene, ether, methanol,
THF, DMF, chloroform and acetonitrile. A similar result was obtained
from the rection when a feed ratio of 10:1 was utilized. Both of
these products are soluble in HC1 (10% w/v aqueous) solution. The
viscosity measurement in 10% HC1 at 25C resulted in intrinsic
viscosities of 0.0025 dl/g and 0.0024 dl/g, respectively. In other
words, the molecular weights of the compounds were about equal. This
can be explained by the fact that the solid product precipitated out
during the reaction, and therefore the propagation of the chain
stopped before the average chain length of 5 was attained.
Studies with Nitromethane
As discussed previously, the methylol derivative of a
nitroalkane (20) is in equilibrium with formaldehyde and 1-
nitropropane. If this is true in the case of the derivative of
nitromethane, a mixture of mono-, di-, and trisubstituted product
should result from the reaction between 2-nitro-1,3-propanediol (15)
and piperidine. An attempt to synthesize (18) by direct condensation
of nitromethane with formaldehyde failed since the product was mainly
the trisubstituted compound, i.e., 2-(hydroxymethyl)-2-nitro-1,3-
propanediol (16).
K2C03
CH3N02 + HCH0 (H0CH2)3CN02
(16)


O J.
However, the desired diol (15) was obtained when this compound (16)
was treated with sodium, followed by salysilic acid. The IR spectrum
of this compound shows peaks at 1540 and 1360 cm-1 characteriStic of
the nitro group. The NMR spectrum shows a muliplet at 3.72 ppm
(hoch2)3cno2
(16)
(H0CH?)CN0
ch3oh
(17)
ether
(H0CH2)2CHM02
(15)
assigned to the methylene protons, a pentet at 4.66 ppm assigned to
methine proton, and a triplet assigned to the hydroxyl protons. This
triplet vanished when a drop of D2O was added to the NMR tube, thus
confirming that the signal is from the hydroxyl protons (Fig. 14).
The NMR spectrum shows two peaks at 59.56 and 91.92 ppm, assigned
to methylene carbons and methine carbon, respectively. This
assignment was confirmed by the off-resonance NMR spectrum (Fig.
15). This compound (15) was then reacted with piperidine to yield a
mixture of mono-, di-., and trisubstituted product as expected. The
amount of disubstituted product was increased when the reaction
temperature was lower.
Model Compounds from Bis-secondary Amines
N,N1-dimethyl-2-butene-l,4-diamine (DMBA) and N,N'-
dimethylhexamethylenediamine (DMHA) were also utilized in the model
compound studies. A reaction between 2-nitropropoane, formaldehyde
and DMBA afforded the model compound (31) in good yield. The IR
-1
spectrum of this compound shows two peaks at 1530 and 1340 cm


82
Fig. 14. 1H NMR spectra of compound (15) in DMS0-d6: (1) without
D2O, (2) 1 drop of D2O was added.


83
a
Fig. 15. 13C spectra compound (15> in DMS0-d6: (1) completely
decoupled, (2) off-resonance.


o*+
CH,
CH.
CH.
CH-j-C-h
3 I
NO.
+ 2 HCHO + HN-CH2CH=CHCH2N-H
9H3 9h3
CHq CH.
131
CH.CCH,IICH,CH-CHCH,NCH,CCH,
I J
3 I
NO.
NO.
(31)
characteristic of the nitro group. The ^H NMR spectrum shows a
multiplet at 5.52 assigned to the protons on the carbon-carbon double
bond (Fig. 16). The 13C NMR spectrum also shows the C-C double bond
at 130.41 ppm (Fig. 17). Similarly, DMHA was reacted with 2-
nitropropane and formaldehyde to yield compound (34) in fair yield.
The IR spectrum shows the characteristic peaks of the nitro group at
CH.
CH.
:h.
ch3 ch3
ch3 ch3
2 CH,CH + 2 HCHO + HN(CH0)cNH
J| L 0
N02
-> CH.CCH0N(CH),NCHCCHq
3 i 2 2 o 21 3
NO,
NO,
(32)
1540 and 1345 cm-'1. The *H NMR spectrum includes peaks at 1.30,
1.58, 2.26, 2.42 and 2.83 ppm, assigned to the methylene protons from
the middle of the amine moiety, methyl protons from the nitropropane
moiety, methyl protons attached to nitrogen, methylene protons
attached to nitrogen, and other methylene protons attached to
nitrogen, respectively. The ^C NMR spectrum and the peak
assignments are shown in Fig. 18.


85
ppm
Fig. 16. *H NMR spectrum of compound (31) in CDC13


Fig. 17. 13C NMR spectra of compound (31) in 000)3: (1) completely
decoupled, (2) off-resonance.


a /
a
ppm
Fig. 18. spectra of compound (32) in CDCl-^: (D completely
decoupled, (2) INEPT (CH,CH3 pos., CH2 neg., C, solvent
suppressed).


88
Polymers
An investigation of the polymerization of NMEA with (19) was
then carried out. The reaction, which was refluxed in THF (66C) for
24 hours in the presence of molecular sieves (4 A), gave an
CH.. ChL
| 3 | 3
HNCH2CH2NH + H0CH2
NMEA
(
excellent yield of polymer 05). The infrared spectrum of the brown,
viscous oil shows IR absorptions at 1535 and 045 cm-1 characteristic
of the nitro group, and is very similar to that of model compound
OO). The NMR spectrum is also very similar to that of model
compound OO) and the peaks are assigned accordingly, i.e., the
singlet at 1.5 ppm to the methyl protons of the nitroethane moiety,
the singlet at 2.3 ppm to the methyl protons next to the nitrogen,
the singlet at 2.4 ppm to methylene protons of the amine moiety and
the singlet at 2.9 ppm to the methylene protons from the
i n
formaldehyde. The 1JC NMR spectrum shows five major peaks, which are
in agreement within 3 ppm to those of the ^C NMR spectrum of
compound (30) (Fig. 19). This polymer, however, showed a molecular
weight of only 2200 by vapor pressure osmometry. The low molecular
weight can be the result of the relatively low conversion (~90%).
NMBA and (19) was then polymerized under identical conditions to
afford polymer C36). The very viscous yellow oil shows IR
absorptions at 1550 and 1335 cm-* characteristic of the nitro group.
CH.
CCHo0H
1 2
NO,
->
C1L CH,
13 1
CH *
13
CH0CCHNCH0CHN
21 2 2 2
NOo
19)
05)


39
d
PPti
Fig. 19. NMR spectra of polymer (35) in CDC^: (1) completely
decoupled, (2) off-resonance.


Full Text
UNIVERSITY



PAGE 1

35(3$5$7,21 2) 32/<0(56 9,$ 0$11,&+ 5($&7,21 %< 6(2. +(8, +21* f $ ',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\ IDPLO\ IRU WKHLU ORYH SDWLHQFH DQG HQFRXUDJHPHQW

PAGE 3

$&.12:/('*0(176 ZLVK WR H[WHQG P\ VLQFHUH DSSUHFLDWLRQ WR 'U *HRUJH % %XWOHU IRU KLV KHOS DGYLFH DQG H[SHUWLVH GXULQJ P\ SURJUDP RI UHVHDUFK ZRXOG DOVR OLNH WR WKDQN WKH PHPEHUV RI P\ VXSHUYLVRU\ FRPPLWWHH &ROOHDJXHV PHPEHUV RI WKH SRO\PHU UHVHDUFK JURXS DUH DSSUHFLDWHG IRU WKH IULHQGO\ DWPRVSKHUH WKH\ SURYLGHG DOVR WKDQN 0V &LQG\ =LPPHUPDQ IRU KHU VNLOOIXO W\SLQJ RI WKLV PDQXVFULSW )LQDOO\ ZRXOG OLNH WR WKDQN 0U 6+
PAGE 4

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f 3LSHUD]LQH 6WXGLHV ZLWK 1LWURPHWKDQH 0RGHO &RPSRXQGV IURP %LVVHFRQGDU\ $PLQHV 3RO\PHUV ,9

PAGE 5

5HGXFWLRQ RI 0RGHO &RPSRXQGV 5HGXFWLRQ RI 3RO\PHUV 0HWK\ODWLRQ 0DQQLFK 5HDFWLRQ RQ 1LWURHWKDQH 8UHWKDQHV DQG 3RO\XUHWKDQHV 6XPPDU\ DQG &RQFOXVLRQ 5()(5(1&(6 %,2*5$3+,&$/ 6.(7&+ Y

PAGE 6

/,67 2) 7$%/(6 7DEOH 3DJH 5HDFWLRQ RI QLWURSURSDQH ZLWK 103' DQG IRUPDOGHK\GH 5HDFWLRQ RI f ZLWK '03$ 5HDFWLRQ RI 1PHWK\LHWKDQRODPLQH DQG FRPSRXQG f YQ

PAGE 7

/,67 2) ),*85(6 )LJXUH 3DJH + 105 VSHFWUXP RI WKH PRGHO FRPSRXQG f LQ &'&, 2 &RPSOHWHO\ GHFRXSOHG & 105 VSHFWUXP RI FRPSRXQG f LQ &'&, 105 VSHFWUXP RI FRPSRXQG f LQ &'&, 2 &RPSOHWHO\ GHFRXSOHG & 105 VSHFWUXP RI FRPSRXQG f LQ &'& 105 VSHFWUD LQ &'&,f RI WKH PRGHO FRPSRXQGV XWLOL]LQJ QLWURSURSDQH DV FKDLQVWRSSLQJ UHDJHQW 3ORW RI WKH QXPEHU RI UHSHDWLQJ OLPLWV YV UHDFWDQW IHHG UDWLR 105 VSHFWUXP RI FRPSRXQG f LQ &'& &RPSOHWHO\ GHFRXSOHG A& 105 VSHFWUXP RI FRPSRXQG f LQ &'&, 105 VSHFWUXP RI FRPSRXQG f LQ &'& &RPSOHWHO\ GHFRXSOHG & 105 VSHFWUXP RI WKH FRPSRXQG f LQ &'&, & 105 VSHFWUD RI FRPSRXQG f LQ '06G f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH 6HOHFWHG WLPH GHSHQGHQW 105 VSHFWUD RI WKH UHDFWLRQ RI 1+(3 ZLWK FRPSRXQG f LQ 06G DW 57 3ORW RI WKH FRQVXPSWLRQ RI 1(3' YV UHDFWLRQ WLPH + 105 VSHFWUD RI FRPSRXQG f LQ '062GR f ZLWKRXW '2 f GURS RI '2 ZDV DGGHG A& 105 VSHFWUD RI FRPSRXQG f LQ '06G f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH 9,

PAGE 8

105 VSHFWUXP RI FRPSRXQG f LQ &'& & 105 VSHFWUD RI FRPSRXQG f LQ f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH & 105 VSHFWUD RI FRPSRXQG f LQ f FRPSOHWHO\ GHFRXSOHG f ,1(37 &+ &+ SRV &+ QHJ & VROYHQW VXSSUHVVHGf & 105 VSHFWUD RI SRO\PHU f LQ f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH & 105 VSHFWUD RI SRO\PHU f LQ f FRPSOHWHO\ GHFRXSOHG f ,1(37 &+ &+ SRV &+ QHJ & VROYHQW VXSSUHVVHGf ,5 VSHFWUD RI f FRPSRXQG f DQG f FRPSRXQG f UHGXFHG E\ 1D%+ DQG 3G&f ,5 VSHFWUD RI f FRPSRXQG f DQG f FRPSRXQG f UHGXFHG E\ +5DQH\ 1Lf & 105 VSHFWUD RI FRPSRXQG f LQ &'&, f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH ,5 VSHFWUD RI f SRO\PHU f DQG f SRO\PHU f ,5 VSHFWUD RI f SRO\PHU f DQG f SRO\PHU f ,5 VSHFWUD RI f SRO\PHU f DQG f SRO\PHU f & 105 VSHFWUD ,1(37 &+ &+ SRV &+ QHJ & VROYHQW VXSSUHVVHGf RI FRPSRXQGV f DQG f UHVSHFWL YHO\ YL L L

PAGE 9

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n GLPH WK\HWK\OHQHGLDPLQH '0($f 11nGLPHWK\OEXWHQHGLDPLQH '0%$f DQG 11fGLPHWK\OKH[DPHWK\OHQHGLDPLQH '0+$f ZHUH DOVR VWXGLHG ,Q DQ DWWHPSW WR SURYLGH D EHWWHU XQGHUVWDQGLQJ RI WKH SRO\PHUL]DWLRQ PRGHO FRPSRXQGV ZLWK FRQWUROOHG PROHFXODU ZHLJKWV ZHUH VWXGLHG XWLOL]LQJ FKDLQVWRSSHU FRPSRQHQWV ,;

PAGE 10

3RO\PHUV RI WKH GHVLUHG VWUXFWXUH ZHUH REWDLQHG IURP UHDFWLRQV RI WKH PHWK\ORO GHULYDWLYH RI QLWURHWKDQH ZLWK ELVVHFRQGDU\ DPLQHV LQFOXGLQJ '0($ '0%$ DQG '0+$ $OWHUQDWLYHO\ 111n1n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r& 6LPLODUO\ WKH VDPH PRGHO FRPSRXQG ZDV UHDFWHG ZLWK KH[DPHWK\OHQHGLLVRF\DQDWH WR \LHOG WKH FRUUHVSRQGLQJ SRO\XUHWKDQH [

PAGE 11

&+$37(5 ,1752'8&7,21 7KH 0DQQLFK UHDFWLRQ LV GHILQHG DV WKH FRQGHQVDWLRQ RI DPPRQLD RU D SULPDU\ RU VHFRQGDU\ DPLQH ZLWK IRUPDOGHK\GH DQG D FRPSRXQG FRQWDLQLQJ DW OHDVW RQH K\GURJHQ DWRP RI SURQRXQFHG UHDFWLYLW\ 7KH ILUVW REVHUYDWLRQ RI WKLV W\SH ZDV PDGH E\ 7ROOHQV ZKR LVRODWHG WKH WHUWLDU\ DPLQH IURP DPPRQLXP FKORULGH IRUPDOGHK\GH DQG 2 DFHWRSKHQRQH f +RZHYHU WKH GHWDLOHG VWXG\ RI WKH UHDFWLRQ ZDV LQLWLDWHG LQ E\ 0DQQLFK ZKR REVHUYHG WKDW DQWLS\ULQH f IRUPDOGHK\GH DQG DPPRQLXP FKORULGH UHDFWHG WR IRUP D WHUWLDU\ DPLQH 7KXV WKH UHDFWLRQ KDV EHFRPH NQRZQ JHQHUDOO\ DV WKH &+ 1 f§ &&+ +&+2 1+& & f§ &+ ,, f 1 f§ &&+ &f§& f§&+ 1+&O ,,

PAGE 12

0DQQLFK UHDFWLRQ DQG LV UHFRJQL]HG DV RQH RI WKH FODVVLFDO UHDFWLRQV RI RUJDQLF FKHPLVWU\ 7KLV UHDFWLRQ KDV EHHQ ZLGHO\ XVHG LQ V\QWKHVLV DQG ZDV WKH VXEMHFW RI PDQ\ UHYLHZVA 7KH PHFKDQLVP RI WKH 0DQQLFK UHDFWLRQ KDV EHHQ ZHOO LQYHVWLJDWHG DQG D FRPSUHKHQVLYH UHYLHZ FRYHULQJ XS WR KDV EHHQ SXEOLVKHGn 2QO\ D IHZ RI WKH PDLQ SRLQWV ZLOO EH GLVFXVVHG KHUH 7KH 0DQQLFK UHDFWLRQ OHDGV WR SURGXFWV RI WKH W\SH f EHDULQJ D VXEVWLWXWHG PHWK\OHQH JURXS FRQQHFWLQJ WKH VXEVWUDWH UHVLGXH ZLWK 5+ +&+2 + f DQ DPLQR JURXS 7KH FRQGHQVDWLRQ UHDFWLRQ RFFXUV LQ VWHSV )LUVW WKH DPLQH UHDFWV ZLWK IRUPDOGHK\GH WR JLYH FRQGHQVDWLRQ SURGXFW AWA 6WHS ,f ZKLFK WKHQ DWWDFNV WKH VXEVWUDWH 5+ 6WHS ,,f (YHQ WKRXJK WKLV LV EHOLHYHG WR EH WKH PDLQ URXWH RI WKH UHDFWLRQ

PAGE 13

VRPH VXFFHVVIXO UHDFWLRQV EHWZHHQ K\GUR[\PHWK\O GHULYDWLYHV f DQG DON\ODPLQHV WR JLYH 0DQQLFK EDVHV f DUH NQRZQ 7KH UHDFWLYH VSHFLHV LQ DFLGLF PHGLXP LV WKH LPLQLXP LRQ f GHULYHG SULQFLSDOO\ IURP PHWK\OHQHELVDPLQH f DQG VHFRQGDULO\ IURP K\GUR[\PHWK\ODPLQH f ,Q EDVLF PHGLXP WKH UHDFWDQW LV SRVWXODWHG WR EH K\GUR[\PHWK\ODPLQH f RU PRUH SUREDEO\ PHWK\OHQHELVDPLQH f 7KH H[LVWHQFH RI FDWLRQ f LQ DTXHRXV VROXWLRQV RI DPLQH DQG IRUPDOGHK\GH KDV EHHQ GHPRQVWUDWHG E\ SRODURJUDSKLF PHWKRGV WKH PD[LPXP FRQFHQWUDWLRQ RI f ZDV UHSRUWHG WR RFFXU DW S+ 7KH 8VH RI $PLQHV 7KH FKRLFH RI WKH DPLQH XVHG LQ WKH UHDFWLRQ LV LPSRUWDQW ,W LV NQRZQ WKDW SULPDU\ DPLQHV FDQ UHDFW DW ERWK DPLQH +DWRPV DQG WKHUHIRUH LW LV GLIILFXOW WR REWDLQ VHFRQGDU\ 0DQQLFK EDVHV IUHH IURP WHUWLDU\ GHULYDWLYHV +RZHYHU XVH RI WKH VWHULFDOO\ KLQGHUHG DPLQH f RU VLPLODU DPLQHV FRQWDLQLQJ EXON\ JURXSV WEXW\O GL RU WUL DU\OPHWK\Of FDQ SUHYHQD VXEVWLWXWLRQ UHDFWLRQ LQYROYLQJ WKH VHFRQG DPLQH +DWRP RI f 7KH EXON\ DON\O JURXSV FDQ VXEVHTXHQWO\ EH UHPRYHG E\ K\GURO\VLV WR JLYH WKH 1XQVXEVWLWXWHG DPLQRNHWRQH f ZKLFK LV QRW GLUHFWO\ REWDLQDEOH IURP DPPRQLD DQG IRUPDOGHK\GHpf

PAGE 14

,W LV DOVR NQRZQ WKDW XVH RI WKH R[DODWH GHULYDWLYHV RI WKH SULPDU\ DPLQHV LQVWHDG RI WKH FRUUHVSRQGLQJ K\GURFKORULGHV PDNHV WKH 2 ,4 V\QWKHVLV RI VHFRQGDU\ 0DQQLFK EDVHV LQ KLJK \LHOGV SRVVLEOH f 7KH XVH RI VHFRQGDU\ ELIXQFWLRQDO DPLQHV VXFK DV SLSHUD]LQH OHDGV WR V\PPHWULF 0DQQLFK EDVHV LQ ZKLFK ERWK RI WKH DPLQR JURXSV KDYH UHDFWHG $WWHPSWV WR UHVWULFW WKH UHDFWLRQ WR RQO\ RQH DPLQH IXQFWLRQ RU K\GURO\VLV RI WKH 0DQQLFK SURGXFWV REWDLQHG IURP SLSHUD]LQHV LQYDULDEO\ OHDGV WR WKH IRUPDWLRQ RI GLVXEVWLWXWHG SLSHUD]LQHV fA A? 5+ +&+2 +1 1+ 9 ? 5&+A 1 &+5 f 7KH 0DQQLFK UHDFWLRQ RI ELVFKORURHWK\OfDPLQH FDQ JLYH D f ELF\FOLF VDOW DV E\SURGXFW 7ZR PROHFXOHV RI WKH DPLQH WKXV FRQGHQVH ZLWK RQH PROHFXOH RI IRUPDOGHK\GH WR JLYH f ZKLFK VKRZV F\WRVWDWLF SURSHUWLHV DV GR KDOJHQD WHG GHULYDWLYHV RI VLPLODU VWUXFWXUH

PAGE 15

? &O n9" Fn +&+2 &O f 1LWURDONDQHV +HQU\ ZDV WKH ILUVW WR VKRZ WKDW 0DQQLFK W\SH UHDFWLRQV ZLOO RFFXU ZLWK QLWURDONDQHVA HVWDEOLVKHG WKDW 1K\GUR[\PHWK\O SLSHULGLQH FRQGHQVHG ZLWK QLWURPHWKDQH DQG QLWURHWKDQH WR \LHOG UHVSHFWLYHO\ QLWUROGLSLSHULGLQRSURSDQH Df DQG PHWK\O QLWURGLSL SHULGLQRSURSDQH Ef 4FKRK FKUQR RKFK4 f f Df 5 + Ef 5 &+ /DWHU 6HQNXV VXFFHVVIXOO\ FDUULHG RXW UHDFWLRQV XVLQJ PHWK\O DPLQH LVRSURS\ODPLQH EXW\ODPLQH EXW\ODPLQH EHQ]\ODPLQH SKHQ\OHWK\ODPLQH DPLQROEXWDQRO DQG DPLQRLQHWK\OSURSDQRO DV PRQRDON\ODPLQH FRPSRQHQWV DQG QLWURHWKDQH DQG QLWURSURSDQH DQG QLWUREXWDQH DV QLWUR FRPSRQHQWVA +H VKRZHG WKDW WKH SURGXFWV FRXOG EH REWDLQHG HLWKHU E\ DOORZLQJ WKH DPLQH WR UHDFW ZLWK IRUPDOGHK\GH DQG WKHUHDIWHU DGGLQJ WKH QLWURDONDQH RU E\ ILUVW

PAGE 16

JHQHUDWLQJ WKH PHWK\ORO GHULYDWLYH RI WKH QLWURDONDQH ZKLFK ZDV WKHQ WUHDWHG ZLWK WKH DPLQH 5 5 1+&+R+ +&1R   5 5 5n1+&+R&1R +R ?   5 5 5n1+&++ 5&+1 5n1+&+&&+1+5n + 1 DO WHUQDWLYHO\ 5 5 1+ +&+R&1   5 5 5 5r1+ +&+R&&+R+ 5f1+&+&&+f1+5n +R A 1 QR -RKQVRQ H[WHQGHG WKH ZRUN RI 6HQNXV WR YDULRXV DOLSKDWLF 2 VHFRQGDU\ DPLQHV r +H DOVR FDUULHG RXW WKHVH UHDFWLRQV E\ WZR GLIIHUHQW PHWKRGV $f UHDFWLRQ RI WKH DPLQHV IRUPDOGHK\GH DQG QLWURSDUDIILQ DQG %f UHDFWLRQ RI WKH DPLQH ZLWK WKH QLWUR DOFRKRO RU QLWUR GLRO $OWKRXJK WKH VDPH HQGSURGXFWV UHVXOWHG LQ HLWKHU FDVH WKH ODWWHU UHDFWLRQ ZDV VORZHU ,W LV DOVR VKRZQ WKDW XQVXEVWLWXWHG SLSHUD]LQH DQG GLPHWK\OSLSHUD]LQH JDYH WKH FRUUHVSRQGLQJ ELV FRQGHQVDWLRQ SURGXFWV fA

PAGE 17

+1 a? 1+ +&+2 QFKFFK f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fV LH ELV0DQQLFK SF EDVHVf ZLWK ELVVHFRQGDU\ DPLQHV WR \LHOG SRO\6DPLQRNHWRQHfV

PAGE 18

$QJHORQL DQG FRZRUNHUV H[WHQGHG WKLV ZRUN WR DURPDWLF 0DQQLFK EDVHV , VXFK DV ELVGLPHWK\ODPLQRSURSLRQ\OfGLSKHQ\O RU ELV6 GLPHWK\ODPLQRSURSLRQ\OfGLSKHQ\OHWKHUArfA *KHGLQL DQG FRZRUNHUV DOVR H[WHQGHG WKLV ZRUN WR SKHQROLF 0DQQLFK EDVHV VXFK DV ELVGL 24 PHWK\O DPL QRPHWK\OfPHWK\O SKHQRO 3URSRVDO RI 5HVHDUFK ,W LV WKH REMHFWLYH RI WKH UHVHDUFK WR XWLOL]H WKH 0DQQLFK UHDFWLRQ EHWZHHQ IRUPDOGHK\GH VHOHFWHG DPLQHV DQG WKH QLWURSDUDIILQV DV WKH DFWLYH K\GURJHQ FRPSRXQGV WR V\QWKHVL]H DPLQHFRQWDLQLQJ DQGRU TXDWHUQDU\ DPPRQLXP FRQWDLQLQJ SRO\PHUV 7KH UHDFWLRQV DQWLFLSDWHG WR RFFXU DUH DV IROORZV

PAGE 19

Q 5&+1 Q +&+2 Q 5 1+ &+&&+1 1R Q + 5HGXFWLRQ 5 5 } &+&&+1   1+ 0HWK\O D WL RQ f§ 5 5 ‘&+"&&+"1 1&+ f Q 4XDWHUQL]DWLRQ f§&+& f§ &+f§1 f§ L / 1&+f &+ Q 5 &+ RU &+ 1LWURHWKDQH DV ZHOO DV QLWURSURSDQH FDQ EH XWLOL]HG DV WKH DFWLYH K\GURJHQ FRPSRXQG %RWK QLWURSDUDIILQV VKRXOG UHVXOW LQ SRO\PHUV RI KLJK FKDUJH GHQVLW\ 7KH UHVXOWLQJ SRO\PHUV IURP QLWURHWKDQH DQG QLWURSURSDQH ZRXOG KDYH DQ HTXLYDOHQW ZHLJKW ZLWK UHVSHFW WR TXDWHUQDU\ DPPRQLXP FHQWHUV FKORULGH IRUPf RI DQG UHVSHFWLYHO\ ,W LV ZHOO UHFRJQL]HG WKDW WKH HIIHFWLYHQHVV RI FDWLRQLF SRO\PHUV LQ WKH IORFFXODWLRQ DQG FRDJXODWLRQ DSSOLFDWLRQV LV D GLUHFW

PAGE 20

IXQFWLRQ RI WKH FKDUJH GHQVLW\ RQ WKH SRO\PHU 7KXV LW ZRXOG EH SUHGLFWHG WKDW WKH TXD WHUPf]HG SRO\PHU GHULYHG IURP SRO\HWK\OHQHDPLQH ZRXOG EH PRVW HIIHFWLYH KDYLQJ DQ HT ZW RI FKORULGH IRUPf +RZHYHU VXFK D SRO\PHU KDV EHHQ VKRZQ WR EH UHODWLYHO\ XQVWDEOH GXH WR WKH SUR[LPLW\ RI WKH SRVLWLYH FKDUJHV $Q DOWHUQDWLYH SRO\PHU RI KLJK FKDUJH GHQVLW\ LV SRO\YLQ\OWULPHWK\ODPPRQLXP FKORULGHf RI HT ZW RI &+f&+ 1&+ Rf R &O +RZHYHU WKLV SRO\PHU LV GLIILFXOW WR V\QWKHVL]H DQG LWV FRVW ZRXOG EH KLJK 7KH PRVW ZLGHO\ XVHG FDWLRQLF SRO\PHU LQ WKH IORFFXODWLRQ DUHD RI DSSOLFDWLRQ LV SHUKDSV SRO\GLDOO\OGLPHWK\ODPPRQLXUQ FKORULGHf RI HT ZW RU ‘&+ &+ 1 + ?K

PAGE 21

$JDLQ WKLV SRO\PHU LV PDGH IURP D IDLUO\ H[SHQVLYH PRQRPHU DQG KDV UHODWLYHO\ KLJK HTXLYDOHQW ZHLJKW SHU FKDUJH &RQVLGHUDEOH YHUVDWLOLW\ LV HQYLVLRQHG LQ WKH DERYH V\VWHP )RU H[DPSOH XVH RI HLWKHU QLWURSURSDQH RU D VHFRQGDU\ DPLQH ZRXOG SURGXFH SRO\PHUV ZLWK PROHFXODU ZHLJKW FRQWURO DV ERWK RI WKHVH UHDFWDQWV ZRXOG IXQFWLRQ DV FKDLQVWRSSHUV &+& f§ &+af§ 1 L 1&+f &+ &+ &+f§ & f§ 1&+f FK QLWURSURSDQH DV FKDLQVWRSSHU 1 &+ ‘&+f§ 1 f§&+ L 1FK` &+ff§ I 1 f§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n WLRQ $QG VXFK SURFHVVHV DUH NQRZQ WR UHTXLUH $f UHODWLYHO\ SXUH

PAGE 22

UHDFWDQWV DQG %f ULJLGO\ FRQWUROOHG VWRLFKLRPHWU\ LQ RUGHU WR DWWDLQ KLJK PROHFXODU ZHLJKWV 7KXV RQH RI WKH PDMRU REMHFWLYHV RI WKH UHVHDUFK LV WR DWWDLQ WKH QHFHVVDU\ VWRLFKLRPHWULF FRQWURO WR OHDG WR WKH GHVLUHG GHJUHHV RI SRO\PHUL]DWLRQ

PAGE 23

&+$37(5 ,, (;3(5,0(17$/ *HQHUDO 0HOWLQJ SRLQWV JLYHQ LQ GHJUHHV &HOVLXV ZHUH GHWHUPLQHG RQ D 7KRPDV+RRYHU &DSLOODU\ 0HOWLQJ 3RLQW $SSDUDWXV DQG DUH UHSRUWHG XQFRUUHFWHG 3UHVVXUHV DUH H[SUHVVHG LQ PLOOLPHWHUV RI PHUFXU\ PP +Jf (OHPHQWDO DQDO\VHV ZHUH SHUIRUPHG E\ HLWKHU $WODQWLF 0LFURODEV ,QF $WODQWD *HRUJLD RU 'HSDUWPHQW RI &KHPLVWU\ 8QLYHUVLW\ RI )ORULGD *DLQHVYLOOH )ORULGD 3URWRQ QXFOHDU PDJQHWLF UHVRQDQFH 105f VSHFWUD 0+]f ZHUH UHFRUGHG RQ D 9DULDQ (0/ LQVWUXPHQW &DUERQ 105 0+]f DQG 0+] SURWRQ 105 VSHFWUD ZHUH UHFRUGHG RQ D -HRO-10); VSHFWURPHWHU &KHPLFDO VKLIWV DUH H[SUHVVHG LQ SDUWV SHU PLOOLRQ SSPf RQ WKH VFDOH GRZQILHOG IURP WH WUDPHWK\OVL ODQH 706f RU VRGLXP GLPHWK\OVLODSHQWDQHVXOIRQDWH '66f XQOHVV RWKHUZLVH LQGLFDWHG ,Q FDVHV ZKHUH QR LQWHUQDO UHIHUHQFH ZDV DGGHG VSHFWUD ZHUH FDOLEUDWHG YLD D FKDUDFWHULVWLF VLJQDO RI WKH GHXWHUDWHG VROYHQW XVHG 7KH VROYHQW XVHG DQG FDOLEUDWLRQ LQIRUPDWLRQ DUH JLYHQ LQ SDUHQWKHVHV IRU HDFK VSHFWUXP UHSRUWHG 0XOWLSOLFLWLHV RI SURWRQ DQG RIIUHVRQDQFH GHFRXSOHG FDUERQ UHVRQDQFHV DUH GHVLJQDWHG DV VLQJOHW Vf GRXEOHW Gf WULSOHW Wf TXDUWHW Tf RU PXOWLSOHW Pf

PAGE 24

,QIUDUHG ,5f VSHFWUD ZHUH UHFRUGHG RQ D 3HUNLQ(OPHU VSHFWURSKRWRPHWHU $EVRUEDQFHV DUH H[SUHVVHG LQ ZDYHQXPEHUV FPrf XVLQJ WKH FP OLQH RI VWDQGDUG 6ROLG VDPSOHV ZHUH UXQ DV D .%U SHOOHW OLTXLG VDPSOHV ZHUH DQDO\]HG QHDW DV D WKLQ ILOP EHWZHHQ 1D&O SODWHV $EVRUSWLRQ EDQGV DUH DVVLJQHG WKH FODVVLILFDWLRQV ZHDN Zf PHGLXP Pf VWURQJ Vf EURDG EUf DQG VKRXOGHU VKf 0ROHFXODU ZHLJKWV RI SRO\PHUV ZHUH GHWHUPLQHG E\ YDSRU SUHVVXUH RVPRPHWU\ 932f RQ D :(6&$1 PRGHO 0ROHFXODU :HLJKW $SSDUDWXV %HQ]LO ZDV XVHG DV D FDOLEUDWLRQ VWDQGDUG ,QWULQVLF YLVFRVLWLHV ZHUH PHDVXUHG ZLWK 8EEHORKGH YLVFRPHWHU GLOXWLRQ YLVFRPHWHUf 5HDJHQWV DQG 6ROYHQWV 5HDJHQWV ZHUH REWDLQHG IURP $OGULFK &KHPLFDO &R (DVWPDQ .RGDN &R )LVFKHU 6FLHQWLILF &R RU 0DO LQFNURGW ,QF XQOHVV RWKHUZLVH QRWHG 'HXWUDWHG VROYHQWV ZHUH SXUFKDVHG IURP 0HUFN t &R ,QF DQG $OGULFK &R $OO VROYHQWV XVHG IRU JHQHUDO DSSOLFDWLRQV ZHUH RI 5HDJHQW JUDGH RU $&6 JUDGH TXDOLW\ )RU VSHFLDO DSSOLFDWLRQV VROYHQWV ZHUH SXULILHG DV QHHGHG E\ IROORZLQJ SURFHGXUHV UHSRUWHG LQ WKH LWHUDWXUHA 7KXV GLPHWK\OVXOIR[LGH '062f DQG 11GLUQHWK\O IRUPDPLGH '0)f ZHUH DOORZHG WR VWDQG RYHU SRWDVVLXP K\GUR[LGH SHOOHWV DQG GLVWLOOHG IURP FDOFLXP R[LGH XQGHU UHGXFHG SUHVVXUH HWKDQROIUHH FKORURIRUP &+&,f ZDV REWDLQHG E\ H[WUDFWLRQ RI UHDJHQW JUDGH &+& ZLWK FRQFHQWUDWHG +62 DQG ZDWHU IROORZHG E\ GLVWLOODWLRQ IURP SKRVSKRUXV SHQWR[LGH 3ATf

PAGE 25

6\QWKHVLV RI 1LWURDOFRKROV 1LWURHWKDQRO f 7KH SURFHGXUH UHSRUWHG E\ %XUPLVWURX DQG %DVKLQRYD ZDV PRGLILHG DV IROORZV 1LWURPHWKDQH J PROHVf DQG SDUDn IRUPDOGHK\GH J PROHf ZHUH SODFHG LQWR D PO WKUHHn QHFNHG URXQGERWWRPHG IODVN ILWWHG ZLWK D WKHUPRPHWHU DQG D UHIOX[ FRQGHQVHU 7KH PL[WXUH ZDV KHDWHG LQ DQ RLO EDWK WR r& DQG SRWDVVLXP FDUERQDWH J b RI WKH UHDFWLRQ PL[WXUHf ZDV DGGHG LQ SRUWLRQV (DFK VXFFHVVLYH SRUWLRQ RI FDWDO\VW .&f ZDV DGGHG DIWHU YLJRURXV ERLOLQJ RI WKH PL[WXUH FHDVHG 'XULQJ WKH DGGLWLRQV WKH FRORU FORXGLQHVVf RI WKH PL[WXUH GLVDSSHDUHG VORZO\ :KHQ WKH SDUDIRUPDOGHK\GH ZDV FRPSOHWHO\ GLVVROYHG WR \LHOG D FOHDU VROXWLRQ WKH PL[WXUH ZDV KHOG IRU PLQXWHV DW WKH VDPH WHPSHUDWXUH FRROHG ILOWHUHG WR VHSDUDWH WKH FDWDO\VW DQG QHXWUDOL]HG ZLWK GURSV RI FRQFHQWUDWHG +6A 7KH OLJKW \HOORZ ILOWUDWH ZDV GLVWLOOHG XQGHU UHGXFHG SUHVVXUH WR UHPRYH H[FHVV QLWURPHWKDQH r& DW PP +J WKHQ KHOG DW PP +J IRU PLQf 7KH \HOORZ UHVLGXH ZDV WUDQVIHUUHG WR D PO URXQG ERWWRPHG IODVN DQG GLVWLOOHG XQGHU YDFXXP r& DW PP +Jf WR \LHOG J bf RI FU\VWDO FOHDU OLTXLG QA >OLWHUDWXUH YDOXH @ ;+ &'&706f P+f P+f 1LWURSURSDQHGLRO f 3URFHGXUH $ 7KH IROORZLQJ SURFHGXUH ZDV PRGLILHG IURP WKH SURFHGXUH RI 'HQ 2WWHU 3DUDIRUPDOGHK\GH J PROHf QLWURPHWKDQH J PROHf DQG GURSV RI b DTXHRXV

PAGE 26

SRWDVVLXP K\GUR[LGH ZHUH KHDWHG ZLWK PO RI PHWKDQRO XQGHU UHIOX[ LQ DQ RLO EDWK 7KH K\GUR[\PHWK\OfQLWUROSURSDQHGLRO f IRUPHG GXULQJ WKH UHDFWLRQ ZDV QRW LVRODWHG EXW XVHG LQ WKH GLVVROYHG FRQGLWLRQ $ VROXWLRQ RI VRGLXP J PROHf LQ PO RI PHWKDQRO ZDV DGGHG GURSZLVH WR WKH VROXWLRQ ZKLFK ZDV VWLUUHG DQG FRROHG LQ DQ LFH EDWK 'XULQJ WKLV DGGLWLRQ D SUHFLSLWDWH RI WKH VRGLXP GHULYDWLYH RI QLWURSURSDQHGLRO f EHJDQ WR VHSDUDWH DQG WKLV VHSDUDWLRQ ZDV FRPSOHWH DIWHU WKH IODVN KDG VWRRG RYHUQLJKW LQ D UHIULJHUDWRU 7KH ILOWHUHG DQG GULHG VRGLXP GHULYDWLYH RI QLWURSURSDQHGLRO Jf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b \LHOGf PS r& >OLWHUDWXUH PS r&@ 6RGLXP GHULYDWLYH RI QLWURSURSDQHGLRO f ''66f 6+f 6+f QLWURSURSDQHGLRO f '06G706f P+f PO+f W+f & '06G! f

PAGE 27

,5 .%Uf VEUf Pf Pf Vf Vf VVKf Vf Pf Pf VVKf Vf Zf ZVKf Pf Zf FPr $QDO\VLV FDOFXODWHG IRU &+1 & + 1 )RXQG & + 1 3URFHGXUH % $ PL[WXUH RI QLWURPHWKDQH J PROHf DQG FDOFLXP K\GUR[LGH Jf ZDV SODFHG LQ D PO URXQGERWWRPHG IODVN HTXLSSHG ZLWK D VWLUUHU DQG D FRQGHQVHU DQG FRROHG LQ DQ H[WHUQDO LFH EDWK $IWHU FRROLQJ J RI IRUPDOLQ VROXWLRQ b ZZ DTXHRXV PROHf ZDV DGGHG VORZO\ IURP D GURSSLQJ IXQQHO $IWHU WKH DGGLWLRQ ZDV FRPSOHWH WKH VROXWLRQ ZDV VWLUUHG DW URRP WHPSHUDWXUH IRU KRXUV &DUERQ GLR[LGH LQ WKH IRUP RI GU\LFH ZDV DGGHG LQ H[FHVV DQG WKH FDOFLXP FDUERQDWH ZDV ILOWHUHG 7KH ILOWUDWH ZDV HYDSRUDWHG DW r& XQGHU UHGXFHG SUHVVXUH WR \LHOG D PROWHQ GDUN EURZQ YLVFRXV RLO ZKLFK XSRQ FRROLQJ VROLGLILHG 7KH UHVXOWLQJ VROLG ZDV UHFU\VWDOOL]HG IURP D HWK\ODFHWDWHFKORURIRUP PL[WXUH WR \LHOG D ZKLWH FU\VWDOOLQH SURGXFW J bf ZKLFK WXUQHG RXW WR EH K\GUR[\PHWK\fQLWUROSURSDQHGLRO f + DFHWRQHG706f G+f W+f 0HWK\OQLWUROSURSDQRO f 7KH IROORZLQJ SURFHGXUH ZDV PRGLILHG IURP WKH SURFHGXUH RI 9DQGHUYLOW DQG +DVVA 7R D PO WKUHHQHFNHG URXQGERWWRPHG IODVN HTXLSSHG ZLWK D PHFKDQLFDO VWLUUHU DQG WKHUPRPHWHU ZDV DGGHG J PROHf RI IUHVKO\ GLVWLOOHG QLWURSURSDQH DQG J RI FDOFLXP K\GUR[LGH 7KH PL[WXUH ZDV FRROHG LQ DQ H[WHUQDO LFH EDWK WR r& DIWHU ZKLFK J PROHf RI IRUPDOLQ VROXWLRQ b ZZ

PAGE 28

DTXHRXVf ZDV DGGHG GURSZLVH IURP WKH GURSSLQJ IXQQHO $IWHU WKH DGGLWLRQ ZDV FRPSOHWH WKH VROXWLRQ ZDV VWLUUHG DW URRP WHPSHUDWXUH IRU KRXUV &DUERQ GLR[LGH LQ WKH IRUP RI GU\LFH ZDV DGGHG LQ H[FHVV DQG WKH FDOFLXP FDUERQDWH SUHFLSLWDWH ZDV UHPRYHG E\ ILOWUDWLRQ 7KH SUHFLSLWDWH ZDV ZDVKHG ZLWK PO RI ZDWHU DQG WKH FRPELQHG ILOWUDWH DQG ZDVKLQJV ZHUH HYDSRUDWHG DW r& XQGHU UHGXFHG SUHVVXUH 7KH UHPDLQLQJ PROWHQ SURGXFW ZKLFK VROLGLILHG XSRQ FRROLQJ ZDV UHFU\VWDOOL]HG IURP EXWDQROEHQ]HQH WR \LHOG J bf RI ZKLWH FU\VWDOOLQH SURGXFW PS r& >OLWHUDWXUH PS r&@ 105 &'&706f V+f VO+f V+f & 105 &'&f ,5 .%Uf VEUf Pf Pf Pf Vf Pf Zf Zf Pf PVKf Zf PVKf Zf ZVKf Zf Zf FP 0HWK\OQLWURSURSDQHGLRO f %\ XVH RI WKH VDPH SURFHGXUH DV UHSRUWHG IRU WKH SUHYLRXV FRPSRXQG RQ SUHSDUDWLRQ RI WKLV FRPSRXQG ZDV DFFRPSOLVKHG E\ DGGLQJ VORZO\ J PROHf RI IRUPDOLQ VROXWLRQ b ZZ DTXHRXVf WR D PL[WXUH RI J PROHf RI QLWURHWKDQH DQG J RI FDOFLXP K\GUR[LGH $IWHU VWLUULQJ IRU KRXUV DW URRP WHPSHUDWXUH DQG D VOLJKW H[FHVV RI FDUERQ GLR[LGH KDG EHHQ DGGHG WKH ZKLWH SUHFLSLWDWH ZKLFK IRUPHG ZDV ILOWHUHG DQG ZDVKHG 7KH ILOWUDWH DQG ZDVKLQJV ZHUH FRPELQHG DQG HYDSRUDWHG DW r& XQGHU UHGXFHG SUHVVXUH WR \LHOG PROWHQ SURGXFW ZKLFK XSRQ FRROLQJ VROLGLILHG 7KH FUXGH SURGXFW ZDV UHFU\VWDOOL]HG IURP EXWDQROEHQ]HQH WR \LHOG J bf

PAGE 29

RI ZKLWH FU\VWDOOLQH SURGXFW PS r& >OLWHUDWXUH PS r&@ ;+ 105 &'&706f V+f W+f G+f & 105 && f ,5 .%Uf VEUf Pf Pf Pf Zf Vf Pf Pf Pf Pf PVKf Pf Pf Zf Pf Pf Pf Vf Pf Pf Pf Pf Pf Pf PVKf PEUf FP (WK\OQLWURSURSDQHGLRO f 3UHSDUDWLRQ RI WKLV FRPSRXQG ZDV DFKLHYHG DV SUHYLRXVO\ GHVFULEHG E\ DGGLQJ J PROHf IRUPDOLQ VROXWLRQ b ZZ DTXHRXVf WR D PL[WXUH RI J PROHf RI QLWURSURSDQH DQG J RI FDOFLXP K\GUR[LGH 7KH UHFU\VWDOOL]DWLRQ \LHOGHG ZKLWH FU\VWDOOLQH SURGXFW J bf PS r& >OLWHUDWXUH PS r&@ + 105 &'&706f W+f T+f V+f P+f & 105 &'&f ,5 .%Uf VEUf Pf Pf Vf Pf Pf Zf ZVKf Zf VVKf Pf Zf Pf Pf Pf Zf Zf FP

PAGE 30

6\QWKHVLV RI 0RGHO &RPSRXQGV 1+\GUR[\HWK\Of1PHWK\OPHWK\OQLWUROSURS\Of DPLQH f 3URFHGXUH $ ,Q D PO URXQGERWWRPHG IODVN ZHUH SODFHG J PROHf RI PHWK\OQLWUROSURSDQRO f LQ PO RI IUHVKO\ GLVWLOOHG 7+) DQG $ PROHFXODU VLHYHV DQG J PROHf RI 1PHWK\OHWKDQRODPLQH LQ PO RI 7+) ZDV DGGHG VORZO\ E\ PHDQV RI D GURSSLQJ IXQQHO $IWHU WKH DGGLWLRQ ZDV FRPSOHWH WKH UHDFWLRQ ZDV VWLUUHG IRU KRXUV ZLWK IUHVK PROHFXODU VLHYHV $f DGGHG HYHU\ KRXUV 7KH PROHFXODU VLHYHV ZHUH ILOWHUHG DQG WKH VROYHQW ZDV HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH WR \LHOG D \HOORZ RLO J bf 3URFHGXUH % 7KH VDPH SURFHGXUH ZDV XVHG ZLWK WKH H[FHSWLRQ RI DGGLWLRQ RI WULHWK\ODPLQH POf WR WKH UHDFWLRQ PL[WXUH 7KXV WKH UHDFWLRQ RI f J PROHf DQG 1PHWK\OHWKDQRODPLQH J PROHf DIIRUGHG \HOORZ RLO J bf 3URFHGXUH & 7KH UHDFWLRQ PL[WXUH DOFRKRO DPLQH DQG FDWDO\VW 1(Wf LQ ZDV VWLUUHG DQG UHIOX[HG IRU KRXUV DQG FRROHG WR URRP WHPSHUDWXUH 7KH VROYHQW ZDV UHPRYHG E\ HYDSRUDWLRQ XQGHU UHGXFHG SUHVVXUH WR \LHOG D \HOORZ RLO J bf $QDO\VLV FDOFXODWHG IRU &+12 & + 1 )RXQG & + 1 + 105 &&706f V+f V+f VO+f W+f V+f W+f & 105 &'&f

PAGE 31

,5 .%Uf VEUf Vf Vf Vf Pf Zf Zf Vf Vf Vf Vf VVKf Zf Zf Zf Zf Pf Vf VVKf Zf Zf Zf PVKf Zf Zf FQIr (WK\ Q L WUROELVK\GUR[\HWK\O1PHWK\O fDPLQR SURSDQH f 7KH VROXWLRQ RI J PROHf RI 1PHWK\OHWKDQRODPLQH DQG J PROHf RI HWK\OQLWUROSURSDQHGLRO f ZLWK $ PROHFXODU VLHYHV LQ PO 7+) ZDV VWLUUHG IRU KRXUV DW URRP WHPSHUDWXUH 7KH PROHFXODU VLHYHV ZHUH ILOWHUHG RXW DQG WKH ILOWUDWH ZDV HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH WR \LHOG D \HOORZ RLO J bf 105 &'&706f W+f T+f V+f V+f W+f V+f W+f V+f 11'LPHWK\O1n 1nELVPHWK\OQLWUROSURS\O fO SURSDQHGLDPLQH f 3URFHGXUH $ 7R D VROXWLRQ RI 11GLPHWK\OOSURSDQHGLDPLQH '03$f J PROHf LQ PO RI GLR[DQH ZDV DGGHG IRUPDOLQ VROXWLRQ J b ZZ DTXHRXV PROHf $ FDWDO\WLF DPRXQW a Jf RI K\GURFKORULF DFLG ZDV DGGHG DQG VWLUUHG 7R WKLV PL[WXUH QLWURSURSDQH J PROHf ZDV DGGHG DQG VWLUULQJ ZDV FRQWLQXHG IRU KRXUV DW r& 7KH UHDFWLRQ PL[WXUH ZDV FRROHG QHXWUDOL]HG ZLWK J RI 1D2+ DQG H[WUDFWHG ZLWK [ PO RI PHWK\OHQH FKORULGH 7KH FRPELQHG RUJDQLF SKDVH ZDV GULHG RYHU 0J62A RYHUQLJKW ILOWHUHG DQG HYDSRUDWHG WR \LHOG D \HOORZ RLO J bf

PAGE 32

3URFHGXUH % 7R D VROXWLRQ RI QLWURSURSDQH J PROHf LQ PO RI GLR[DQH DW r& LQ DQ H[WHUQDO LFH EDWKf ZDV DGGHG IRUPDOLQ VROXWLRQ J b ZZ DTXHRXV PROHf DQG SRWDVVLXP FDUERQDWH Jf 7KH LFH EDWK ZDV UHPRYHG DQG WKH PL[WXUH ZDV VWLUUHG DW URRP WHPSHUDWXUH IRU KRXUV 7KHQ 11 GLPHWK\OOSURSDQHGLDPLQH J PROHf LQ PO RI GLR[DQH ZDV DGGHG 7KH UHDFWLRQ PL[WXUH ZDV EURXJKW WR UHIOX[ DQG H[WUDFWHG ZLWK [ PO RI HWKHU 7KH FRPELQHG RUJDQLF SKDVH ZDV GULHG RYHU 0J62A RYHUQLJKW ILOWHUHG DQG HYDSRUDWHG WR \LHOG \HOORZ RLO J bf 3URFHGXUH & 7R DQ LFHFRROHG PO URXQGERWWRPHG IODVN FRQWDLQLQJ QLWURPHWK\OSURSDQRO J PROHf LQ PO RI fZDWHU ZDV VORZO\ DGGHG 11GLPHWK\OOSURSDQHGLDPLQH J PROHf LQ PO RI GLR[DQH $IWHU WKH DGGLWLRQ ZDV FRPSOHWH WKH VROXWLRQ ZDV VWLUUHG DW r& IRU KRXU WKHQ DW r& IRU KRXUV 7KLV ZDV H[WUDFWHG ZLWK [ PO RI PHWK\OHQH FKORULGH DQG WKH FRPELQHG RUJDQLF SKDVH ZDV GULHG RYHU 0J6 ILOWHUHG DQG HYDSRUDWHG WR \LHOG D \HOORZ RLO J b \LHOGf $QDO\VLV FDOFXODWHG IRU &ALAJ1A2A & + 1 )RXQG & + 1 ;+ 105 &'&706f V+f P+f V+f P+f P+f & 105 &'&rf ,5 1HDWf PEUf Vf Vf Vf Vf Vf Vf Vf Pf Vf Vf

PAGE 33

PEUf Zf PVKf Pf Pf Pf Zf Zf Zf Vf PVKf ZEUf Zf FPn 10O%LVPHWK\QLWUROSURS\fSLSHUD]LQH f ,Q D PO QHFNHG URXQGERWWRPHG IODVN HTXLSSHG ZLWK D GURSSLQJ IXQQHO FKDUJHG ZLWK GLR[DQH D VWLUUHU DQG D 'HDQ6WDUN WUDS ZHUH SODFHG QLWURSURSDQH J PROHf IRUPDOLQ VROXWLRQ J b ZZ DTXHRXV PROHf DQG SLSHUD]LQH J 2 PROHf LQ PO RI GLR[DQH $ FDWDO\WLF DPRXQW a POf RI VRGLXP K\GUR[LGH VROXWLRQ b ZY DTXHRXVf ZDV DGGHG DQG WKH UHDFWLRQ PL[WXUH ZDV EURXJKW WR UHIOX[ 7KH VROYHQW ZDV DGGHG IURP WKH GURSSLQJ IXQQHO WR NHHS WKH YROXPH FRQVWDQW :KHQ WKH ERLOLQJ SRLQW RI WKH D]HRWURSLF PL[WXUH UHDFKHG r& DGGLWLRQ RI VROYHQW ZDV VWRSSHG DQG WKH YROXPH RI WKH UHDFWLRQ PL[WXUH ZDV UHGXFHG WR a9 RI WKH RULJLQDO YROXPH 3HWUROHXP HWKHU ZDV DGGHG WR WKLV UHDFWLRQ PL[WXUH DQG WKH XSSHU OD\HU ZDV GHFDQWHG 7KH UHVXOWLQJ RLO ZDV FU\VWDOOL]HG IURP DFHWRQH WR \LHOG D \HOORZLVK ZKLWH SRZGHU J b \LHOGf $QDO\VLV FDOFXODWHG IRU &+L1 & + 1 )RXQG & + 1 ;+ 105 &'&706f V+f V+f V+f & 105 &'&f ,5 .%Uf PVKf ZVKf PVKf ZVKf Zf Vf Pf Pf PVKf Vf Vf Zf Zf Zf Vf Pf Pf Zf ZVKf Zf Kf PVKf Zf FP

PAGE 34

0HWK\OQLWUROELV 1nK\GUR[\HWK\Of1 SLSHUD]LQR SURSDQH @ 3URFHGXUH $ 7R D IRUPDOLQ VROXWLRQ J PROHf ZHUH DGGHG QLWURHWKDQH J PROHf DQG 1HK\GUR[\HWK\Of SLSHUD]LQH J PROHf 6RGLXP K\GUR[LGH VROXWLRQ b ZY DTXHRXV POf ZDV DGGHG WR WKLV PL[WXUH 8SRQ DGGLWLRQ DQ H[RWKHUPLF UHDFWLRQ RFFXUUHG LPPHGLDWHO\ DQG D ZKLWH SUHFLSLWDWH IRUPHG ZKLFK ZDV QRW VROXEOH LQ GLR[DQH 3HWUROHXP HWKHU ZDV DGGHG WR WKLV PL[WXUH DQG WKH VROLG ZDV ILOWHUHG DQG GULHG WR \LHOG ZKLWH FU\VWDOV J b \LHOGf ZKLFK ZHUH UHFU\VWDOOL]HG LQ DFHWRQH PS r& 3URFHGXUH % ,Q D PO URXQGERWWRPHG IODVN ZDV SODFHG D VROXWLRQ RI 1K\GUR[\HWK\OfSLSHUD]LQH J PROHf LQ PO RI GLR[DQH ZLWK VRGLXP K\GUR[LGH VROXWLRQ b ZY DTXHRXV POf 7R WKLV VROXWLRQ ZDV VORZO\ DGGHG D PL[WXUH RI IRUPDOLQ VROXWLRQ b ZZ DTXHRXV J PROHf DQG QLWURHWKDQH J PROHf LQ PO RI GLR[DQH 7KLV UHDFWLRQ PL[WXUH ZDV EURXJKW WR UHIOX[ IRU KRXUV WKHQ WKH VROYHQW ZDV GLVWLOOHG XQWLO WKH YROXPH RI WKH UHPDLQGHU EHFDPH a PO 8SRQ FRROLQJ D \HOORZLVK ZKLWH SUHFLSLWDWH IRUPHG DIWHU ZKLFK SHWUROHXP HWKHU a POf ZDV DGGHG ZLWK VWLUULQJ WKH SUHFLSLWDWH ZKLFK IRUPHG ZDV ILOWHUHG DQG GULHG XQGHU UHGXFHG SUHVVXUH WR \LHOG J b \LHOGf RI \HOORZLVK ZKLWH FU\VWDOV 5HFU\VWDOOL]DWLRQ IURP DFHWRQH JDYH ZKLWH FU\VWDOV RI PS r& $QDO\VLV FDOFXODWHG IRU &LJA1J2A & + 1 )RXQG & + 1

PAGE 35

+ 105 &'&706f V+f V+f G RI G+f W+f & 105 &2&,rf ,5 .EUf V%Uf VVKf Pf Pf Pf VVKf Pf Vf Pf Zf Pf Pf Pf Pf VVKf LQf Zf Vf Pf PVKf PVKf Pf Pf Vf Zf Zf Zf Zf Zf Pf Zf ZVKf ZVKf FPr (WK\OQLWUROELV^1nJK\GUR[\HWK\f1 SLSHUD]LQ\OMSURSDQH f 7KLV PDWHULDO ZDV SUHSDUHG E\ WKH PHWKRGV UHSRUWHG IRU FRPSRXQG f 3URFHGXUH $ 7R D VROXWLRQ RI 1K\GUR[\HWK\OfSLSHUD]LQH J PROHf LQ PO RI GLR[DQH ZDV DGGHG D PL[WXUH IRU IRUPDOLQ VROXWLRQ b ZZ DTXHRXV J PROHf DQG QLWURSURSDQH J PROHf LQ PO RI GLR[DQH 6RGLXP K\GUR[LGH VROXWLRQ b ZY DTXHRXV POf ZDV DGGHG DQG WKH PL[WXUH ZDV UHIOX[HG IRU KRXUV 7KH D]HRWURSLF PL[WXUH RI GLR[DQH DQG +2 ZDV GLVWLOOHG XQWLO WKH YROXPH RI WKH UHPDLQLQJ VROXWLRQ EHFDPH PO 7KH UHVXOWLQJ GDUN EURZQ RLO ZDV FU\VWDOOL]HG IURP DFHWRQH WR \LHOG D ZKLWH IODN\ VROLG J b \LHOGf ZKLFK WXUQHG RXW WR EH PHWK\OHQHELV>LLK\GUR[\HWK\O f@1SLSHUD]LQH f 7KH ILOWUDWH ZDV HYDSRUDWHG WR \LHOG D EURZQ RLO J b \LHOGf ZKLFK ZDV FU\VWDOOL]HG IURP DFHWRQH 7KH \HOORZLVK ZKLWH FU\VWDOV REWDLQHG ZHUH WKH GHVLUHG SURGXFW PS r&

PAGE 36

3URFHGXUH % $ VROXWLRQ RI 1K\GUR[\HWK\OfSLSHUD]LQH J PROHf LQ PO RI 7+) ZDV VORZO\ DGGHG WR D VROXWLRQ RI HWK\OQLWURSURSDQHGLRO J PROHf ZLWK 1(WM Jf LQ PO RI 7+) 7KH UHDFWLRQ PL[WXUH ZDV UHIOX[HG IRU KUV DQG FRROHG WR URRP WHPSHUDWXUH 7KH VROYHQW ZDV UHPRYHG XQGHU UHGXFHG SUHVVXUH WR \LHOG D \HOORZ RLO ZKLFK ZDV GULHG RYHU PROHFXODU VLHYHV $f IRU KRXUV DW ar& 'XULQJ WKLV WLPH ZKLWH FU\VWDOV IRUPHG ZKLFK ZHUH ILOWHUHG DQG GULHG J b \LHOGf O+ 105 &'&706f W+f T+f V+f V+f W+f & 105 '06Gf ,5 .%Uf VEUf Vf Vf Vf VVKf Zf Vf Vf Pf Zf Pf Pf Vf Vf VVKf PVKf Zf Zf Zf Vf Pf PVKf PVKf Pf Vf Vf Zf PVKf Zf Zf Pf Pf Zf Pf Zf ZEUf Zf Zf FPr 0HWK\HQHELV^1fHK\GUR[\HWK\Of1SLSHUD]LQH` f $ IRUPDOLQ VROXWLRQ b DTXHRXV J PROHf ZDV DGGHG WR D VROXWLRQ RI 1JK\GUR[\HWK\OfSLSHUD]LQH J PROHf LQ PO RI GLR[DQH $ VRGLXP K\GUR[LGH VROXWLRQ b ZY DTXHRXV POf ZDV DGGHG WR WKLV PL[WXUH IROORZHG E\ DQ DGGLWLRQDO PO RI GLR[DQH 7KLV UHDFWLRQ PL[WXUH ZDV UHIOX[HG IRU KRXUV WKHQ FRROHG WR URRP WHPSHUDWXUH 3HWUROHXP HWKHU ZDV DGGHG DQG WKH XSSHU

PAGE 37

OD\HU ZDV GHFDQWHG 7KH UHVXOWLQJ \HOORZ RLO ZDV FU\VWDOOL]HG IURP FROG DFHWRQH WR \LHOG ZKLWH IODN\ FU\VWDOV J b \LHOGf PS r& $QDO\VLV FDOFXODWHG IRU &+12 & + 1 )RXQG & + 1 &'& 706f V+f V+f W+f & &'&f ,5 .%Uf V%Uf Vf Vf VVKf Zf Zf PVKf Pf Pf Vf PVKf PVKf Pf Pf VVKf Pf Pf Pf PVKf PVKf Zf PVKf Zf FP 0HWK\OQLWUROGLSLSHULGLQRSURSDQH Ef ,Q D PO URXQGERWWRPHG IODVN HTXLSSHG ZLWK D FRQGHQVHU ZDV SODFHG D VROXWLRQ RI PHWK\OQLWURSURSDQHGLRO J PROHf LQ PO RI 7+) $ VROXWLRQ RI SLSHULGLQH J PROHf LQ PO RI 7+) ZDV DGGHG DQG WKH PL[WXUH ZDV VWLUUHG IRU KRXUV DW URRP WHPSHUDWXUH IROORZHG E\ HYDSRUDWLRQ RI WKH VROYHQW 7KH UHVXOWLQJ OLJKW \HOORZ YLVFRXV RLO ZDV FU\VWDOOL]HG LQ FROG PHWKDQRO WR \LHOG ZKLWH FU\VWDOV J b \LHOGf $QDO\VLV FDOFXODWHG IRU &+12 & + 1 )RXQG & + 1 O+ 105 &'&706f P+f V+f P+f P+f

PAGE 38

& 105 &&Of ,5 .%Uf Vf Pf PVKf Zf Vf PVKf Zf Pf Zf Zf Pf Pf Pf PVKf Pf Pf Zf PVKf Zf Zf Zf FPn 0HWK\QLWUROELVGLPHWK\ODPLQRfSURSDQH f 7KH IROORZLQJ SURFHGXUH ZDV DGRSWHG IURP -RKQVRQ ,Q D PO (UOHQPH\HU IODVN ZDV SODFHG D PL[WXUH RI PHWK\OQLWUR SURSDQHGLRO f J PROHf DQG GLPHWK\ODPLQH b DTXHRXV J PROHf DQG OHIW LQ WKH UHIULJHUDWRU IRU KRXUV $ UHDFWLRQ WRRN SODFH DQG SKDVH VHSDUDWLRQ RFFXUUHG WKH WRS OD\HU EHLQJ VROLG (WK\O HWKHU POf ZDV DGGHG DQG WKH DTXHRXV SKDVH ZDV VHSDUDWHG DQG ZDVKHG ZLWK PO RI HWKHU 7KH FRPELQHG HWKHU OD\HU ZDV GULHG RYHU .&2 ILOWHUHG DQG HYDSRUDWHG WR \LHOG D \HOORZ OLTXLG J b \LHOGf ZKLFK ODWHU VROLGLILHG PS r& >OLWHUDWXUH PS r&@ ;+ 105 &'&706f V+f V+f P+f & &2&,f ,5 1HDWf Vf Pf VVKf VVKf Vf Zf Pf VVKf Pf VVKf Pf PVKf Vf ZVKf Pf Zf Zf Zf FP (WK\OQLWUR11nELVPHWK\OSURSDQR SURS\OfDPLQH 7 7KLV PDWHULDO ZDV SUHSDUHG DV GHVFULEHG HDUOLHU IRU WKH FDVH RI f E\ DOORZLQJ HWK\OQLWURSURSDQHGLRO f J

PAGE 39

PROHf DQG GLPHWK\ODPLQH b ZZ DTXHRXV J PROHf WR UHDFW RYHUQLJKW LQ D UHIULJHUDWRU $ UHDFWLRQ WRRN SODFH DQG D QRQDTXHRXV SKDVH VHSDUDWHG 7KH DTXHRXV SKDVH ZDV H[WUDFWHG ZLWK [ PO RI HWK\O HWKHU DQG WKH FRPELQHG RUJDQLF SKDVH ZDV GULHG RYHU .&2 ILOWHUHG DQG HYDSRUDWHG WR \LHOG D JUHHQLVK \HOORZ RLO J b \LHOGf $Q DWWHPSW DW IXUWKHU SXULILFDWLRQ E\ YDFXXP GLVWLOODWLRQ IDLOHG GXH WR WKH GHFRPSRVLWLRQ RI WKH FRPSRXQG O+ 105 &'&706f W+f T+f V+f V+f & 105 &'&f ,5 1HDWf Pf Pf PVKf Pf Vf Vf VVKf Zf PVKf Zf Zf Zf PVKf Zf Zf Zf Zf FP 11O'LPHWK\O11nELVPHWK\QLWUROSURS\Of HWK\OHQHGLDPLQH f ,Q D PO URXQGERWWRPHG IODVN HTXLSSHG ZLWK D FRQGHQVHU ZDV SODFHG D VROXWLRQ RI 11nGLPHWK\OHWK\OHQHGLDPLQH J PROHf QLWURSURSDQH J PROHf DQG IRUPDOLQ VROXWLRQ b ZZ DTXHRXV J PROHf LQ PO RI GLR[DQH $ FDWDO\WLF DPRXQW RI SRWDVVLXP K\GUR[LGH b DTXHRXV POf ZDV DGGHG DQG WKH UHDFWLRQ PL[WXUH ZDV KHDWHG WR UHIOX[ IRU KRXUV 7KH VROYHQW D]HRWURSLF PL[WXUH RI GLR[DQH DQG ZDWHUf ZDV GLVWLOOHG ZLWK FRQVWDQW DGGLWLRQ RI IUHVK GLR[DQH XQWLO WKH ERLOLQJ SRLQW RI WKH D]HRWURSLF PL[WXUH UHDFKHG r& 7KH UHVXOWLQJ YLVFRXV \HOORZ OLTXLG FU\VWDOOL]HG XSRQ FRROLQJ 7KLV FUXGH SURGXFW ZDV GLVVROYHG LQ PO RI HWK\O HWKHU ZDVKHG ZLWK [ PO RI ZDWHU

PAGE 40

GULHG RYHU .&2 RYHUQLJKW ILOWHUHG DQG HYDSRUDWHG WR \LHOG ZKLWH FU\VWDOV J b \LHOGf PS r& $QDO\VLV FDOFXODWHG IRU &LAAA & + 1 )RXQG & + 1 + 105 &'&706f V+f V+f V+f V+f & 105 &'&f ,5 .%Uf VVKf UQf VVKf Vf Pf Pf Pf Pf UQVKf VVKf Pf Zf PVKf Zf PVKf Vf Pf Zf Zf Zf Pf Pf ZVKf FP 11'LPHWK\O11ELVPHWK\OQLWUROSURS\Of EXWHQHGLDPLQH f ,Q D PO URXQGERWWRPHG IODVN HTXLSSHG ZLWK D FRQGHQVHU ZDV SODFHG D VROXWLRQ RI 11fGLPHWK\OEXWHQHOGLDPLQH J 2 PROHf LQ PO RI GLR[DQH )RUPDOLQ VROXWLRQ b ZZ DTXHRXV J PROHf QLWURSURSDQH J PROHf DQG SRWDVVLXP K\GUR[LGH b ZZ DTXHRXV POf ZHUH DGGHG DQG WKH UHDFWLRQ PL[WXUH ZDV EURXJKW WR UHIOX[ IRU KRXUV IROORZHG E\ GLVWLOODWLRQ RI WKH D]HRWURSLF PL[WXUH RI GLR[DQH DQG ZDWHU ZLWK FRQVWDQW DGGLWLRQ RI IUHVK GLR[DQH :KHQ WKH WHPSHUDWXUH RI WKH RXWFRPLQJ YDSRU UHDFKHG r& WKH DGGLWLRQ RI GLR[DQH ZDV VWRSSHG DQG WKH GLVWLOODWLRQ ZDV VWRSSHG ZKHQ WKH UHVLGXDO UHDFWLRQ PL[WXUH EHFDPH FORXG\ (WK\O HWKHU POf ZDV DGGHG WKH VROLG SRUWLRQ ZDV ILOWHUHG DQG WKH ILOWUDWH ZDV HYDSRUDWHG WR \LHOG D YLVFRXV \HOORZ RLO J b \LHOGf 6WRUDJH RYHUQLJKW LQ D UHIULJHUDWRU

PAGE 41

UHVXOWHG LQ D \HOORZZKLWH VROLG ZKLFK ZDV UHFU\VWDO L]HG IURP PHWKDQRO WR \LHOG ZKLWH FU\VWDOV PS r& $QDO\VLV FDOFXODWHG IRU &+12 & + 1 )RXQG & + 1 O+ 105 &'&706f V+f V+f V+f P+f P+f & 105 &'&f ,5 .%Uf VVKf Pf PVKf PVKf Pf VVKf VVKf VVKf Zf Pf Pf Vf VVKf Pf ZVKf Zf Zf Zf PVKf Zf Vf Zf Vf Pf Pf Zf Vf Zf Zf Zf FPn 11'LPHWK\O11ELVPHWK\OQLWUROSURS\Of KH[DPHWK\OHQHGLDPLQH f 7KLV FRPSRXQG ZDV SUHSDUHG E\ WKH SURFHGXUH SUHYLRXVO\ GHVFULEHG IRU WKH FDVH RI f 11n'LPHWK\OKH[DPHWK\OHQHGLDPLQH J 2 PROHf IRUPDOLQ VROXWLRQ b DTXHRXV J PROHf DQG QLWURSURSDQH J PROHf ZHUH DOORZHG WR UHDFW LQ WKH SUHVHQFH RI SRWDVVLXP K\GUR[LGH b DTXHRXV POf WR DIIRUG \HOORZ RLO J b \LHOGf $QDO\VLV FDOFXODWHG IRU AA & + 1 )RXQG & + 1 105 &&706f V+f V+f V+f P+f V+f & 105 &'&f

PAGE 42

,5 .%Uf Pf Vf Vf VVKf Zf Zf Vf VVKf Pf Pf Pf Pf Pf Pf PVKf Zf Zf Pf Zf ZVKf ZVKf FP 5HDFWLRQV 8WLOL]LQJ &KDLQ6WRSSLQJ 5HDJHQWV *HQHUDO 3URFHGXUH $ ,Q D URXQGERWWRPHG QHFNHG IODVN HTXLSSHG ZLWK D 'HDQ6WDUN WUDS DQG D GURSSLQJ IXQQHO FKDUJHG ZLWK IUHVK GLR[DQH ZDV SODFHG WKH PL[WXUH RI WKH VWDUWLQJ PDWHULDOV LH DPLQH FRPSRQHQW IRUPDOLQ VROXWLRQ DQG QLWURDONDQH LQ GLR[DQH $ FDWDO\WLF DPRXQW RI VRGLXP K\GUR[LGH ZDV DGGHG DQG WKH D]HRWURSLF PL[WXUH RI GLR[DQH DQG ZDWHU ZDV GLVWLOOHG RII ZLWK FRQVWDQW DGGLWLRQ RI IUHVK GLR[DQH :KHQ WKH WHPSHUDWXUH RI WKH RXWFRPLQJ YDSRU UHDFKHG r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

PAGE 43

IURP DFHWRQH RU PHWKDQRO 7KH IHHG UDWLR RI WKH VWDUWLQJ PDWHULDOV DQG UHDFWLRQ FRQGLWLRQV DUH GHVFULEHG LQ &KDSWHU ,,, S 6\QWKHVLV RI 3RO\PHUV 3RO\PHUL]DWLRQ RI PHWK\OQLWURSURSDQHGLRO f ZLWK 11GLPHWK\OOSURSDQHGLDPLQH f ,Q D PO LFHFRROHG URXQGERWWRPHG IODVN ZDV SODFHG D VROXWLRQ RI PHWK\OQLWURSURSDQHGLRO f J PROHf LQ PO RI GLR[DQH 7R WKLV IUHVKO\ GLVWLOOHG 11 GLPHWK\OSURSDQHGLRO J PROHf PO RI + DQG +& 1OPOf ZDV DGGHG $IWHU WKH DGGLWLRQ ZDV FRPSOHWH WKH UHDFWLRQ PL[WXUH ZDV VWLUUHG IRU KRXU DW r& IROORZHG E\ KRXUV DW r& 7KH UHDFWLRQ PL[WXUH ZDV FRROHG PDGH EDVLF ZLWK VRGLXP K\GUR[LGH S+ af DQG H[WUDFWHG ZLWK [ PO RI PHWK\OHQH FKORULGH 7KH FRPELQHG RUJDQLF SKDVH ZDV GULHG RYHU .&2 ILOWHUHG DQG HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH WR \LHOG D GDUN EURZQ YLVFRXV RLO J b \LHOGf 105 &&706f V+f P+f V+f P+f V+f & 105 &&f ,5 1HDWf Vf Pf Vf Vf Vf Vf Vf PVKf Pf ZVKf PVKf Pf ZVKf VVKf Pf PVKf Zf Zf Pf Vf Pf ZVKf Zf FPn

PAGE 44

3RO\PHUL]DWLRQ RI f ZLWK 11GLPHWK\OOSURSDQHGLDUQLQH f 7KLV PDWHULDO ZDV SUHSDUHG E\ WKH VDPH SURFHGXUH GHVFULEHG IRU f 7KXV J PROHf RI f ZDV UHDFWHG ZLWK J PROHf RI 11GLPHWK\OSURSDQHGLRO WR \LHOG D GDUN EURZQ RLO J b \LHOGf K 105 &'&706f V+f P+f V+f P+f W+f & 105 &'&f ,5 1HDWf Vf Vf LQf Pf Vf VVKf Vf VVKf PVKf Pf Pf PVKf PVKf Pf Zf PVKf PVKf Zf Z%Uf Zf Zf Pf Zf Zf Zf Zf FP 3ROPHUL]DWLRQ RI f ZLWK 11GLPHWK\OHWK\OHQHGLDPLQH f ,Q D PO URXQGERWWRPHG IODVN HTXLSSHG ZLWK D FRQGHQVHU ZDV DGGHG D VROXWLRQ RI f J PROHf LQ PO RI 7+) DQG 11rGLPHWK\OHWK\OHQHGLDPLQH J PROHf 7R WKLV VROXWLRQ ZHUH DGGHG D FDWDO\WLF DPRXQW RI 1(W POf DQG $ PROHFXODU VLHYHV 7KH UHDFWLRQ PL[WXUH ZDV EURXJKW WR UHIOX[ IRU KRXUV FRROHG DQG ILOWHUHG 7KH ILOWUDWH ZDV HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH WR \LHOG D EURZQ YLVFRXV RLO J b \LHOGf $QDO\VLV FDOFXODWHG IRU &J+MM1A & + 1 )RXQG & + 1 O+ 105 &'&706f m V+f V+f V+f P+f

PAGE 45

& 105 &2&,f ,5 1HDWf PEUf Pf Pf Pf Pf Pf PVKf Pf Pf Pf Vf Vf Pf PVKf Pf Zf Zf Zf Z%Uf Pf UDVKf Zf Zf Pf Zf FP 3RO\PHUL]DWLRQ RI f ZLWK '0%$ f 7KH SURFHGXUH HPSOR\HG IRU WKH SRO\PHU f ZDV IROORZHG WKXV FRPSRXQG f J PROHf ZDV DOORZHG WR UHDFW ZLWK '0%$ J PROHf LQ WKH SUHVHQFH RI 1(W POf DQG PROHFXODU VLHYHV $f 7KH UHVXOWLQJ \HOORZ VROLG J \LHOGf ZDV GLVVROYHG LQ 7+) DQG UHSUHFLSLWDWHG LQ PHWKDQRO WR \LHOG D ZKLWH SRZGHU $QDO\VLV FDOFXODWHG IRU &LRKQr & + 1 )RXQG & + 1 ;+ 105 &'&706f V+f V+f P+f V+f & 105 &&f ,5 .%Uf PVKf PVKf Vf Vf Vf PVKf ZVKf ZEUf Vf PVKf PVKf FPr 3RO\PHUL]DWLRQ RI f ZLWK '0+$ f 7KH SURFHGXUH HPSOR\HG IRU WKH SRO\PHU f ZDV IROORZHG WKXV FRPSRXQG f J PROHf ZDV DOORZHG WR UHDFW ZLWK '0+$

PAGE 46

J PROHf LQ 7+) LQ WKH SUHVHQFH RI 1(W DQG $ PROHFXODU VLHYHV WR \LHOG D EURZQ RLO J b \LHOGf $QDO\VLV FDOFXODWHG IRU &LAAp + 1 )RXQG & + 1 ;+ 105 &&706f V+f V+f V+f V+f P+f & 105 &'&f ,5 1HDWf VVKf Vf Vf VVKf VVKf Zf PVKf PVKf ZEUf Zf PEUf Pf Zf PVKf Zf FP 3RO\PHUL]DWLRQ RI f ZLWK 20($ f 3URFHGXUH $ 7KH IROORZLQJ SURFHGXUH ZDV PRGLILHG IURP WKH PHWKRG UHSRUWHG E\ $QJHORQL DQG FRZRUNHUV cQ D ATR PO QHFNHG URXQGERWWRPHG IODVN HTXLSSHG ZLWK D VWLUUHU D FRQGHQVHU DQG D JDV LQOHW WXEH ZDV SODFHG D VROXWLRQ RI FRPSRXQG f J PROHf DQG '0($ J PROHf LQ PO RI b HWKDQRO 1LWURJHQ JDV ZDV EXEEOHG WKURXJK WKH VROXWLRQ IRU KRXUV DW URRP WHPSHUDWXUH ZLWK FRQVWDQW VWLUULQJ 'XULQJ WKLV SHULRG WKH FRORU RI WKH VROXWLRQ FKDQJHG IURP \HOORZ WR GDUN EURZQ 7KH VROYHQW ZDV HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH WR DIIRUG D GDUN EURZQ YLVFRXV RLO J b \LHOGf ZKLFK ZDV LGHQWLFDO ZLWK WKH SRO\PHU REWDLQHG IURP WKH FRPSRXQG f DQG '0($ 3URFHGXUH % 3URFHGXUH $ ZDV PRGLILHG DV IROORZV FRPSRXQG f J PROHf DQG '0($ J PROHf ZHUH GLVVROYHG LQ PO RI '06 DQG SODFHG LQ D PO URXQGERWWRPHG

PAGE 47

IODVN 1LWURJHQ JDV ZDV SDVVHG WKURXJK WKH VROXWLRQ IRU KRXUV DW r& 8SRQ KHDWLQJ WKH FRORU RI WKH VROXWLRQ FKDQJHG VORZO\ WR GDUN EURZQ 7KH VROYHQW ZDV UHPRYHG E\ PHDQV RI UHGXFHG SUHVVXUH WR \LHOG D GDUN EURZQ YLVFRXV RLO J b \LHOGf ZKLFK ZDV LGHQWLFDO ZLWK WKH SRO\PHU REWDLQHG IURP SURFHGXUH $f 3RO\PHUL]DWLRQ RI f ZLWK '0%$ f )RU WKH SUHSDUDWLRQ RI WKLV SRO\PHU SURFHGXUH %f RI WKH SRO\PHU f ZDV XWLOL]HG 7KXV FRPSRXQG f J PROHf DQG '0%$ J PROHf ZHUH DOORZHG WR UHDFW LQ '06 XQGHU 1 IORZ $IWHU KRXUV DW r& WKH UHDFWLRQ PL[WXUH ZDV SRXUHG LQWR LFHZDWHU WR \LHOG D OLJKW EURZQ VROLG J b \LHOGf 7KH ,5 A+ DQG & 105 VSHFWUD ZHUH LGHQWLFDO ZLWK WKRVH RI WKH PDWHULDO REWDLQHG IURP WKH UHDFWLRQ EHWZHHQ WKH FRPSRXQG f DQG '0%$ 3RO\PHUL]DWLRQ RI f ZLWK '0+$ f 3UHSDUDWLRQ RI WKLV SRO\PHU ZDV DFKLHYHG E\ WKH SURFHGXUH $f RI WKH SRO\PHU f 7KXV FRPSRXQG f J PROHf DQG '0+$ J PROHf ZHUH GLVVROYHG LQ PO RI b HWKDQRO DQG VWLUUHG IRU KRXUV DW URRP WHPSHUDWXUH ZLWK D FRQWLQXRXV IORZ RI 1 JDV 7KH UHVXOWLQJ VROXWLRQ ZDV HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH WR \LHOG D EURZQ RLO J b \LHOGf 7KH ,5 r+ DQG & 105 VSHFWUD RI ZKLFK ZHUH LGHQWLFDO ZLWK WKRVH RI SRO\PHU f IURP WKH UHDFWLRQ RI f ZLWK '0+$

PAGE 48

3RO\PHUL]DWLRQ RI f ZLWK SLSHUD]LQH f 3URFHGXUH $ ,Q D PO QHFNHG URXQGERWWRPHG IODVN HTXLSSHG ZLWK D FRQGHQVHU D VWLUUHU DQG D JDV LQOHW WXEH ZDV SODFHG D VROXWLRQ RI FRPSRXQG f J PROHf DQG SLSHUD]LQH J PROHf LQ PO RI b HWKDQRO 7KLV UHDFWLRQ PL[WXUH ZDV VWLUUHG IRU KRXUV DW URRP WHPSHUDWXUH IROORZHG E\ KRXUV DW r& ZLWK FRQWLQXRXV IORZ RI A JDV 'XULQJ WKH UHDFWLRQ WLPH D ZKLWH SUHFLSLWDWH IRUPHG $IWHU WKH UHDFWLRQ PL[WXUH ZDV FRROHG WKH VROLG ZKLFK LV LQVROXEOH LQ PRVW RI WKH FRPPRQ RUJDQLF VROYHQWV ZDV FROOHFWHG J b \LHOGf 3URFHGXUH % ,Q D PO QHFNHG URXQGERWWRPHG IODVN HTXLSSHG ZLWK D FRQGHQVHU VWLUUHU DQG D JDV LQOHW WXEH ZDV SODFHG D VROXWLRQ RI FRPSRXQG f J PROHf DQG SLSHUD]LQH J PROHf LQ PO RI '06 7KH UHDFWLRQ PL[WXUH ZDV VWLUUHG IRU KRXUV DW r& ZLWK D FRQWLQXRXV IORZ RI 1 JDV 7KH UHDFWLRQ PL[WXUH ZKLFK EHFDPH D GDUN EURZQ OLTXLG DQG D \HOORZ SUHFLSLWDWH ZDV SRXUHG LQWR PO RI FROG PHWKDQRO 7KH VROLG ZDV ILOWHUHG ZDVKHG ZLWK FROG PHWKDQRO DQG GULHG LQ D YDFXXP RYHQ WR \LHOG DQ RII ZKLWH SRZGHU J b \LHOGf $QDO\VLV FDOFXODWHG IRU &+A & + 1 )RXQG & + 1 ,5 .%Uf Pf Pf VVKf Vf VVKf Zf Pf VVKf Pf PVKf Pf Zf Zf Vf Zf PVKf Zf Zf FPr

PAGE 49

5HGXFWLRQ RI 0RGHO &RPSRXQGV 5HGXFWLRQ RI FRPSRXQG Ef f 3URFHGXUH $ 7KH SURFHGXUH UHSRUWHG E\ 3DUKDP DQG 5DPS ZDV HPSOR\HG DV IROORZV ,Q D PO QHFNHG URXQGERWWRPHG IODVN HTXLSSHG ZLWK D GURSSLQJ IXQQHO DQG D FRQGHQVHU ZDV SODFHG DQ HWKHUDO VROXWLRQ RI OLWKLXP DOXPLQXP K\GULGH Jf $ VROXWLRQ RI FRPSRXQG Ef J PROHf LQ PO RI DEVROXWH HWKHU ZDV DGGHG GURSZLVH IURP WKH GURSSLQJ IXQQHO XQGHU 1 DWPRVSKHUH DQG WKH UHDFWLRQ PL[WXUH ZDV KHDWHG DW UHIOX[ IRU KRXU DIWHU WKH DGGLWLRQ ZDV FRPSOHWH :DWHU ZDV DGGHG GURSZLVH XQWLO WKH H[FHVV /L$O+A ZDV GHFRPSRVHG DQG WKH VROXWLRQ ZDV PDGH DONDOLQH 7KH DWWHPSW WR GLVWLOO WKH DPLQH ZLWK VWHDP IDLOHG ([WUDFWLRQ ZLWK HWKHU \LHOGHG DQ XQLGHQWLILDEOH PL[WXUH 3URFHGXUH ,Q D PO (UOHQPH\HU IODVN ZDV SODFHG D VROXWLRQ RI VRGLXP ERURK\GULGH Jf LQ PO PHWKDQRO ZLWK VWLUULQJ $ VROXWLRQ RI FRPSRXQG Ef J PROHf LQ PO RI FKORURIRUP ZDV DGGHG GURSZLVH DIWHU WKH DGGLWLRQ RI D FDWDn O\WLF DPRXQW RIf SDOODGLXP RQ FKDUFRDO :KHQ WKH EXEEOLQJ KDG FHDVHG DGGLWLRQDO VRGLXP ERURK\GULGH ZDV DGGHG 7KLV SURFHVV ZDV UHSHDWHG VHYHUDO WLPHV $IWHU WKH DGGLWLRQ ZDV FRPSOHWH WKH UHDFWLRQ PL[WXUH ZDV VWLUUHG IRU KRXU DW URRP WHPSHUDWXUH IROORZHG E\ WKH DGGLWLRQ RI K\GURFKORULF DFLG 1 DTXHRXVf :KHQ WKH UHDFn WLRQ PL[WXUH EHFDPH DFLGLF RQ WR S+ SDSHU WKH VROLG FKDUFRDOf ZDV ILOWHUHG 7KH ILOWUDWH ZDV FRQGHQVHG XQGHU UHGXFHG SUHVVXUH WR \LHOG D OLJKW \HOORZ OLTXLG 7R WKLV VROXWLRQ VRGLXP FDUERQDWH ZDV DGGHG XQWLO WKH IRUPDWLRQ RI &2 EXEEOHV FHDVHG S+ af 7KH UHVXOWLQJ

PAGE 50

VROXWLRQ ZDV H[WUDFWHG ZLWK [ PO RI PHWK\OHQHFKORULGH DQG WKH FRPELQHG RUJDQLF SKDVH ZDV GULHG RYHU .&2 ILOWHUHG DQG GULHG WR DIIRUG D SDOH \HOORZ RLO J b \LHOGf 3URFHGXUH & ,Q D PO SUHVVXUH ERPE ZDV SODFHG D VXVSHQVLRQ RI FRPSRXQG Ef J PROHf LQ PO RI '0) ZLWK 5DQH\ 1L Jf 7KH ERPE ZDV FKDUJHG ZLWK K\GURJHQ JDV SVLf DQG UHOHDVHG WLPHV EHIRUH EHLQJ FKDUJHG XSWR SVL 7KH UHDFWLRQ PL[WXUH ZDV VWLUUHG IRU KRXUV DW r& SUHVVXUH URVH WR SVLf WKHQ KRXUV DW URRP WHPSHUDWXUH 7KH FDWDO\VW 5DQH\ 1Lf ZDV ILOWHUHG DQG WKH ILOWUDWH ZDV HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH DW r& WR \LHOG D \HOORZ RLO J b \LHOGf $QDO\VLV FDOFXODWHG IRU &+1 & + 1 )RXQG & + 1 105 &'&706f V+f V+f V+f V+f P+f & 105 &'&Of ,5 1HDWf PEUVKf Vf Vf VVKf Zf ZVKf PVKf Pf Pf Pf Zf PVKf Pf Pf Zf Zf Pf VVKf PVKf Pf Pf ZVKf ZVKf Pf PVKf Zf FP 5HGXFWLRQ RI FRPSRXQG f f ,Q D PO SDUU ERPE HTXLSSHG ZLWK D VWLUUHU ZDV SODFHG D VROXWLRQ RI FRPSRXQG f J PROHf LQ PO RI PHWKDQRO ZLWK 5DQH\ 1L Jf 7KH UHDFWLRQ PL[WXUH ZDV IOXVKHG ZLWK K\GURJHQ JDV IRU KRXUV EHIRUH WKH SUHVVXUH RI WKH ERPE ZDV VHW DW

PAGE 51

SVL 7KH UHDFWRU ZDV KHDWHG WR r& IRU KRXUV FRROHG DQG ILOWHUHG 7KH ILOWUDWH ZDV HYDSRUDWHG WR \LHOG D \HOORZ RLO J \LHOGf ZKLFK WXUQHG RXW QRW WR EH WKH GHVLUHG SURGXFW EXW O11GLPHWK\ODPLQRfEXW\ODPLQH f $QDO\VLV FDOFXODWHG IRU &J+AJA & + 1 )RXQG & + 1 ;+ 105 &'&706f W+f T+f V+f P+f G+f & 105 &'&f Tf Wf Tf Gf Wf ,5 1HDWf VEUf VEUf Vf Vf Vf Vf Vf VVKf Zf Zf PEUf PVKf ZVKf ZEUf Zf Zf Zf PVKf Zf Zf Zf Zf FP 5HGXFWLRQ RI 3RO\PHUV 5HGXFWLRQ RI 3RO\PHU f f 3URFHGXUH &f SUHYLRXVO\ GHVFULEHG IRU PRGHO FRPSRXQG f ZDV HPSOR\HG 7KXV SRO\PHU f J PROHf LQ PHWKDQRO ZDV SODFHG LQ D 3DUU ERPE ZLWK D FDWDO\WLF DPRXQW a Jf RI 5DQH\ QLFNHO DQG WKH ERPE ZDV FKDUJHG ZLWK K\GURJHQ XSWR SVL 7KH FORVHG V\VWHP ZDV KHDWHG WR r& IRU KRXUV WR DIIRUG D EURZQ RLO J f $QDO\VLV FDOFXODWHG IRU &+1 & + 1 )RXQG & + 1 105 '06G706f Vf Vf Vf VEUf Pf

PAGE 52

& 105 '06Gf ,5 1HDWf VEUf Vf Vf Vf PEUf ZEUf Pf Pf Zf Zf PVKf Zf Zf Pf Vf Pf Pf ZVKf Zf Zf Zf PEUf FP 5HGXFWLRQ RI 3RO\PHU f f 3URFHGXUH $ 3URFHGXUH %f GHVFULEHG SUHYLRXVO\ IRU PRGHO FRPSRXQG f ZDV HPSOR\HG 7KXV SRO\PHU f J PROHf ZDV UHGXFHG ZLWK 1D%+A&1 LQ WKH SUHVHQFH RI D FDWDO\WLF DPRXQW RI SDOODGLXPFKDUFRDO WR \LHOG D OLJKW \HOORZ RLO J bf $QDO\VLV FDOFXODWHG IRU & + 1 )RXQG & + 1 3URFHGXUH 3URFHGXUH &f SUHYLRXVO\ GHVFULEHG IRU FRPSRXQG f ZDV DSSOLHG ,Q D 3DUU ERPE ZDV SODFHG D VROXWLRQ RI SRO\PHU f J PROHf LQ PO RI '0) ZLWK D FDWDO\WLF DPRXQW RI 5DQH\ QLFNHO 7KH ERPE ZDV FKDUJHG ZLWK K\GURJHQ JDV WR SVL DQG KHDWHG WR r& IRU KRXUV IROORZHG E\ r& IRU KRXUV 7KH UHDFWLRQ PL[WXUH ZDV WKHQ VWLUUHG RYHUQLJKW DW URRP WHPSHUDWXUH DQG WKH FDWDO\VW ZDV ILOWHUHG 7KH UHVXOWLQJ OLTXLG ZDV HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH DW r& WR DIIRUG D OLJKW EURZQ RLO J bf $QDO\VLV FDOFXODWHG IRU &LJAOA & + 1 )RXQG & + 1 ;+ 105 &'&706f Vf Pf Vf PEUf VEUf & 105 &'&f

PAGE 53

,5 1HDWf PEUf Vf Vf Vf Zf Vf Vf PEUf ZEUf Pf PEUf Pf PEUf Zf Zf FP 5HGXFWLRQ RI 3RO\PHU f f 3URFHGXUH &f SUHYLRXVO\ GHVFULEHG IRU FRPSRXQG f ZDV DSSOLHG ,Q D 3DUU ERPE ZDV SODFHG D VROXWLRQ RI SRO\PHU f J PROHf LQ PO RI HWKR[\HWKDQRO ZLWK D FDWDO\WLF DPRXQW RI 5DQH\ QLFNHO 7KH ERPE ZDV FKDUJHG ZLWK K\GURJHQ JDV XSWR SVL DQG KHDWHG WR r& IRU KRXUV 7KH UHDFWLRQ PL[WXUH ZDV ILOWHUHG DQG WKH ILOWUDWH ZDV HYDSRUDWHG XQGHU UHGXFHG SUHVVXUH WR \LHOG D OLJKW \HOORZ RLO J bf $QDO\VLV FDOFXODWHG IRU &AA1r r + 1 )RXQG & + 1 + 105 &'&706f Vf Vf Vf VEUf Pf & 105 '06Gf ,5 1HDWf PEUf VVKf Vf Vf Zf ZEUf Pf Pf Zf ZEUf ZEUf Zf PVKf PEUf Zf ZEUf Zf FP 0HWK\O D WL RQ 0HWK\ODWLRQ RI 3RO\PHU f f 3URFHGXUH $ 7KH SURFHGXUH UHSRUWHG E\ 3LQH DQG 6DQFKH]A ZDV PRGLILHG DV IROORZV ,Q D PO URXQGERWWRPHG IODVN ZDV SODFHG

PAGE 54

SRO\PHU f J PROHf DQG WKH IODVN ZDV FRROHG LQ DQ H[WHUQDO LFH EDWK 7R WKLV IRUPLF DFLG b ZZ DTXHRXV J PROHf ZDV VORZO\ DGGHG IROORZHG E\ IRUPDOLQ VROXWLRQ b ZZ DTXHRXV J PROHf 7KH IODVN ZDV HTXLSSHG ZLWK D PDJQHWLF VWLUUHU DQG D FRQGHQVHU DQG SODFHG LQ DQ r& FRQVWDQW WHPSHUDWXUH EDWK IRU KRXUV 7KH PL[WXUH ZDV FRROHG DQG PO RI 1 +& ZDV DGGHG 7KLV ZDV WKHQ H[WUDFWHG ZLWK [ PO RI HWK\O HWKHU DQG WKH FRPELQHG HWKHU H[WUDFWV ZHUH ZDVKHG ZLWK PO RI + DQG GULHG RYHU .&2 RYHUQLJKW (YDSRUDWLRQ RI HWKHU JDYH D ZKLWH VROLG Jf 7KH DTXHRXV OD\HU ZDV PDGH EDVLF ZLWK VRGLXP K\GUR[LGH b ZY DTXHRXVf DQG H[WUDFWHG ZLWK [ PO RI PHWK\OHQH FKORULGH 7KH FRPELQHG RUJDQLF OD\HU ZDV ZDVKHG ZLWK PO RI A DQG GULHG RYHU .&2 )LOWUDWLRQ DQG VXEVHTXHQW HYDSRUDWLRQ \LHOGHG D OLJKW EURZQ FOHDU YLVFRXV RLO J b \LHOGf 3URFHGXUH % 7KH PHWKRG SUHYLRXVO\ UHSRUWHG E\ %RUFK DQG FRZRUNHUV ZDV DSSOLHG 7R D VWLUUHG VROXWLRQ RI SRO\PHU f J PROHf DQG IRUPDOGHK\GH b ZZ DTXHRXV PO PROHf LQ PO RI DFHWRQLWULOH ZDV DGGHG VRGLXP F\DQRERURK\GULGH 1D%OA&+f *ODFLDO DFHWLF DFLG ZDV DGGHG XQWLO WKH UHDFWLRQ PL[WXUH VKRZHG WKH S+ RI 6WLUULQJ ZDV FRQWLQXHG IRU KRXUV DQG WKH PL[WXUH ZDV SRXUHG LQWR PO RI HWKHU 7KH UHVXOWLQJ PL[WXUH ZDV ZDVKHG ZLWK [ PO RI .+ VROXWLRQ 1f DQG [ PO RI VDWXUDWHG 1D&O VROXWLRQ 7KH FRPELQHG .+ ZDVK ZDV EDFNZDVKHG ZLWK PO RI HWKHU 7KH FRPELQHG HWKHU OD\HU ZDV GULHG RYHU .&2 RYHUQLJKW DQG HYDSRUDWHG WR \LHOG D OLJKW EURZQ FOHDU YLVFRXV RLO J bf

PAGE 55

$QDO\VLV FDOFXODWHG IRU &AJ+1 & + 1 )RXQG & + 1 ;+ 105 &2&,706f Vf Vf Vf Vf Pf & 105 &'&f ,5 1HDWf PEUf VVKf VVKf VVKf Pf Vf Pf Zf Zf Pf PVKf Zf Zf Zf Pf Pf VVKf Pf Pf Zf Zf Zf Zf Zf Pf ZEUf Zf FP 0HWK\ODWLRQ RI 3RO\PHU f f 3URFHGXUH $f XVHG IRU WKH PHWK\ODWLRQn RI SRO\PHU f ZDV HPSOR\HG 7KXV SRO\PHU f J PROHf ZDV UHDFWHG ZLWK IRUPLF DFLG DTXHRXV J PROHf DQG IRUPDOGHK\GH b DTXHRXV J PROHf WR \LHOG D EURZQ RLO J bf $QDO\VLV FDOFXODWHG IRU & + 1 )RXQG & + 1 + 105 &'&706f Vf Vf Vf Pf Pf & 105 &'&f ,5 1HDWf ZEUf VVKf Vf Vf Vf Zf Zf ZEUf Zf Vf Pf ZEUf Zf Zf Zf Pf Pf VVKf Pf Pf ZVKf Zf FP

PAGE 56

0LVFHOODQHRXV 5HDFWLRQV 1LWURHWK\OHQH 1LWURHWKHQHf f 7KH IROORZLQJ SURFHGXUH ZDV PRGLILHG IURP WKH SUHYLRXVO\ UHSRUWHG SURFHGXUH $ PL[WXUH RI SKWKDOLF DQK\GULGH J PROHf DQG QLWURHWKDQRO f J PROHf ZDV SODFHG LQ D PO URXQG ERWWRP IODVN HTXLSSHG ZLWK D IUDFWLRQDWLQJ FROXPQ DQG GLVWLOODWLRQ KHDG 7KH RLO EDWK ZDV KHDWHG WR r& DQG SUHVVXUH ZDV UHGXFHG WR PP+J $IWHU WKH PL[WXUH EHFDPH KRPRJHQHRXV WKH RLO EDWK WHPSHUDWXUH ZDV UDLVHG WR r& XQWLO GLVWLOODWLRQ FHDVHG 7KH GLVWLOODWH ZDV GULHG RYHU &D&O \LHOGLQJ D SDOH \HOORZ RLO J PROH b \LHOGf ;+ 105 &'&706f GO+f GO+f G RI GO+f & 105 &'&rf 5HDFWLRQ RI 1LWURHWKHQH f ZLWK )RUPDOGHK\GH DQG 'LHWK\ODPLQH 7KH PHWKRG UHSRUWHG E\ 7VXFKLGD DQG 7RPRQR ZDV IROORZHG ,Q D PO QHFNHG URXQGERWWRPHG IODVN ILWWHG ZLWK D PDJQHWLF VWLUUHU D WKHUPRPHWHU D UHIOX[ FRQGHQVHU DQG D GURSSLQJ IXQQHO ZDV SODFHG D VXVSHQVLRQ RI QLWURHWKHQH J PROHf LQ PO RI PHWKDQRO $OWHUQDWLYHO\ GLHWK\ODPLQH J PROHf ZDV GLVVROYHG LQ PO RI PHWKDQRO DQG WKHQ IRUPDOLQ VROXWLRQ b ZZ DTXHRXV J PROHf ZDV DGGHG ZLWK FRROLQJ 7R WKLV PL[WXUH J PROHf RI DFHWLF DQK\GULGH ZDV DGGHG 7KH WKXV SUHSDUHG DPLQHIRUPDO LQ VROXWLRQ ZDV DGGHG GURSZLVH WR WKH QLWURHWKHQH VXVSHQVLRQ DW r& 7KH UHDFWLRQ PL[WXUH WXUQHG UHGGLVK EURZQ DQG \LHOGHG XQLGHQWLILDEOH WDU

PAGE 57

5HDFWLRQ RI 1LWURHWKHQH ZLWK )RUPDOGHK\GH DQG 'LPHWK\ODPLQH +\GURFKORULGH 7KH PHWKRG RI 7VXFKLGD DQG 7RPRQR ZDV HPSOR\HG 7KXV WKH DPLQHIRUPDO LQ VROXWLRQ ZDV SUHSDUHG E\ DGGLQJ IRUPDOLQ VROXWLRQ ZZ DTXHRXV J PROHf WR GLPHWK\ODPLQH K\GURFKORULGH J PROHf LQ PO RI '0) 7KLV VROXWLRQ ZDV DGGHG VORZO\ WR WKH SUHYLRXVO\ SUHSDUHG QLWURHWKHQH VROXWLRQ J PROHf LQ PO RI '0) DQG WKH UHDFWLRQ PL[WXUH ZDV VWLUUHG IRU KRXUV DW r& 7KH UHVXOWLQJ GDUN EURZQ VROXWLRQ ZDV QHXWUDOL]HG ZLWK VRGLXP FDUERQDWH WR \LHOG GDUN EURZQ WDU 3RO\PHUL]DWLRQ RI 1LWURHWKHQH f f )UHVKO\ GLVWLOOHG 7+) ZDV DWWDFKHG WR D KLJK YDFXXP OLQH GHJDVVHG WZLFH DQG WUDQVIHUUHG WR D SRO\PHUL]DWLRQ WXEH 1LWURHWKHQH ZDV GLVWLOOHG ZLWK &D&O LQ WKH UHFHLYLQJ IODVN DQG DWWDFKHG WR WKH OLQH GHJDVVHG WZLFH DQG WUDQVIHUUHG WR WKH SRO\PHUL]DWLRQ WXEH 7KH SUHYLRXVO\ SXULILHG S\ULGLQH FDWDO\VWf ZDV WUDQVIHUUHG WR WKH SRO\PHUL]DWLRQ WXEH DW r& 3RO\PHUL]DWLRQ ZDV FDUULHG RXW LQ D FRQVWDQW WHPSHUDWXUH EDWK r&f IRU KRXU 7KH WXEH ZDV RSHQHG DQG WKH FRQWHQWV SUHFLSLWDWHG LQWR 1 +& VROXWLRQ 7KH \HOORZ VROLG ZDV FROOHFWHG GLVVROYHG LQ '0) DQG UHSUHFLSLWDWHG LQ ZDWHU 7KH VROLG ZDV DJDLQ FROOHFWHG DQG GULHG LQ D YDFXXP RYHQ r&f RYHUQLJKW WR DIIRUG DQ RIIZKLWH SRZGHU $QDO\VLV FDOFXODWHG IRU &+12 & + 1 )RXQG & + 1 & 105 '06Gf ,QWULQVLF YLVFRVLW\ '0)r&f >Q@ GOJ

PAGE 58

,5 .%Uf Zf Zf Zf VVKf Pf Zf PVKf Zf Zf ZEUf Pf Zf Zf FP 5HDFWLRQ RI &RPSRXQG f ZLWK 0HWK\O ,VRF\DQDWH 0,f f ,Q D PO URXQGERWWRPHG IODVN ZDV SODFHG D VROXWLRQ RI FRPSRXQG f J PROHf LQ PO RI 0) $ VROXWLRQ RI PHWK\O LVRF\DQDWH 0,f PO PROHf LQ PO RI '0) DQG D FDWDO\WLF DPRXQW RI WLQ RFWRDWH 72f GURSVf ZHUH DGGHG GURSZLVH RYHU D PLQXWH SHULRG $IWHU WKH DGGLWLRQ ZDV FRPSOHWH ZKLFK ZDV GRQH XQGHU D QLWURJHQ DWPRVSKHUH WKH UHDFWLRQ PL[WXUH ZDV VWLUUHG IRU KRXUV DW URRP WHPSHUDWXUH $GGLWLRQDO 0, PO PROHf ZDV DGGHG DQG VWLUULQJ ZDV FRQWLQXHG IRU KRXUV DW URRP WHPSHUDWXUH (YDSRUDWLRQ RI VROXHQW JDYH D OLJKW EURZQ YLVFRXV OLTXLG J b \LHOGf + 105 '06G706f V+f V+f V+f G+f P+f W+f V+f & 105 '06Gf ,5 1HDWf PEUVKf PVKf LQf VVKf VVKf Pf Pf Pf Pf UQf Pf PEUf Pf PVKf Zf Zf Zf Zf Zf Zf FP 5HDFWLRQ RI &RPSRXQG f ZLWK 3KHQ\O ,VRF\DQDWH 3,f f 3URFHGXUH $ 7R D VROXWLRQ RI FRPSRXQG f J PROHf DQG D FDWDO\WLF DPRXQW Jf RI IUHVKO\ VXEOLPHG GLD]DELF\FORfRFWDQH '$%&f LQ PO RI DQK\GURXV '0) ZDV DGGHG

PAGE 59

D VROXWLRQ RI SKHQ\O LVRF\DQDWH 3,f J PROHf LQ PO RI DQK\GURXV '0) $IWHU WKH DGGLWLRQ ZKLFK ZDV FDUULHG RXW XQGHU QLWURJHQ ZDV FRPSOHWH WKH PL[WXUH ZDV VWLUUHG IRU KRXUV DW r& XQGHU QLWURJHQ 7KH UHDFWLRQ PL[WXUH ZDV FRROHG WR URRP WHPSHUDWXUH DQG SRXUHG LQWR LFHZDWHU WR \LHOG D ZKLWH SUHFLSLWDWH ZKLFK ZDV GULHG LQ D YDFXXP GHVLFFDWRU IRU KRXUV J bf 7KH UHVXOWLQJ VROLG ZDV UHFU\VWDOOL]HG IURP WROXHQH WR \LHOG D ZKLWH SRZGHU 3URFHGXUH % 7KH SURFHGXUH GHVFULEHG LQ $f ZDV XVHG H[FHSW WKH FDWDO\VW WLQ RFWRDWH 72f GURSVf ZDV XVHG LQVWHDG RI '$& 7KH ZKLWH SRZGHU J bf ZKLFK ZDV REWDLQHG ZDV LGHQWLFDO ZLWK WKH FRPSRXQG REWDLQHG IURP SURFHGXUH $f $QDO\VLV FDOFXODWHG IRU &R+1r F! L +! } 1} )RXQG & + 1 O+ 105 &'&706f V+f P+f W+f P+f & 105 &'&f Tf Wf Wf Wf Wf Wf Vf Gf Gf Gf Vf Vf ,5 .%Uf Zf ZEUf PEUf Zf Zf ZVKf Zf Pf Zf Pf VVKf Zf Vf VVKf Pf LQf Vf Zf Zf Zf VVKf VVKf Zf Pf Zf PVKf Pf PVKf Zf Zf ZEUf PVKf Zf Pf FP

PAGE 60

3RO\PHUL]DWLRQ RI &RPSRXQG f ZLWK +H[DUQHWK\OHQH 'LLVRF\DQDWH +0-,f f 7R D VROXWLRQ RI +0', J PROHf LQ PO RI DQK\GURXV 20) ZHUH DGGHG D VROXWLRQ RI FRPSRXQG f J PROHf LQ PO RI DQK\GURXV '0) DQG GURSV RI FDWDO\VW 72f $IWHU WKH DGGLWLRQ ZKLFK ZDV FDUULHG RXW XQGHU QLWURJHQ ZDV FRPSOHWH WKH PL[WXUH ZDV VWLUUHG XQGHU QLWURJHQ DW r& IRU KRXUV 'XULQJ WKLV SHULRG WKH UHDFWLRQ PL[WXUH WXUQHG FORXG\ 7KH UHVXOWLQJ \HOORZ FORXG\ OLTXLG ZDV SRXUHG LQWR LFHZDWHU WR DIIRUG D ZKLWH VROLG J bf ZKLFK ZDV H[WUDFWHG ZLWK HWKHU RYHUQLJKW DQG WKHQ GULHG XQGHU UHGXFHG SUHVVXUH 105 '06G706f Vf Vf Vf Vf Vf Vf & 105 '06Gf ,5 .%Uf VEUf Vf Vf Pf VVKf VVKf Vf Vf Vf VVKf Pf PVKf Zf PVKf VEUf PEUf PVKf Zf Zf Zf Zf FP 3RO\PHUL]DWLRQ RI &RPSRXQG f ZLWK 0HWK\OHQHGLS SKHQ\OHQHGLLVRF\DQDWH 0',f f 7KH VDPH PHWKRG SUHYLRXVO\ GHVFULEHG IRU WKH FDVH RI f ZDV DSSOLHG 7KXV FRPSRXQG f J PROHf DQG 0', J PROHf ZHUH DOORZHG WR UHDFW LQ WKH SUHVHQFH RI D FDWDO\VW 72f IRU KRXUV DW r& XQGHU QLWURJHQ 7KH UHVXOWLQJ ZKLWH VROLG J bf GHFRPSRVHG DW r&

PAGE 61

$QDO\VLV FDOFXODWHG IRU &+1 & + 1 )RXQG & + 1 O+ 105 '06G706f Vf Vf VEUf Vf Pf Vf Vf & 105 '06Gf ,5 .%Uf PEUVKf Zf Zf Pf PVKf VEUf Vf Vf Vf Vf Vf VVKf Zf Pf PVKf Zf Zf Pf Pf FPnrf >Q@ '06r&f GOJ 3RO\PHUL]DWLRQ RI &RPSRXQG f ZLWK 0', f 7KH SURFHGXUH GHVFULEHG IRU FRPSRXQG f ZDV HPSOR\HG 7KXV FRPSRXQG f J PROHf DQG 0', J PROHf ZHUH DOORZHG WR UHDFW LQ WKH SUHVHQFH RI 72 XQGHU QLWURJHQ IRU KRXUV DW r& 7KH UHVXOWLQJ ZKLWH SRZGHU J bf ZDV H[WUDFWHG ZLWK HWKHU RYHUQLJKW DQG GULHG XQGHU UHGXFHG SUHVVXUH O+ 105 '06G706f Vf Pf Vf VEUf Pf Gf Vf ,5 .%Uf VEUf Zf Pf Pf Zf Vf Vf VVKf Zf Pf Pf PEUf Zf Zf Zf Zf Pf Zf Zf Pf Pf FPr

PAGE 62

&+$37(5 ,,, 5(68/76 $1' ',6&866,21 $V LQGLFDWHG LQ WKH ,1752'8&7,21 WKH PDMRU REMHFWLYH RI WKLV UHVHDUFK ZDV WKH SUHSDUDWLRQ RI QHZ SRO\PHUV FRQWDLQLQJ DPLQR JURXSV XWLOL]LQJ WKH 0DQQLFK UHDFWLRQ RI QLWURDONDQHV ZLWK IRUPDOGHK\GH DQG D SULPDU\ RU D ELVVHFRQGDU\ DPLQH 6LQFH WKLV SRO\PHUL]DWLRQ FDQ EH FODVVLILHG DV D VWHSJURZWK SRO\PHUL]DWLRQ WKH ULJRURXV UHTXLUHPHQWV IRU WKH VXFFHVVIXO V\QWKHVLV RI KLJK SRO\PHUV ZHUH H[SHFWHG,Q D VWHSJURZWK SRO\PHUL]DWLRQ LW LV QHFHVVDU\ WR DOORZ WKH UHDFWLRQ WR SURFHHG WR D YHU\ KLJK GHJUHH RI FRQYHUVLRQ RU LQ RWKHU ZRUGV WR D SURGXFW WKDW FRQWDLQV D YHU\ VPDOO QXPEHU RI IXQFWLRQDO JURXSV &DURWKHUV GHULYHG D VLPSOH HTXDWLRQ UHODWLQJ WKH GHJUHH RI SRO\PHUL]DWLRQ WR WKH H[WHQW RI WKH UHDFWLRQ,I WKHUH DUH 14 QXPEHU RI PRQRPHU $f§$ DQG 14 QXPEHU RI PRQRPHU %f§% PROHFXOHV DW WKH VWDUW RI WKH SRO\PHUL]DWLRQ HTXDWLRQ f DQG DW D JLYHQ VWDJH RI WKH UHDFWLRQ ZKHQ WKHUH DUH 1 PROHFXOHV RI DQ\ VL]H UHPDLQLQJ WKH WRWDO QXPEHU RI IXQFWLRQDO JURXSV RI HLWKHU W\SH ZKLFK KDYH UHDFWHG 1 $ nn‘P$ 1 % f§% !f $ aa$ ( % f§ $ aA$ A % aa% f 22 ; LV 1T1f $W WKDW SRLQW WKH UHDFWLRQ FRQYHUVLRQ 3 LV JLYHQ E\ WKH UDWLR RI WKH UHDFWHG QXPEHU RI PROHFXOHV WR WKH RULJLQDO QXPEHU RI PROHFXOHV HTXDWLRQ f

PAGE 63

3 1T1f1R f ZKLFK FDQ EH UHZULWWHQ DV HTXDWLRQ f 1 1T3f f 7KH DYHUDJH QXPEHU RI UHSHDWLQJ XQLWV LQ DOO PROHFXOHV DW WKDW VWDJH LQ WKH SRO\PHUL]DWLRQ ;Q LV WKH RULJLQDO QXPEHU RI PROHFXOHV GLYLGHG E\ WKH UHPDLQLQJ QXPEHU RI PROHFXOHV HTXDWLRQ f ; Q 1 R 1 f &RPELQLQJ WKHVH WZR HTXDWLRQV JLYHV DQ H[SUHVVLRQ IRU ;Q WKH QXPEHU DYHUDJH GHJUHH RI SRO\PHUL]DWLRQ LQ WHUPV RI UHDFWLRQ FRQYHUVLRQ 3 HTXDWLRQ f ; A Q 1T3f 3 $FFRUGLQJ WR WKLV OLPLWLQJ HTXDWLRQ D UHDFWLRQ RI b FRQYHUVLRQ ZRXOG JLYH D SRO\PHU ZLWK RQO\ UHSHDWLQJ XQLWV LQ WKH DYHUDJH FKDLQ )XUWKHUPRUH WKH VWHSJURZWK SRO\PHUL]DWLRQ UHTXLUHV WKDW DQ HTXDO FRQFHQWUDWLRQ RI UHDFWLYH IXQFWLRQDO JURXSV EH PDLQWDLQHG WKURXJKRXW WKH UHDFWLRQ WR SURGXFH D KLJK SRO\PHU 7KLV PHDQV WKDW QRW RQO\ PXVW WKH UHDFWLRQ EH LQLWLDWHG ZLWK VWRLFKLRPHWULF UHDFWDQW UDWLRV EXW WKH V\VWHP PXVW DOVR EH IUHH IURP VLGH UHDFWLRQV WKDW

PAGE 64

VHOHFWLYHO\ FRQVXPH HLWKHU IXQFWLRQDO JURXS DQG WKHUHE\ GHVWUR\ WKH HTXDOLW\ RI WKH IXQFWLRQDO JURXS FRQFHQWUDWLRQVA 7KLV DOVR PHDQV WKDW ERWK UHDFWDQWV DUH IUHH IURP LPSXULWLHV WKDW PLJKW DIIHFW WKH FRQFHQWUDWLRQV RI HLWKHU IXQFWLRQ JURXS )ORU\ GHULYHG D VLPLODU HTXDWLRQ IRU WKH FDVH LQ ZKLFK WKHUH LV DQ H[FHVV RI RQH RI WKH PRQRPHUV LQ DQ $f§$ DQG %f§% SRO\PHUL]DWLRQ UHDFWLRQ /HW 14 $ DQG 1!E f AH UHVSHFWLYH QXPEHU RI PRQRPHUV $f§$ DQG %f§% DQG WKHLU UDWLR EH U 7KLV JLYHV WKH WRWDO PRQRPHU FRQFHQWUDWLRQ 14 LQ WHUPV RI DQG U HTXDWLRQ f RU 1 1 1 'f R R$ R% 1  1 f§f R R$ U f 6LQFH WKH IXQFWLRQDO JURXSV $ DQG % UHDFW ZLWK HDFK RWKHU RQ D EDVLV DW D JLYHQ VWDJH RI WKH SRO\PHUL]DWLRQ WKH QXPEHU RI $f§f$ PRQRPHU UHDFWHG VKRXOG EH HTXDO WR WKH QXPEHU RI %f§% PRQRPHUV UHDFWHG 14 7KXV WKH IUDFWLRQ RI % JURXSV WKDW KDYH UHDFWHG LV US DV VKRZQ E\ HTXDWLRQ f 3 R$ R% R% Un1 R$ U r 3 f f

PAGE 65

7KH WRWDO QXPEHU RI PROHFXOHV SUHVHQW 1 LV KDOI RI WKH QXPEHU RI WKH IXQFWLRQDO JURXSV ZKLFK PXVW EH HTXDO WR WKH VXP RI WKH QXPEHUV RI WKH XQUHDFWHG $ DQG % JURXSV $IXQFWLRQDO JURXSV O3f1A BU3A!% f 6LQFH 1!E 1T $U HTXDWLRQ f FDQ EH HDVLO\ FRQYHUWHG LQWR f 1 IJ & 3f f 7KHUHIRUH IJ 1$3 f $V GLVFXVVHG SUHYLRXVO\ WKH QXPEHU DYHUDJH GHJUHH RI SRO\PHUL]DWLRQ ;Q LV JLYHQ E\ WKH UDWLR RI WKH WRWDO QXPEHU RI PROHFXOHV DQG WKH RULJLQDO QXPEHU RI PROHFXOHV HTXDWLRQ f &RPELQLQJ HTXDWLRQV f f DQG f JLYHV ;Q LQ WHUPV RI FRQYHUVLRQ 3 DQG UHDFWDQW UDWLR U HTXDWLRQ f rQ UO3fOU f 7KLV HTXDWLRQ FDQ EH UHGXFHG WR HTXDWLRQ f ZKHQ U LV HTXDO WR ,Q WKH FDVH ZKHQ WKH PRQRPHU %f§% LV LQ b H[FHVV LH U DQG WKH FRQYHUVLRQ LV TXDQWLWDWLYH LH 3 WKH DYHUDJH PROHFXOH ZRXOG KDYH ;Q RI ,Q WKH FDVH ZKHQ WKH PRQRPHU %f§% KDV b RI XQUHDFWLYH LPSXULW\ LH U DQG WKH FRQYHUVLRQ LV b WKH

PAGE 66

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f ZDV FDUULHG RXW WR \LHOG PRGHO FRPSRXQG f 7KH ,5 VSHFWUXP RI WKLV FRPSRXQG FRQWDLQV DEVRUSWLRQ EDQGV DW FP DQG FP FKDUDFWHULVWLF RI WKH QLWUR JURXS 7KH + 105 RI WKLV FRPSRXQG VKRZHG D SHDN DW SSP ZKLFK +1+ &+ &++&+2 &K/&+ _ 1 +F ;F+ 12 FDW &+ &+ KFF FKQ f§ FKFFK 1f &+_ 1 +F ;F+ 12 f

PAGE 67

ZDV DVVLJQHG WR WKH IRXU PHWK\O JURXSV WR WKH QLWUR JURXS 7KH SHDN DW SSP ZDV DVVLJQHG WR WKH LQHWK\O JURXSV DWWDFKHG WR WKH QLWURJHQ DWRP ,Q RUGHU WR GHWHUPLQH WKH UHDFWLRQ FRQGLWLRQV ZKLFK ZRXOG DIIRUG WKH KLJKHVW FRQYHUVLRQ VHYHUDO GLIIHUHQW UHDFWLRQ FRQGLWLRQV ZHUH VWXGLHG 7KH UHVXOWV DUH VKRZQ LQ 7DEOH 7DEOH 5HDFWLRQ RI QLWURSURSDQH ZLWK 103' DQG IRUPDOGHK\GH 6ROYHQW 7HPS 7 LPH &DW b
PAGE 68

SRVVLEOH ZHLJKLQJ HUURU DQG H[DFW VWRLFKLRPHWU\ WKH PHWK\ORO GHULYDWLYH RI QLWURSURSDQH ZDV XWLOL]HG &RPSRXQG f &+ &+ L M &+ &+ +&+2 &+&&+a+ , 1 QR f ZKLFK LV DQ DGGXFW RI QLWURSURSDQH DQG IRUPDOGHK\GH ZDV REWDLQHG LQ DOPRVW TXDQWLWDWLYH \LHOG 7KLV WKHQ ZDV UHDFWHG ZLWK '03$ WR DIIRUG WKH VDPH SURGXFW f LQ PXFK LPSURYHG \LHOG 5HVXOWV DUH VKRZQ LQ +1+ f r f 1 ;F+ '03$f 7DEOH 5HDFWLRQ RI f ZLWK '03$ 6ROYHQW 7HPS 7 L PH &DW b
PAGE 69

7DEOH 7KH SUHVHQFH RI D FDWDO\WLF DPRXQW RI EDVH LQFUHDVHG WKH FRQYHUVLRQ ZKLOH WKH ORQJHU WLPH KDG OLWWOH LPSDFW 7KH HWKDQRODPLQH GHULYDWLYH LH 1PHWK\OHWKDQRODPLQH ZDV UHDFWHG ZLWK FRPSRXQG f WR DIIRUG WKH DGGXFW 1 K\GUR[\HWK\Of1PHWK\OPHWK\OQLWUROSURS\OfDPLQH f LQ JRRG \LHOG 7KH DQG & 105 VSHFWUD DQG WKH DVVLJQPHQW RI WKH SHDNV DUH VKRZQ LQ )LJXUHV DQG 7KH ,5 VSHFWUXP VKRZV W\SLFDO QLWUR SHDNV DW DQG FPr 7KH \LHOG RI WKLV UHDFWLRQ UDQJHG IURP b WR b 7KH UHDFWLRQ FRQGLWLRQV DQG \LHOGV DUH VKRZQ LQ 7DROH &+ KQFKFKRK &+ &+&&+2+ 1f &+ &+ , &+&&+1&+&+2+    QR f 7DEOH 5HDFWLRQ RI 1 PH WK\OHWKDQRODPLQH DQG FRPSRXQG f 6ROYHQW 7HPS 7LPH &DW b
PAGE 70

H aL L L SSP )LJ 105 VSHFWUXP RI FRPSRXQG f LQ &'&r

PAGE 71

&+ &+ r L AW D E HO A +2&+f&+B1&+f&&+ G 12 &'&O 9 N 7 U SSP &RPSOHWHO\ GHFRXSOHG & 105 VSHFWUXP RI FRPSRXQG f LQ &'&, )LJ

PAGE 72

 1PHWK\OHWKDQRODPLQH ZDV UHDFWHG ZLWK WKH PHWK\ORO GHULYDWLYH RI QLWURHWKDQH LH PHWK\OQLWUROSURSDQHGLRO f WR DIIRUG DGGXFW f LQ JRRG \LHOG bf 6LQFH WKH JLYHQ b \LHOG LV WKH VHSDUDWHG \LHOG DFWXDO FRQYHUVLRQ VKRXOG EH KLJKHU &+ &+ &+ &+ &+B _ _ +1&+&+2+ +2&+&&+2+ +&+f&+R1&+R&&+R1&+R&+R+   ?  M 1 1 f 0RGHO &RPSRXQGV ZLWK 1LWURSURSDQH DV &KDLQ6WRSSLQJ 5HDJHQW 3LSHUD]LQH D ELVVHFRQGDU\ DPLQH ZDV UHDFWHG ZLWK IRUPDOGHK\GH DQG QLWURSURSDQH WR IRUP WKH DGGXFW FRPSRXQG f 7KH 105 VSHFWUXP VKRZHG WKUHH VLQJOHWV RI PHWK\O JURXSV PHWK\OHQH JURXSV DQG SLSHUD]LQHPHWK\OHQH JURXSV DW DQG SSP UHVSHFWLYHO\ )LJ f 7KH 105 VSHFWUXP LV VKRZQ LQ )LJXUH ZLWK LWV SHDN DVVLJQPHQW %RWK SLSHUD]LQH DQG QLWURSURSDQH DUH GLIXQFWLRQDO FRPSRXQGV DQG WKXV ZLOO UHDFW WR IRUP D SRO\PHU LQ WKH SUHVHQFH RI IRUPDOGHK\GH ZKLOH QLWURSURSDQH LV D PRQRIXQFWLRQDO FRPSRXQG DQG WKXV ZLOO VWRS WKH FKDLQ SURSDJDWLRQ $VVXPLQJ WKDW WKH UHDFWLYLW\ RI QLWURSURSDQH SURWRQ LV HTXDO WR WKRVH RI QLWURSURSDQH SURWRQV

PAGE 73

D )LJ 105 VSHFWUXP RI FRPSRXQG f LQ &'&,

PAGE 74

)LJ &RPSOHWHO\ GHFRXSOHG 105 VSHFWUXP RI FRPSRXQG f LQ &'&

PAGE 75

&K/ &+&+ +&+2 -_ 12 ? +1 1+ &+&&+1 1&+&&+ ? 1 QR f D VHULHV RI PRGHO FRPSRXQGV ZDV V\QWKHVL]HG 7KH UHSHDWLQJ XQLWV RI WKHVH PRGHO FRPSRXQGV VKRXOG FRPH IURP WKH UHDFWLRQ RI QLWURSURSDQH &+ ? Q &+&+&+1 Qf +1 1+ Qf +&+2 &+&+ 12 FK &+&&+ ? f§ Z 12 &+ &+ &+&&+f1 1n B QR &+ f§&+f&&+A Q 12f Q DQG ZLWK QLWURSURSDQH VHUYLQJ DV D FKDLQVWRSSLQJ UHDJHQW %\ YDU\LQJ WKH UDWLR RI UHDFWDQWV RQH FDQ WKHRUHWLFDOO\ FRQWURO WKH OHQJWK RI WKH FKDLQ RU LQ RWKHU ZRUGV WKH QXPEHU RI WKH UHSHDWLQJ XQLWV $V VKRZQ LQ )LJXUH WKH + VSHFWUD RI WKHVH FRPSRXQGV FDQ EH XWLOL]HG WR GHWHUPLQH WKH DFWXDO QXPEHU RI WKH UHSHDWLQJ XQLWV IURP WKH LQWHJUDWLRQ RI WKH GLIIHUHQW PHWK\O SHDNV 7KH WULSOHW DW SSP

PAGE 76

E )LJ r+ 105 VSHFWUD LQ &'&,f RI WKH PRGHO FRPSRXQGV XWLOL]LQJ QLWURSURSDQH DV FKDLQVWRSSLQJ UHDJHQW

PAGE 77

UHSUHVHQWV WKH PHWK\O JURXS RI WKH UHSHDWLQJ XQLWV ZKLOH WKH VLQJOHW DW SSP UHSUHVHQWV WKH PHWK\O JURXSV DW WKH HQG RI WKH PROHFXOH )URP WKH LQWHJUDWLRQ RI WKHVH WZR SHDNV RI HDFK VSHFWUXP WKH UDWLRV RI DQG ZHUH REWDLQHG IRU WKH WKHRUHWLFDO GHJUHHV RI SRO\PHUL]DWLRQ RI DQG UHVSHFWLYHO\ ,Q RWKHU ZRUGV WKH DFWXDO GHJUHHV RI SRO\PHUL]DWLRQ RI WKHVH FRPSRXQGV ZHUH DQG UHVSHFWLYHO\ DV VKRZQ LQ )LJXUH 6LPLODUO\ DQRWKHU ELVVHFRQGDU\ DPLQH LH 11nGLPHWK\OHWK\OHQHGLDPLQH ZDV UHDFWHG ZLWK IRUPDOGHK\GH DQG DQG QLWURSURSDQH WR \LHOG WKH FRUUHVSRQGLQJ PRGHO FRPSRXQGV :KHQ Q LH QLWURSURSDQH ZDV &+ &+ &+ , Q &+&+&+1 Qf +1&+&+1+ Qf +&+2 &+&+ 12 "+ &+ &+T &+ LL U ‘! &+&&+1&+&+1 f§_&+&&+1&+&+1 12 &+ &+f _ &+ / 12 U &+ &+&2/ 12 Q DQG QRW XVHG WKH ZKLWH SRZGHU RI 11nGLPHWK\O11nELVPHWK\O QLWUROSURS\OfHWK\OHQHGLDPLQH f ZDV REWDLQHG 7KH A+ 105 DQG A& 105 VSHFWUD DUH VKRZQ LQ )LJXUHV DQG ZLWK SHDN DVVLJQPHQW ,Q WKH RWKHU WZR FDVHV D VLPLODU UHVXOW ZDV REWDLQHG ZKHQ VDPH PHWKRG RI DQDO\VLV ZDV DSSOLHG WR WKHLU 105 VSHFWUD 7KH UDWLRV RI WKH PHWK\O SHDN DW SSP DQG SSP DUH DQG IRU WKH

PAGE 78

)LJ 3ORW RI WKH QXPEHU RI UHSHDWLQJ OLPLWV YV UHDFWDQW IHHG UD WL R

PAGE 79

D )LJ ‘rf+ 105 VSHFWUXP RI FRPSRXQG f LQ &'&

PAGE 80

D )LJ &RPSOHWHO\ GHFRXSOHG & 105 VSHFWUXP RI FRPSRXQG f LQ &'&

PAGE 81

WKHRUHWLFDO FKDLQ OHQJWK RI DQG UHVSHFWLYHO\ ,Q RWKHU ZRUGV WKH FDOFXODWHG FKDLQ OHQJWK RI DQG LV REWDLQHG IRU WKHVH FRPSRXQGV 7KH UHVXOW VKRZV WKDW $f WKH UHDFWLYLW\ RI WKH SURWRQV RI QLWURSURSDQH LV OHVV WKDQ WKDW RI QLWURSURSDQH WKXV WKH SURSDJDWLRQ VWRSV EHIRUH DOO WKH SUHVHQWLQJ QLWURSURSDQH LV FRQVXPHG DQG PRUH SUREDEO\ %f WKH UHDFWLRQ FRQYHUVLRQ LV QRW b WKHUHIRUH WKH JURZWK RI WKH FKDLQ VWRSV EHIRUH DOO WKH UHDFWDQWV DUH FRQVXPHG 0RGHO &RPSRXQGV ZLWK 1+\GUR[\HWK\OfSLSHUD]LQH 1LWURHWKDQH ZDV UHDFWHG ZLWK IRUPDOGHK\GH DQG 1 K\GUR[\HWK\OfSLSHUD]LQH 1+(3f WR DIIRUG DGGXFW f 7KH ,5 VSHFWUXP RI WKLV FRPSRXQG VKRZV WKH FKDUDFWHULVWLF SHDNV RI WKH QLWUR JURXS DW DQG FPr 7KH r+ 105 VSHFWUXP DV VKRZQ LQ )LJXUH VKRZV D VLQJOHW DW SSP ZKLFK LV DVVLJQHG WR WKH PHWK\O SURWRQV 7KH RWKHU VLQJOHW DW SSP LV IURP WKH PHWK\OHQH &+&+1 +&+ +1 ,1&A&A2+ FP A +&+&+1 ? QR f SURWRQV RI WKH SLSHUD]LQH ULQJ ZKLOH WKH WULSOHW DW SSP LV IURP WKH PHWK\OHQH SURWRQV RI WKH VXEVWLWXWHG HWKDQRO PRLHW\ 7KH & 105 VSHFWUXP DQG WKH SHDN DVVLJQPHQW DUH VKRZQ LQ )LJXUH $ VLPLODU UHVXOW ZDV H[SHFWHG ZKHQ OQLWURSURSDQH ZDV UHDFWHG ZLWK IRUPDOGHK\GH DQG 1+(3 7KH ZKLWH VROLG ZKLFK VHSDUDWHG ILUVW

PAGE 82

706 )LJ ‘n‘+ 105 VSHFWULXP RI FRPSRXQG f LQ &'&A

PAGE 83

SSP &RPSOHWHO\ GHFRXSOHG & 105 VSHFWUXP RI FRPSRXQG f LQ &'& )LJ

PAGE 84

IURP WKH UHDFWLRQ PL[WXUH WXUQHG RXW WR EH FRPSRXQG f LQVWHDG RI FRPSRXQG f 7KH ,5 VSHFWULXP RI WKLV FRPSRXQG GRHV QRW LQFOXGH WKH FKDUDFWHULVWLF SHDNV RI WKH QLWUR JURXS DQG WKH r+ 105 VSHFWUXP GRHV QRW KDYH WKH W\SLFDO WULSOHW FKDUDFWHULVWLF RI PHWK\O SURWRQV RI WKH HWK\O JURXS 7KH VSHFWUXP RI WKLV FRPSRXQG VKRZV WKDW WKHUH LV QHLWKHU SULPDU\ QRU TXDWHUQDU\ FDUERQ 7KLV ZDV FRQILUPHG ? &+&+&+1 +&+2 +1 1&+&++ &+T & ? +2&+&+1 1&+&&+ 1 1&+R&+R+ ? I ? 12 f ? +&+&+1 1&+1 1&+&++ f E\ WKH RIIUHVRQDQFH VSHFWUXP DV VKRZQ LQ )LJXUH &RPSRXQG f ZDV VHSDUDWHG IURP WKH UHDFWLRQ PL[WXUH DIWHUZDUGV LQ ORZ \LHOG &RPSRXQG f LV D FRQGHQVDWLRQ SURGXFW RI IRUPDOGHK\GH DQG 1+(3 DQG D VLPLODU UHDFWLRQ LV NQRZQ WR RFFXU EHWZHHQ IRUPDOGHK\GH DQG SLSHULGLQHLQ RUGHU WR DYRLG WKH IRUPDWLRQ RI WKH XQZDQWHG SURGXFW f WKH SUHIRUPHG PHWK\ORO GHULYDWLYH RI QLWURSURSDQH f ZDV UHDFWHG ZLWK 1+(3 ,Q WKLV FDVH WKHUH LV QR IUHH IRUPDOGHK\GH DQG WKHUHIRUH OLWWOH FRQGHQVDWLRQ EHWZHHQ IRUPDOGHK\GH DQG 1+(3 ZDV H[SHFWHG +RZHYHU ERWK f DQG f ZHUH VHSDUDWHG IURP WKH UHFWLRQ PL[WXUH GHVSLWH WKH IDFW WKDW WKH \LHOG RI f ZDV

PAGE 85

'062 OLm,,, ‘ f§ Y-r mn‘! LnArr nL 0 f SSQ )LJ & 105 VSHFWUD RI FRPSRXQG f LQ '062G f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH

PAGE 86

KLJKHU WKDQ LQ WKH SUHYLRXV UHDFWLRQ 7KH SUHVHQFH RI WKLV FRQGHQVDWLRQ SURGXFW f LQGLFDWHV WKDW WKH PHWK\ORO GHULYDWLYH RI QLWURSURSDQH LV DFWXDOO\ LQ HTXLOLEULXP ZLWK IRUPDOGHK\GH DQG QLWURSURSDQH DQG WKXV SUHVHQWV WKH FKDQFH RI FRQGHQVDWLRQ EHWZHHQ &+f+ &+f+ 1 &+B&+R&1R &+R&+R&1R +&+2 &++ K ? +2&+&+1 1+ +&+2 9 ? KRFKFKQ Q FKRK ? ? +1 1&+&+2+ ? nV 1 ? ? +&+R&+R1 1&+f1 1&+R&+R+ ? 1 f IRUPDOGHK\GH DQG 1+(3 )RU FRPSRXQG f WKH ,5 nnn+ DQG 105 VSHFWUD FRQILUP WKH VWUXFWXUH E\ WKH FKDUDFWHULVWLF SHDNV RI DQG FPL IRU WKH QLWUR JURXS D WULSOHW FKDUDFWHULVWLF RI WKH PHWK\O SURWRQV RI WKH HWK\O JURXS DQG D SHDN IRU WKH SULPDU\ FDUERQ DW SSP DQG DQRWKHU DW SSP IRU D TXDWHUQDU\ FDUERQ UHVSHFWLYHO\ ,Q RUGHU WR GHWHUPLQH ZKLFK UHDFWLRQ FRQGLWLRQV UHVXOW LQ KLJKHU FRQYHUVLRQ D VHULHV RI WKH FRQGHQVDWLRQ EHWZHHQ 1+(3 DQG FRPSRXQG f ZDV IROORZHG E\ 105 6LQFH WKH FKHPLFDO VKLIW RI WKH PHWK\OHQH

PAGE 87

&+ +&+R&+R1 ? 1+ +&+ UUX TK 1D'' f 7+)G% RU '06G f SURWRQV DGMDFHQW WR R[\JHQ UHPDLQHG YLUWXDOO\ XQFKDQJHG WKH WULSOHW FRUUHVSRQGLQJ WR WKHVH SURWRQV ZDV XVHG DV UHIHUHQFH $V VKRZQ LQ )LJXUH WKH UHODWLYH LQWHQVLW\ RI WKH SHDN FRUUHVSRQGLQJ WR WKH PHWK\OHQH SURWRQV QH[W WR 1+ GHFUHDVHG DV WKH UHDFWLRQ SURFHHGHG 7KH UHVXOW LV VKRZQ LQ )LJXUH 7KH UHDFWLRQ ZDV QRW DIIHFWHG PXFK E\ WKH VROYHQW VLQFH WKHUH LV QRW PXFK GLIIHUHQFH LQ FRQYHUVLRQ EHWZHHQ WKH VROYHQWV 7+) DQG '062 7KH KLJKHVW FRQYHUVLRQ ZDV REVHUYHG DW r& UDWKHU WKDQ DW r& SUREDEO\ GXH WR WKH UHYHUVLEOH UHDFWLRQ 6LQFH 1+(3 FDQ EH XVHG DV D FKDLQVWRSSLQJ UHDJHQW D VHULHV RI PRGHO FRPSRXQGV IURP QLWURHWKDQH IRUPDOGHK\GH SLSHUD]LQH DQG 1+(3 ZDV SUHSDUDWHG :KHQ D IHHG UDWLR RI SLSHUD]LQH WR 1+(3 ZDV VR

PAGE 88

)LJ 6HOHFWHG WLPH GHSHQGHQW r+ 105 VSHFWUD RI WKH UHDFWLRQ RI 1+(3 ZLWK FRPSRXQG f LQ '06G DW 57

PAGE 89

R R , L 2 7+)G 57 $ '062G 57 '062G & 2 '062G & 2 ’ f§, O 7LPH PLQXWH f Bf§ )LJ 3ORW RI WKH FRQVXPSWLRQ RI 1(3' YV UHDFWLRQ WLPH

PAGE 90

RX WKDW WKH H[SHFWHG GHJUHH RI SRO\PHUL]DWLRQ ZDV D ZKLWH SUHFLSLWDWH IRUPHG GXULQJ WKH UHDFWLRQ 7KLV VROLG ZDV QRW VROXEOH LQ PRVW RI WKH FRPPRQ RUJDQLF VROYHQWV LH DFHWRQH WROXHQH HWKHU PHWKDQRO 7+) '0) FKORURIRUP DQG DFHWRQLWULOH $ VLPLODU UHVXOW ZDV REWDLQHG IURP WKH UHFWLRQ ZKHQ D IHHG UDWLR RI ZDV XWLOL]HG %RWK RI WKHVH SURGXFWV DUH VROXEOH LQ +& b ZY DTXHRXVf VROXWLRQ 7KH YLVFRVLW\ PHDVXUHPHQW LQ b +& DW r& UHVXOWHG LQ LQWULQVLF YLVFRVLWLHV RI GOJ DQG GOJ UHVSHFWLYHO\ ,Q RWKHU ZRUGV WKH PROHFXODU ZHLJKWV RI WKH FRPSRXQGV ZHUH DERXW HTXDO 7KLV FDQ EH H[SODLQHG E\ WKH IDFW WKDW WKH VROLG SURGXFW SUHFLSLWDWHG RXW GXULQJ WKH UHDFWLRQ DQG WKHUHIRUH WKH SURSDJDWLRQ RI WKH FKDLQ VWRSSHG EHIRUH WKH DYHUDJH FKDLQ OHQJWK RI ZDV DWWDLQHG 6WXGLHV ZLWK 1LWURPHWKDQH $V GLVFXVVHG SUHYLRXVO\ WKH PHWK\ORO GHULYDWLYH RI D QLWURDONDQH f LV LQ HTXLOLEULXP ZLWK IRUPDOGHK\GH DQG QLWURSURSDQH ,I WKLV LV WUXH LQ WKH FDVH RI WKH GHULYDWLYH RI QLWURPHWKDQH D PL[WXUH RI PRQR GL DQG WULVXEVWLWXWHG SURGXFW VKRXOG UHVXOW IURP WKH UHDFWLRQ EHWZHHQ QLWURSURSDQHGLRO f DQG SLSHULGLQH $Q DWWHPSW WR V\QWKHVL]H f E\ GLUHFW FRQGHQVDWLRQ RI QLWURPHWKDQH ZLWK IRUPDOGHK\GH IDLOHG VLQFH WKH SURGXFW ZDV PDLQO\ WKH WULVXEVWLWXWHG FRPSRXQG LH K\GUR[\PHWK\OfQLWUR SURSDQHGLRO f .& &+1 +&+ ‘ +&+f&1 f

PAGE 91

2 +RZHYHU WKH GHVLUHG GLRO f ZDV REWDLQHG ZKHQ WKLV FRPSRXQG f ZDV WUHDWHG ZLWK VRGLXP IROORZHG E\ VDO\VLOLF DFLG 7KH ,5 VSHFWUXP RI WKLV FRPSRXQG VKRZV SHDNV DW DQG FP FKDUDFWHUL6WLF RI WKH QLWUR JURXS 7KH 105 VSHFWUXP VKRZV D PXOLSOHW DW SSP KRFKfFQR f +&+"ff&1 FKRK  f HWKHU +&+f&+0 f DVVLJQHG WR WKH PHWK\OHQH SURWRQV D SHQWHW DW SSP DVVLJQHG WR PHWKLQH SURWRQ DQG D WULSOHW DVVLJQHG WR WKH K\GUR[\O SURWRQV 7KLV WULSOHW YDQLVKHG ZKHQ D GURS RI '2 ZDV DGGHG WR WKH 105 WXEH WKXV FRQILUPLQJ WKDW WKH VLJQDO LV IURP WKH K\GUR[\O SURWRQV )LJ f 7KH 105 VSHFWUXP VKRZV WZR SHDNV DW DQG SSP DVVLJQHG WR PHWK\OHQH FDUERQV DQG PHWKLQH FDUERQ UHVSHFWLYHO\ 7KLV DVVLJQPHQW ZDV FRQILUPHG E\ WKH RIIUHVRQDQFH 105 VSHFWUXP )LJ f 7KLV FRPSRXQG f ZDV WKHQ UHDFWHG ZLWK SLSHULGLQH WR \LHOG D PL[WXUH RI PRQR GL DQG WULVXEVWLWXWHG SURGXFW DV H[SHFWHG 7KH DPRXQW RI GLVXEVWLWXWHG SURGXFW ZDV LQFUHDVHG ZKHQ WKH UHDFWLRQ WHPSHUDWXUH ZDV ORZHU 0RGHO &RPSRXQGV IURP %LVVHFRQGDU\ $PLQHV 11GLPHWK\OEXWHQHOGLDPLQH '0%$f DQG 11n GLPHWK\OKH[DPHWK\OHQHGLDPLQH '0+$f ZHUH DOVR XWLOL]HG LQ WKH PRGHO FRPSRXQG VWXGLHV $ UHDFWLRQ EHWZHHQ QLWURSURSRDQH IRUPDOGHK\GH DQG '0%$ DIIRUGHG WKH PRGHO FRPSRXQG f LQ JRRG \LHOG 7KH ,5 VSHFWUXP RI WKLV FRPSRXQG VKRZV WZR SHDNV DW DQG FP

PAGE 92

)LJ + 105 VSHFWUD RI FRPSRXQG f LQ '06G f ZLWKRXW '2 f GURS RI '2 ZDV DGGHG

PAGE 93

D )LJ & VSHFWUD FRPSRXQG LQ '06G f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH

PAGE 94

Rr &+ &+ &+ &+M&K 12 +&+2 +1&+&+ &+&+1+ + K &+T &+ &+&&+,,&+&+&+&+1&+&&+    , 12 12 f FKDUDFWHULVWLF RI WKH QLWUR JURXS 7KH A+ 105 VSHFWUXP VKRZV D PXOWLSOHW DW DVVLJQHG WR WKH SURWRQV RQ WKH FDUERQFDUERQ GRXEOH ERQG )LJ f 7KH & 105 VSHFWUXP DOVR VKRZV WKH && GRXEOH ERQG DW SSP )LJ f 6LPLODUO\ '0+$ ZDV UHDFWHG ZLWK QLWURSURSDQH DQG IRUPDOGHK\GH WR \LHOG FRPSRXQG f LQ IDLU \LHOG 7KH ,5 VSHFWUXP VKRZV WKH FKDUDFWHULVWLF SHDNV RI WKH QLWUR JURXS DW &+ &+ K FK FK FK FK &+&+ +&+2 +1&+fF1+ -_ / 1 &+&&+1&+ff1&+f&&+T L R 12 12 f DQG FPnf 7KH r+ 105 VSHFWUXP LQFOXGHV SHDNV DW DQG SSP DVVLJQHG WR WKH PHWK\OHQH SURWRQV IURP WKH PLGGOH RI WKH DPLQH PRLHW\ PHWK\O SURWRQV IURP WKH QLWURSURSDQH PRLHW\ PHWK\O SURWRQV DWWDFKHG WR QLWURJHQ PHWK\OHQH SURWRQV DWWDFKHG WR QLWURJHQ DQG RWKHU PHWK\OHQH SURWRQV DWWDFKHG WR QLWURJHQ UHVSHFWLYHO\ 7KH A& 105 VSHFWUXP DQG WKH SHDN DVVLJQPHQWV DUH VKRZQ LQ )LJ

PAGE 95

SSP )LJ r+ 105 VSHFWUXP RI FRPSRXQG f LQ &'&

PAGE 96

)LJ & 105 VSHFWUD RI FRPSRXQG f LQ f f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH

PAGE 97

D D SSP )LJ VSHFWUD RI FRPSRXQG f LQ &'&OA FRPSOHWHO\ GHFRXSOHG f ,1(37 &+&+ SRV &+ QHJ & VROYHQW VXSSUHVVHGf

PAGE 98

3RO\PHUV $Q LQYHVWLJDWLRQ RI WKH SRO\PHUL]DWLRQ RI 10($ ZLWK f ZDV WKHQ FDUULHG RXW 7KH UHDFWLRQ ZKLFK ZDV UHIOX[HG LQ 7+) r&f IRU KRXUV LQ WKH SUHVHQFH RI PROHFXODU VLHYHV $f JDYH DQ &+ &K/ _ +1&+&+1+ +&+ 10($ H[FHOOHQW \LHOG RI SRO\PHU f 7KH LQIUDUHG VSHFWUXP RI WKH EURZQ YLVFRXV RLO VKRZV ,5 DEVRUSWLRQV DW DQG FP FKDUDFWHULVWLF RI WKH QLWUR JURXS DQG LV YHU\ VLPLODU WR WKDW RI PRGHO FRPSRXQG 22f 7KH 105 VSHFWUXP LV DOVR YHU\ VLPLODU WR WKDW RI PRGHO FRPSRXQG 22f DQG WKH SHDNV DUH DVVLJQHG DFFRUGLQJO\ LH WKH VLQJOHW DW SSP WR WKH PHWK\O SURWRQV RI WKH QLWURHWKDQH PRLHW\ WKH VLQJOHW DW SSP WR WKH PHWK\O SURWRQV QH[W WR WKH QLWURJHQ WKH VLQJOHW DW SSP WR PHWK\OHQH SURWRQV RI WKH DPLQH PRLHW\ DQG WKH VLQJOHW DW SSP WR WKH PHWK\OHQH SURWRQV IURP WKH L Q IRUPDOGHK\GH 7KH -& 105 VSHFWUXP VKRZV ILYH PDMRU SHDNV ZKLFK DUH LQ DJUHHPHQW ZLWKLQ SSP WR WKRVH RI WKH A& 105 VSHFWUXP RI FRPSRXQG f )LJ f 7KLV SRO\PHU KRZHYHU VKRZHG D PROHFXODU ZHLJKW RI RQO\ E\ YDSRU SUHVVXUH RVPRPHWU\ 7KH ORZ PROHFXODU ZHLJKW FDQ EH WKH UHVXOW RI WKH UHODWLYHO\ ORZ FRQYHUVLRQ abf 10%$ DQG f ZDV WKHQ SRO\PHUL]HG XQGHU LGHQWLFDO FRQGLWLRQV WR DIIRUG SRO\PHU &f 7KH YHU\ YLVFRXV \HOORZ RLO VKRZV ,5 DEVRUSWLRQV DW DQG FPr FKDUDFWHULVWLF RI WKH QLWUR JURXS &+ &&+R+ 12 &/ &+ &+ r f&+&&+f1&+&+f1 12R f f

PAGE 99

G 33WL )LJ 105 VSHFWUD RI SRO\PHU f LQ &'&A f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH

PAGE 100

&+ &+ KQFKFK FKFKQK 10%$ f FQ &+ &+ &+&&+1&+&+ &+&+0 12 f 7KH + 105 DQG & 105 VSHFWUD DUH YHU\ VLPLODU WR WKRVH RI WKH PRGHO FRPSRXQG f DQG SHDNV DUH DVVLJQHG DFFRUGLQJO\ 7KH & 105 LV VKRZQ LQ )LJ 7KLV SRO\PHU VKRZHG D ORZ PROHFXODU ZHLJKW af E\ 932 ZKLFK FDQ DOVR EH DWWULEXWHG WR WKH ORZ FRQYHUVLRQ 6LPLODUO\ 10+$ DQG f ZDV SRO\PHUL]HG XQGHU LGHQWLFDO FRQGLWLRQV WR \LHOG SRO\PHU f 7KH YLVFRXV EURZQ RLO DOVR VKRZV FKDUDFWHULVWLF QLWUR DEVRUSWLRQV LQ ,5 DQG + DQG & 105 VSHFWUD DUH DOVR VLPLODU WR WKRVH RI WKH FRUUHVSRQGLQJ PRGHO FRPSRXQG f &+ &+ KQFKfQK 10+$ f f§! &+ &+ &+ , ‘&+&&+1&+f1 OB 1 B[ f 7KH SRO\PHUL]DWLRQ EHWZHHQ 11GLPHWK\OOSURSDQHGLDPLQH DQG f \LHOGHG D VLPLODU UHVXOW 3RO\PHU f ZDV LGHQWLILHG E\ ,5 r+ DQG & 105 VSHFWUD DFFRUGLQJ WR WKH FRUUHVSRQGLQJ PRGHO FRPSRXQG f 6LQFH WKHVH SRO\PHUV REWDLQHG IURP WKH FRQGHQVDWLRQ RI DPLQH DQG WKH

PAGE 101

)LJ & VSHFWUD RI SRO\PHU f LQ f FRPSOHWHO\ ? UZUR7 FX &+ SRV &+ QHJ & VROYHQW 2 2 S& 9, X Z f GHFRXSOHG f ,1(37 &+ VXSSUHVVHGf

PAGE 102

+1+ &+af f L 1 +F 1F+ ‘! &+ FKFFK  12 O Ar 1 } 1F+ f PHWK\ORO GHULYDWLYHV RI QLWURDONDQHV ZHUH QRW YHU\ KLJK PROHFXODU ZHLJKW SRO\PHUV WKH PHWKRG UHSRUWHG E\ $QJHORQL DQG FRZRUNHUV ZDV 2 e7 22 HPSOR\HG QH[W 7KXV PHWK\OQLWUROELVGLPHWK\O DPLQRfSURSDQH f ZDV SUHSDUHG E\ DOORZLQJ f WR UHDFW ZLWK GLPHWK\ODPLQH &RPSRXQG f ZDV VHSDUDWHG DQG FKDUDFWHUL]HG E\ ,5 + DQG -& 105 VSHFWUD 7KLV WKHQ ZDV UHDFWHG ZLWK 10($ WR &+ +2&+&&+2+ +1 QR f KF KF FK 1&+&&+1 1 &+ &+ f DIIRUG SRO\PHU f 7KH EURZQ YLVFRXV RLO VKRZHG LGHQWLFDO ,5 r+ DQG & 105 WR WKRVH RI SRO\PHU f REWDLQHG SUHYLRXVO\ E\ WKH UHDFWLRQ RI f DQG 10($ f 10($ &+ &+ &+ L D L D R fFKFFKQFKFKQ 1 -[ f 6LPLODUO\ FRPSRXQG f ZDV UHDFWHG ZLWK 10%$ DQG 10+$ WR DIIRUG SRO\PHUV f DQG f UHVSHFWLYHO\ 7KHVH SRO\PHUV ZHUH

PAGE 103

LGHQWLFDO WR WKRVH REWDLQHG SUHYLRXVO\ E\ WKH FRQGHQVDWLRQ RI f DQG 10%$ DQG 10+$ UHVSHFWLYHO\ 7KH PROHFXODU ZHLJKW RI WKH SRO\PHUV DOVR UDQJHG IURP WR f 10%$ + L+ + ‘&+f&&+1&+f&+ &+&+1 O 12 f [ f 10+$ &+ &+ &+ f O O &+&&+1&+f1 1R [ f &RPSRXQG f ZDV WKHQ SRO\PHUL]HG ZLWK SLSHUD]LQH XQGHU VLPLODU FRQGLWLRQV +RZHYHU WKH ZKLWH VROLG SUHFLSLWDWHG IURP WKH UHDFWLRQ PL[WXUH KRXUV DIWHU WKH UHDFWLRQ VWDUWHG 7KLV SRZGHU ZDV QRW f ? +1 1+ U &+ ? ‘&+&&+1 1n QR f VROXEOH LQ PRVW RI WKH FRPPRQ RUJDQLF VROYHQWV 7KH ,5 VSHFWUXP RI WKH SRO\PHU ZDV YHU\ VLPLODU WR WKDW RI FRPSRXQG f ZLWK SHDNV DW DQG FP 7KH LQWULQVLF YLVFRVLW\ PHDVXUHG LQ b +& VROXWLRQ DW r& ZDV RQO\ JGO DQG WKXV VKRZHG WKDW WKLV SRO\PHU KDG D GHJUHH RI SRO\PHUL]DWLRQ OHVV WKDQ

PAGE 104

5HGXFWLRQ RI 0RGHO &RPSRXQGV 5HGXFWLRQ RI WKH QLWUR JURXS FDQ EH DFKLHYHG LQ PDQ\ ZD\V $PRQJ WKHVH WKH PHWKRG XVLQJ OLWKLXP DOXPLQXP K\GULGH /L$O+Af ZDV FKRVHQ EHFDXVH RI LWV PLOG FRQGLWLRQA 7KXV DQ DWWHPSW ZDV PDGH WR UHGXFH PRGHO FRPSRXQG f f / L $+ A UHGXFWLRQf 7+) +RZHYHU WKH GHVLUHG SURGXFW ZDV QRW REWDLQHG WKH UHDFWLRQ PL[WXUH WXUQHG WR D GDUN EURZQ OLTXLG DQG EHFDPH XQLGHQWLILDEOH $QRWKHU DWWHPSW ZDV PDGH WR UHGXFH FRPSRXQG f WR WKH FRUUHVSRQGLQJ DPLQH XVLQJ VRGLXP ERURK\GULGH 1D%+Af LQ WKH SUHVHQFH RI SDOODGLXP DFWLYDWHG FKDUFRDO 1D%+ /! 3G& &+ ?O&+&&+1 1 n 1+R R f $OWKRXJK FRPSRXQG f ZDV WKH PDMRU SURGXFW WKH ,5 VSHFWUXP VWLOO VKRZHG ,5 DEVRUSWLRQV DW DQG FP FKDUDFWHULVWLF RI QLWUR JURXS )LJ f

PAGE 105

&RPSRXQG f ZDV WKHQ UHGXFHG E\ WKH PHWKRG UHSRUWHG E\ 2 -RKQVRQ 7KH UHGXFWLRQ WRRN SODFH LQ D 3DUU ERPE FKDUJHG ZLWK SVL RI K\GURJHQ JDV ZLWK 5DQH\ QLFNHO FDWDO\VW 7KH ,5 VSHFWUXP VKRZHG D EURDG 1+ DEVRUSWLRQ DQG OLWWOH QLWUR DEVRUSWLRQV )LJ f f f 7KH UHGXFWLRQ RI QLWUR FRPSRXQG f ZDV WKHQ VWXGLHG $ VLPLODU UHVXOW ZDV H[SHFWHG KRZHYHU WKH SURGXFW REWDLQHG ZDV QRW &+ &0 +&? KF &+ 0&+f&&+1 1 f &+ &+ 5DQH\ 1L +R &+ + & f !&+&+ +H 8 1+ f WKH GHVLUHG UHGXFHG FRPSRXQG EXW 11GLPHWK\ODPLQREXW\OfDPLQH f 7KH r+ 105 VSHFWUXP VKRZHG D PHWKLQH SURWRQ SHDN DW SSP DQG WKH UDWLR RI PHWK\O SURWRQV ZHUH LQVWHDG RI DV Q H[SHFWHG 7KH & 105 VSHFWUD ERWK FRPSOHWHO\ GHFRXSOHG DQG RII UHVRQDQFH DJUHHG ZLWK WKH SURSRVHG VWUXFWXUH )LJ f

PAGE 106

\W! )LJ ,5 VSHFWUD RI f FRPSRXQG f DQG f FRPSRXQG f UHGXFHG E\ 1D%+A DQG 3G&f

PAGE 107

f )LJ ,5 VSHFWUD RI f FRPSRXQG f DQG f FRPSRXQG f UHGXFHG E\ +5DQH\ 1Lf

PAGE 108

\} )LJ 105 VSHFWUD RI FRPSRXQG f LQ &'&OA f FRPSOHWHO\ GHFRXSOHG f RIIUHVRQDQFH

PAGE 109

5HGXFWLRQ RI 3RO\PHUV 6LQFH WKH VWXG\ RI UHGXFWLRQ RI WKH PRGHO FRPSRXQG f LQGLFDWHG WKDW 5DQH\ QLFNHO FDWDO\]HG K\GURJHQDWLRQ \LHOGHG WKH EHVW UHVXOWV DPRQJ WKH WKUHH PHWKRGV WULHG SRO\PHUV f DQG f ZHUH UHGXFHG XQGHU LGHQWLFDO FRQGLWLRQV f 5DQH\ 1L f§ + + &+n f&+T&&+1&+&+1 QK f f 5DQH\ 1L &+B &+ &+ ‘&+&&+1&+&+ &+&+T1 QK f 7KH ,5 VSHFWUD RI ERWK SRO\PHUV f DQG f VKRZHG GUDVWLFDOO\ UHGXFHG QLWUR DEVRUSWLRQV UHODWLYH WR &+ DEVRUSWLRQ )LJV DQG f )RU FRPSDULVRQ SRO\PHU f ZDV UHGXFHG E\ 1D%+A LQ WKH SUHVHQFH RI 3DOODGLXP DFWLYDWHG FKDUFRDO WR \LHOG DQ DOPRVW LGHQWLFDO SURGXFW +RZHYHU WKH UHODWLYH LQWHQVLW\ RI WKH QLWUR DEVRUSWLRQV DUH VWURQJHU ZKHQ WKH ,5 VSHFWUXP RI WKLV SURGXFW ZDV FRPSDUHG WR WKDW RI WKH SUHYLRXVO\ REWDLQHG SRO\PHU f 7KLV LQGLFDWHV WKDW K\GURJHQDWLRQ ZLWK 5DQH\ QLFNHO LV PRUH HIILFLHQW RQ WKLV W\SH RI SRO\PHU 'XH WR WKH ORZ VROXELOLW\ RI SRO\PHU f LQ '0) ZKLFK ZDV XVHG DV WKH VROYHQW IRU WKHVH UHDFWLRQV HWKR[\HWKDQRO ZDV HPSOR\HG IRU WKH UHGXFWLRQ RI SRO\PHU f 7KXV REWDLQHG SRO\PHU f VKRZHG OLWWOH QLWUR JURXS DEVRUSWLRQ RQ LWV ,5 VSHFWUXP DV VKRZQ LQ )LJ

PAGE 110

)LJ ,5 VSHFWUD RI f SRO\PHU f DQG f SRO\PHU f

PAGE 111

)LJ ,5 VSHFWUD RI f SRO\PHU f DQG f SRO\PHU f

PAGE 112

,6 -2 0,&W20,756 2 m2 +)LJ ,5 VSHFWUD RI f SRO\PHU f DQG f SRO\PHU f

PAGE 113

f 5DQH\ 1L &+&+&+&++ FKT FIO FK Q O L f&+&&+1&+f1 R 1+e f [ 0HWK\ODWLRQ 0HWK\ODWLRQ RI SRO\PHU f ZDV FDUULHG RXW XWLOL]LQJ VRGLXP F\DQRERURK\GULGH DQG IRUPDOGHK\GH 7KH SURGXFW f ZDV D OLJKW f +&+2 1D%+&1 &E/ &+f &+ _ L f§&+&&+1&+&+1n ? +F FK ; f EURZQ YLVFRXV RLO + 105 VSHFWUXP RI ZKLFK VKRZHG D QHZ SHDN DW SSP ZKLFK ZDV DVVLJQHG WR WKH QHZ PHWK\O SURWRQV DWWDFKHG WR WKH SHQGDQW DPLQR JURXS 7KH r& 105 VSHFWUXP VKRZHG D VKLIW RI WKH PHWK\O DQG PHWK\OHQH SHDNV DV ZHOO DV D QHZ PHWK\O SHDN )LJ f $Q DWWHPSW WR PHWK\ODWH SRO\PHU f E\ WKH VDPH PHWKRG IDLOHG XH WR WKH ORZ VROXELOLW\ RI WKH PDWHULDO LQ WKH VXJJHVWHG VROYHQW DFHWRQL WULOH 3RO\PHU f ZDV WKHQ PHWK\ODWHG XWLOL]LQJ IRUPLF DFLG DQG IRUPDOGHK\GH 7KH UHVXOWLQJ SRO\PHU ZDV LGHQWLFDO ZLWK SRO\PHU f REWDLQHG SUHYLRXVO\ 6LPLODUO\ SRO\PHU f ZDV PHWK\ODWHG E\ IRUPLF DFLG DQG IRUPDOGHK\GH WR DIIRUG D EURZQ YLVFRXV RLO 7KH 105 VSHFWUXP VKRZHG D QHZ PHWK\O SHDN DW SSP LQGLFDWLQJ WKDW WKH

PAGE 114

f B &+ Fn &7 &&+ Dn n&+&&+1&+&+1 1 Gn ? [ )LJ & 105 VSHFWUD ,1(37 &K8 VXSSUHVVHGf RI FRPSRXQGV f &+ SRV &+ QHJ & VROYHQW DQG f UHVSHFWLYHO\

PAGE 115

+&+ f +&+2 &+ &K/ &+ Q , f§&+&&+1&+&+ &+&+1 > 1 m& 1F+ f DPLQR JURXS RI SRO\PHU f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k &+1 +&+2 +&+&+1 2f§! &+ &+1 f f SSP RI WKH PHWKLQH SURWRQ DQG WZR GRXEOHWV RI WKH PHWK\OHQH SURWRQV DW DQG SSP 7KH VSHFWUXP VKRZHG PHWKLQH FDUERQ DW SSP DQG PHWK\OHQH FDUERQ DW SSP 7KH WKXV V\QWKHVL]HG

PAGE 116

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f ZDV WKHQ UHDFWHG ZLWK IRUPDOGHn K\GH DQG GLHWK\ODPLQH 7KH UHVXOWLQJ SRO\PHU ZDV D GDUN EURZQ VROLG &+&+ 12 Q +&+2 Q +1&+&+f f FKF 12 O1&+&+ff @ Q RI ORZ VROXELOLW\ LQ PRVW RI WKH FRPPRQ RUJDQLF VROYHQWV 2XH WR WKLV SURSHUW\ WKLV UHDFWLRQ ZDV QRW SXUVXHG IXUWKHU 8UHWKDQHV DQG 3RO\XUHWKDQHV 7KH FRQGHQVDWLRQ UHDFWLRQ EHWZHHQ DQ LVRF\DQDWH DQG DQ DOFRKRO & 2 LV ZHOO NQRZQ 6LQFH PRGHO FRPSRXQG f FDQ EH FODVVLILHG DV D GLRO LW FDQ IRUP D SRO\XUHWKDQH ZKHQ UHDFWHG ZLWK D GLLVRF\DQDWH 0RGHO FRPSRXQG f ZDV UHDFWHG ZLWK SKHQ\O LVRF\DQDWH WR DIIRUG

PAGE 117

0&2 &+ +2&+f&+f1 1&+&&+1 ? ? 0 f 1&+&+2+ FDWDO\VWA 1+&2&+R&+Q1 Z &+ QFKFFKQ O 1 f 9B 1&+&+&1+ XUHWKDQH f 7ZR GLIIHUHQW FDWDO\VWV ZHUH LQYHVWLJDWHG LH GLD]DELF\FOR>@RFWDQH '$%&2f DQG WLQ RFWRDWH 72f $OWKRXJK ERWK DUH NQRZQ WR EH H[FHOOHQW FDWDO\VWV IRU XUHWKDQH IRUPDWLRQ f WLQ RFWRDWH JDYH WKH EHWWHU \LHOG $ GLLVRF\DQDWH PHWKHOHQHGL SKHQ\OHQHGLLVRF\DQDWH 0',f ZDV WKHQ SRO\PHUL]HG ZLWK FRPSRXQG f WR \LHOG SRO\PHU f 7KH ZKLWH SRZGHU ZDV VROXEOH LQ '062 DQG ')0 f 2&1 &+ QKFRFKRKQ f &+ QFKFFKQ QR QFKFKR DQG GHFRPSRVHG DURXQG r& 7KH ,5 A DQG & 105 VSHFWUD RI WKLV SRO\PHU ZHUH VLPLODU WR WKRVH RI WKH PRGHO FRPSRXQG f LQFOXGLQJ WKH ,5 DEVRUSWLRQ DW FPnf FKDUDFWHULVWLF RI WKH FDUERQ\O JURXS RI XUHWKDQH FRPSRXQGV 7KH LQWULQVLF YLVFRVLW\ RI WKLV SRO\PHU LQ '062 DW r& ZDV GOJ

PAGE 118

0RGHO FRPSRXQG f ZDV WKHQ SRO\PHUL]HG ZLWK 0', WR \LHOG SRO\PHU f 7KH OLJKW EURZQ VROLG VKRZHG DQ ,5 DEVRUSWLRQ DW KRFKFKQ ? 1&+1 1&+&+2+ ? f 0', QKFRFKFKQ U? FKQ 1&+&+ f FP FKDUDFWHULVWLF RI WKH XUHWKDQH FDUERQ\O JURXS 6LPLODUO\ PRGHO FRPSRXQG f ZDV UHDFWHG ZLWK PHWK\O LVRF\DQDWH WR DIIRUG XUHWKDQH f DV D OLJKW EURZQ RLO %HFDXVH &+ ? ? ,, f &+1& &+1+&&+&+1 QFKFFKQ 1&+&+&1+&+ [ “R 1 f PHWK\O LVRF\DQDWH LV D YHU\ YRODWLOH OLTXLG DQG WKH UHDFWLRQ ZDV UXQ XQGHU FRQVWDQW IORZ RI A PHWK\OLVRF\DQDWH ZDV XVHG LQ H[n FHVV &RPSRXQG f ZDV WKHQ SRO\PHUL]HG ZLWK DQ DOLSKDWLF GLLVRn F\DQDWH LH KH[DPHWK\OHQHGLLVRF\DQDWH WR DIIRUG SRO\PHU f f &1&+ffF1& 72 2+ +2 ,, , ,, f§FQFKfQFRFKFKQ &+ ? 1&+&&+1 ?  ? 1f 1&+&+ f

PAGE 119

7KH ZKLWH SRZGHU VKRZHG ORZ VROXELOLW\ LQ PRVW RI WKH FRPPRQ RUJDQLF VROYHQWV 6XPPDU\ DQG &RQFOXVLRQV 7KH PRGHO FRPSRXQG VWXGLHV ZHUH FDUULHG RXW LQ RUGHU WR HVWDEOLVK WKH EHVW FRQGLWLRQV IRU WKH SRO\PHU IRUPLQJ UHDFWLRQV 7KURXJK WKLV VWXG\ KLJK FRQYHUVLRQ RI WKH VWDUWLQJ PDWHULDOV LQWR WKH 0DQQLFK EDVH ZDV DFKLHYHG &KDLQVWRSSLQJ UHDJHQWV ZHUH XWLOL]HG WR SURYLGH D EHWWHU XQGHUVWDQGLQJ RI WKH SRO\PHUL]DWLRQ 7KH SRO\PHUV REWDLQHG IURP WKH UHDFWLRQ RI QLWURHWKDQH DQG ELV VHFRQGDU\ DPLQHV VKRZHG UDWKHU ORZ PROHFXODU ZHLJKWV RI 7KHVH SRO\PHUV ZHUH WKHQ PRGLILHG E\ UHGXFWLRQ DQG PHWK\ODWLRQ WR DFKLHYH WKH REMHFWLYH RI WKLV UHVHDUFK 6LQFH WKH SRO\PHUV ZHUH RI ORZ PROHFXODU ZHLJKW RWKHU URXWHV WR SUHSDUH KLJK PROHFXODU ZHLJKW SRO\PHUV ZHUH LQYHVWLJDWHG 7KH 0DQQLFK EDVHV ZLWK GLRO IXQFWLRQV ZHUH SRO\PHUL]HG ZLWK GLLVRF\DQDWHV WR DIIRUG SRO\XUHWKDQHV RI KLJKHU PROHFXODU ZHLJKW $OWKRXJK WKH SRO\PHUV REWDLQHG IURP WKH 0DQQLFK UHDFWLRQ VKRZHG RQO\ ORZ PROHFXODU ZHLJKWV WKHLU IXUWKHU PRGLILFDWLRQ VXFK DV FURVVOLQNLQJ YLD WKH GRXEOH ERQG LQ SRO\PHUV GHULYHG IURP 11n GLPHWK\OEXWHQHOGLDPLQH FDQ EH YHU\ XVHIXO DQG VKRXOG EH VWXGLHG LQ WKH IXWXUH

PAGE 120

5()(5(1&(6 &0 YDQ 0DULH DQG % 7ROOHQV %HU B f + 6FK£7HU DQG % 7ROOHQV %HU f & 0DQQLFK DQG : .URVFKH $UFK 3KDUP f )) %OLFNH 7KH 0DQQLFK 5HDFWLRQ 2UJ 5HDFWLRQV BB f 5 $GDPV (G -RKQ :LOH\ DQG 6RQV ,QF 1HZ @ f 0 6HQNXV $P &KHP 6RF B f +* -RKQVRQ $P &KHP 6RF B f 7 7VXML DQG 7 8HGD &KHP 3KDUP %XOO 7RN\Rf BB f

PAGE 121

,OO +$ %UXQVRQ DQG %XWOHU 6 3DW 0D\ *% %XWOHU DQG %0 %HQMDPLQ 6 3DW $SULO ( 7VXFKLGD DQG 7 7RPRQR 3RO\P 6FL 3RO\P &KHP (G f 7 7RPRQR ( +DVHJDZD DQG ( 7VXFKLGD 3RO\P 6FL &KHP f &0F'RQDOG DQG 5+ %HDYHU 0DFURPROHFXOHV B f ) $QGUHDQL $6 $QJHORQL / $QJLROLQL 3 &RVWD %L]]DUUL & 'HOOD &DVD $ )LQL 1 *KHGLQL 0 7UDPRQWLQL DQG 3 )HUUXWL 3RO\P 6FL 3RO\P /HWW (G B f $6 $QJHORQL 3 )HUUXWL 0 7UDPRQWLQL DQG 0 &DVDODUR 3RO\PHU B f $6 $QJHORQL 3 )HUUXWL 0 /DXV 0 7UDPRQLWLQL ( &KLHOOLQL DQG *DOOL 3RO\P &RPP BB f 1 *KHGLQL & 'HOOD &DVD 3 &RVWD %L]]DUUL DQG 3 )HUUXWL 0DNURPRO &KHP 5DSLG &RPPXQ B f 50 6LOYHUVWHLQ *& %DVVOHU DQG 7& 0RUULOO 6SHFWURPHWULF ,GHQWLILFDWLRQ RI 2UJDQLF &RPSRXQGV WK (G -RKQ :LOH\ DQG 6RQV 1HZ $SSO &KHP 8665 f (QJO (Gf@ :( 1RODQG 2UJ 6\QWK f +3 'HQ 2WWHU 5HF 7UDY &KLP B f %0
PAGE 122

' 5DQJDQDWKDQ &% 5DR 6 5DQJDQDWKDQ $. 0HKURWUD DQG 5 ,\HQJDU 2UJ &KHP MMB f *' %XFNOH\ DQG &: 6FDLIH &KHP 6RF f 3)ORU\ 3ULQFLSOHV RI 3RO\PHU &KHPLVWU\ &RUQHOO 8QLYHUVLW\ 3UHVV ,WKDFD 1HZ
PAGE 123

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

PAGE 124

, 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\ n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 R 7KLHR ( +RJHQ(VFK 3URIHVVRU RI &KHPLVWU\ 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\ AB :LDP 0 -RQHV 3URIHVVRU RI &KHPL

PAGE 125

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

PAGE 126

81,9(56,7<


PREPARATION OF POLYMERS
VIA MANNICH REACTION
BY
SEOK HEUI HONG •
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
1985

To my family, for their love,
patience and encouragement

ACKNOWLEDGMENTS
I wish to extend my sincere appreciation to Dr. George B. Butler
for his help, advice and expertise during my program of research. I
would also like to thank the members of my supervisory committee.
Colleagues, members of the polymer research group, are
appreciated for the friendly atmosphere they provided. I also thank
Ms. Cindy Zimmerman for her skillful typing of this manuscript.
Finally, I would like to thank Mr. S.H. Yoon and Mr. M. Muría for
their help.
Financial support for this work from the Department of
Chemistry, Graduate School, International Minerals and Chemical
Corporation, Allied Chemical Company and National Institute of Health
is gratefully acknowledged.
i i i

TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS iii
LIST OF TABLES vi
LIST OF FIGURES vii
ABSTRACT ix
CHAPTERS
I INTRODUCTION 1
The Use of Amines 3
Ni troal kanes 5
Polymeric Mannich Bases 7
Proposal of Research 8
II EXPERIMENTAL 13
General 13
Reagents and Solvents 14
Synthesis of Nitroalcohols 15
Synthesis of Model Compounds 20
Reactions Utilizing Chain-Stopping Reagents 32
Synthesis of Polymers 33
Reduction of Model Compounds 39
Reduction of Polymers 41
Methyl a ti on 43
Miscellaneous Reactions 46
IIIRESULTS AND DISCUSSION 52
Model Compounds 56
Model Compounds with 2-Nitropropane as
Chain-Stopping Reagent 62
Model Compounds with N-(8-hydroxyethyl)
Piperazine 71
Studies with Nitromethane 80
Model Compounds from Bis-secondary Amines 81
Polymers 88
IV

Reduction of Model Compounds 94
Reduction of Polymers 99
Methylation 103
Mannich Reaction on Nitroethane 105
Urethanes and Polyurethanes 106
Summary and Conclusion 109
REFERENCES 110
BIOGRAPHICAL SKETCH 113
v

LIST OF TABLES
Table Page
1 Reaction of 2-nitropropane with NMPD and formaldehyde 57
2 Reaction of (18) with DMPA 58
3 Reaction of N-methyiethanolamine and compound (18) 59
vn

LIST OF FIGURES
Figure Page
1 1H NMR spectrum of the model compound (21) in CDCI3 60
1 O
2 Completely decoupled C NMR spectrum of compound
(21) in CDCI3 61
3 NMR spectrum of compound (13) in CDCI3 63
1 O
4 Completely decoupled C NMR spectrum of compound
(13) in CDC13 64
5 NMR spectra (in CDCI3) of the model compounds
utilizing 2-nitropropane as chain-stopping reagent 66
6 Plot of the number of repeating limits vs. reactant
feed ratio 68
7 NMR spectrum of compound (30) in CDC13 69
8 Completely decoupled ^C NMR spectrum of compound
(30) in CDCI3 70
9 NMR spectrum of compound (24) in CDC13 72
10 Completely decoupled 13C NMR spectrum of the compound
(24) in CDCI3 73
11 13C NMR spectra of compound (26) in DMS0-d6:
(1) completely decoupled; (2) off-resonance 75
12 Selected time dependent NMR spectra of the reaction of
NHEP with compound (19) in 0MS0-d6 at RT 73
13 Plot of the consumption of NEPD vs. reaction time 79
14 1H NMR spectra of compound (15) in DMSO-do:
(1) without D2O, (2) 1 drop of D2O was added 82
15 ^C NMR spectra of compound (15) in DMS0-d6:
(1) completely decoupled; (2) off-resonance 83
VI 1

16 NMR spectrum of compound (31) in CDC13 85
17 13C NMR spectra of compound (31) in 00013:
(1) completely decoupled; (2) off-resonance 86
18 33C NMR spectra of compound (32) in 00013:
(1) completely decoupled, (2) INEPT (CH, CH3 pos.,
CH2 neg., C, solvent suppressed) 87
19 13C NMR spectra of polymer (35) in 00013:
(1) completely decoupled; (2) off-resonance 89
20 13C NMR spectra of polymer (36) in 00013:
(1) completely decoupled, (2) INEPT (CH, CH3 pos.,
CH2 neg., C, solvent suppressed) 91
21 IR spectra of (1) compound (27), and (2) compound
(39) (reduced by NaBH4 and Pd/C) 96
22 IR spectra of (1) compound (27), and (2) compound
(39) (reduced by H2/Raney Ni) 97
23 13C NMR spectra of compound (39) in CDCI3:
(1) completely decoupled; (2) off-resonance 98
24 IR spectra of (1) polymer (35), and (2) polymer (40) 100
25 IR spectra of (1) polymer (36), and (2) polymer (41) 101
26 IR spectra of (1) polymer (37), and (2) polymer (42) 102
27 13C NMR spectra (INEPT: CH3, CH pos., CH2 neg.;
C, solvent suppressed) of compounds (40) and (43),
respecti vely 104
vi i i

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
PREPARATION OF POLYMERS
VIA MANNICH REACTION
BY
SEOK HEUI HONG
May, 1985
Chairman: Dr. George B. Butler
Major Department: Chemistry
In order to achieve the objective of this research, which was to
utilize the Mannich reaction to synthesize new water-soluble
polymers, several model compounds were studied. The reaction of N,N-
dimethyl-l,3-propanediamine with formaldehyde and 2-nitropropane was
carried out, and the best result was obtained utilizing the methylol
derivative of 2-nitropropane at a lower temperature with a base
catalyst. The reactions of other amines, i.e., N-methylethanolamine
and piperazine, with formaldehyde and 2-nitropropane were undertaken
with similar results. Some bis-secondary amines, i.e., N,N'-
dime thy1ethylenediamine (DMEA), N,N'-dimethyl-2-butene-1,4-diamine
(DMBA) and N.N'-dimethylhexamethylenediamine (DMHA), were also
studied. In an attempt to provide a better understanding of the
polymerization, model compounds with controlled molecular weights
were studied utilizing chain-stopper components.
IX

Polymers of the desired structure were obtained from reactions
of the methylol derivative of nitroethane with bis-secondary amines,
including DMEA, DMBA, and DMHA. Alternatively, N,N,N',N'-
tetramethyl-2-methyl-2-nitro-l,3-propanediamine was reacted with
DMEA, DMBA and DMHA to yield polymers of the same structure. These
polymers containing nitro groups were reduced by hydrogen gas in the
presence of Raney nickel to afford the corresponding amine-containing
polymers. Upon treatment with formic acid and formaldehyde, the
polymers underwent methylation to afford the corresponding
polyamines. Since the polymers prepared were of relatively low
molecular weight, an attempt was made to prepare high molecular
weight polymers utilizing nitroethane. However, the Mannich reaction
of nitroethene with formaldehyde and dimethylamine yielded a dark
brown tar-like material which was not identifiable. The model
compound prepared from nitroethane, formaldehyde and N-(3-
hydroxyethylJpiperazine was reacted with methylenedi-_p-phenylene-
diisocyanate to afford the corresponding polyurethane, which has the
intrinsic viscosity of 0.194 dl/g in DMSO at 30°C. Similarly, the
same model compound was reacted with hexamethylenediisocyanate to
yield the corresponding polyurethane.
x

CHAPTER I
INTRODUCTION
The Mannich reaction is defined as the condensation of ammonia
or a primary or secondary amine with formaldehyde and a compound
containing at least one hydrogen atom of pronounced reactivity. The
first observation of this type was made by Tollens, who isolated the
tertiary amine from ammonium chloride, formaldehyde and
1 O
acetophenone. ’ However, the detailed study of the reaction was
initiated in 1912 by Mannich who observed that antipyrine (1),
formaldehyde and ammonium chloride reacted to form a tertiary
amine. Thus, the reaction has become known generally as the
CH
3
N — CCH
3
+ 3 HCHO + NH4C1
C — CH
II
0
(1)
N — CCH
3
C—C —CH
2
N-HCl
II
0
3
1

2
Mannich reaction, and is recognized as one of the classical reactions
of organic chemistry. This reaction has been widely used in
synthesis and was the subject of many reviews.^
The mechanism of the Mannich reaction has been well
investigated, and a comprehensive review covering up to 1968 has been
published.'7 Only a few of the main points will be discussed here.
The Mannich reaction leads to products of the type (6), bearing a
substituted methylene group connecting the substrate residue with
R-H + HCHO + Hf<
2
(6)
an amino group. The condensation reaction occurs in 2 steps. First,
the amine reacts with formaldehyde to give condensation product
2^3t^4 (Step I), which then attacks the substrate R-H (Step II).
Even though this is believed to be the main route of the reaction,

3
some successful reactions between hydroxymethyl derivatives (5) and
alkylamines to give Mannich bases (6) are known.
The reactive species in acidic medium is the iminium ion (2),
derived principally from methylene-bis-amine (4) and secondarily from
hydroxymethylamine (3). In basic medium, the reactant is postulated
to be hydroxymethylamine (3) or, more probably, methylene-bis-amine
(4). The existence of cation (2) in aqueous solutions of amine and
formaldehyde has been demonstrated by polarographic methods; the
maximum concentration of (2) was reported to occur at pH 10-11.
The Use of Amines
The choice of the amine used in the reaction is important. It
is known that primary amines can react at both amine H-atoms, and
therefore it is difficult to obtain secondary Mannich bases free from
tertiary derivatives. However, use of the sterically hindered amine
(7), or similar amines containing bulky groups (t-butyl, di- or tri-
arylmethyl), can prevenía substitution reaction involving the second
amine H-atom of (7). The bulky alkyl groups can subsequently be
removed by hydrolysis to give the N-unsubstituted aminoketone (9),
which is not directly obtainable from ammonia and formaldehyde.^»^

4
It is also known that use of the oxalate derivatives of the primary
amines instead of the corresponding hydrochlorides makes the
O IQ
synthesis of secondary Mannich bases in high yields possible. ’
The use of secondary bifunctional amines such as piperazine
leads to symmetric Mannich bases, in which both of the amino groups
have reacted. Attempts to restrict the reaction to only one amine
function or hydrolysis of the Mannich products obtained from
piperazines invariably leads to the formation of disubstituted
piperazines (10).^
/—\
R-H + HCHO + HN NH
\ /
. / \
-> RCH^ N CH2R
(10)
The Mannich reaction of bis-(2-chloroethyl)amine can give a
• 1 ?
bicyclic salt as by-product. Two molecules of the amine thus
condense with one molecule of formaldehyde to give (11), which shows
cytostatic properties as do halógena ted derivatives of similar
13,14
structure.

/ \
Cl '"V-? c'
+
HCHO > Cl
(11)
Nitroalkanes
Henry was the first to show that Mannich type reactions will
occur with nitroalkanes.^,16 established that N-hydroxymethyl-
piperidine condensed with nitromethane and nitroethane to yield,
respectively, 2-nitro-l,3-dipiperidinopropane (12a) and 2-methyl-2-
nitro-1,3-dipi peridinopropane (12b).
2 Qo2oh + ch2rno2 > o2h-¿-(ch2Q )2
(12)
(12a), R = H
(12b), R = CH3
Later, Senkus successfully carried out reactions using methyl amine,
isopropylamine, 1-butylamine, 2-butylamine, benzylamine, 1-
phenylethylamine, 2-amino-l-butanol, and 2-amino-2-methyl-1-propanol
as monoalkylamine components; and nitroethane, 1- and 2-nitropropane,
and 2-nitrobutane as nitro components.^ He showed that the products
could be obtained either by allowing the amine to react with
formaldehyde and thereafter adding the nitroalkane, or by first

5
generating the methylol derivative of the nitroalkane, which was then
treated with the amine.
R
, I
R NHCHo0H + HC-N0o
¿ I ¿
R
R
> R'NHCHoCN0o + Ho0
¿\ ¿ ¿
R
R
2r'nhch2oh + rch2no2 > r'nhch2cch2nhr' + h2o
no2
al ternatively,
R
, I
R NH0 + H0CHo-C-N0
¿ ¿ I
R
R R
2R*NH0 + H0CHo-C-CHo0H > R‘NHCH0C-CH„NHR' + Ho0
2 2 | 2 ^ 21 2 2
N02 no2
Johnson extended the work of Senkus to various aliphatic
IQ
secondary amines. ° He also carried out these reactions by two
different methods: (A) reaction of the amines, formaldehyde and
nitroparaffin; and (B) reaction of the amine with the nitro alcohol
or nitro diol. Although the same end-products resulted in either
case, the latter reaction was slower. It is also shown that
unsubstituted piperazine and 3,5-dimethylpiperazine gave the
corresponding bis condensation products (13).^

7
HN
/~\
V_/
NH + 2 HCHO
n-ch2-cch3
(13)
Polymeric Mannich Bases
Even though the Mannich reaction has been widely investigated
mechanically and used extensively in synthesis of small molecules, it
has been used only in a very limited manner in synthesis of
macromolecules. Apparently, the first application to synthesis of
macromolecules was by Bruson and Butler, who condensed 2,4,5-
trinitrotoluene with formaldehyde and ammonia to yield explosive
plastics. This was followed by Butler and Benjamin who condensed
phenols with formaldehyde and primary or secondary amines to
synthesize ion-exchange resins.23 Later, Tsuchida and Tomono
Op
condensed pyrrole, formaldehyde and amines to yield polymers.
Tomono, Hasegawa and Tsuchida extended the earlier work to include
other active hydrogen compounds as well.23 McDonald and Beaver later
published some of the details of modification of polyacrylamide by
use of the Mannich reaction. Recently, Andreani and coworkers
reported a synthetic route to tertiary amino polymers, namely the
polycondensation of bis(6-dialkylaminoketone)s, i.e. bis(Mannich
pc
bases) with bis-secondary amines to yield poly(S-aminoketone)s.

8
Angeloni and co-workers extended this work to aromatic Mannich bases
I I
such as 4,4 -bis(0-dimethylaminopropionyl)diphenyl or 4,4 -bis(B-
dimethylaminopropionyl)di-phenylether.^°’^7 Ghedini and coworkers
also extended this work to phenolic Mannich bases such as 2,6-bis(di-
OQ
methyl ami nomethyl)-4-methyl phenol.
Proposal of Research
It is the objective of the research to utilize the Mannich
reaction between formaldehyde, selected amines and the nitroparaffins
as the active hydrogen compounds to synthesize amine-containing
and/or quaternary ammonium containing polymers. The reactions
anticipated to occur are as follows:

9
n RCH2NÜ2 + 2n HCHO + n R NH2
CH0-C-CH0-N-
2 I 2
N0o
+ 2n H20
Reduction,
R
I
R
I
» CH,-C-CH,-N
¿ I ¿
NH0
Methyl a ti on
> —
R
R
â– CH?-C-CH?-N-
I
N(CH )
J n
Quaternization
> —CH0-C — CH0—N —
21 2 i
L +N(CH3)3 CH3 J n
R = CH3 or C2H5
Nitroethane, as well as 1-nitropropane, can be utilized as the active
hydrogen compound. Both nitroparaffins should result in polymers of
high charge density. The resulting polymers from nitroethane and 1-
nitropropane would have an equivalent weight with respect to
quaternary ammonium centers (chloride form) of 114.5 and 121.5,
respectively.
It is well recognized that the effectiveness of cationic
polymers in the flocculation and coagulation applications is a direct

10
function of the charge density on the polymer. Thus, it would be
predicted that the qua term’zed polymer derived from polyethyleneamine
would be most effective having an eq. wt. of 107.5 (chloride form):
However, such a polymer has been shown to be relatively unstable due
to the proximity of the positive charges. An alternative polymer of
high charge density is poly(vinyltrimethylammonium chloride) of eq.
wt. of 121.5:
CH„-CH
21
- +N(CH o) o
Cl J J
However, this polymer is difficult to synthesize and its cost would
be high. The most widely used cationic polymer in the flocculation
area of application is perhaps poly(diallyldimethylammoniurn chloride)
of eq. wt. 161.5:
or
â– CH,
CH,
N
H3
11
Again, this polymer is made from a fairly expensive monomer and has
relatively high equivalent weight per charge.
Considerable versatility is envisioned in the above system. For
example, use of either 2-nitro-propane or a secondary amine would
produce polymers with molecular weight control, as both of these
reactants would function as chain-stoppers:
CH9C — CH~— N
2| 2 i
+N(CH 3)3
CH
3 J
CH.
CH0—
C — N(CH3)3
ch3
2-nitropropane as chain-stopper
1 +
N -
I
CH.
■CH„— N —CH0-
2 1 2
+N (ch3}3
CH„—
f+
N —CH.
Secondary amine as chain-stopper
Use of nitromethane or ammonia would result in crosslinked
polymers. Thus, it is apparent that a wide variety of products are
possible from the proposed reactions.
The problem anticipated is the known requirement of considerably
high molecular weights for effective flocculation and coagulation
character!-sties in cationic polymers. The reaction proposed, the
Mannich reaction, for polymer synthesis can be classified as an
example of condensation polymerization or step-growth polymeriza¬
tion. And such processes are known to require (A) relatively pure

12
reactants; and (B) rigidly controlled stoichiometry in order to
attain high molecular weights. Thus one of the major objectives of
the research is to attain the necessary stoichiometric control to
lead to the desired degrees of polymerization.

CHAPTER II
EXPERIMENTAL
General
Melting points, given in degrees Celsius, were determined on a
Thomas-Hoover Capillary Melting Point Apparatus and are reported
uncorrected. Pressures are expressed in millimeters of mercury (mm
Hg). Elemental analyses were performed by either Atlantic Microlabs,
Inc., Atlanta, Georgia, or Department of Chemistry, University of
Florida, Gainesville, Florida.
Proton nuclear magnetic resonance (NMR) spectra (60 MHz) were
recorded on a Varian EM360L instrument. Carbon-13 NMR (25 MHz) and
100 MHz proton NMR spectra were recorded on a Jeol-JNM-FX-100
spectrometer. Chemical shifts are expressed in parts per million
(ppm) on the <$ scale downfield from te tramethylsi lane (TMS) or sodium
2,2-dimethyl-2-silapentane-5-sulfonate (DSS) unless otherwise
indicated. In cases where no internal reference was added, spectra
were calibrated via a characteristic signal of the deuterated solvent
used. The solvent used and calibration information are given in
parentheses for each spectrum reported. Multiplicities of proton and
off-resonance decoupled carbon resonances are designated as singlet
(s), doublet (d), triplet (t), quartet (q) or multiplet (m).
13

14
Infrared (IR) spectra were recorded on a Perkin-Elmer 281
spectrophotometer. Absorbances are expressed in wavenumbers (cm~^)
using the 1601 cm-3 line of standard. Solid samples were run as a
KBr pellet; liquid samples were analyzed neat as a thin film between
NaCl plates. Absorption bands are assigned the classifications weak
(w), medium (m), strong (s), broad (br) and shoulder (sh).
Molecular weights of polymers were determined by vapor pressure
osmometry (VPO) on a WESCAN model 233 Molecular Weight Apparatus.
Benzil was used as a calibration standard. Intrinsic viscosities
were measured with Ubbelohde viscometer (dilution viscometer).
Reagents and Solvents
Reagents were obtained from Aldrich Chemical Co., Eastman Kodak
Co., Fischer Scientific Co. or Mallinckrodt, Inc., unless otherwise
noted. Deutrated solvents were purchased from Merck & Co., Inc., and
Aldrich Co.
All solvents used for general applications were of Reagent grade
or ACS grade quality. For special applications, solvents were
purified as needed by following procedures reported in the
1iterature.3^ Thus, dimethylsulfoxide (DMSO) and N.N-dirnethyl -
formamide (DMF) were allowed to stand over potassium hydroxide
pellets and distilled from calcium oxide under reduced pressure;
ethanol-free chloroform (CHCI3) was obtained by extraction of reagent
grade CHC13 with concentrated H2SO4 and water, followed by
distillation from phosphorus pentoxide (P^q).

15
Synthesis of Nitroalcohols
2-Nitroethanol (14)
The procedure reported by Burmistrou and Bashinova31 was
modified as follows. Nitromethane (610 g, 10 moles) and para¬
formaldehyde (30.0 g, 1 mole) were placed into a 2,000 ml three¬
necked round-bottomed flask fitted with a thermometer and a reflux
condenser. The mixture was heated in an oil bath to 105-110°C and
potassium carbonate (0.64 g, 0.1% of the reaction mixture) was added
in 10 portions. Each successive portion of catalyst (K2C03) was
added after vigorous boiling of the mixture ceased. During the
additions, the color (cloudiness) of the mixture disappeared
slowly. When the paraformaldehyde was completely dissolved to yield
a clear solution, the mixture was held for 30 minutes at the same
temperature, cooled, filtered to separate the catalyst, and
neutralized with 4 drops of concentrated H-^SO^. The light yellow
filtrate was distilled under reduced pressure to remove excess
nitromethane (30-34°C at 30-60 mm Hg, then held at 5-7 mm Hg for 30
min.). The yellow residue was transferred to a 100 ml. round-
bottomed flask and distilled under vacuum (59-63°C at .25 mm Hg) to
yield 52 g (57.1%) of crystal clear liquid, n^4 1.4434 [literature
value 1.4438].32
XH (CDC13,TMS): 6 4.14 (m,2H), 4.54 (m,2H).
2-Nitro-1,3-propanediol (15)
Procedure A: The following procedure was modified from the
procedure of Den Otter.33 Paraformaldehyde (38 g, 1.265 mole),
nitromethane (22.5 g, 0.369 mole) and 10 drops of 33% aqueous

16
potassium hydroxide were heated with 350 ml of methanol under reflux
in an oil bath. The 2-(hydroxymethyl)-2-nitrol-1,3-propanediol (16),
formed during the reaction, was not isolated, but used in the
dissolved condition. A solution of sodium (10.5 g, 0.457 mole) in
150 ml of methanol was added dropwise to the solution, which was
stirred and cooled in an ice bath. During this addition, a
precipitate of the sodium derivative of 2-nitro-1,3-propanediol (17)
began to separate and this separation was complete after the flask
had stood overnight in a refrigerator. The filtered and dried sodium
derivative of 2-nitro-1,3-propanediol (60 g) was mixed in 300 ml of
ether and added in 5 equal portions to a solution of 40 g of
salicylic acid in 250 ml of ether, which was brought to reflux.
After 3 hours of reflux, the mixture was cooled, the sodium
salicylate filtered off and the ether evaporated. The resulting oil
was added to a hot mixture of 1:1.7 ethylacetate and chloroform to
yield a clear yellow solution, which was placed in a refrigerator
overnight to yield white crystals. The filtered crystals were
recrystal 1ized from a 1:1.7 ethylacetate and chloroform mixture to
yield needle-like white crystals (33 g, 73.9% yield), m.p. 53°C
[literature m.p. 54°C].33
Sodium derivative of 2-nitro-1,3-propanediol (17)
(D20,DSS): 6 4.37 (S,2H), 3.31 (S,4H).
2-nitro-1,3-propanediol (15)
1H (DMS0-d6,TMS): 6 3.72 (m,4H), 4.66 (m,lH), 5.27 (t,2H).
13C (DMS0-d6> 39.5): <5 59.555, 91.917.

17
IR (KBr): 3380 (s.br), 2950 (m), 2900 (m), 1550 (s), 1460 (s),
1360 (s,sh), 1330 (s), 1245 (m), 1210 (m), 1075 (s,sh), 1010 (s), 975
(w), 915 (w,sh), 865 (m), 770 (w) cm--*-.
Analysis, calculated for C3H7N04: C, 29.75; H, 5.83; N, 11.57.
Found: C, 29.83; H, 5.84; N, 11.55.
Procedure B: A mixture of nitromethane (12.108 g, 0.2 mole) and
calcium hydroxide (0.065 g) was placed in a 250 ml round-bottomed
flask equipped with a stirrer and a condenser, and cooled in an
external ice bath. After cooling, 32.465 g of formalin solution (37%
w/w aqueous, 0.4 mole) was added slowly from a dropping funnel.
After the addition was complete, the solution was stirred at room
temperature for 66 hours. Carbon dioxide in the form of dry-ice was
added in excess and the calcium carbonate was filtered. The filtrate
was evaporated at 90°C under reduced pressure to yield a molten, dark
brown, viscous oil, which upon cooling, solidified. The resulting
solid was recrystallized from a 1:1.7 ethylacetate-chloroform mixture
to yield a white crystalline product (18.3 g, 60.6%) which turned out
to be 2-(hydroxymethy1)-2-nitro-l,3-propanediol (16).
:H (acetone-d6,TMS): 6 4.05 (d,6H), 4.33 (t,3H).
2-Methyl-2-nitro-l-propanol (18)
The following procedure was modified from the procedure of
Vandervilt and Hass.^ To a 500 ml three-necked round-bottomed flask
equipped with a mechanical stirrer and thermometer was added 44.5 g
(0.499 mole) of freshly distilled 2-nitropropane and 0.125 g of
calcium hydroxide. The mixture was cooled in an external ice bath to
0-5°C, after which 41 g (0.505 mole) of formalin solution (37% w/w

18
aqueous) was added dropwise from the dropping funnel. After the
addition was complete, the solution was stirred at room temperature
for 43 hours. Carbon dioxide in the form of dry-ice was added in
excess and the calcium carbonate precipitate was removed by
filtration. The precipitate was washed with 10 ml of water, and the
combined filtrate and washings were evaporated at 90°C under reduced
pressure. The remaining molten product, which solidified upon
cooling, was recrystallized from 1:10 butanol-benzene to yield 54.5 g
(91.S%) of white crystalline product, m.p. 88-89°C [literature m.p.
89.5-90°C].34
NMR (CDC13,TMS): 6 1.58 (s,6H), 2.86 (s,lH), 3.84 (s,2H).
13C NMR (CDC13,77.0): 6 22.73, 68.13, 88.72.
IR (KBr): 3440 (s,br), 3000 (m), 2940 (m), 2880 (m), 1545 (s),
1465 (m), 1410 (w), 1400 (w), 1375 (m), 1350 (m,sh), 1150 (w), 1067
(m,sh), 990 (w), 860 (w,sh), 820 (w), 730 (w) cm-3.
2-Methyl-2-nitro-1,3-propanediol (19)
By use of the same procedure as reported for the previous
compound on preparation of this compound was accomplished by adding
slowly 160 g (2 mole) of formalin solution (37* w/w aqueous) to a
mixture of 75 g (1 mole) of nitroethane and 0.25 g of calcium
hydroxide. After stirring for 43 hours at room temperature, and a
slight excess of carbon dioxide had been added, the white precipitate
which formed was filtered and washed. The filtrate and washings were
combined and evaporated at 90°C under reduced pressure to yield
molten product, which upon cooling, solidified. The crude product
was recrystallized from 1:10 butanol-benzene to yield 113 g (83.1%)

19
of white crystalline product, m.p. 153-155°C [literature m.p. 149-
150°C].34
XH NMR (CDC13,TMS): 6 1.52 (s,3H), 2.46 (t,2H), 4.07 (d,4H).
13C NMR (C0C13, 77.0): 6 16.93, 64.02, 93.11.
IR (KBr): 3300 (s,br), 3000 (m), 2960 (m), 2390 (m), 2100 (w),
1540 (s), 1470 (m), 1440 (m), 1410 (m), 1370 (m), 1360 (m,sh), 1305
(m), 1240 (m), 1215 (w), 1180 (m), 1130 (m), 1080 (m), 1035 (s), 985
(m), 950 (m), 905 (m), 870 (m), 835 (m), 745 (m), 740 (m,sh), 675
(m,br) cm-1.
2-Ethyl-2-nitro-1,3-propanediol (20)
Preparation of this compound was achieved as previously
described by adding 160 g (2 mole) formalin solution (37% w/w
aqueous) to a mixture of 89 g (1 mole) of 1-nitro-propane and 0.25 g
of calcium hydroxide. The recrystallization yielded white
crystalline product (126 g, 84.5%), m.p. 55-56.5°C [literature m.p.
56°C].34
NMR (CDC13,TMS): 6 0.90 (t,3H), 1.90 (q,2H), 3.04 (s,2H),
4.11 (m,4H).
13C NMR (CDC13,77.0): 6 7.650, 25.777, 63.743, 94.253.
IR (KBr): 3400 (s,br), 2980 (m), 2890 (m), 1540 (s), 1425 (m),
1360 (m), 1310 (w), 1250 (w,sh), 1190 (w), 1065 (s,sh), 975 (m), 905
(w), 860 (m), 815 (m), 785 (m), 720 (w), 640 (w) cm-1.

20
Synthesis of Model Compounds
N-(2-Hydroxyethyl)-N-methyl-(2-methyl-2-nitro-l-propyl)
amine (21)
Procedure A: In a 100 ml round-bottomed flask were placed 5.955
g (0.0500 mole) of 2-methyl-2-nitro-l-propanol (18) in 20 ml of
freshly distilled THF and 4 A molecular sieves, and 3.756 g (0.0500
mole) of N-methylethanolamine in 10 ml of THF was added slowly by
means of a dropping funnel. After the addition was complete, the
reaction was stirred for 72 hours, with fresh molecular sieves (4 A)
added every 12 hours. The molecular sieves were filtered, and the
solvent was evaporated under reduced pressure to yield a yellow oil,
4.88 g (55.4%).
Procedure B: The same procedure was used with the exception of
addition of triethylamine (1 ml) to the reaction mixture. Thus, the
reaction of (18) (5.957 g, 0.05 mole) and N-methyl-ethanolamine
(3.757 g, 0.05 mole) afforded yellow oil (5.86 g, 66.5%).
Procedure C: The reaction mixture (alcohol, amine and catalyst
NEt3) in was stirred and refluxed for 20 hours and cooled to room
temperature. The solvent was removed by evaporation under reduced
pressure to yield a yellow oil (5.95 g, 76.5%).
Analysis, calculated for C7H15N2O3: C, 47.71; H, 9.15; N, 15.90.
Found: C, 47.72; H, 9.11; N, 15.78.
1H NMR (C0C13,TMS): 6 1.57 (s,6H), 2.27 (s,3H), 2.54 (s,lH),
2.62 (t,2H), 2.88 (s,2H), 3.53 (t,2H).
13C NMR (CDC13,77.0): 6 23.24, 43.13, 58.63, 60.77, 66.18,
88.26.

21
IR (KBr): 3400 (s,br), 2980 (s), 2945 (s), 2370 (s), 2800 (m),
1770 (w), 1640 (w), 1530 (s), 1455 (s), 1400 (s), 1370 (s), 1345
(s,sh), 1280 (w), 1220 (w), 1185 (w), 1160 (w), 1120 (m), 1065 (s),
1035 (s,sh), 980 (w), 945 (w), 900 (w), 855 (m,sh), 815 (w), 790 (w)
cm--*-.
2-Ethyl-2-ni tro-l,3-bis(2-hydroxyethyl-N-methyl )amino
propane (22)
The solution of 3.756 g (0.0500 mole) of N-methylethanolamine
and 3.729 g (0.025 mole) of 2-ethyl-2-nitro-l,3-propanediol (21) with
4 A molecular sieves in 70 ml THF was stirred for 60 hours at room
temperature. The molecular sieves were filtered out and the filtrate
was evaporated under reduced pressure to yield a yellow oil (4.76 g,
72.4%).
NMR (CDC13,TMS): 6 0.94 (t,3H), 1.89 (q,2H), 2.30 (s,3H),
2.42 (s,3H), 2.91 (t,4H), 3.23 (s,4H), 3.57 (t,4H), 4.21 (s,2H).
N,N-Dimethyl-N',N'-bis(2-methyl-2-nitro-l-propyl)-l,3-
propanediamine (23)
Procedure A: To a solution of N,N-dimethyl-l,3-propanediamine
(DMPA) (5.109 g, 0.050 mole) in 20 ml of 1,4-dioxane was added
formalin solution (8.303 g, 37% w/w aqueous, 0.100 mole). A
catalytic amount (~0.1 g) of hydrochloric acid was added and
stirred. To this mixture, 2-nitropropane (9.091 g, 0.102 mole) was
added and stirring was continued for 50 hours at 60°C. The reaction
mixture was cooled, neutralized with 1 g of NaOH and extracted with
3x30 ml of methylene chloride. The combined organic phase was dried
over MgSO^ overnight, filtered and evaporated to yield a yellow oil
(7.55 g, 49.7%).

22
Procedure B: To a solution of 2-nitropropane (4.546 g, 0.051
mole) in 20 ml of 1,4-dioxane at 0-5°C (in an external ice bath) was
added formalin solution (4.015 g, 37% w/w aqueous, 0.0495 mole) and
potassium carbonate (0.235 g). The ice bath was removed and the
mixture was stirred at room temperature for 45 hours. Then N,N-
dimethyl-l,3-propanediamine (2.555 g, 0.025 mole) in 10 ml of
1,4-dioxane was added. The reaction mixture was brought to reflux
and extracted with 3x40 ml of ether. The combined organic phase was
dried over MgSO^ overnight, filtered and evaporated to yield yellow
oil (1.87 g, 24.6%).
Procedure C: To an ice-cooled 250 ml round-bottomed flask
containing 2-nitro-2-methyl-propanol (11.91 g, 0.1 mole) in 25 ml of
’water was slowly added N,N-dimethyl-l,3-propanediamine (5.109 g,
0.050 mole) in 20 ml of 1,4-dioxane. After the addition was
complete, the solution was stirred at 0-5°C for 1 hour, then at 60-
70°C for 18 hours. This was extracted with 3x30 ml of methylene
chloride, and the combined organic phase was dried over MgS04,
filtered and evaporated to yield a yellow oil (7.73 g, 50.9% yield).
Analysis, calculated for C^l^gN^: C, 51.31; H, 9.21; N,
18.42. Found: C, 51.18; H, 9.13; N, 18.52.
XH NMR (CDC13,TMS): 6 1.55 (s,12H), 2.15 (m,2H), 2.19 (s,6H),
2.6 (m,4H), 3.08 (m,4H).
13C NMR (CDC13,77.0): 6 22.41, 24.22, 45.08, 52.68, 57.02,
63.89, 88.45.
IR (Neat): 3350 (m,br), 2995 (s), 2950 (s), 2870 (s), 2830 (s),
2790 (s), 1540 (s), 1470 (s), 1400 (m), 1375 (s), 1350 (s), 1285

23
(m,br), 1200 (w), 1160 (m,sh), 1080 (m), 1040 (m), 1025 (m), 990 (w),
950 (w), 910 (w), 860 (s), 820 (m,sh), 750 (w,br), 650 (w) cm'1.
N,N'-Bis(2-methy1-2-nitro-l-propyl)piperazine (13)
In a 100 ml 3-necked round-bottomed flask equipped with a
dropping funnel charged with 1,4-dioxane, a stirrer and a Dean-Stark
trap were placed 2-nitropropane (1.72 g, 0.02 mole), formalin
solution (1.62 g, 37% w/w aqueous, 0.02 mole) and piperazine (0.86 g,
O.01 mole) in 20 ml of 1,4-dioxane. A catalytic amount (~0.5 ml) of
sodium hydroxide solution (10% w/v, aqueous) was added and the
reaction mixture was brought to reflux. The solvent was added from
the dropping funnel to keep the volume constant. When the boiling
point of the azeotropic mixture reached 100°C, addition of solvent
was stopped and the volume of the reaction mixture was reduced to
~V2 of the original volume. Petroleum ether was added to this
reaction mixture and the upper layer was decanted. The resulting oil
was crystallized from acetone to yield a yellowish white powder (1.98
g, 71.2% yield).
Analysis, calculated for C12Hi4N4°4: c> 50.00; H, 8.33; N,
19.44. Found; C, 49.78; H, 8.90; N, 19.32.
XH NMR (CDC13,TMS): 5 1.54 (s,12H), 2.47 (s,8H), 2.83 (s,4H).
13C NMR (CDC13,77.0): 6 24.072, 55.117, 65.669, 88.648.
IR (KBr): 2940 (m,sh), 2860 (w,sh), 2800 (m,sh), 2740 (w,sh),
1700 (w), 1560 (s), 1455 (m), 1400 (m), 1370 (m,sh), 1340 (s), 1320
(s), 1285 (w), 1235 (w), 1190 (w), 1155 (s), 1115 (m), 1015 (m), 990
(w), 945 (w,sh), 890 (w), 855 (h), 830 (m,sh), 640 (w) cm-1.

24
2-Methyl-2-nitro-l,3-bis
N'-(8-hydroxy-ethyl)-N-
piperazino
propane (24]
Procedure A: To a formalin solution (3.28 g, 0.0404 mole) were
added nitroethane (1.501 g, 0.0200 mole) and N-(e-hydroxyethyl)-
piperazine (5.208 g, 0.0400 mole). Sodium hydroxide solution (5% w/v
aqueous, 1 ml) was added to this mixture. Upon addition, an
exothermic reaction occurred immediately and a white precipitate
formed, which was not soluble in 1,4-dioxane. Petroleum ether was
added to this mixture, and the solid was filtered and dried to yield
white crystals (5.34 g, 74.4% yield) which were recrystallized in
acetone, m.p. 118-120°C.
Procedure B: In a 100 ml round-bottomed flask was placed a
solution of N-(8-hydroxyethyl)piperazine (5.209 g, 0.04 mole) in 20
ml of 1,4-dioxane with sodium hydroxide solution (5% w/v aqueous, 1
ml). To this solution was slowly added a mixture of formalin
solution (37% w/w aqueous, 3.28 g, 0.04 mole) and nitroethane (1.502
g, 0.02 mole) in 10 ml of 1,4-dioxane. This reaction mixture was
brought to reflux for 2 hours, then the solvent was distilled until
the volume of the remainder became ~25 ml. Upon cooling, a yellowish
white precipitate formed after which petroleum ether (~50 ml) was
added with stirring; the precipitate which formed was filtered and
dried under reduced pressure to yield 5.94 g (82.7% yield) of
yellowish white crystals. Recrystallization from acetone gave white
crystals of mp 118-120°C.
Analysis, calculated for C16H33N504: C, 53.46; H, 9.25; N,
19.48. Found: C, 52.96; H, 9.34; N, 19.01.

25
:H NMR (CDC13,TMS): 5 1.59 (s,3H), 2.51 (s,20H), 2.78 (d of
d,4H), 3.59 (t,4H).
13C NMR (COCI3*77.0): 6 19.32, 53.0Ü, 55.02, 57.68, 59.11,
63.45, 92.52.
IR (Kbr): 3320 (s,Br), 2950 (s,sh), 2910 (m), 2905 (m), 2885
(m), 2805 (s,sh), 2700 (m), 1530 (s), 1460 (m), 1420 (w), 1400 (m),
1380 (m), 1360 (m), 1340 (m), 1330 (s,sh), 1280 (in), 1225 (w), 1160
(s), 1120 (m), 1100 (m,sh), 1060 (m,sh), 1050 (m), 1040 (m), 1010
(s), 990 (w), 965 (w), 930 (w), 920 (w), 870 (w), 860 (m), 840 (w),
830 (w,sh), 770 (w,sh) cm--*-.
2-Ethyl-2-nitro-l,3-bis{N‘-(g-hydroxyethy1)-N-
piperazinyljpropane (25)
This material was prepared by the methods reported for compound
(24).
Procedure A: To a solution of N-(8-hydroxyethyl)piperazine
(5.208 g, 0.04 mole) in 20 ml of 1,4-dioxane was added a mixture for
formalin solution (37% w/w aqueous, 3.28 g, 0.04 mole) and 1-
nitropropane (1.782 g, 0.02 mole) in 10 ml of 1,4-dioxane. Sodium
hydroxide solution (5% w/v aqueous, 1 ml) was added and the mixture
was refluxed for 2 hours. The azeotropic mixture of 1,4-dioxane and
H2O was distilled until the volume of the remaining solution became
25 ml. The resulting dark brown oil was crystallized from acetone to
yield a white flaky solid (3.9 g, 69.9% yield) which turned out to be
methylenebis[ii1-(8-hydroxyethyl )]-N-piperazine (26). The filtrate
was evaporated to yield a brown oil (1.03 g, 13.8% yield) which was
crystallized from acetone. The yellowish white crystals obtained
were the desired product, m.p. 98-101°C.

26
Procedure B: A solution of N-(0-hydroxyethyl)piperazine (5.226
g, 0.0041 mole) in 10 ml of THF was slowly added to a solution of 2-
ethyl-2-nitro-1,3-propanediol (2.984 g, 0.02 mole) with NEt-j (0.82 g)
in 10 ml of THF. The reaction mixture was refluxed for 23 hrs and
cooled to room temperature. The solvent was removed under reduced
pressure to yield a yellow oil which was dried over molecular sieves
(4 A) for 20 hours at ~0°C. During this time, white crystals formed
which were filtered and dried (2.611 g, 35.2% yield).
lH NMR (CDC13,TMS): 5 0.86 (t,3H), 2.02 (q,2H), 2.49 (s,20H),
2.87 (s,4H), 3.60 (t,4H).
13C NMR (DMS0-d6,39.5): 6 7.97, 24.19, 51.05, 53.17, 54.24,
58.39, 60.14, 94.87.
IR (KBr): 3300 (s,br), 2960 (s), 2940 (s), 2880 (s), 2820
(s,sh), 1700 (w), 1530 (s), 1460 (s), 1445 (m), 1420 (w), 1390 (m),
1365 (m), 1345 (s), 1330 (s), 1305 (s,sh), 1280 (m,sh), 1230 (w),
1205 (w), 1190 (w), 1160 (s), 1140 (m), 1120 (m,sh), 1090 (m,sh),
1050 (m), 1040 (s), 1005 (s), 990 (w), 930 (m,sh), 890 (w), 880 (w),
860 (m), 830 (m), 810 (w), 770 (m), 720 (w), 700 (w,br), 660 (w), 630
(w) cm"-*-.
Methylene-bis{N‘-(8-hydroxyethyl)-N-piperazine} (26)
A formalin solution (37% aqueous, 0.8116 g, 0.01 mole) was added
to a solution of N-(g-hydroxyethyl)piperazine (2.604 g, 0.02 mole) in
10 ml of 1,4-dioxane. A sodium hydroxide solution (10% w/v aqueous,
2 ml) was added to this mixture followed by an additional 10 ml of
1,4-dioxane. This reaction mixture was refluxed for 3 hours, then
cooled to room temperature. Petroleum ether was added and the upper

27
layer was decanted. The resulting yellow oil was crystallized from
cold acetone to yield white flaky crystals (2.4 g, 88.2% yield), m.p.
134-135.5°C.
Analysis, calculated for C13H23N4O2: C, 57.32; H, 10.36; N,
20.57.
Found: C, 57.06; H, 10.33; N, 20.48.
:H (CDC13,TMS): <5 2.52 (s,20H), 2.93 (s,2H), 3.63 (t,4H).
13C (CDC13,77.0): 6 51.32, 52.88, 57.75, 59.50, 80.70.
IR (KBr): 3300 (s,Br), 2960 (s), 2940 (s), 2820 (s.sh), 1580
(w), 1510 (w), 1460 (m.sh), 1420 (m), 1370 (m), 1350 (s), 1320
(m,sh), 1290 (m,sh), 1270 (m), 1190 (m), 1170 (s,sh), 1140 (m), 1080
(m), 1060 (m), 1010 (m,sh), 930 (m,sh), 880 (w), 815 (m,sh), 770 (w)
cm-3.
2-Methyl-2-nitro-l,3-dipiperidinopropane (12b)
In a 500 ml round-bottomed flask equipped with a condenser was
placed a solution of 2-methyl-2-nitro-1,3-propanediol (40.439 g,
0.299 mole) in 250 ml of THF. A solution of piperidine (50.980 g,
0.599 mole) in 50 ml of THF was added, and the mixture was stirred
for 36 hours at room temperature, followed by evaporation of the
solvent. The resulting light yellow, viscous oil was crystallized in
cold methanol to yield white crystals (68.7 g, 85.3% yield).
Analysis, calculated for C34H27N3O2: C, 62.42; H, 10.10; N,
15.60. Found: C, 62.48; H, 10.13; N, 15.60.
lH NMR (CDC13,TMS): 6 1.43 (m,12H), 1.57 (s,3H), 2.40 (m,8H),
2.73 (m,4H).

28
13C NMR (CüCl3,77.0): 6 13.9o, 23.88, 26.24, 56.53, 64.47,
93.06.
IR (KBr): 2930 (s), 2840 (m), 2730 (m,sh), 2340 (w), 1540 (s),
1440 (m,sh), 1380 (w), 1330 (m), 1295 (w), 1270 (w), 1150 (m), 1100
(m), 1090 (m), 1045 (m,sh), 1035 (m), 995 (m), 940 (w), 850 (m,sh),
880 (w), 790 (w), 775 (w) cm'1.
2-Methyl-2-nitro-l,3-bis(dimethy1amino)propane (27)
The following procedure was adopted from Johnson.13 In a 500 ml
Erlenmeyer flask was placed a mixture of 2-methyl-2-nitro-l,3-
propanediol (19) (67.56 g, 0.5 mole) and dimethylamine (40% aqueous,
112.73 g, 1 mole) and left in the refrigerator for 20 hours. A
reaction took place and phase separation occurred, the top layer
being solid. Ethyl ether (200 ml) was added and the aqueous phase
was separated, and washed with 50 ml of ether. The combined ether
layer was dried over K2CO3, filtered and evaporated to yield a yellow
liquid (81.6 g, 86.2% yield) which later solidified, m.p. 30-31°C
[literature m.p. 32°C].
XH NMR (CDC13,TMS): 6 1.61 (s,3H), 2.22 (s,12H), 2.74 (m,4H).
13C (COCI3,77.0): 6 18.91, 47.49, 65.33, 92.53.
IR (Neat): 2940 (s), 2860 (m), 2795 (s,sh), 1525 (s.sh), 1450
(s), 1390 (w), 1370 (m), 1325 (s,sh), 1280 (m), 1150 (s,sh), 1090
(m), 1040 (m,sh), 1005 (s), 920 (w.sh), 850 (m), 810 (w), 790 (w),
650 (w) cm-1.
2-Ethyl-2-nitro-N,N'-bis(2-methyl-2-propano-
1-propyl)amine (2BT
This material was prepared as described earlier for the case of
(27) by allowing 2-ethyl-2-nitro-1,3-propanediol (20) (74.58 g, 0.05

29
mole) and dimethylamine (40% w/w aqueous, 112.74 g, 1 mole) to react
overnight in a refrigerator. A reaction took place and a non-aqueous
phase separated. The aqueous phase was extracted with 3x30 ml of
ethyl ether and the combined organic phase was dried over I^CO^,
filtered and evaporated to yield a greenish yellow oil (83.4 g, 82.2%
yield). An attempt at further purification by vacuum distillation
failed due to the decomposition of the compound.
lH NMR (CDC13,TMS): 6 0.89 (t,3H), 2.07 (q,2H), 2.21 (s,12H),
2.74 (s,4H).
13C NMR (COCI3,77.0): 6 8.11, 24.43, 47.19, 61.29, 95.05.
IR (Neat): 2980 (m), 2950 (m), 2860 (m,sh), 2825 (m), 2780 (s),
1535 (s), 1460 (s,sh), 1385 (w), 1340 (m,sh), 1270 (w), 1150 (w),
1100 (w), 1040 (m,sh), 870 (w), 850 (w), 835 (w), 795 (w) cm-1.
N,Nl-Dimethyl-N,N'-bis(2-methyl-2-nitro-l-propyl)-
ethylenediamine (29)
In a 100 ml round-bottomed flask equipped with a condenser was
placed a solution of N,N'-dimethylethylenediamine (3.717 g, 0.0422
mole), 2-nitropropane (7.521 g, 0.0844 mole) and formalin solution
(37% w/w aqueous, 6.845 g, 0.0844 mole) in 50 ml of 1,4-dioxane. A
catalytic amount of potassium hydroxide (33% aqueous, 1 ml) was
added, and the reaction mixture was heated to reflux for 2 hours.
The solvent (azeotropic mixture of 1,4-dioxane and water) was
distilled with constant addition of fresh 1,4-dioxane until the
boiling point of the azeotropic mixture reached 100°C. The resulting
viscous, yellow liquid crystallized upon cooling. This crude product
was dissolved in 125 ml of ethyl ether, washed with 3x30 ml of water,

30
dried over K2CO3 overnight, filtered and evaporated to yield white
crystals (6.8 g, 55.6% yield), m.p. 63-64.5°C.
Analysis calculated for Ci2^26^4^4: 49.63; H, 9.03; N,
19.30. Found: C, 49.67; H, 9.04; N, 19.22.
:H NMR (CDC13,TMS): <5 1.55 (s,12H), 2.28 (s,6H), 2.47 (s,4H),
2.84 (s,4H).
13C NMR (CDC13,77.0): 6 23.88, 44.36, 57.93, 67.08, 88.91.
IR (KBr): 2980 (s,sh), 2860 (rn), 2820 (s,sh), 1530 (s), 1470
(m), 1455 (m), 1435 (m), 1400 (m), 1375 (rn.sh). 1340 (s,sh), 1260
(m), 1240 (w), 1200 (m.sh), 1160 (w), 1100 (m,sh), 1040 (s), 1020
(m), 730 (w), 980 (w), 945 (w), 860 (m), 850 (m), 820 (w,sh) cm-1.
N,N1-Dimethyl-N,N1-bis(2-methyl-2-nitro-l-propyl)-2-
butene-1,4-diamine (30)
In a 250 ml round-bottomed flask equipped with a condenser was
placed a solution of N,N‘-dimethyl-2-butene-l,4-diamine (3.342 g,
O.0293 mole) in 100 ml of 1,4-dioxane. Formalin solution (37% w/w
aqueous, 5.227 g, 0.0644 mole), 2-nitropropane (5.655 g, 0.0635 mole)
and potassium hydroxide (33% w/w aqueous, 3 ml) were added and the
reaction mixture was brought to reflux for 2 hours followed by
distillation of the azeotropic mixture of 1,4-dioxane and water with
constant addition of fresh dioxane. When the temperature of the
outcoming vapor reached 100°C, the addition of dioxane was stopped,
and the distillation was stopped when the residual reaction mixture
became cloudy. Ethyl ether (150 ml) was added, the solid portion was
filtered, and the filtrate was evaporated to yield a viscous yellow
oil (7.88 g, 85.1% yield). Storage overnight in a refrigerator

31
resulted in a yellow-white solid which was recrystal 1ized from
methanol to yield white crystals, m.p. 62-53°C.
Analysis, calculated for C, 53.14; H, 8.92; N,
17.71. Found: C, 53.23; H, 8.95; N, 17.68.
lH NMR (CDC13,TMS): 6 1.55 (s,12H), 2.25 (s,6H), 2.85 (s,4H),
3.03 (m,4H), 5.52 (m,2H).
13C NMR (CDC13,77.0): 5 24.20, 44.15, 61.35, 65.33, 88.85,
130.41.
IR (KBr): 2980 (s,sh), 2960 (m), 2920 (m,sh), 2860 (m,sh), 2940
(m), 2780 (s,sh), 1530 (s,sh), 1450 (s,sh), 1410 (w), 1395 (m), 1380
(m), 1370 (s), 1340 (s,sh), 1310 (m), 1255 (w.sh), 1210 (w), 1195
(w), 1165 (w), 1120 (m,sh), 1080 (w), 1040 (s), 1015 (w), 985 (s),
975 (m), 970 (m), 910 (w), 855 (s), 815 (w), 730 (w), 670 (w) cm'1.
N,N1-Dimethyl-N,N1-bis(2-methyl-2-nitro-l-propyl)-
hexamethylenediamine (31)
This compound was prepared by the procedure previously described
for the case of (30). N,N'-Dimethyl-hexamethylenediamine (1.561 g,
O.0108 mole), formalin solution (37% aqueous, 1.926 g, 0.0237 mole)
and 2-nitropropane (1.939 g, 0.0218 mole) were allowed to react in
the presence of potassium hydroxide (33% aqueous, 1 ml) to afford
yellow oil (2.14 g, 57.2% yield).
Analysis, calculated for C16Hg4N404: C, 55.46; H, 9.89; N,
16.17. Found: C, 55.52; H, 9.91; N, 16.23.
NMR (COClg.TMS): 6 1.30 (s,8H), 1.58 (s,12H), 2.26 (s,6H),
2.42 (m,4H), 2.83 (s,4H).
13C NMR (CDC13,77.0): 6 23.97, 26.78, 27.33, 43.74, 59.70,
66.57, 88.77.

32
IR (KBr): 2990 (m), 2940 (s), 2860 (s), 2790 (s,sh), 1680 (w),
1640 (w), 1540 (s), 1460 (s,sh), 1400 (m), 1370 (m), 1345 (m), 1320
(m), 1240 (m), 1120 (m), 1050 (m,sh), 940 (w), 910 (w), 860 (m), 820
(w), 800 (w,sh), 730 (w,sh) cm-1.
Reactions Utilizing Chain-Stopping Reagents
General Procedure A: In a round-bottomed 3-necked flask
equipped with a Dean-Stark trap and a dropping funnel charged with
fresh 1,4-dioxane was placed the mixture of the starting materials,
i.e., amine component, formalin solution and nitroalkane in 1,4-
dioxane. A catalytic amount of sodium hydroxide was added and the
azeotropic mixture of 1,4-dioxane and water was distilled off with
constant addition of fresh 1,4-dioxane. When the temperature of the
outcoming vapor reached 100°C, the addition was stopped and the
volume of the residual mixture was reduced to half of the original
volume by continuous distillation. Petroleum ether was added to the
reaction mixture and the upper layer was decanted. The resulting oil
was crystallized from acetone or methanol. The feed ratio of the
starting materials and reaction conditions are described in Chapter
III, p. 62.
General procedure B: In a round bottom flask equipped with a
condensor was placed the mixture of the methylol derivative of the
nitroalkane and the amine in THF. A catalytic amount of
triethylamine and 4 A molecular sieves were added. The reaction
mixture was refluxed for 10-15 hours, cooled and filtered. The
filtrate was evaporated to yield a yellow oil, which was crystallized

33
from acetone or methanol. The feed ratio of the starting materials
and reaction conditions are described in Chapter III, p. 62.
Synthesis of Polymers
Polymerization of 2-methyl-2-nitro-1,3-propanediol (19)
with N,N-dimethyl-l,3-propanediamine (32)
In a 100 ml ice-cooled round-bottomed flask was placed a
solution of 2-methyl-2-nitro-1,3-propanediol (19) (13.512 g, 0.10
mole) in 30 ml of 1,4-dioxane. To this, freshly distilled N,N-
dimethyl-1,3-propanediol (10.218 g, 0.10 mole) 30 ml of H20 and HC1
(6N,lml) was added. After the addition was complete, the reaction
mixture was stirred for 1 hour at 0-5°C, followed by 16 hours at
70°C. The reaction mixture was cooled, made basic with sodium
hydroxide (pH 10~11), and extracted with 3x50 ml of methylene
chloride. The combined organic phase was dried over K2CO3, filtered
and evaporated under reduced pressure to yield a dark brown, viscous
oil (14.23 g, 70.7% yield).
NMR (CDC13,TMS): 5 3.7 (s,4H), 2.75 (m,4H), 2.22 (s,6H), 1.6
(m,2H), 1.56 (s,3H).
13C NMR (C0C13,77.0): 5 24.44, 25.17, 45.10, 51.78, 56.90,
58.02, 58.85, 85.80.
IR (Neat): 2940 (s), 2880 (m), 2850 (s), 2810 (s), 2760 (s),
1540 (s), 1450 (s), 1380 (m,sh), 1340 (m), 1320 (w,sh), 1250 (m,sh),
1210 (m), 1150 (w,sh), 1120 (s,sh), 1080 (m), 1040 (m,sh), 965 (w),
910 (w), 880 (m), 870 (s), 840 (m), 730 (w,sh), 705 (w) cm'1.

34
Polymerization of (20) with N,N-dimethyl-l,3-propanediarnine (33)
This material was prepared by the same procedure described for
(32). Thus, 14.915 g (0.10 mole) of (20) was reacted with 10.213 g
(0.10 mole) of N,N-dimethyl-1,3-propanediol to yield a dark brown oil
(13.75 g, 63.8% yield).
lH NMR (CDC13,TMS): 6 3.7 (s,4H), 2.7 (m,4H), 2.25 (s,6H), 1.75
(m,4H), 0.85 (t,3H).
13C NMR (CDC13,77.0): <5 7.09, 24.50, 30.83, 45.06, 51.88,
56.90, 57.84, 87.21.
IR (Neat): 2980 (s), 2940 (s), 2880 (in), 2860 (m), 2820 (s),
2770 (s,sh), 1540 (s), 1460 (s,sh), 1375 (m,sh), 1360 (m), 1345 (m),
1325 (m,sh), 1270 (m,sh), 1215 (m), 1155 (w), 1110 (m,sh), 1040
(m,sh), 1015 (w), 970 (w,Br), 920 (w), 890 (w), 845 (m), 310 (w), 780
(w), 750 (w), 720 (w) cm-1.
Polmerization of (19) with N,N1-dimethylethylenediamine (34)
In a 100 ml round-bottomed flask equipped with a condenser was
added a solution of (19) (8.665 g, 0.0641 mole) in 20 ml of THF and
N,N*-dimethylethylenediamine (5.653 g, 0.0641 mole). To this
solution were added a catalytic amount of NEt3 (1 ml) and 4 A
molecular sieves. The reaction mixture was brought to reflux for 20
hours, cooled and filtered. The filtrate was evaporated under
reduced pressure to yield a brown, viscous oil (9.73 g, 81.0% yield).
Analysis, calculated for CgHjjN-^: C, 51.33; H, 9.09; N,
22.45. Found: C, 50.45; H, 9.02; N, 22.39.
lH NMR (CDC13,TMS): « 1.49 (s,3H), 2.41 (s,6H), 2.58 (s,4H),
3.09 (m,4H).

35
13C NMR (COCI3,77.0): 624.46, 48.10, 60.53, 65.01, 90.70.
IR (Neat): 3370 (m,br), 2980 (m), 2940 (m), 2870 (m), 2820 (m),
2800 (m), 2780 (m,sh), 1670 (m), 1645 (m), 1635 (m), 1535 (s), 1455
(s), 1395 (m), 1345 (m.sh), 1290 (m), 1270 (w), 1225 (w), 1165 (w),
1130 (w,Br), 1085 (m), 1040 (m,sh), 955 (w), 945 (w), 855 (m), 830
(w) cm-x.
Polymerization of (19) with DMBA (35)
The procedure employed for the polymer (34) was followed; thus,
compound (19) (13.860 g, 0.1026 mole) was allowed to react with DMBA
(11.714 g, 0.1026 mole) in the presence of NEt3 (3 nil) and molecular
sieves (4 A). The resulting yellow solid (14.68 g, 67.12 yield) was
dissolved in THF and reprecipitated in methanol to yield a white
powder.
Analysis, calculated for Cioh19n3°2: C, 56.31; H, 8.98; N,
19.70. Found: C, 54.99; H, 8.84; N, 19.04.
XH NMR (CDC13,TMS): 6 1.50 (s,3H), 2.21 (s,6H), 3.0 (m,3H),
5.53 (s,2H).
13C NMR (C0C13,77.0): 6 19.06, 44.15, 61.45, 63.26, 93.13,
130.37.
IR (KBr): 2940 (m,sh), 2840 (m,sh), 2780 (s), 1530 (s), 1450
(s), 1335 (m,sh), 1120 (w,sh), 1070 (w,br), 1020 (s), 975 (m,sh), 855
(m,sh) cm_X.
Polymerization of (19) with DMHA (36)
The procedure employed for the polymer (34) was followed; thus,
compound (19) (5.157 g, 0.0332 mole) was allowed to react with DMHA

36
(5.516 g, 0.0382 mole) in THF in the presence of NEt3 and 4 A
molecular sieves to yield a brown oil (6.43 g, 69.1% yield).
Analysis, calculated for Ci2^25^3®2: 59.23; H, 10.36; N,
17.27. Found: C, 57.62; H, 9.83; N, 17.36.
lH NMR (C0C13,TMS): 6 1.33 (s,8H), 1.59 (s,3H), 2.24 (s,6H),
2.43 (s,4H), 2.81 (m,4H).
13C NMR (CDC13,77.0):6 18.86, 26.95, 27.29, 43.86, 59.89, 64.57,
93.33.
IR (Neat): 2940 (s,sh), 2850 (s), 2790 (s), 1535 (s,sh), 1450
(s,sh), 1420 (w), 1390 (m,sh), 1340 (m.sh), 1240 (w,br), 1120 (w),
1050 (m,br), 1020 (m), 940 (w), 850 (m,sh), 730 (w) cm"1.
Polymerization of (27) with OMEA (34)
Procedure A: The following procedure was modified from the
method reported by Angeloni and coworkers.25,27 ¡n a iqo ml 3 necked
round-bottomed flask equipped with a stirrer, a condenser and a gas
inlet tube was placed a solution of compound (27) (8.057 g, 0.0426
mole) and DMEA (3.753 g, 0.0426 mole) in 70 ml of 95% ethanol.
Nitrogen gas was bubbled through the solution for 120 hours at room
temperature with constant stirring. During this period, the color of
the solution changed from yellow to dark brown. The solvent was
evaporated under reduced pressure to afford a dark brown, viscous oil
(6.07 g, 76.2% yield), which was identical with the polymer obtained
from the compound (19) and DMEA.
Procedure B: Procedure A was modified as follows: compound
(27) (7.408 g, 0.0391 mole) and DMEA (3.455 g, 0.0392 mole) were
dissolved in 50 ml of DMS0, and placed in a 100 ml round-bottomed

3/
flask. Nitrogen gas was passed through the solution for 70 hours at
70°C. Upon heating, the color of the solution changed slowly to dark
brown. The solvent was removed by means of reduced pressure to yield
a dark brown, viscous oil (5.14 g, 70.2% yield) which was identical
with the polymer obtained from procedure (A).
Polymerization of (27) with DMBA (35)
For the preparation of this polymer, procedure (B) of the
polymer (34) was utilized. Thus, compound (27) (17.160 g, 0.0907
mole) and DMBA (10.356 g, 0.0907 mole) were allowed to react in DMS0
under N2 flow. After 70 hours at 70-80°C, the reaction mixture was
poured into ice-water to yield a light brown solid (12.4 g, 64.1%
yield). The IR, and 13C NMR spectra were identical with those of
the material obtained from the reaction between the compound (19) and
DMBA.
Polymerization of (27) with DMHA (36)
Preparation of this polymer was achieved by the procedure (A) of
the polymer (34). Thus, compound (27) (3.407 g, 0.0180 mole) and
DMHA (2.598 g, 0.0180 mole) were dissolved in 60 ml of 95% ethanol
and stirred for 96 hours at room temperature with a continuous flow
of N2 gas. The resulting solution was evaporated under reduced
pressure to yield a brown oil (2.88 g, 65.7% yield). The IR, *H and
13
C NMR spectra of which were identical with those of polymer (36)
from the reaction of (19) with DMHA.

38
Polymerization of (27) with piperazine (37)
Procedure A: In a 250 ml 3-necked round-bottomed flask equipped
with a condenser, a stirrer and a gas inlet tube was placed a
solution of compound (27) (11.11 g, 0.0587 mole) and piperazine (5.06
g, 0.0587 mole) in 100 ml of 95% ethanol. This reaction mixture was
stirred for 60 hours at room temperature followed by 24 hours at 50-
60°C, with continuous flow of ^ gas. During the reaction time, a
white precipitate formed. After the reaction mixture was cooled, the
solid, which is insoluble in most of the common organic solvents, was
collected (7.58 g, 69.7% yield).
Procedure B: In a 100 ml 3-necked round-bottomed flask equipped
with a condenser, stirrer and a gas inlet tube was placed a solution
of compound (27) (7.641 g, 0.0404 mole) and piperazine (3.480 g,
0.0404 mole) in 75 ml of DMS0. The reaction mixture was stirred for
60 hours at 70°C with a continuous flow of N2 gas. The reaction
mixture, which became a dark brown liquid and a yellow precipitate,
was poured into 400 ml of cold methanol. The solid was filtered,
washed with cold methanol and dried in a vacuum oven to yield an off-
white powder (5.49 g, 73.4% yield).
Analysis, calculated for C8H15^2: C, 51.87; H, 8.16, N,
22.69. Found: C, 54.98; H, 9.04; N, 24.66.
IR (KBr): 2940 (m), 2870 (m), 2800 (s.sh), 1530 (s), 1460
(s,sh), 1400 (w), 1375 (m), 1330 (s,sh), 1280 (m), 1150 (m,sh), 1100
(m), 1070 (w), 1040 (w), 1010 (s), 925 (w), 855 (m,sh), 815 (w), 650
(w) cm--*-.

39
Reduction of Model Compounds
Reduction of compound (12b) (38)
Procedure A: The procedure reported by Parham and Ramp35 was
employed as follows: In a 100 ml 3-necked round-bottomed flask
equipped with a dropping funnel and a condenser was placed an etheral
solution of lithium aluminum hydride (4 g). A solution of compound
(12b) (8.87 g, 0.0329 mole) in 50 ml of absolute ether was added
dropwise from the dropping funnel under N2 atmosphere, and the
reaction mixture was heated at reflux for 1 hour after the addition
was complete. Water was added dropwise until the excess LiAlH^ was
decomposed, and the solution was made alkaline. The attempt to
distill the amine with steam failed. Extraction with ether yielded
an unidentifiable mixture.
Procedure 3: In a 1000 ml Erlenmeyer flask was placed a
solution of sodium borohydride (5 g) in 250 ml methanol with
stirring. A solution of compound (12b) (1.68 g, 0.00624 mole) in 40
ml of chloroform was added dropwise after the addition of (a cata¬
lytic amount of) palladium on charcoal. When the bubbling had
ceased, additional sodium borohydride was added. This process was
repeated several times. After the addition was complete, the
reaction mixture was stirred for 1 hour at room temperature followed
by the addition of hydrochloric acid (1 N aqueous). When the reac¬
tion mixture became acidic on to pH paper, the solid (charcoal) was
filtered. The filtrate was condensed under reduced pressure to yield
a light yellow liquid. To this solution, sodium carbonate was added
until the formation of CO2 bubbles ceased (pH ~8). The resulting

40
solution was extracted with 3x100 ml of methylenechloride and the
combined organic phase was dried over K2CO3, filtered and dried to
afford a pale yellow oil (1.04 g, 69.6% yield).
Procedure C: In a 250 ml pressure bomb was placed a suspension
of compound (12b) (4.23 g, 0.0157 mole) in 100 ml of DMF with Raney
Ni (3 g). The bomb was charged with hydrogen gas (400 psi) and
released 3 times before being charged upto 800 psi. The reaction
mixture was stirred for 4 hours at 60°C (pressure rose to 840 psi),
then 3 hours at room temperature. The catalyst (Raney Ni) was
filtered and the filtrate was evaporated under reduced pressure at
50°C to yield a yellow oil (3.14 g, 83.5% yield).
Analysis, calculated for C14H29N3: C, 70.24; H, 12.21; N,
17.55. Found: C, 70.14; H, 12.25; N, 17.51.
NMR (CDC13,TMS): 6 0.96 (s,3H), 1.43 (s,8H), 1.55 (s,4H),
2.14 (s,4H), 2.48 (m,8H).
13C NMR (CDCl3*77.0): 6 23.93, 25.05, 26.41, 54.97, 57.31,
67.35.
IR (Neat): 3350 (m,br,sh), 2935 (s), 2850 (s), 2780 (s,sh),
1570 (w), 1555 (w,sh), 1450 (m,sh), 1440 (m), 1380 (m), 1365 (m),
1345 (w), 1320 (m,sh), 1310 (m), 1300 (m), 1270 (w), 1260 (w), 1155
(m), 1110 (s,sh), 1055 (m,sh), 1035 (m), 1000 (m), 945 (w,sh), 890
(w,sh), 860 (m), 790 (m,sh), 770 (w) cm-1.
Reduction of compound (28) (39)
In a 450 ml parr bomb equipped with a stirrer was placed a
solution of compound (28) (21.307 g, 0.105 mole) in 200 ml of
methanol with Raney Ni (5 g). The reaction mixture was flushed with
hydrogen gas for 2 hours before the pressure of the bomb was set at

41
1000 psi. The reactor was heated to 50°C for 2 hours, cooled and
filtered. The filtrate was evaporated to yield a yellow oil (8.37 g,
68.72 yield) which turned out not to be the desired product but
l-(N,N-dimethylamino)-2-butylamine (39).
Analysis, calculated for CgH^^: C, 62.01; H, 13.88; N,
24.11 Found: C, 62.11; H, 13.76; N, 24.18.
XH NMR (CDC13,TMS): 6 0.96 (t,3H), 1.42 (q,2H), 2.21 (s,6H),
2.80 (m,1H), 3.50 (d,2H).
13C NMR (CDC13,77.0): 6 10.23 (q), 28.41 (t), 45.57 (q), 49.71
(d), 66.57 (t).
IR (Neat): 3350 (s,br), 3280 (s,br), 2960 (s), 2940 (s), 2880
(s), 2860 (s), 2820 (s) 2770 (s,sh), 1660 (w), 1640 (w), 1600 (m,br),
1460 (m,sh), 1380 (w,sh), 1300 (w,br), 1265 (w), 1150 (w), 1100 (w),
1040 (m,sh), 975 (w), 910 (w), 850 (w), 780 (w) cm-1.
Reduction of Polymers
Reduction of Polymer (35) (40)
Procedure (C) previously described for model compound (27) was
employed. Thus, polymer (35) (8.20 g, 0.0438 mole) in methanol was
placed in a Parr bomb with a catalytic amount (~2 g) of Raney nickel
and the bomb was charged with hydrogen upto 800 psi. The closed
system was heated to 70°C for 15 hours to afford a brown oil (5.88 g,
85.42).
Analysis, calculated for C8H19N3: C, 61:10; H, 12.18; N,
26.72. Found: C, 60.07; H, 11.54; N, 26.10.
NMR (DMS0-d6,TMS): 6 0.87 (s), 2.23 (s), 2.44 (s), 3.16
(s,br), 3.44 (m).

42
13C NMR (DMS0-d6,39.5): 6 26.68, 48.76, 52.37, 60.46, 71.47.
IR (Neat): 3400 (s,br), 2950 (s), 2860 (s), 2820 (s), 1650
(m,br), 1600 (w,br), 1460 (m), 1380 (m), 1330 (w), 1300 (w), 1280
(m.sh), 1200 (w), 1170 (w), 1130 (m), 1090 (s), 1060 (m), 1040 (m),
960 (w,sh), 940 (w), 920 (w), 890 (w), 810 (m,br) cm"1.
Reduction of Polymer (36) (41)
Procedure A: Procedure (B) described previously for model
compound (27) was employed. Thus, polymer (36) (1.68 g, 0.0079 mole)
was reduced with NaBH^CN in the presence of a catalytic amount of
palladium-charcoal to yield a light yellow oil (1.16 g, 80.3%).
Analysis, calculated for C, 65.52; H, 11.55; N,
22.93. Found: C, 61.83; H, 10.75; N, 21.71
Procedure 3: Procedure (C) previously described for compound
(27) was applied. In a Parr bomb was placed a solution of polymer
(36) (2.017 g, 0.00946 mole) in 100 ml of DMF with a catalytic amount
of Raney nickel. The bomb was charged with hydrogen gas to 800 psi,
and heated to 50°C for 2 hours followed by 60°C for 6 hours. The
reaction mixture was then stirred overnight at room temperature and
the catalyst was filtered. The resulting liquid was evaporated under
reduced pressure at 50°C to afford a light brown oil (1.46 g, 84.3%).
Analysis, calculated for Ciq^I^: C, 65.52; H, 11.55; N,
22.93. Found: C, 64.21; H, 11.34; N, 22.20.
XH NMR (CDC13,TMS): 6 1.00 (s), 1.5 (m), 2.2 (s), 2.95 (m,br),
5.55 (s,br).
13C NMR (CDC13,77.0): 6 25.66, 45.27, 55.12, 60.87, 67.59,
130.37.

43
IR (Neat): 3340 (m,br), 3000 (s), 2920 (s), 2860 (s), 1700 (w),
1570 (s), 1490 (s), 1400 (m,br), 1380 (w,br), 1150 (m), 1070 (m,br),
1005 (m), 385 (m.br), 790 (w), 750 (w) cm"1.
Reduction of Polymer (37) (42)
Procedure (C) previously described for compound (27) was
applied. In a Parr bomb was placed a solution of polymer (37) (1.46
g, 0.006 mole) in 100 ml of 2-ethoxyethanol with a catalytic amount
of Raney nickel. The bomb was charged with hydrogen gas upto 800
psi, and heated to 60°C for 15 hours. The reaction mixture was
filtered and the filtrate was evaporated under reduced pressure to
yield a light yellow oil (1.1 g, 85.9%).
Analysis, calculated for Ci2^27N3: 67*55; H, 12.76; N,
19.69. Found: C, 66.16; H, 12.25; N, 19.02.
1H NMR (CDC13,TMS): 6 1.00 (s), 1.32 (s), 2.20 (s), 2.68
(s,br), 3.6 (m).
13C NMR (DMS0-d6,39.5): 6 26.83, 27.12, 45.15, 60.26, 65.52,
71.76.
IR (Neat): 3300 (m.br), 2940 (s.sh), 2860 (s), 2790 (s), 1675
(w), 1580 (w,br), 1460 (m), 1380 (m), 1350 (w), 1310 (w.br), 1270
(w,br), 1230 (w), 1120 (m.sh), 1070 (m,br), 890 (w), 850 (w,br), 730
(w) cm-1.
Methyl a ti on
Methylation of Polymer (41) (43)
Procedure A: The procedure reported by Pine and Sanchez3^ was
modified as follows: In a 50 ml round-bottomed flask was placed

44
polymer (96) (2.31 g, 0.0179 mole), and the flask was cooled in an
external ice bath. To this, formic acid (88% w/w aqueous, 3.6 g,
0.075 mole) was slowly added followed by formalin solution (37% w/w
aqueous, 5.1 g, 0.063 mole). The flask was equipped with a magnetic
stirrer and a condenser and placed in an 80°C constant temperature
bath for 26 hours. The mixture was cooled and 10 ml of 6 N HC1 was
added. This was then extracted with 3x20 ml of ethyl ether, and the
combined ether extracts were washed with 10 ml of H20 and dried over
K2CO3 overnight. Evaporation of ether gave a white solid (0.23 g).
The aqueous layer was made basic with sodium hydroxide (50% w/v
aqueous) and extracted with 3x20 ml of methylene chloride. The
combined organic layer was washed with 10 ml of ^0, and dried over
K2CO3. Filtration and subsequent evaporation yielded a light brown,
clear, viscous oil (1.52 g, 45.9% yield).
Procedure B: The method previously reported by Borch and
coworkers37,33 was applied. To a stirred solution of polymer (95)
(2.31 g, 0.0179 mole) and formaldehyde (37% w/w aqueous, 11 ml, 0.136
mole) in 40 ml of acetonitrile was added sodium cyanoborohydride
(NaBH3CH). Glacial acetic acid was added until the reaction mixture
showed the pH of 6. Stirring was continued for 10 hours and the
mixture was poured into 200 ml of ether. The resulting mixture was
washed with 4x75 ml of K0H solution (2 N) and 1x60 ml of saturated
NaCl solution. The combined K0H wash was backwashed with 100 ml of
ether. The combined ether layer was dried over K2CO3 overnight and
evaporated to yield a light brown clear, viscous oil (1.72 g, 51.9%).

45
Analysis, calculated for CjgHg;^: C, 64.31; H, 12.51; N,
22.68. Found: C, 63.55; H, 12.18; N, 22.07.
XH NMR (COCI3,TMS): 5 0.91 (s), 2.04 (s), 2.28 (s), 2.33 (s),
2.65 (m).
13C NMR (CDC13,77.0): 6 16.67, 36.94, 46.98, 59.12, 64.04,
93.01.
IR (Neat): 3320 (m,br), 2940 (s,sh), 2840 (s,sh), 2300 (s,sh),
1660 (m), 1450 (s), 1370 (m), 1350 (w), 1325 (w), 1280 (m), 1270
(m,sh), 1235 (w), 1195 (w), 1170 (w), 1145 (m), 1130 (m), 1090
(s,sh), 1060 (m), 1040 (m), 1010 (w), 975 (w), 960 (w), 940 (w), 905
(w), 890 (m), 810 (w,br), 750 (w) cm--1-.
Methylation of Polymer (42) (44)
Procedure (A) used for the methylation' of polymer (41) was
employed. Thus, polymer (41) (1.01 g, 0.0055 mole) was reacted with
formic acid (88$ aqueous, 1.5 g, 0.029 mole) and formaldehyde (37%
aqueous, 2.5 g, 0.031 mole) to yield a brown oil (0.57 g, 49.0%).
Analysis, calculated for Ci2^25M3: C, 69.19; H, 11.92; N,
19.88. Found: C, 66.55; H, 10.89; N, 19.72.
1H NMR (CDC13,TMS): 5 1.02 (s), 2.21 (s), 2.42 (s), 2.90 (m),
5.65 (rn).
13C NMR (CDC13,77.0): 6 18.33, 44.79, 45.13, 45.47, 61.56,
66.43, 93.53, 138.71.
IR (Neat): 3340 (w,br), 2940 (s.sh), 2850 (s), 2810 (s), 2735
(s), 1675 (w), 1645 (w), 1600 (w.br), 1540 (w), 1450 (s), 1360 (m),
1300 (w,br), 1260 (w), 1230 (w), 1170 (w), 1120 (m), 1095 (m), 1040
(s,sh), 1010 (m), 970 (m), 840 (w,sh), 770 (w) cm-1.

46
Miscellaneous Reactions
Nitroethy lene (Nitroethene) (45)
The following procedure was modified from the previously
reported procedure.39,40 A mixture of phthalic anhydride (99.0 g,
.66 mole) and 2-nitroethanol (45) (49.9 g, .548 mole) was placed in a
200 ml round bottom flask equipped with a fractionating column and
distillation head. The oil bath was heated to 140-150°C and pressure
was reduced to 70-30 mmHg. After the mixture became homogeneous, the
oil bath temperature was raised to 175-180°C until distillation
ceased. The distillate was dried over CaCl2 yielding a pale yellow
oil (35.8 g, 0.49 mole, 89% yield).
XH NMR (CDC13,TMS): 5 5.93 (d,lH), 6.64 (d,lH), 7.21 (d. of
d,lH).
13C NMR (CDC13,77.0): 6 122.2, 144.9.
Reaction of Nitroethene (45) with Formaldehyde and Diethylamine
The method reported by Tsuchida and Tomono was followed. In a
100 ml 3-necked round-bottomed flask fitted with a magnetic stirrer,
a thermometer, a reflux condenser and a dropping funnel was placed a
suspension of nitroethene (1.229 g, 0.0168 mole) in 15 ml of
methanol. Alternatively, diethylamine (1.231 g, 0.0168 mole) was
dissolved in 10 ml of methanol and then formalin solution (37% w/w
aqueous, 1.366 g, 0.0168 mole) was added with cooling. To this
mixture, 1.718 g (0.0168 mole) of acetic anhydride was added. The
thus prepared amine-formal in solution was added dropwise to the
nitroethene suspension at 0°C. The reaction mixture turned reddish
brown and yielded unidentifiable tar.

47
Reaction of Nitroethene with Formaldehyde and Dimethylamine
Hydrochloride
The method of Tsuchida and Tomono22 was employed. Thus, the
amine-formal in solution was prepared by adding formalin solution (37?
w/w aqueous, 1.334 g, 0.0164 mole) to dimethylamine hydrochloride
(1.344 g, 0.0165 mole) in 15 ml of DMF. This solution was added
slowly to the previously prepared nitroethene solution (1.200 g,
0.0164 mole) in 20 ml of DMF, and the reaction mixture was stirred
for 2 hours at 70°C. The resulting dark brown solution was
neutralized with sodium carbonate to yield dark brown tar.
Polymerization of Nitroethene (45) (46)
Freshly distilled THF was attached to a high vacuum line,
degassed twice and transferred to a polymerization tube. Nitroethene
was distilled with CaCl2 in the receiving flask and attached to the
line, degassed twice and transferred to the polymerization tube. The
previously purified pyridine (catalyst) was transferred to the
polymerization tube at -78°C. Polymerization was carried out in a
constant temperature bath (-73°C) for 1 hour. The tube was opened
and the contents precipitated into 1 N HC1 solution. The yellow
solid was collected, dissolved in DMF and reprecipitated in water.
The solid was again collected and dried in a vacuum oven (30°C)
overnight to afford an off-white powder.
Analysis, calculated for C2H3NO2: C, 32.83; H, 4.13; N,
19.17. Found: C, 32.92; H, 4.22; N, 19.10.
13C NMR (DMS0-d6,39.5):6 35.5, 81.1.
Intrinsic viscosity (DMF,25°C): [n] = 0.306 dl/g.

48
IR (KBr): 3000 (w), 2970 (w), 2890 (w), 1550 (s,sh), 1430 (m),
1330 (w), 1360 (m,sh), 1310 (w), 1230 (w), 1050 (w,br), 845 (m), 720
(w), 690 (w) cm"1.
Reaction of Compound (24) with Methyl Isocyanate (MI) (47)
In a 100 ml round-bottomed flask was placed a solution of
compound (24) (0.895 g, 0.00249 mole) in 20 ml of ÃœMF. A solution of
methyl isocyanate (MI) (1 ml, 0.017 mole) in 15 ml of DMF and a
catalytic amount of tin octoate (TO) (5 drops) were added dropwise
over a 10 minute period. After the addition was complete, which was
done under a nitrogen atmosphere, the reaction mixture was stirred
for 10 hours at room temperature. Additional MI (1 ml, 0.017 mole)
was added and stirring was continued for 10 hours at room
temperature. Evaporation of soluent gave a light brown, viscous
liquid (0.63 g, 53.4% yield).
:H NMR (DMS0-d6,TMS): 6 1.49 (s,3H), 2.36 (s,20H), 2.48 (s,4H),
2.64 (d,6H), 2.92 (m,4H), 3.97 (t,4H), 7.93 (s,2H).
13C NMR (DMS0-d6,39.5): 6 16.75, 30.73, 53.05, 54.51, 56.56,
61.04, 62.91, 92.53, 156.62.
IR (Neat): 3340 (m.br.sh), 2950 (m,sh), 2320 (in), 1680 (s,sh),
1530 (s,sh), 1460 (m), 1420 (m), 1380 (m), 1315 (m), 1260 (rn), 1215
(m), 1160 (m,br), 1095 (m), 1080 (m,sh), 1010 (w), 945 (w), 865 (w),
775 (w), 760 (w), 670 (w) cm"1.
Reaction of Compound (24) with Phenyl Isocyanate (PI) (48)
Procedure A: To a solution of compound (24) (1.797 g, 0.005
mole) and a catalytic amount (0.02 g) of freshly sublimed 1,4-
diazabicyclo(2,2,2)octane (DABC0) in 25 ml of anhydrous DMF was added

49
a solution of phenyl isocyanate (PI) (1.192 g, 0.010 mole) in 20 ml
of anhydrous DMF. After the addition, which was carried out under
nitrogen, was complete, the mixture was stirred for 24 hours at 60-
70°C under nitrogen. The reaction mixture was cooled to room
temperature and poured into ice-water to yield a white precipitate,
which was dried in a vacuum desiccator for 40 hours (2.36 g,
79.0%). The resulting solid was recrystallized from toluene to yield
a white powder.
Procedure B: The procedure described in (A) was used except the
catalyst, tin octoate (TO) (5 drops) was used instead of DA8C0. The
white powder (2.71 g, 90.7%), which was obtained, was identical with
the compound obtained from procedure (A).
Analysis, calculated for C3qH43N706: C, 60.28; H, 7.25; M,
16.41. Found: C, 59.56; H, 73.9; N, 15.30.
lH NMR (CDC13,TMS): 6 1.56 (s,3H), 2.4 (m,22H), 4.28 (t,4H),
7.1 (m,12H).
13C NMR (CDC13,77.0): 6 19.40 (q), 53.51 (t), 54.82 (t), 56.92
(t), 62.04 (t), 63.45 (t), 92.55 (s), 118.72 (d), 123.45 (d), 129.05
(d), 137.87 (s), 153.42 (s).
IR (KBr): 3630 (w), 3550 (w,br), 3330 (m,br), 3200 (w), 3140
(w), 3060 (w,sh), 3005 (w), 2950 (m), 2880 (w), 2320 (m), 1705
(s.sh), 1650 (w), 1600 (s), 1540 (s,sh), 1500 (in), 1460 (in), 1440
(s), 1405 (w), 1380 (w), 1360 (w), 1320 (s,sh), 1250 (s,sh), 1130
(w), 1155 (m), 1130 (w), 1085 (m,sh), 1060 (m), 1010 (m,sh), 940 (w),
900 (w), 850 (w,br), 755 (m,sh), 720 (w), 690 (m) cm"1-

50
Polymerization of Compound (24) with Hexarnethylene
Diisocyanate (HMD1) (49)
To a solution of HMDI (2.152 g, 0.0128 mole) in 15 ml of
anhydrous OMF were added a solution of compound (24) (4.599 g, 0.0128
mole) in 25 ml of anhydrous DMF and 10 drops of catalyst (TO). After
the addition, which was carried out under nitrogen, was complete, the
mixture was stirred under nitrogen at 40-45°C for 60 hours. During
this period, the reaction mixture turned cloudy. The resulting
yellow, cloudy liquid was poured into ice-water to afford a white
solid (6.1 g, 92%), which was extracted with ether overnight and then
dried under reduced pressure.
NMR (DMS0-d6,TMS): 6 1.27 (s), 1.52 (s), 2.36 (s), 2.89 (s),
3.90 (s), 4.32 (s).
13C NMR (DMS0-d6,39.5): 5 18.59, 26.15, 29.46, 30.09, 53.15,
54.56, 56.75, 60.99, 67.13, 92.62, 136.19.
IR (KBr): 3340 (s,br), 2940 (s), 2860 (s), 2820 (m), 1720
(s,sh), 1650 (s,sh), 1580 (s), 1560 (s), 1540 (s), 1520 (s,sh), 1480
(m), 1460 (m,sh), 1380 (w), 1340 (m,sh), 1250 (s,br), 1160 (m,br),
1010 (m,sh), 930 (w), 860 (w), 775 (w), 730 (w) cm"1.
Polymerization of Compound (24) with Methylenedi-p-
phenylenediisocyanate (MDI) (50)
The same method previously described for the case of (49) was
applied. Thus, compound (24) (1.799 g, 0.005 mole) and MDI (1.251 g,
0.005 mole) were allowed to react in the presence of a catalyst (TO)
for 40 hours at 45°C under nitrogen. The resulting white solid (2.6
g, 85.3%) decomposed at 180°C.

51
Analysis, calculated for C31H43N7Ü5: C, 61.06; H, 7.11; N,
16.08. Found: C, 59.08; H, 7.38; N, 15.24.
1H NMR (DMS0-d6,T,MS): 6 1.51 (s), 2.33 (s), 3.4 (s,br), 4.16
(s), 7.2 (m), 8.5 (s), 9.5 (s).
13C NMR (DMS0-d6,39.5): 6 18.59, 53.03, 54.49, 56.46, 61.29,
62.75, 92.51, 118.32, 128.85, 134.84, 137.62, 152.54, 153.41.
IR (KBr): 3320 (m,br,sh), 3120 (w), 3040 (w), 2950 (m), 2820
(m,sh), 1700 (s,br), 1600 (s), 1540 (s), 1520 (s), 1420 (s), 1310
(s), 1230 (s,sh), 1115 (w), 1070 (m), 1020 (m,sh), 920 (w), 860 (w),
815 (m), 770 (m) cm-'*’.
[nl (DMS0,30°C) = 0.1944 dl/g.
Polymerization of Compound (26) with MDI (51)
The procedure described for compound (49) was employed. Thus,
compound (24) (1.608 g, 0.0059 mole) and MDI (1.477 g, 0.0059 mole)
were allowed to react in the presence of TO under nitrogen for 68
hours at 40-45°C. The resulting white powder (2.2 g, 71.3%) was
extracted with ether overnight and dried under reduced pressure.
lH NMR (DMS0-d6,TMS): 6 2.4 (s), 3.45 (m), 3.8 (s), 4.2 (s,br),
7.3 (m), 8.5 (d), 9.6 (s).
IR (KBr): 3320 (s,br), 3040 (w), 2960 (m), 2820 (m), 1720 (w),
1650 (s), 1600 (s), 1520 (s,sh), 1460 (w), 1415 (m), 1310 (m), 1240
(m,br), 1150 (w), 1120 (w), 1060 (w), 1020 (w), 1000 (m), 925 (w),
860 (w), 820 (m), 770 (m) cm-3.

CHAPTER III
RESULTS AND DISCUSSION
As indicated in the INTRODUCTION, the major objective of this
research was the preparation of new polymers containing amino groups
utilizing the Mannich reaction of nitroalkanes with formaldehyde and
a primary or a bis-secondary amine. Since this polymerization can be
classified as a step-growth polymerization, the rigorous requirements
for the successful synthesis of high polymers were expected.In
a step-growth polymerization, it is necessary to allow the reaction
to proceed to a very high degree of conversion or, in other words, to
a product that contains a very small number of functional groups.
Carothers derived a simple equation relating the degree of
polymerization to the extent of the reaction.If there are NQ
number of monomer A—A and NQ number of monomer B—B molecules at the
start of the polymerization (equation 1), and at a given stage of the
reaction when there are 2 N molecules of any size remaining, the
total number of functional groups of either type which have reacted
N A ''■"mA + N B —B A ~~A E B — A 3 B ~~B (1)
OO X
is (Nq-N). At that point the reaction conversion, P, is given by the
ratio of the reacted number of molecules to the original number of
molecules (equation 2),
52

53
P = (No-N)/Nq (2)
which can be rewritten as equation (3).
N = Nq(1-P) (3)
The average number of repeating units in all molecules at that stage
in the polymerization, Xn, is the original number of molecules
divided by the remaining number of molecules (equation 4).
X
n
N
o
N
(4)
Combining these two equations gives an expression for Xn, the number
average degree of polymerization, in terms of reaction conversion, P
(equation 5).
X = 2 - ^ (5
n Nq(1-P) 1-P 10
According to this limiting equation, a reaction of 95% conversion
would give a polymer with only 20 repeating units in the average
chain.
Furthermore, the step-growth polymerization requires that an
equal concentration of reactive functional groups be maintained
throughout the reaction to produce a high polymer. This means that
not only must the reaction be initiated with stoichiometric reactant
ratios, but the system must also be free from side reactions that

54
selectively consume either functional group and thereby destroy the
equality of the functional group concentrations.^ This also means
that both reactants are free from impurities that might affect the
concentrations of either function group. Flory derived a similar
equation for the case in which there is an excess of one of the
monomers in an A—A and B—B polymerization reaction.^ Let MQ A and
N0>b 1)6 the respective number of monomers A—A and B—B, and their
ratio be r. This gives the total monomer concentration NQ in terms
of and r (equation 6).
or
N = i(N . + N D)
o 2 o,A o,B
N =iN . (—)
o 2 o,A r
(6)
Since the functional groups A and B react with each other on a 1:1
basis, at a given stage of the polymerization the number of A—’A
monomer reacted, should be equal to the number of B—B monomers
reacted, Ng. Thus the fraction of B groups that have reacted is rp
as shown by equation (3).
= P
o,A
r'N,
o,B
N D M .
o,B o,A
= r * P
(7)
(3)

55
The total number of molecules present, N, is half of the number of
the functional groups, which must be equal to the sum of the numbers
of the unreacted A and B groups.
Afunctional groups (l-P)N0^+( 1_rP^0>B
(9)
Since N0>b = Nq A/r, equation (9) can be easily converted into (10).
N
f-g
[2(1-P)+ ~p~]
(10)
Therefore,
f-g
- Va(1-p
♦if1»
mi
As discussed previously, the number average degree of polymerization,
Xn, is given by the ratio of the total number of molecules and the
original number of molecules (equation 4). Combining equations (4),
(6) and (11) gives Xn in terms of conversion, P, and reactant ratio,
r (equation 12).
*n 2r(l-P)+l-r (12)
This equation can be reduced to equation (5) when r is equal to 1.
In the case when the monomer B—B is in 10% excess, i.e., r = 0.9,
and the conversion is quantitative, i.e., P = 1, the average molecule
would have Xn of 19. In the case when the monomer B—B has 2% of
unreactive impurity, i.e., r = 0.98, and the conversion is 95%, the

56
average chain would have only 16.8 repeating units, compared to 20
when there is no impurity.
With this information in mind, the synthesis of model compounds
was initiated since the starting materials chosen are commercially
available.
Model Compounds
In order to obtain model compounds whose structures could be
correlated with those of analogous polymers, a series of model
reactions was carried out. The model compounds were characterized by
IR, 3H and 13C NMR and elemental analysis.
A series of reactions between 2-nitropropane, formaldehyde and
N,N-dimethyl-l,3-propanediamine (DMPA) was carried out to yield model
compound (23). The IR spectrum of this compound contains absorption
bands at 1550 cm-3 and 1450 cm-3, characteristic of the nitro
group. The 3H NMR of this compound showed a peak at 1.52 ppm which
HNH
CH.
(CHJ- + 2 HCHO + 2 ChL-CH
|2 3 3 |
N
H3c/ XcH3
NO,
cat.
>
CH,
CH.
h3c-c -ch2-n — ch2-cch3
NO, (CHJ.
2 | 2 3
N
H3c/ XcH3
NO,
(23)

57
was assigned to the four methyl groups 3 to the nitro group. The
peak at 2.18 ppm was assigned to the inethyl groups attached to the
nitrogen atom. In order to determine the reaction conditions which
would afford the highest conversion, several different reaction
conditions were studied. The results are shown in Table 1.
Table 1. Reaction of 2-nitropropane with NMPD and formaldehyde.
Solvent
Temp.
T ime
Cat.
% Yield
Dioxane/H20
60°C
50 hrs
HC1
50
Dioxane
60°C
24
HC1
50
room temp.
20
Dioxane
75-80°C
15
h2so4
45
Dioxane
room temp.
45
K?C0„
25
reflux*
16
Dioxande
room temp.
45
KoCOo
40
70 °C
16
* Boiling Point of 1,4-dioxane = 101°C.
The higher temperature was less favorable than a lower temperature
(60-8ü°C) and the catalyst, being acidic or basic, did not
drastically alter the degree of conversion of the reaction. The poor
yield can be attributed to the lack of exact stoichiometry arising
from the formaldehyde concentration as well as the complexity of the
system. To reduce the complexity of the system, thereby reducing the

58
possible weighing error and exact stoichiometry, the methylol
derivative of 2-nitro-propane was utilized. Compound (18)
CH, CH..
i I j
CH_ - CH + HCHO > CH..-CCH90H
I I
N02 no2
(18)
which is an adduct of 2-nitropropane and formaldehyde was obtained in
almost quantitative yield. This then was reacted with DMPA to afford
the same product (23) in much improved yield. Results are shown in
HNH
(13) * I (23)
I
N
H3c/ XcH3
(DMPA)
Table 2. Reaction of (18) with DMPA.
Solvent
Temp.
T i me
Cat.
% Yield
Dioxane/H20
7D°C
18 hrs
-
50
Dioxane/H2D
70°C
22
Ha OH
70
THF
reflux3
24
N(CH2CH3)3
90
THFb
room temp.
70
n(ch2ch3)3
85
3 Boiling Point of THF = 66°C.
b 4 A molecular sieves were added.

59
Table 2. The presence of a catalytic amount of base increased the
conversion while the longer time had little impact.
The ethanolamine derivative, i.e., N-methylethanolamine, was
reacted with compound (18) to afford the 1:1 adduct, N-(2-
hydroxyethyl)-N-methyl-(2-methyl-2-nitro-l-propyl)amine (21), in good
yield. The and 13C NMR spectra and the assignment of the peaks
are shown in Figures 1 and 2. The IR spectrum shows typical nitro
peaks at 1530 and 1370 cm--*-. The yield of this reaction ranged from
60% to 77%. The reaction conditions and yields are shown in Taole 3.
CH-
hnch2ch2oh
CH.
CH,-C-CH0OH
3 ! 2
N0„
CH- CH-
. I I
> CH^-C-CHo-N-CHoCHo0H
0 | ¿ ¿ ¿
m2
(21)
Table 3.
Reaction of N-
methylethanolamine
and compound
(18).
Solvent
Temp.
Time
Cat.
% Yield
THF
66°Ca
20 hrs
NEt3
77
THFb
room temp
72
NEt3
67
THFb
room temp
72
-
60
® Reflux
b Molecular sieves (4 A)
were added.

60
e
~i i i 1 1 1
5.0 4.0 3.0 2.0 1.0 0.0 ppm
Fig. 1. NMR spectrum of compound (21) in CDC13*

61
CH- CH.. * -
, I 3 i 3^-t
a b I ei S
HO-CH„CH_-N-CH„C-CH-,
22 d 2| 3
NO-
CDCl-
V- k.
1 I 1 T 1 1 r
100
80
60
40
20
0 ppm
Completely decoupled 13C NMR spectrum of compound (21)
in CDCI3.
Fig. 2.

0¿
N-methylethanolamine was reacted with the methylol derivative of
nitroethane, i.e., 2-methyl-2-nitro-l,3-propanediol (19) to afford
2:1 adduct (22) in good yield (72.4%). Since the given % yield is
the separated yield, actual conversion should be higher.
CH- CH. CH0 CH0 CH_
3 | 3 | 3 | 3 | 3
HN-CH„CH0OH + H0CHoC-CHo0H > H0CHoCHoNCHoCCHoNCHoCHo0H
¿ ¿ ¿\ ¿ 2 2 2 j 2 2 2
N02 N02
(22)
Model Compounds with 2-Nitropropane as Chain-Stopping Reagent
Piperazine, a bis-secondary amine, was reacted with formaldehyde
and 2-nitropropane to form the 1:2 adduct, compound (13). The *H NMR
spectrum showed three singlets of methyl groups, methylene groups and
piperazine-methylene groups at 1.54, 2.47 and 2.83 ppm, respectively
(Fig. 3). The NMR spectrum is shown in Figure 4 with its peak
assignment. Both piperazine and 1-nitropropane are difunctional
compounds and thus will react to form a polymer in the presence of
formaldehyde, while 2-nitropropane is a mono-functional compound and
thus will stop the chain propagation. Assuming that the reactivity
of 2-nitropropane proton is equal to those of 1-nitropropane protons,

63
a
Fig. 3. NMR spectrum of compound (13) in CDCI3.

64
Fig. 4. Completely decoupled NMR spectrum of compound (13)
in CDC13.

65
ChL
I 3
2CH-.CH + 2 HCHO
J|
NO
/ \
+ HN NH
CH,-C-CH0-N N-CH0-C-CH
3 | 2 \ / 2 |
N02 no2
(13)
a series of model compounds was synthesized. The repeating units of
these model compounds should come from the reaction of 1-nitropropane,
CH.
/ \
n CH3CH2CH2N02 + (n+1) HN NH + (2n+2) HCHO + 2 CH3CH
NO,
->
ch3
CH,C-CH0/ \ —
3I 2 w
NO,
CH.
CH,
CH0C-CH„N N'
2I 2 V_V
1_ N02
CH.
—CH„CCH^
2| 3
n NO„
n = 1, 5, 20 and 100
with 2-nitropropane serving as a chain-stopping reagent. By varying
the ratio of reactants, one can theoretically control the length of
the chain, or in other words, the number of the repeating units. As
shown in Figure 5, the 1H spectra of these compounds can be utilized
to determine the actual number of the repeating units from the
integration of the different methyl peaks. The triplet at 0.97 ppm

66
b
Fig. 5. *H NMR spectra (in CDCI3) of the model compounds utilizing
2-nitropropane as chain-stopping reagent.

67
represents the methyl group of the repeating units while the singlet
at 1.54 ppm represents the methyl groups at the end of the
molecule. From the integration of these two peaks of each spectrum,
the ratios of 4:1, 5:6, 1:4 and 1:9 were obtained for the theoretical
degrees of polymerization of 1, 5, 20 and 100, respectively. In
other words, the actual degrees of polymerization of these compounds
were 1, 5, 16 and 36, respectively, as shown in Figure 6. Similarly,
another bis-secondary amine, i.e., N,N'-dimethylethylenediamine was
reacted with formaldehyde and 1-, and 2-nitropropane to yield the
corresponding model compounds. When n=0, i.e., 1-nitropropane was
CH.
CH.
CH.
I 3 I 3 I 3
n CH3CH2CH2N02 + (n+1) HNCH2CH2NH + (2n+2) HCHO + 2CH3CH
N0„
?H3
CH0 CHq CH.
. ii I;
■> CH3CCH2NCH2CH2N —|-CH0CCH0NCH0CH0N
NO,
CH0 CH„
| 2 | 3
CH.
2| 2
L NO,
r 2
CH.
CH0COL
2| 3
N0o
n = 0, 1 and 20.
not used, the white powder of N,N'-dimethyl-N,N'-bis(2-methyl-2-
nitro-l-propyl)ethylenediamine (30) was obtained. The ^H NMR and ^C
NMR spectra are shown in Figures 7 and 8, with peak assignment. In
the other two cases, a similar result was obtained when same method
of analysis was applied to their NMR spectra. The ratios of the
methyl peak at 0.97 ppm and 1.55 ppm are 4:1 and 3:11 for the

68
Fig. 6. Plot of the number of repeating limits vs. reactant feed
ra ti o.

69
a
Fig. 7. ■*’H NMR spectrum of compound (30) in CDC13.

70
a
Fig. 8. Completely decoupled 13C NMR spectrum of compound (30)
in CDC13.

71
theoretical chain length of 1 and 20, respectively. In other words,
the calculated chain length of 1 and 15 is obtained for these
compounds. The result shows that (A): the reactivity of the protons
of 1-nitropropane is less than that of 2-nitropropane, thus the
propagation stops before all the presenting 1-nitropropane is
consumed, and more probably (B): the reaction conversion is not
100%; therefore the growth of the chain stops before all the
reactants are consumed.
Model Compounds with N-(8-Hydroxyethyl)piperazine
Nitroethane was reacted with formaldehyde and N-(3-
hydroxyethyl)piperazine (NHEP) to afford 1:2 adduct (24). The IR
spectrum of this compound shows the characteristic peaks of the nitro
group at 1530 and 1330 cm--*-. The *H NMR spectrum, as shown in Figure
9, shows a singlet at 1.59 ppm which is assigned to the methyl
protons. The other singlet at 2.51 ppm is from the methylene
CH3CH2N02 + 2 HCH0 + 2 HN INC^C^OH
cm
^ H0CH-CH-N I
2 2 \ /
no2
(24)
protons of the piperazine ring while the triplet at 3.59 ppm is from
the methylene protons of the substituted ethanol moiety. The 13C NMR
spectrum and the peak assignment are shown in Figure 10.
A similar result was expected when l-nitropropane was reacted
with formaldehyde and NHEP. The white solid which separated first

72
TMS
Fig. 9. â– 'â– H NMR spectrium of compound (24) in CDC^.

73
100 80 60 40
20
0 ppm
Completely decoupled 13C NMR spectrum of compound (24)
in CDC13.
Fig. 10.

74
from the reaction mixture turned out to be compound (26) instead of
compound (25). The IR spectrium of this compound does not include
the characteristic peaks of the nitro group, and the *H NMR spectrum
does not have the typical triplet, characteristic of methyl protons
of the ethyl group. The spectrum of this compound shows that
there is neither primary nor quaternary carbon. This was confirmed
/ \
CH3CH2CH2N02 + 2 HCHO + 2 HN NCH2CH20H
CHq
C / \ I 3 /“\
HOCH0CH0N NCH0CCH N ,NCH0CH0OH
2 2 \ f 2| \ / 2 2
NO,
(25)
/ \
H0CH2CH2N NCH2N NCH2CH20H
(26)
by the off-resonance spectrum, as shown in Figure 11. Compound
(25) was separated from the reaction mixture afterwards in low
yield. Compound (26) is a condensation product of formaldehyde and
NHEP, and a similar reaction is known to occur between formaldehyde
and piperidine.in order to avoid the formation of the unwanted
product (26), the preformed methylol derivative of 1-nitropropane
(20) was reacted with NHEP. In this case, there is no free
formaldehyde, and therefore little condensation between formaldehyde
and NHEP was expected. However, both (26) and (25) were separated
from the rection mixture despite the fact that the yield of (25) was

75
DMSO
160 140 120
I li«III ■ —
100 30
vJ1* »'«p i'^** 'i M
(2)
0 ppn
Fig. 11. 13C NMR spectra of compound (26) in DMSO-dó: (1)
completely decoupled; (2) off-resonance.

76
higher than in the previous reaction. The presence of this
condensation product (26) indicates that the methylol derivative of
1-nitropropane is actually in equilibrium with formaldehyde and 1-
nitropropane and thus presents the chance of condensation between
CH„0H CH„0H
1 N I
CH_CHoC-N0o â– - CHoCHoC-N0o + HCHO
3 21 2 n 2 21 2
CH20H h
/ \
HOCH0CH0N NH + HCHO
2 2 V /
x / \
-> hoch9ch9n n ch9oh
2 2 \ / 2
/~A
HN NCH0CH0OH
\ / 2 2
's
N
/ \ / \
H0CHoCHoN NCH0N NCHoCHo0H
2 2 \ / 2 N / 2 2
(26)
formaldehyde and NHEP. For compound (25), the IR, "''H and NMR
spectra confirm the structure by the characteristic peaks of 1530 and
1330 cm-i for the nitro group, a triplet characteristic of the methyl
protons of the ethyl group, and a peak for the primary carbon at 7.97
ppm and another at 94.87 ppm for a quaternary carbon, respectively.
In order to determine which reaction conditions result in higher
conversion, a series of the condensation between NHEP and compound
(19) was followed by NMR. Since the chemical shift of the methylene

//
CH
3
H0CHoCHoN
/ \
,NH + HÃœCH rru qh
Na0D/D20
(24)
2 2
THF-dB
or
DMS0-d6
(19)
protons adjacent to oxygen remained virtually unchanged, the triplet
corresponding to these protons was used as reference. As shown in
Figure 12, the relative intensity of the peak corresponding to the
methylene protons next to NH decreased as the reaction proceeded.
The result is shown in Figure 13. The reaction was not affected much
by the solvent since there is not much difference in conversion
between the solvents, THF and DMSO. The highest conversion was
observed at 60°C rather than at 100°C, probably due to the reversible
reaction.
Since NHEP can be used as a chain-stopping reagent, a series of
model compounds from nitroethane, formaldehyde, piperazine and NHEP
was preparated. When a feed ratio of piperazine to NHEP was 5:2 so

78
Fig. 12. Selected time dependent *H NMR spectra of the reaction of
NHEP with compound (19) in DMS0-d6 at RT.

100
o
o
_J I
100 200
1
300
i
400
I
500
O THF-d8, RT
A DMSO-d6, RT
â–¼ DMSO-d6, 60 C
O DMSO-d6, 100 C
O
â–¡
â–¼
—I l I
600 700 800
Time ( minute )
é
â–¼
_J 1—
900 1000
Fig. 13. Plot of the consumption of NEPD vs. reaction time

ou
that the expected degree of polymerization was 5, a white precipitate
formed during the reaction. This solid was not soluble in most of
the common organic solvents, i.e., acetone, toluene, ether, methanol,
THF, DMF, chloroform and acetonitrile. A similar result was obtained
from the rection when a feed ratio of 10:1 was utilized. Both of
these products are soluble in HC1 (10% w/v aqueous) solution. The
viscosity measurement in 10% HC1 at 25°C resulted in intrinsic
viscosities of 0.0025 dl/g and 0.0024 dl/g, respectively. In other
words, the molecular weights of the compounds were about equal. This
can be explained by the fact that the solid product precipitated out
during the reaction, and therefore the propagation of the chain
stopped before the average chain length of 5 was attained.
Studies with Nitromethane
As discussed previously, the methylol derivative of a
nitroalkane (20) is in equilibrium with formaldehyde and 1-
nitropropane. If this is true in the case of the derivative of
nitromethane, a mixture of mono-, di-, and trisubstituted product
should result from the reaction between 2-nitro-1,3-propanediol (15)
and piperidine. An attempt to synthesize (18) by direct condensation
of nitromethane with formaldehyde failed since the product was mainly
the trisubstituted compound, i.e., 2-(hydroxymethyl)-2-nitro-1,3-
propanediol (16).
K2C03
CH3N02 + HCH0 â–  (H0CH2)3CN02
(16)

Ü1
However, the desired diol (15) was obtained when this compound (16)
was treated with sodium, followed by salysilic acid. The IR spectrum
of this compound shows peaks at 1540 and 1360 cm-1 character!'Stic of
the nitro group. The NMR spectrum shows a muliplet at 3.72 ppm
(hoch2)3cno2
(16)
■> (H0CH?)„CN0
ch3oh ¿
(17)
ether
(H0CH2)2CHN02
(15)
assigned to the methylene protons, a pentet at 4.66 ppm assigned to
methine proton, and a triplet assigned to the hydroxyl protons. This
triplet vanished when a drop of D2O was added to the NMR tube, thus
confirming that the signal is from the hydroxyl protons (Fig. 14).
The iJC NMR spectrum shows two peaks at 59.56 and 91.92 ppm, assigned
to methylene carbons and methine carbon, respectively. This
assignment was confirmed by the off-resonance NMR spectrum (Fig.
15). This compound (15) was then reacted with piperidine to yield a
mixture of mono-, di-., and trisubstituted product as expected. The
amount of disubstituted product was increased when the reaction
temperature was lower.
Model Compounds from Bis-secondary Amines
N,N1-dimethyl-2-butene-l,4-diamine (DMBA) and N,N‘-
dimethylhexamethylenediamine (DMHA) were also utilized in the model
compound studies. A reaction between 2-nitropropoane, formaldehyde
and DMBA afforded the model compound (31) in good yield. The IR
-1
spectrum of this compound shows two peaks at 1530 and 1340 cm

82
Fig. 14. 1H NMR spectra of compound (15) in DMS0-d6: (1) without
^20, (2) 1 drop of D2O was added.

83
a
Fig. 15. 13C spectra compound (15> in DMS0-d6: (1) completely
decoupled, (2) off-resonance.

OH
ChL CH- CH0
I 3 | 3 |
2 CH,-C-H + 2 HCHO + HN-CH0CH=CHCH0N-H
3 I
N02
>
characteristic of the nitro group. The *H NMR spectrum shows a
multiplet at 5.52 assigned to the protons on the carbon-carbon double
bond (Fig. 16). The NMR spectrum also shows the C-C double bond
at 130.41 ppm (Fig. 17). Similarly, ÃœMHA was reacted with 2-
nitropropane and formaldehyde to yield compound (34) in fair yield.
The IR spectrum shows the characteristic peaks of the nitro group at
9H3 9H3
Cl-L CH.
I 3 I
CHnCCH0NCH„CH=CHCH„NCH0CCH.,
22 2 2| o
3
NO.
NO.
nn
CH.
2 CHoCH
3I
NO,
CH.
+ 2 HCHO + HN(CH2)6NH
ch3 ch3
CH^ CH..
| 3 | 3
-> CH^CCH0N(CH0)rNCH0CCH„
o | 2 2 o 21 J
NO,
NO,
(32)
1540 and 1345 cm-'*’. The *"H NMR spectrum includes peaks at 1.30,
1.58, 2.26, 2.42 and 2.83 ppm, assigned to the methylene protons from
the middle of the amine moiety, methyl protons from the nitropropane
moiety, methyl protons attached to nitrogen, methylene protons
attached to nitrogen, and other methylene protons attached to
nitrogen, respectively. The ^3C NMR spectrum and the peak
assignments are shown in Fig. 18.

85
ppm
Fig. 16. *H NMR spectrum of compound (31) in CDC13

Fig. 17. NMR spectra of compound (31) in 000)3: (1) completely
decoupled, (2) off-resonance.

a/
a
ppn
Fig. 18. 13C spectra of compound (32) in CDCl^: (1) completely
decoupled, (2) INEPT (CH,CH3 pos., CH2 neg., C, solvent
suppressed).

88
Polymers
An investigation of the polymerization of NMEA with (19) was
then carried out. The reaction, which was refluxed in THF (66°C) for
24 hours in the presence of molecular sieves (4 A), gave an
CH.. ChL
| 3 | 3
HNCH2CH2NH + H0CH2
NMEA
(
excellent yield of polymer 05). The infrared spectrum of the brown,
viscous oil shows IR absorptions at 1535 and 1545 cm-1 characteristic
of the nitro group, and is very similar to that of model compound
OO). The NMR spectrum is also very similar to that of model
compound OO) and the peaks are assigned accordingly, i.e., the
singlet at 1.5 ppm to the methyl protons of the nitroethane moiety,
the singlet at 20 ppm to the methyl protons next to the nitrogen,
the singlet at 2.4 ppm to methylene protons of the amine moiety and
the singlet at 2.9 ppm to the methylene protons from the
i n
formaldehyde. The 1JC NMR spectrum shows five major peaks, which are
in agreement within 3 ppm to those of the ^C NMR spectrum of
compound OO) (Fig. 19). This polymer, however, showed a molecular
weight of only 2200 by vapor pressure osmometry. The low molecular
weight can be the result of the relatively low conversion (~90%).
NMBA and (19) was then polymerized under identical conditions to
afford polymer 06). The very viscous yellow oil shows IR
absorptions at 1550 and 1335 cm-* characteristic of the nitro group.
CH.
CCHo0H
1 2
NO,
->
C1L CH,
13 1
CH *
13
•CH0CCH0NCH0CH„N
21 2 2 2
NOo
19)
05)

39
’ Y3 'Y3 df3'
¿OíAÍCH^-CW-
NO.
-Ix
(1)
N-Jmv-
-I 1 1 1 1 1 1—
120 100 80 60 40 20 0
PPti
Fig. 19. NMR spectra of polymer (35) in CDC^: (1) completely
decoupled, (2) off-resonance.

90
CH.,
CH.
hnch2ch=chch2nh +
NMBA
(19)
cn3 CH3
CH,
CH2CCH2NCH2CH=CHCH2M
NO,
(36)
The 3H NMR and 33C NMR spectra are very similar to those of the model
compound (31), and peaks are assigned accordingly. The -^C NMR is
shown in Fig. 20. This polymer showed a low molecular weight (~2500)
by VPO, which can also be attributed to the low conversion.
Similarly, NMHA and (19) was polymerized under identical
conditions to yield polymer (37). The viscous brown oil also shows
characteristic nitro absorptions in IR, and 3H and 33C NMR spectra
are also similar to those of the corresponding model compound (32).
CH.
CH.
hn(ch2)6nh +
NMHA
(19) —> --
CH, CH. CH,
I 3 I 3 I 3
â– CH2CCH2N(CH2)6N
l_ N02
_J x
(37)
The polymerization between N,N-dimethyl-l,3-propanediamine and (20)
yielded a similar result. Polymer (33) was identified by IR, *H and
13C NMR spectra according to the corresponding model compound (23).
Since these polymers, obtained from the condensation of amine and the

91
Fig. 20.
13C spectra of polymer (36) in 0003: (1) completely
,0\ rwroT ir.n. CH3 pos., CH2 neg., C, solvent
O O p C. Ul u v 1 p- ^ .
decoupled, (2) INEPT (CH,
suppressed)

HNH
(CH~), + (19)
|2 i
N
H3c/ NcH3
â– >
CH..
I 3
ch9cch,
2! ¿
NO,
l ^2*3
N
»/ NcH3
(33)
methylol derivatives of nitroalkanes, were not very high molecular
weight polymers, the method reported by Angeloni and coworkers was
O £T OO
employed next. Thus, 2-methyl-2-nitro-l,3-bis(dimethyl-
amino)propane (28) was prepared by allowing (19) to react with
dimethyl-amine. Compound (23) was separated and characterized by IR,
H and JC NMR spectra. This then was reacted with NMEA to
CH-
I 3
HOCH-CCH-OH + HN
2| 2
no2
(19)
->
h3c
h3c
ch9
I 3
N-CH9CCH9N
21 2
N02
CH,
CH-
(28)
afford polymer (35). The brown, viscous oil showed identical IR, *H
and 13C NMR to those of polymer (35) obtained previously by the
reaction of (19) and NMEA.
(28) + NMEA >
ch3 ch3 ch3
•ch9cch9nch9ch9n-
2| 2 2 2
N02
Jx
(35)
Similarly, compound (28) was reacted with NMBA and NMHA to
afford polymers (36) and (37), respectively. These polymers were

93
identical to those obtained previously by the condensation of (19)
and NMBA and NMHA, respectively. The molecular weight of the
polymers also ranged from 2000 to 2500.
(23) + NMBA
->
9H3 iH3
9H3 i
â– CH0CCH0NCH0CH=CHCH0N
:l
NO,
(36)
-J x
(28) + NMHA
->
CH, CH, CH ‘
I 3 l3 l3
-CH2CCH2N(CH2)6N
N0o
J x
(37)
Compound (28) was then polymerized with piperazine under similar
conditions. However, the white solid precipitated from the reaction
mixture 1-2 hours after the reaction started. This powder was not
(28)
/ \
HN NH
r CH,
I 3 / \
â– CH0CCH0N N'
21 2
no2
(38)
soluble in most of the common organic solvents. The IR spectrum of
the polymer was very similar to that of compound (27) with peaks at
1530 and 1330 cm-1. The intrinsic viscosity measured in 10% HC1
solution at 25°C was only 0.0024 g/dl, and thus showed that this
polymer had a degree of polymerization less than 5.

Reduction of Model Compounds
Reduction of the nitro group can be achieved in many ways. 48
Among these, the method using lithium aluminum hydride (LiAlH^) was
chosen because of its mild condition.^5 Thus, an attempt was made to
reduce model compound (27).
(27)
L i A1H 4
^ (reduction)
THF
However, the desired product was not obtained; the reaction mixture
turned to a dark brown liquid and became unidentifiable. Another
attempt was made to reduce compound (27) to the corresponding amine
using sodium borohydride (NaBH^) in the presence of palladium
activated charcoal.
NaBH.
L>
Pd/C
CH.
/ \ich2cch2k
N ' NHo
o
(39)
Although compound (39) was the major product, the IR spectrum still
showed IR absorptions at 1550 and 1350 cm-1 characteristic of nitro
group (Fig. 21).

95
Compound (27) was then reduced by the method reported by
1 O
Johnson. The reduction took place in a Parr bomb charged with 800
psi of hydrogen gas with Raney nickel catalyst. The IR spectrum
showed a broad N-H absorption and little nitro absorptions (Fig. 22).
(27)
(39)
The reduction of nitro compound (39) was then studied. A
similar result was expected, however the product obtained was not
CH.
CM.
H3C\
h3c
CH.
,MCH„CCH0N
2| 2
N02
(29)
CH.
CH.
Raney Ni
Ho
CH.
H C | ‘
J >-CH0CH
He/ 21
"3U NH,
(39)
the desired reduced compound but N,N-dimethyl-(2-aminobutyl)amine
(39). The *H NMR spectrum showed a methine proton peak at 2.80 ppm,
and the ratio of methyl protons were 2:1 instead of 4:1 as
n
expected. The C NMR spectra, both completely decoupled and off-
resonance, agreed with the proposed structure (Fig. 23).

yo
Fig. 21. IR spectra of (1) compound (27), and (2) compound (39)
(reduced by NaBH^ and Pd/C).

97
Fig. 22. IR spectra of (1) compound (27)
(reduced by H2/Raney Ni).
and (2) compound (39)

y«
Fig. 23. NMR spectra of compound (39) in CDCl^: (1) completely
decoupled, (2) off-resonance.

Reduction of Polymers
Since the study of reduction of the model compound (27)
indicated that Raney nickel catalyzed hydrogenation yielded the best
results among the three methods tried, polymers (35) and (36) were
reduced under identical conditions.
(35)
Raney Mi
-> —
9H3 ÍH3
CH.,'
•CHqCCH0NCH0CH0N
21 2 2 2
nh2
(40)
(36)
->
Raney Mi
CH_ CH0
! J | J
CH.,
â– CH0CCH0MCH0CH=CHCHqN
21 2 2 2
nh2
(41)
The IR spectra of both polymers (40) and (41) showed drastically
reduced nitro absorptions relative to C-H absorption (Figs. 24 and
25). For comparison, polymer (36) was reduced by MaBH^ in the
presence of Palladium activated charcoal to yield an almost identical
product. However, the relative intensity of the nitro absorptions
are stronger when the IR spectrum of this product was compared to
that of the previously obtained polymer (41). This indicates that
hydrogenation with Raney nickel is more efficient on this type of
polymer. Due to the low solubility of polymer (37) in DMF, which was
used as the solvent for these reactions, 2-ethoxyethanol was employed
for the reduction of polymer (37). Thus obtained polymer (42) showed
little nitro group absorption on its IR spectrum as shown in Fig. 26.

100
Fig. 24
IR spectra of (1) polymer (35), and (2) polymer (40)

101
Fig. 25
IR spectra of (1) polymer (36), and (2) polymer (41)

102
Fig. 26.
IR spectra of (1) polymer (37), and (2) polymer (42).

(37)
Raney Ni
CH3CH20CH2CH20H
chq cfl ch., n
l 3 i 3 | 3
•CH0CCH9N(CH0)-N
2| 2 2 o
NH£
(42)
x
Methylation
Methylation of polymer (40) was carried out utilizing sodium
cyanoborohydride and formaldehyde.37,38 The product (43) was a light
(40)
HCHO
>
NaBH3CN
CbL CH„ CH.,-,
| 3 | 3 i 3
—CH2CCH2NCH2CH2N'
" /\
H3c ch3
J X
(43)
brown, viscous oil, 3H NMR spectrum of which showed a new peak at 2.3
ppm which was assigned to the new methyl protons attached to the
pendant amino group. The *3C NMR spectrum showed a shift of the
methyl and methylene peaks as well as a new methyl peak (Fig. 27).
An attempt to methylate polymer (41) by the same method failed ue to
the low solubility of the material in the suggested solvent
acetoni trile.
Polymer (40) was then methylated utilizing formic acid and
formaldehyde.30 The resulting polymer was identical with polymer
(43) obtained previously. Similarly, polymer (41) was methylated by
formic acid and formaldehyde to afford a brown, viscous oil. The
NMR spectrum showed a new methyl peak at 2.3 ppm indicating that the

104
(2) _
CH.
c'
CT3
CCH-. -
al
'CH2C-CH2NCH2CH2N-
N d'
/\
â– J x
Fig. 27.
13C NMR spectra (INEPT: ChU,
suppressed) of compounds (40)
CH pos., CH2 neg; C, solvent
and (43), respectively.

105
HC00H
(41) >
HCHO
CH- CH- CH- n
l 3 I 3 l3
—CH0CCH0NCH0CH*CHCH0N
2 [ 2 2 2
N
H3c/ \h3
(44)
amino group of polymer (47) had been methylated. The NMR
spectrum also confirmed that the structure of the product was
identical with the suggested one.
Mannich Reaction on Nitroethene
Since the polymers obtained from condensation polymerization of
nitroalkanes with formaldehyde and amines were of low molecular
weight, the possibility of addition polymerization of the Mannich
base containing the carbon-carbon double bond was considered. In
other to prepare nitroethene, nitroethanol was prepared by the
reaction of nitromethane and formaldehyde. The NMR of the product
showed peaks at 4.14 and 4.54 ppm, character!'stic of nitroethanol.
This was then heated with phthalic anhydride to yield nitroethene, a
pale yellow oil. The NMR spectrum showed a doublet of doublets at
0
K2C03 ©ó0
CH3N02 + HCHO > H0CH2CH2N02 CH2=CHN02
(14) (45)
7.21 ppm of the methine proton and two doublets of the methylene
protons at 6.64 and 5.93 ppm. The spectrum showed methine carbon
at 144.9 ppm and methylene carbon at 122.2 ppm. The thus synthesized

and characterized nitroethene was reacted with dime thylamine
hydrochloride and formaldehyde in an attempt to prepare a Mannich
base containing the vinyl group. However, the reaction mixture
became a brown tar which was unidentifiable. Other attempts to
condense nitroethene with formaldehyde and a secondary amine failed,
probably due to the extreme reactivity of the nitroethene.
Nitroethene was then polymerized anionically on a vacuum line
using pyridine as an initiator.50-52 The off-white powdery polymer
showed a methylene peak at 35.5 ppm and a methine peak at 81.1 ppm i
its NMR spectrum. Poly(nitroethene) was then reacted with formalde¬
hyde and diethylamine. The resulting polymer was a dark brown solid
CH0CH
2I
NO
+ n HCHO + n HN(CH2CH3)2
(46)
ch9c
2I
NO
l2N(CH2CH3)2“
]2 _
n
of low solubility in most of the common organic solvents. Oue to
this property, this reaction was not pursued further.
Urethanes and Polyurethanes
The condensation reaction between an isocyanate and an alcohol
C O
is well known. J Since model compound (24) can be classified as a
diol, it can form a polyurethane when reacted with a diisocyanate.
Model compound (24) was reacted with phenyl isocyanate to afford

MCO
CH.
H0CH„CHoN NCH0CCH0N
2 2 \ / 2I 2 \
M02
(26)
NCH2CH2OH +
catalyst.
0
II
NHCOCHoCHoN
ZwlZ
W
CH.
,NCH0CCH„N
2l 2
N02
(48)
V_/
0
NCH2CH20CNH
urethane (48). Two different catalysts were investigated, i.e., 1,4-
diazabicyclo-[2,2,2]-octane (DABCO) and tin octoate (TO). Although
54 55
both are known to be excellent catalysts for urethane formation, *
tin octoate gave the better yield. A diisocyanate, methelene-di
phenylenediisocyanate (MDI) was then polymerized with compound (24)
to yield polymer (50). The white powder was soluble in DMSO and DFM,
(24) + OCN
CH
nhcoch2oh2n
(50)
CH.
/nch2cch2n
no2
nch2ch2o
and decomposed around 180°C. The IR, *H and ^C NMR spectra of this
polymer were similar to those of the model compound (48) including
the IR absorption at 1730 cm--'- characteristic of the carbonyl group
of urethane compounds. The intrinsic viscosity of this polymer in
DMSO at 30°C was 0.194 dl/g.

108
Model compound (26) was then polymerized with MDI to yield
polymer (51). The light brown solid showed an IR absorption at
hoch2ch2n
/ \
NCH-N NCH-CH-OH
2 \ / 2 2
(26)
+ MDI
nhcoch2ch2n
r\
ch2n
NCH2CH20
(51)
1720 cm-1 characteristic of the urethane carbonyl group.
Similarly, model compound (24) was reacted with methyl
isocyanate to afford urethane (47) as a light brown oil. Because
0 CH. 0
, 4 .11 / \ I 3 / \ II
(24) + CH3NC0 > CH3NHC0CH2CH2N nch2cch2n NCH2CH20CNHCH3
X / N02 n /
(47)
methyl isocyanate is a very volatile liquid, and the reaction was
run under constant flow of ^ methyl-isocyanate was used in ex¬
cess. Compound (24) was then polymerized with an aliphatic diiso¬
cyanate, i.e., hexamethylenediisocyanate to afford polymer (50).
(24) + 0CN-(CHo)c-NC0
2 6
T.O.
OH HO
II I I II /
—c-n-(ch2)6n-c-och2ch2n
CH..
\ I 3 /
NCH0CCH0N
/ ¿\ ¿ \
N0„
NCH2CH20
(50)

The white powder showed low solubility in most of the common organic
solvents.
Summary and Conclusions
The model compound studies were carried out in order to
establish the best conditions for the polymer forming reactions.
Through this study, high conversion of the starting materials into
the Mannich base was achieved. Chain-stopping reagents were utilized
to provide a better understanding of the polymerization.
The polymers obtained from the reaction of nitroethane and bis-
secondary amines showed rather low molecular weights of 2000-2500.
These polymers were then modified by reduction and methylation to
achieve the objective of this research. Since the polymers were of
low molecular weight, other routes to prepare high molecular weight
polymers were investigated. The Mannich bases with diol functions
were polymerized with diisocyanates to afford polyurethanes of higher
molecular weight.
Although the polymers obtained from the Mannich reaction showed
only low molecular weights, their further modification, such as
crosslinking via the double bond in polymers derived from N,N'-
dimethyl-2-butene-l,4-diamine, can be very useful and should be
studied in the future.

REFERENCES
1. C.M. van Marie and B. Tollens, Ber., _36.» 1351 (1903).
2. H. ScháTer and B. Tollens, Ber., 39, 2181 (1906).
3. C. Mannich and W. Krosche, Arch. Pharm., 250, 647 (1912).
4. F.F. Blicke, "The Mannich Reaction," Org. Reactions, _1_, 303
(1942), R. Adams, Ed., John Wiley and Sons, Inc., New York.
5. H. Hellmann and G. Opitz, Angew. Chem., j)8_, 265 (1956).
6. M. Tramontini, Synthesis, 1973, 703 (1973).
7. B.B. Thompson, J. Pharm. Sci., jH_, 715 (1968).
8. H. Becker, E. Fanghanel and W. Ecknig, Angew. Chem., 72, 633
(1960).
9. H. Becker and E. Fanghanel, J. Prakt. Chem., 26_, 58 (1964).
10. H. Becker, W. Ecknig, E. Fanghá'nel and S. Rommel, Wiss. Z.
Techn., _U, 38 (1968): C.A. 71, 60938 (1970).
11. H.J. Roth and M. Muhlenbruch, Arch. Pharm., 303, 156 (1970).
12. G.R. Pettit and A.K. Das Gupta, Chem. & Ind., 1962, 1016 (1962)
13. G.R. Pettit and J.A. Settepani, Chem. & Ind., 1964, 1085 (1964)
14. H. Bó'hme and H. Orth, Arch. Pharm., 300, 148 (1967).
15. L. Henry, Ber., 38, 2027 (1905).
16. L. Henry, Bull. Acad. Roy. Belg., [3], 412 (1897).
17. M. Senkus, J. Am. Chem. Soc., _68, 10 (1946).
18. H.G. Johnson, J. Am. Chem. Soc., 68_, 12 (1948).
19. T. Tsuji and T. Ueda, Chem. Pharm. Bull. (Tokyo), _12_, 946
(1964).
110

Ill
20. H.A. Brunson and G.8. Butler, Ü.S. Pat. 2,400,806, May 21, 1946.
21. G.B. Butler and B.M. Benjamin, Ü.S. Pat. 2,636,019, April 12,
1953.
22. E. Tsuchida and T. Tomono, J. Polym. Sci., Polym. Chem. Ed., 11_,
723 (1973).
23. T. Tomono, E. Hasegawa and E. Tsuchida, J. Polym. Sci., Chem.,
12, 953 (1974).
24. C.J. McDonald and R.H. Beaver, Macromolecules, 12, 203 (1979).
25. F. Andreani, A.S. Angeloni, L. Angiolini, P. Costa Bizzarri, C.
Della Casa, A. Fini, N. Ghedini, M. Tramontini and P. Ferruti,
J. Polym. Sci., Polym. Lett. Ed., 29_, 443 (1981).
26. A.S. Angeloni, P. Ferruti, M. Tramontini, and M. Casalaro,
Polymer, _23, 1693 (1982).
27. A.S. Angeloni, P. Ferruti, M. Laus, M. Tramonitini, E. Chiellini
and G. Galli, Polym. Comm., _24_, 87 (1983).
28. N. Ghedini, C. Della Casa, P. Costa Bizzarri and P. Ferruti,
Makromol. Chem., Rapid Commun., _5, 181 (1984).
29. R.M. Silverstein, G.C. Bassler and T.C. Morrill, "Spectrometric
Identification of Organic Compounds," 4th Ed., John Wiley and
Sons, New York, 1981.
30. A.J. Cordon and R.A. Ford, "The Chemists Companion: A Handbook
of Practical Data, Techniques and References," John Wiley and
Sons, New York, 1972.
31. V.I. Burmistrou and Y.M. Bashinova, Zh. Prikl. Khim.
(Leningrad), 41.(8), 1853 (1968). [J. Appl. Chem. USSR, 41, 1744
(1968) (Engl. Ed.)].
32. W.E. Noland, Org. Synth., .41., 67 (1961).
33. H.P. Den Otter, Rec. Trav. Chim., 57_, 13 (1938).
34. B.M. Yandervilt and H.B. Hass, Ind. End. Chem., _32., 34 (1940).
35. W.E. Parham and F.L. Ramp, J. Am. Chem. Soc., 73_, 1293 (1951).
36. S.H. Pine and B.L. Sanchez, J. Org. Chem., .36., 829 (1971).
37. R.F. Bosch, M.D. Bernstein and H.D. Durst, J. Am. Chem. Soc.,
93_, 2897 (1971).
38. R.F. Bosch and A.I. Hassid, J. Org. Chem., 37, 1673 (1972).

112
39. D. Ranganathan, C.B. Rao, S. Ranganathan, A.K. Mehrotra and R.
Iyengar, J. Org. Chem., 4j>, 1185 (1980).
40. G.D. Buckley and C.W. Scaife, J. Chem. Soc., 1947, 1471 (1947).
41. P.J. Flory, "Principles of Polymer Chemistry," Cornell
University Press, Ithaca, New York, 1953.
42. George Odian, "Principles of Polymerization," 2nd Ed., John
Wiley and Sons, Inc., New York, 1981.
43. Robert W. Lenz, "Organic Chemistry of Synthetic High Polymers,"
Interscience Publishers, New York, 1967.
44. Harry R. Allcock and Frederick W. Lampe, "Contemporary Polymer
Chemistry," Prentice-Hall, Inc., Englewood, New Jersey, 1981.
45. S.R. Sandler and M.L. Delgado, J. Polym. Sci., Part A-l, 7, 1373
(1969).
46. J.E. Fernandez and J.S. Fowler, J. Org. Chem., 29_, 402 (1964).
47. P.A.S. Smith, "The Chemistry of Open-Chain Organic Nitrogen
Compounds," Vol. II., W.A. Benjamin, Inc., New York, 1966.
48. J. March, "Advanced Organic Chemistry," 2nd Ed., McGraw-Hill
Book Company, New York, 1977.
49. S.H. Yoon, personal communication, University of Florida.
50. H. Wieland and E. Sakellarios, Ber., 52_, 898 (1919).
51. G.D. Jones, J. Zomlefer and K. Hawkins, J. Org. Chem., 9, 500
(1944).
52. D. Vofsi and A. Katchalsky, J. Polym. Sci., 26_, 127 (1957).
53. D.L. Lyman, "Polyurethanes," Rev. Macromo1. Chem., 1, 191
(1966). ~
54. J.H. Saunders and K.C. Frisch, "Polyurethanes: Chemistry and
Technology," Part I, Interscience, New York, 1962.
55. J.W. Britain, Ind. Eng. Chem. Prod. Res. Develop., 1, 261
(1962). “

BIOGRAPHICAL SKETCH
Seok Heui Hong was born in Seoul, Korea, on May 28, 1952. He
received his B.S. degree in applied chemistry at Engineering College,
Seoul National University, Seoul, Korea, in 1974.
In 1977, he came to the United States and subsequently enrolled
in the Graduate School at Wright State University, Dayton, Ohio,
where he received the M.S. degree in organic/polymer chemistry. Upon
graduating in 1979, he joined the Department of Chemistry at the
University of Florida.
He is married to the former Kyung Sook Joo and is the father of
two children, Brian and Janice. He is a member of the American
Chemical Society.
113

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
/] /¿l-LZL/
'George B. 1Butler, Chairman
Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
Wallace S. Brey, Jr.
Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
/
/ /¿-¿ ¿-o o -t
Thieo E. Hogen-Esch
Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
^_
Wi11íam M. Jones
Professor of Chemi

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is
fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.
Eugene P. Goldberg
Professor of Materials Science and
Engineering
This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences
and to the Graduate School and was accepted as partial fulfillment of
the requirements for the degree of Doctor of Philosophy.
May, 1985
Dean for Graduate Studies and
Research

UNIVERSITY