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The synthesis of spiro and bridged aziridines, by Emmett S. McCaskill

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The synthesis of spiro and bridged aziridines, by Emmett S. McCaskill
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McCaskill, Emmett Scott
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Acetates ( jstor )
Anhydrides ( jstor )
Azides ( jstor )
Aziridines ( jstor )
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Ethanol ( jstor )
Ethers ( jstor )
Room temperature ( jstor )
Sodium ( jstor )
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THE SYNTHESIS OF SPIRO AND BRIDGED AZIRIDINES


BY



Emmett S. McCaskill, Jr.














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





UNIVERSITY OF FLORIDA
1974

































Copyright by

Emmett S. McCaskill, Jr.

1974














ACKNOWLEDGEMENTS


Several people made significant contributions at appropriate

stages of this study. Working with Dr. James A. Deyrup was a

stimulating intellectual experience. Jim Gill, Bill Szabo and

George Kuta are thanked for their assistance and contributions

of ideas. My graduate committee members, Drs. Butler, Dolbier,

Weltner and Baers were an immense help in their critique of this

research. The several versions of this dissertation were effi-

ciently and insightfully typed by Gerda Covell.

The gestation period of this doctoral study was quite a

sacrifice for my family. I am grateful to my children who, young

as they are, tried to understand it all. I would be remiss if

I did not thank my wife's parents, George and Evelyn Brown and

my parents, Emmett and Rosie McCaskill, for their concern and

support. I am grateful for my wife's understanding throughout

these years. For this, it is a pleasure to be able, at last, to

dedicate this dissertation to all members of my family.










TABLE OF CONTENTS


Page

ACKNOWLEDGEMENTS ............................................... i i i

LIST OF TABLES ................................................. vii i

ABSTRACT ....................................................... ix

CHAPTER I Attempted Synthesis of a l-azabicyclo-[l.l.O]-
butane-2-one ..................................

Introduction ...................................... 1
Discussion ........................................ 5
Conclusion ........................................ 38

II Attempted Synthesis of a Benzo-2-Azirine .......... 42

Introduction ...................................... 42
Proposed Plan ..................................... 45
Discussion ....................................... 50
Summary and Conclusions ........................... 77

III Experimental ...................................... 78

General ........................................... 78
Ethyl c-hydroxy-a-(9-fluorenyl acetate) (22.)....... 79
Ethyl fluorenylidene acetate (2]).................. 80
Ethyl azidoformate ................................ 80
Attempted synthesis of 1,2-dicarbothoxy-3-spiro- 80
(fluorenyl) aziridine ..........................
Ethyl a-bromo-a-(9-bromofluorenyl) acetate 42) .... 80
Reaction of ethyl a-bromo-c-(9-bromof l uorenyl)
acetate with ammonia ......................... 81
a-Bromofluorenylideneacetate (z5) ................. 81
Attempted reaction of a-bromofluorenyl ideneacetate
with ammonia ................................. 81
Ethyl c&-bromo-ca-(9-isocyanatofluorenyl) acetate(26) 81
Ethyl -a-bromo-a-(9-carbethoxyaminof l uorenyl)
acetate (2) .................................... 82
Ethyl-f[-ethoxy-5-spi ro-(9-fluorenyl) oxazolin e]
acetate (31) ................................... 82









Page


4-Carbethoxy-5-spiro-(9-fluorenyl)-2-oxazol done (32) .... 83
Reaction of Ethyl-[2-ethoxy-5-spiro-(9-fluorenyl)-
oxazoline acetate with hydrobromic acid ............... 83
4-Methyl-5-spiro-(9-f1uorenyl)-2-oxazolidone (36) ........ 84
9-Aminofluorene (40) .................................... 84
9-Carbethoxyiminofluorene (37) ........................... 85
9-Carbethoxyaminofluorene (41) ........................... 86
9-Carbethoxyiminofluorene (37) ........................... 86
Fluorenylideneimine (42) ................................. 86
Methyl a-bromo-o-(9-carbethoxyaminofluorenyl) acetate (29) 86
Reaction of Methyl a-bromo-a-(9-carbethoxyamino-
fluorenyl) acetate with alcoholic potassium
hydroxide ............................................. 87
Reaction of 9-Carbethoxyiminofluorene with alcoholic
potassium hydroxide .................................. 87
Attempted Reaction of 9-Carbethoxyiminofluorene
with Benzoyl Peroxide ................................ 87
Attempted Reaction of 9-Carbethoxyiminofluorene
with Ditertbutyl Peroxide ............................ 88
Ethyl a-bromo-o-(9-aminofluorenyl) acetate (44) .......... 88
Ethyl 2-spiro-(9-fluorenyl) aziridine carboxylate (20) ... 88
Sodium 2-spiro-(9-fluorenyl)-aziridinecarboxylate (j6) ... 89
Reaction of Sodium 2-spiro-(9-fluorenyl) aziridine
carboxylate with Thionvl Chloride (Attempted) ........ 90
Anthracene-9, 10-endo-c, p-succinic anhydride (65) ...... 90
Disodium 9, 10-endo-a, p-succinate (67) .................. 90
Anthracene-9, 10-endo-a, p-succinic acid (68) ............ 91
Electrolytic Bisdecarboxylation (General Method).......... 91
Bisdecarboxylation with Lead Tetraacetate (General) ...... 92
Electrolytic Bisdecarboxylation of anthracene-9, 10-
endo-a, p-succinic anhydride .......................... 93
Electrolytic Bisdecarboxylation of disodium 9, 10-
endo-a, p3-succinate ................................... 93
Electrolytic Bisdecarboxylation of 9, 10-endo-a,
p-succinic acid ....................................... 93
Bisdecarboxylation of 9, 10-endo-a, p-succinic acid
with Lead Tetraacetate ................................ 94
R-Methoxyphenylazide (70) ................................ 94
l-(p-Methoxyphenyl)-9, 10-ethanoanthracene Z\2
triazoline (71) ....................................... 95
N-(p-Methoxyphenyl)-9, 10-ethanoanthracene aziridine (72) 95
9, lO-dihydro-9, 10-ethenoanthracene-i1l, 12-di-
carboxylic acid (74) .................................. 95








Page


Dimethyl 9, lO-dihydro-9, 10-ethenoanthracene 11
12-dicarboxylate (73).............................. 96
9, lO-dihydro-9, lO-ethenoanthracene carboxylic
anhydride (75) ..................................... 96
4, 5-[9, 10-anthrylene]-cyclohexene-cis-l, 2-di-
carboxylic anhydride (63).......................... 97
Attempted Electrolytic Bisdecarboxylation of 4,
5-[9, 10-anthrylene]-cyclohexene-cis-l, 2-di-
carboxyl ic anhydride ............................... 97
Attempted Electrolytic Bisdecarboxylation of 4,
5-[9, 10-anthrylene]-cyclohexene-cis-l, 2-di-
sodium carboxylate ................................. 97
Attempted Synthesis of 4, 5-[9, 10-anthrylene]-
cyclohexene-cis-l, 2-dicarboxylic acid ............. 98
Attempted Electrolytic Bisdecarboxylation of 4,
5-[9, 10-anthrylene-cyclohexene-cis-l, 2-di-
carboxylic anhydride with Lead Tetraacetate ........ 99
Meso-2, 3-[9, 10-anthrylene]-l, 4-butanediol (81)...... 99
Meso-2, 3-[9, 10-anthrylene]-l, 4-butane-di-p-
toluene-sulfonate (82) ............................ 100
11, 12 Dimethyl-9, lO-dihydro-9, 10-ethanoanthracene .. 100
1, 2-[9, l0-anthrylene]-cyclohexene-cis-4, 5-di-
carboxylic anhydride (79) ......................... 102
1, 2-[9, 10-anthrylene]-cyclohexene-cis-4, 5-di-
carboxylic acid (80) ............................... 102
Electrolytic Bisdecarboxylation of 1, 2-[9, 10-
anthrylenel-cyclohexene-cis-4, 5-dicarboxylic
anhydride .......................................... 103
Electrolytic Bisdecarboxylation of I, 2-[9, 10-
anthrylene]-cyclohexene-cis-4, 5-dicarboxylic acid 103
Triptycene [9, 10-0-Benzenoanthracene (85) ............ 104
Oxidative Bisdecarboxylation of 1, 2-[9, lO-anthry-
lenel-cyclohexene-cis-4, 5-dicarboxylate anhydride
with lead tetraacetate ............................. 104
4, 5-Dimethyl-[1,2,4,5-(9,10-anthrylene)-cyclo-
hexadiene] dicarboxylate (a2 ) ..................... 104
4, 5-Dimethyl-[4, 5-(9, 10-anthrylene)-cyclohexane-l,
2-1-(p-methoxyphenyl-AZ2-triazoline] dicarboxylate(_77) 105
4, 5-Dimethyl-[9, 10-O-Benzenoanthracene] di-
carboxylate (89) ................................... 106
4, 5-Dimethyl-[4, 5-(9, 10-anthrylene)-cyclohexene-
N-(p-methoxyphenyl)-l, 2-aziridine] dicarboxylate (91)106









Page


Attempted allylic Bromination of 4, 5-dimethyl-
[4, 5-(9, 10-anthrylene) cyclohexene-N-(p-
methoxyphenyl)-1, 2-aziridine] dicarboxylate ........ 107
4-Ethyl -([9, 10-anthrylene)-cycl ohexadiene]
carboxylate (95) ................................... 107
Attempted addition of p-mniethoxy azide to 4-Ethyl-
[1,2,4,5-(9, lO-anthrylene) cyclohexadiene]
carboxylate ........................................ 108
4-Carbethoxy-triptycene (98) ........................... 109
1, 2-(9, 10-anthrylene)-cyclohexane-1-p-methoxy-
phenylA2 triazoline-cis-4, 5-dicarboxylic
anhydride (99) ...................................... 109
Photolysis of 1, 2-(9, 10-anthrylene)-cyclohexane-
1-p-methoxyphenyl-A2' triazoline-cis-4, 5-
dicarboxylic anhydride .............................. 110
4, 5-Dimethyl-[(9, 10-anthrylene)-cyclohexane-l,
2-1'(p-methoxyphenyl)A2' triazoline] di-
carboxylate (103) ................................... 110
4, 5-Dimethyl-[1, 2-(9, 10-anthrylene)-cyclo-
hexene] dicarboxylate (102) ........................ 111I
4, 5-Dimethyl-[9, 10-anthrylene-cyclohexane-N-
(p-methoxyphenyl)-1, 2-aziridine] dicarboxylate (104) 112
Disodium [9, 10-anthrylenecyclohexene-N-(p-methoxy-
phenyl)-!, 2-aziridine] dicarboxylate (105) ......... 112
Attempted esterification of disodium [9, 10-anthry-
lenecyclohexene-N-(p-methoxyphenyl)-1, 2-aziri-
dine] dicarboxylate ................................. 113
Electrolytic Bisdecarboxylation of disodium [9, 10-
anthylenecyclohexene-N-(p-methoxyphenyl)-1,
2-aziridine] dicarboxylate .......................... 113

APPENDIX ........................................................ 114

BIBLIOGRAPHY .................................................... 125

BIOGRAPHICAL SKETCH ............................................. 129













LIST OF TABLES


Table Page

I Ring Strain in Three-Membered Rings ..................... 6

II Substituent Reactions of a-Bromo Carbamates ............. 33


viii











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


THE SYNTHESIS OF SPIRO AND BRIDGED AZIRIDINES

By

Emmett S. McCaskill, Jr.

December, 1974

Chairman: James A. Deyrup
Major Department: Chemistry

Attempts were made to synthesize a stable I-azabicyclo-[l.l.O]-

butane-2-one system, and confirm this proposed intermediate in the

aziridine-azetidinone ring expansion. Although the 1-azabicyclo-

([l.l.0]-butane-2-one system was not synthesized, this research re-

sulted in corroboration of the oxazoline-oxazolidone interconversion,

a new cyclization of 3-halo-carbamates and the synthesis of a spiro-

(9-fluorenyl)-aziridine. An explanation of these results is pre-

sented.

Attempts were also made to synthesize a benzo-2-aziridine system

by a Retro-Diels-Alder reaction. This involved the synthesis of a

N-aziridinyl-(9, 10-anthrylene)-cyclohexa-3, 5-diene derivative.

Realizing the importance of synthesizing this compound, the synthesis

of bridged aziridines was pursued initially. We were successful in

obtaining three precursors. The results of this work are discussed.












CHAPTER I


ATTEMPTED SYNTHESIS OF A I-AZABICYCLO-[I.i.O]-BUTANE-2-ONE


INTRODUCTION

A previous investigation by Deyrup and Clough led to the dis-

covery that certain aziridine derivatives undergo ring expansion to

3-chloro-2-azet i dinone (J).








"R
C10













Their work began when an attempt to synthesize a 2-aziridine-carbonyl

chloride (2) resulted in a new path to the 3-halo-2-azetidinone system,

Scheme I. Thus, when the lithium or sodium salt of 1-tert-butyl-2-

aziridine carboxylate (3) was treated with thionyl chloride or oxalyl

chloride in the presence of excess sodium hydride, the resultant pro-

duct was 1-tert-butyl-3-chloro-2-azetidinone (4) in 33% yield. Struct-

ure proof of this azetidinone 4 was based on ir and nmr spectroscopy,

elemental and mass spectral analysis. Further proof of the structure


- 1 -




-2-


Scheme I


0
&0-ONa
V-7
I
1-Bu
3


SOC!2


c-c'

N
it-Bu
2






4tBu
4


was obtained by reduction of the azetidinone 4 with zinc to give

l-tert-butyl-2-azetidinone (5) in 41% yield. Azetidinone 5 was

synthesized from 3-tert-butylaminopropronic acid (6), and thionyl

chloride, Scheme II.

Scheme I I


Zn
4
EtOH


- SOC12 H
-Bu N(CH2)2COOH

5 t-Bu 6




- 3 -


The ring expansion was of both mechanistic and synthetic inter-

est. The similar behavior of thionyl chloride and oxalyl chloride

with the aziridinium salts suggested that in both reactions a common

intermediate is present and opposes intermediates such as 1 or 8.


0
cT^ ^oo

C1 30 C1 0


1 0,
t Bu t-Bu
t-B U tB

7 8


A symmetrical carbonium-type intermediate can also be overruled

since the reaction was found to be stereospecific, Scheme III.

Scheme I II


(CO C12)2


R = CH3;

R H;


R = H
R, = CH3


R = CH ;

R = H;


R = H

R = CH




-4--


An appropriate mechanism, Scheme IV, capable of explaining these

results is the initial formation of the 2-aziridinecarbonyl chloride

(). Interaction of the unshared electron pair on the annular nitro-

gen and the carbonyl carbon results in the formation of a 1-azabicyclo-

[l.1.0]-butane-2-one cation (10). This strained bicyclic ion 10

proposed as the intermediate for this reaction gave 1-tert-butyl-3-

chloro-2-azetidone (4) by a stereospecific attack by chloride ion.

Scheme IV





0
It
C-ONa


1 9B
I _.C_-
t-Bu
0
3 9







I-Bu 0



CF t-Bu




- 5 -


The purpose of this study was to synthesize a stable 1-aza-

bicyclo-[l.l.0]-butane-2-one, establish the intermediate of this

reaction and to investigate the chemistry of this new system.


DISCUSSION

In an effort to select a derivative of a l-azabicyclo-[l.l.0]-

butane-2-one system (Il) that would be stable, strain energies and





R24

II



synthetic routes for stable azabicyclobutanes, aziridines and aziri-

dinones were considered. The stability of the azabicyclobutane ring

2
has been recently demonstrated by Hortman and coworkers. They syn-

thesized and isolated 3-phenyl-l-azabicyclo-[l.1.0]-butane. An estim-

ation of the increase in strain energy for introducing a carbonyl

group into the l-azabicyclo-[1.1.0]O-butane ring system seemed reason-

able. The corresponding values of strain energies for cyclopropane

and the aziridine ring are similar (26.9 and 27.5 kcal/mole3). Wiberg4

has shown that the introduction of a trigonal carbon into a three-

membered ring results in approximately 13 kcal/mole additional strain

energy (Table 1).




-6-


Table 1

Ring Strain in Three-Membered Rings


Compound Strain Energy (kcal/mole)

Cyclopropane 27.5
Methylenecyclopropane 41.0
Cyclopropene 55.0


An equivalent or greater increase in the strain energy of the azabi-

cyclo-[l.l.0]-butane-2-one system was expected but perhaps not to the

extent that it would make the synthesis impossible or greater than

the isolated cyclopropene (55.1 kcal/mole).

In order to stabilize the strained ring system, appropriate R

and R2 groups on the azabicyclo-[1.1.0]-butane-2-one system were

sought. Many ring opening reactions of aziridine may be formulated

as substitutions involving attack of a nucleophile at the aziridine

carbon atom. It seemed reasonable that steric protection of this

carbon atom with large groups would aid in the stabilization of this

ring system. In other highly strained systems such as a-lactones5
6
and a-lactams, tertiary butyl groups have been used with great

success and were considered here. Selection of R and R groups

which would destabilize positive charge at this carbon should inhibit

ring opening. The fluorenyl group seemed to suit these criteria.

Its derivative, l-azabicyclo-[l.l.O]-butane-2-one 12 was chosen

for synthesis.




-7-


NY
0
12


Ring closures from precursors 13, 14 and 15 were considered for
the synthesis of 12, Scheme V.


Scheme V


HN ?R
C=0
x
13


0x0
HN R
X
0
14


X R
00?
HN 0r
15


Base


YHN
0
12




-8-


The first precursor 13 would require synthesis of the spiro-

aziridine and ring closure of the a-lactam ring under appropriate

reaction conditions. The second precursor 14 would necessitate

synthesis of a P-lactam with a suitable leaving group in the 3-posi-

tion followed by elimination of HX to give the bicyclic product 12.

The third precursor 15 would require preparation of an Q-lactam

followed by ring closure of the aziridine to give the product 12.

Precursor 15 was eliminated on the basis of work by Lengyel and

Sheehan who have shown that the greater the steric requirements of

the substituents on N and on C-3, the easier the preparation and

purification of the a-lactam. This has been attributed to greater

thermal stability and lower reactivity towards nucleophiles. N-un-

substituted a-lactams have not been synthesized to date. If the

sodium or lithium salts of 1_6 could be synthesized, Scheme VI,

reaction with thionyl chloride might produce the desired product 12.

If nucleophilic attack by Cl occurs prior to deprotonation, the

Scheme VI



Q Q 0OC1 0 Q

HN HN H PCl
COONa
0 0
16 17 18




12




- 9 -


result should be 18. Proper treatment of 18 with a strong non-

nucleophilic base should give the desired product 12.

In an attempt to synthesize precursor 13, two spiroaziridines,

19 and 20, were chosen. Either one of these spiroaziridines could


EtO-C-N eiP
0 Et
19


O0

C-,
"0 Et
20


oe treated with strong base to produce the desired precursor 16,

Scheme VII.

Scheme VII


NaOH 0


C-ONa


129






20




- 10 -


Seemingly the most feasible way to obtain N-substituted spiro-
aziridines 19 would be to react ethyl azidoformate with ethyl
fluorenylidene acetate (2l), Scheme VIII. Huisgen, Szeimier and

Scheme VIII


~bEt


0
+ N3-C-OEt -- TrEazoIrw


21


hu Or
A


DOc
0I 00Et
EtC Q- 0
11j


8
Mbbius have studied the addition reaction of aryl azides to G, 3-un-
saturated esters and nitriles. Aryl azides could not be used here due
to the difficult removal of aryl group. The reaction of ethyl azido-
9
format with alkenes has been studied by Lwowski and Mattingly. Even
though no examples of a, P-unsaturated esters were given, success with
other azides warranted investigation.




- 11 -


The synthesis of precursor 19 began with the preparation of

ethyl fluorenylidene acetate (21) according to the procedure of
10
Sieglitz and Jossay. Ethyl a-hydroxy-cQ-(9-fluorenyl) acetate (22)

was prepared from 9-fluorenone (_3) and ethyl bromoacetate in a Re-

formatsky reaction, Scheme IX. The product was not isolated but

Scheme IX





0 HO0 CH2
+ ZnBrCH2C OEf A v
0^

23 "0 'Et
22


HOTs Q
C6H6
HA K COOEt
21




dehydrated by a catalytic amount of toluensulfonic acid to give ethyl

fluorenylidene acetate (21) in an overall yield of 91%.

Ethyl azidoformate was allowed to react with ethyl fluorenylidene

acetate (21) in methylene chloride, Scheme X.




- 12 -


Scheme X


0
+ N3-C-OEt CH2CI2
R.T.
I yr.


No Reaction


The reaction was monitored with infrared spectroscopy at one-,three-,

sixjqnd twelve-month intervals. After one-year reaction time, only

starting materials were recovered. The reaction was terminated. The

unreactivity of this alkene may be attributed to the deactivation of

the double bond by the ester group.

Bromination of the unsaturated ester 21_ according to the published
11
procedures of Gilchrist and Rees gave ethyl Q-bromo-a-(9-bromo-

fluorenyl) acetate (24), Scheme XI.

Scheme XI


CCl4
-. Br2 CC1
R.T.


H COOEt


00
Br COOEt
24


H/ COOEt




- 13 -


Synthesis of the unsubstituted spiroaziridine 20 was attempted
by the reaction of ammonia with a, f-dibromo ester 24, Scheme XII.
This approach was patterned after a series of papers by Cromwell and
Scheme XII


BO B H + NH3 0
Br <
Br Br COOEt

24


% 0
HN _
COOEt
20


12 -
coworkers which dealt with the reaction of a, p-dibromo ketones with
ammonia, primary and secondary amines, Scheme XIII.
Scheme XIII


0
R-CH-CH- C-R +
Br Br
Br Br


R'-NH2 ..




- 14 -


The reaction has been shown to proceed not by initial displacement

but by elimination to give the O-bromo-a-p-unsaturated ketone,

Scheme XIV. The ac-amino-p-bromo ketone obtained by the Michael

Scheme XIV


~~NH3 .
R-CH-CH-C-R 3 R-CH=C- C-R
I I "I
Br Br Br




NxNH3

\-v -b
0
II
0 R C-R
II / ^ --7
R-CH-CH-C-R-----\
NH2 Br N
H






addition of the nitrogeneous base with a-bromo-a-p-unsaturated ketone,

cyclizes to the aziridine. Dibrcmides of a, p-unsaturated acids and

their derivatives were shown to follow the same course of reaction.

Reactions of dibromo ester 24 with liquid ammonia for eight

hours did not give the expected aziridine 20. Instead, ethyl

a-bromofluorenylidene acetate (25) was isolated, Scheme XV. This

product had physical and spectral properties identical to those of a




- 15 -


Scheme XV


NH3


Br H
Br COOEt

24


compound prepared by Gilchrist and Rees.'

with ammnonia was unsuccessful, Scheme XVI.

Scheme XVI


Br CdOOEt

25


NH3
//,>


COOEt
20







Br COOEt

25



Further reaction of 25

It is evident in this


HN O
COOEt


20




- Ib -


case, that ammonia is strong as a base to form the intermediate, but

not nucleophilic enough to give ring closure to the aziridine.

Another synthetic approach to the aziridine precursor 19 en-

tails the nucleophilic displacement of a bromide by cyanate to give

the Dromo-isocyanate, Scheme XVII. This bromo-isocyanate can react

Scheme XVII


I I
Br-9- Br-
Br Br


I I
+ OCN -C C-
I
N Br
II
C
I)
0


ROH


Base


NH Br
C=0
00
6
R


W
C=O
0
R


with alcohol to give a bromo-carbamate. Subsequent cyclization with

a base can give the N-substituted aziridine. The dibromo ester 24

was then treated with silver cyanate, Scheme XVIII. The product 26

was isolated as deep yellow oil in yields that varied from 70 85%




- 17 -


Scheme XVIII


0^I'~ +
Br H
Br COOEt

24


Et2
AgNCO E0 ,H
R.T.H
O=C=N I^
gr COOEf
Br

26


(depending on the quality of silver cyanate). As expected, 26 was

not the only product. Since both bromines could be displaced by cy-

anate ion, it was speculated that the other isomer 27 would also

be present. There was no advantage in separating these isomers be-





Br H
(COOEt


27



cause ring closure of either isomer would give the same desired aziri-

dine precursor. One other product, ethyl fluorenylidine acetate (21)

was present in the reaction mixture. Even though the ester 21 was

not isolated, the nmr spectrum showed a vinyl proton at 6.63cf and an

aromatic proton at 8.92tef situated in the deshielding cone of the









carbonyl group of the ester.

The major product 26 was characterized by conversion to the

carbamate, Scheme XIX. Warming the isocyanate 26 in the presence

Scheme XIX




=0 EtOH *r
00
0=-C=N \XX / >
r COOEt Br COOEt

26 28









of ethanol for a few minutes gave ethyl Q'-bromo-a-(9-carbethoxy amino-

fluorenyl) acetate (28) in excellent yield. The carbamate 28 was

characterized by elementary analysis, nmr and ir spectroscopy and

mass spectral analysis. The structure of isomer 26 is supported

by both chemical and mass spectral data. As demonstrated earlier,

a bromine atom substituted on the beta position of dibromo ester 24

should dehydrohalogenate quite easily. Thus, if the major product

is 28, this isomer should not dehydrohalogenate under these condi-

tions. The carbamate 28 was treated with triethyl amine in benzene,

Scheme XX.


- la -




- 19 -


Scheme XX


0 0

EtOC. COOEt N(Et)3


28



Only starting material was recovered.


No Reaction


9H 9H
Me0- C-N" R Z
MeBr COOEt

29






A high resolution mass spectrum of methoxy derivative 29 showed at
base peak at 238 (m/e calculated C5 H 12NO = 238.0867; found 238.0879).

Structure 30 may be assigned to this fragment. Since there are




- 20 -


+NH
C=0
I
OMe

30


no peaks between 405 and 238 mass units, this fragment probably was

formed as depicted in Scheme XXI.

Scheme XXI


00-
10 H \ H
Me O-C-N^ r, I.CO
Me Br C OOEt



29





m/e =405


+NH
I
C=0
I
OMe

30





m/e = 238


Ring closures of 26 and 28 to the aziridine with ethoxide

in ethanol were attempted. The expected aziridine 19 was not ob-




- LI -


stained, but a 2-oxazoline 31 was isolated in 80% yield, Scheme XXII.
Scheme XXII


Br COOEB


Et O.IV0 C OQB


EtO
EtOH


O- 00
11 H
Et O-C-NC
Br COOE
28


00
Et O-( -N
0 COOE1




- 22 -


It has been shown that cyclization of N-(2-substituted alkyl)-carboxy-

amide may proceed by two pathways, Scheme XXIII. The first pathway

Scheme XXIII


L
I I
i) -y-9-
HN-COOR






L
I I
2) -c C-
I I
H-N
CC=0
6
R


Strong
Base







'I


v
c=O
OR





F--\
N "Y0
V
0
R


yields a 1-acyl aziridine and the second leads to the formation of
oxazolines.

Instances in which aziridines are formed rather than oxazolines
have been attributed mainly to two factors.13 Decreased resonance

stabilization of the anion resulting from the removal of a proton




- 23 -


from the mono-N-substituted urethan apparently favors three-membered

ring formation. The second factor relates to leaving groups effect-

iveness. The formation of aziridines are facilitated by very effect-

ive leaving groups such as tosylate and mesylate. The examples

studied also involved trans groups on six-membered rings. The dis-

tinguishing factors between the two pathways may be more complicated

and need further investigation.

14
Katchalsky and Ben Ishai have shown that P-halocarbamates

may be converted to 2-oxazolidones by pyrolysis at 120 to 200 C,

Scheme XXIV.

Scheme XXIV




H 0
R- C R
I __ A_6
HN H------- ____
C=0

R 0








Heating the carbamate 2_ at 200C for five minutes gave the

expected 2-oxazolidone 32, Scheme XXV. The by-product, ethyl

bromide,could be detected when the reaction was conducted in a Carius




- 24 -


Scheme XXV


0C 0 2000C
EtOOC-0 I
Br COOEt


0 pCOO E
0


29


tube Hasnerandcowoker15
tube. H1assner and coworkers have shown that the pyrolysis of methyl
N-(trans-2-iodocyclohexyl) carbamate (33) gives a 2-oxazolidone 34
melting at 55 56C, Scheme XXVI. The reported melting point for
Scheme XXVI



N-CO Me

x N O e ,,.-N
A ,,.._0
v '. ...""""0X




- 25 -


cis-cyclo-hexano[b]-2-oxazolidone (34) is 55 C; the isomeric trans-

cyclohexano[b]-2-oxazolidone melts at 110 C 5. This reaction

establishes the fact that an inversion of the iodine-bearing

carbon is involved in the pyrolytic conversion of iodo-carbamate

to 2-oxazolidones and with this evidence Hassner proposed the follow-

ing mechanism, Scheme XXVII. If this mechanism is correct, it

Scheme XXVII


HH
cx ~N-COMeQ N
N 0e



33 35
/



aH
Q=0 + Mel


34



should be possible to convert a 2-oxazoline to a 2-oxazolidone with
the addition of HBr under anhydrous conditions, Scheme XXVIII. This
conversion was then carried out with 2-oxazoline 31 in ether pre-




- 26 -


Scheme XXVIII


HBr


NOCH3
OCH3


HN^ o

0'CH3

Br


----0
v HN O

0


+ CH3Br





viously saturated with dry HBr. The isolated product was the 2-oxa-

zolidone 32, Scheme XXXIX. These results support the reaction inter-

Scheme XXXIX


HBr .
EtOH


0HN OCCOOEt
00


32


mediate 35 proposed by Hassner and coworkers.
16
Hassner and other workers have synthesized a large number of

aziridines by cyclization of iodocarbamates with a base, Scheme XXX.




- 27 -


Scheme XXX


H
cX N COOMe NaOH


QNH


Treatment of carbamate 28 under similar conditions did not give
the expected aziridine 20. Instead, 2-oxazolidone 36 and 9-
fluorenone 2? were isolated, each in 20% yield, Scheme XXXI.
Scheme XXXI


10a
H H
EtOON COOE
Br COQEt


q NaOH ,o
A HN ".H
0CH3
^0


36


This reaction was quite unique in that the total process involved the
formation of a carbon-carbon bond on a carbon which contains a nitrogen
atom. Since this reaction has potential synthetic utility, attempts


+ 23




- 28 -


were made to investigate in detail its mechanism. Anionic and cationic
rearrangements were considered but do not reasonably explain these re-
sults. As a working model a radical mechanism was proposed because
alkyloxy radicals are stable intermediates and account for the pro-
ducts, Scheme XXXII.
Scheme XXXII


00OH
H H
EtOOCN X
Br COOEt
28




OoD




RH


36


~H
+ C -COOEt
r^BrI
N
C=O
6
Et
37

R-


0 + RH
N
I .
C-O-C HCH3
!1
0

38




- 29 -


In this proposed mechanism, hydroxide ion first abstracts the proton

from the amide nitrogen to give 9-carbethoxyiminofluorene (37). The

resulting anion is probably destroyed under reaction conditions.

The intermediate 37 reacts further in an oxidative or radical chain

process to give radical 38 which cyclizes to 39 and subsequent

hydrogen abstraction gives the product 36. Because the reaction

conditions were strongly basic, radical scavengers could not be used

to confirm the radical process. In order to investigate the mechanism

of this reaction 9-carbethoxyiminofluorene 3J was synthesized and

subjected to free radical initiators.

9-Carbethoxyiminofluorene 37 was synthesized by two methods.

The first method was the synthesis of 9-(carbethoxyamino) fluorene 41,

Scheme XXXIII, by the reaction of 9-aminofluorene 40 with ethyl chloro-

Scheme XXXIII







0Y: + Ci-COOEt C 6H6
NH2 NH
I
CkO
40 I
OEt

41




- 30 -


17
format utilizing the published procedure of Neish. Oxidation of

41 _with activated MnO according to the procedure of Deyrup and Gill18

gave 9-carbethoxyiminofluorene (37) in acceptable yield, Scheme XXXIV.

Scheme XXXIV


HN
C=0O
OEt

41


MnO2
C6H6


N
CO=0
OEt


37


In a second method, 9-iminofluorene (42) was synthesized from

ammonia and 9-fluorene (23) at 165 C, Scheme XXXV. Subsequent re-

Scheme XXXV



No 15H CICOOEt 37


0 N


action of imine 42 with ethyl chloroformate gave the desired 9-carbo-

thoxyiminofluorene 37.




- 31 -


The reaction of 9-carbethoxyfluorene 37 under the above con-

ditions did not give the desired 2-oxazolidone 36. The only product

isolated was 9-fluorenone (23) in 20% yield, Scheme XXXVI.

Scheme XXXVI


aq. NaOH


c=O
I
OEt

37


a 0
0

23


19
Urry and coworkers19 have studied the free radical reactions of

alcohols with alkenes. The radical chain process involved the formation


-- CH2=CHR


t-BuO)2 .


OH
I
R-C-CH2CH2R
H


of alkyoxy radicals and subsequent attack on the alkene by the radical.


OH
IS
RCH2OH + CH2:CHR R-CH-CH2CHR


RCH2OH




- 32 -


It was found that displacement was on the hydrogen attached to the

carbon bearing the primary and secondary alcohols. Ethers have also
20
been shown to react with alkenes under radical conditions, Scheme

XXXVII.

Scheme XXXVII


Bz202


0

CH2(OCH3)2 + 0

0


H 0
(CH3 O)2C


0


The reaction of 9-carbethoxyiminofluorene (37) with benzoyl peroxide

and tert-butyl peroxides under similar reaction conditions were un-

successful and only starting material was recovered, Scheme XXXVIII.

Scheme XXXVIII


Bz202
t-BuO)2 v


No Reaction


0:0
N
I
C=0
I
OEt
37










In a final effort to explore the mechanism, some substituent

reactions were investigated. These data are summarized in Table II.

Table II

Substituent Reactions of o-Bromo Carbamates







Solvent
H I NaOH Q
ROC HN
() Br COOEt L0o
0










R Solvent Yield (%)
Et EtOH 20 20
Me EtOH 20 20
Me MeOH 0 2


As shown earlier, the 2-oxazolidone and fluorene are produced in equal

amounts. Substituting a methoxy in the carbamate portion of the

molecule using ethanol as the solvent produced no change in the yield

of products. This showed that transesterification was quite rapid.

However, changing the solvent to methanol did not give the expected

product 43, but instead gave only 9-fluorenone (23), Scheme XXXIX.


- ->J ~




- 34 -


ORP
HN -
0-
43


Scheme XXXIX


9H H H
MeQOON BrCOl
Br C -~


0r;0
0


29


Since the carbamate 28 did not give ring closure to the desired
aziridine 19, hydrolysis of the isocyanate to the amine was attempted.
Treatment with an appropriate base could possibly cause ring closure
of a-amino-p-bromo derivative to the spiroaziridine 20. Hydrolysis




- 35 -


of bromo-isocyanate 26 with 47% hydroiodic acid gave the desired

bromo-amine 44 in 50% yield, Scheme XL. This bromo-amine 44 isolated
Scheme XL




~~~HI HN
o^ }-( HI i -f
Acetone H N

O=C=N HXOE "N"I
Br COOEt Br COOEt

26 44







as a colorless oil. The structure is supported by ir and nmr spectro-

scopy.

The cyclization of the a-amino-a-(9-bromofluorenyl) acetate (44)

was finally accomplished. The reaction of 44 with triethyl amine at

room temperature using ethanol as the solvent gave ethyl-2-spiro-

(9-fluorenyl) aziridine carboxylate (20) as white crystals in 98%

yield, Scheme XLI. This structure is supported by ir, nmr, and mass

spectral analysis. The nmr spectrum was interesting and merits some

comment. The N-H proton appeared at 2.58cf as a broad doublet

(J=9Hz). The proton on C-3 appeared at 3.43c" also as a broad doublet




- 50 -


Scheme XLI






N(Et)3
0 'EtOH
H2N H 3Days HN
Br COOEt COOEt


44 20









(J=9Hz). On addition of D 0 the 2.58J resonance disappeared and the

doublet at 3.43JC collapsed to a singlet. This last result elegantly

supports the assigned structure of the spiroaziridine 20.

Following the synthesis of the spiroaziridine 20 as discussed

above, an attempt was made to convert 20 to the sodium salt according

to the reaction conditions of Deyrup and Clough with the intent of

obtaining the l-azabicyclo-[l.l.O]-butane-2-one following subsequent

reaction with thionyl chloride.

Ethyl 2-spiro-(9-fluorenyl)-aziridine carboxylate (20) was

refluxed in aqueous alcoholic sodium hydroxide for one hour. The

sodium salt 1_6 was isolated as a white powder in quantitative yield,




- 37 -


Scheme XLII. This structure is supported from spectral analysis.

Scheme XLII


HN
COOEt


NaOH


HN
COONa


20


Sodium 2-spiro-(9-fluorenyl) aziridine (16) was treated with

thionyl chloride following the procedure of Deyrup and dClough. On

work-up no products could be identified by nmr spectroscopy. It

appeared that thionyl chloride had caused total destruction of the

molecule. The use of alternative reaction conditions at low temper-

atures using different proton scavengers were without success.
21
Tomalia studied the reaction of some N-unsubstituted aziri-

dines with thionyl chloride, Scheme XLIII. He found that by react-

ing equimolar amounts of aziridines and triethyl amine with thionyl




- 38 -


Scheme XLIII




S 02CI2 I
V + Et3N 1,50C > -S-C J
N
H CCI4




25 CI CH2CHI N;S40
250C




chloride at reduced temperatures it was possible to trap and character-

ize the new class of aziridine derivatives, l-(aziridine) sulfinyl

chlorides. When these compounds stood at room temperature for several

hours, 2-chloro-N-sulfinyl ethylamine was isolated. Although none of

these derivatives were isolated, this doas suggest that there is

probably an attack of the thionyl chloride on the nitrogen which

changed the reaction path.

CONCLUSION

Although the l-azabicyclo-[.l.O]-butane-2-one was not syn-

thesized there are at least two approaches which might warrant future

study. The first is the ring closure of the a-lactam ring. Since

the synthesis of this ring involves the formation of a N-C bond and

removal of an OH group in 16, this is closely related to the syn-

thesis of peptide with carbodiimide derivatives, Scheme XLIV. Since




- 39 -


Scheme XLIV


RCOOH -6 RNH2 + R N=C=N R


0 H
R-C- N-R

+

H 0 H
R N-C-N R


aziridines are unstable to acid, the free acid derivative of 16 can

not be generated. If, however, the carbodiimide could be activated

so that the first step is no longer acid dependent, a similar reaction

may occur with the aziridinium salt 16. An ideal reagent would be

a methylated carbodiimide 45. If the methylated carbodiimide 4.




CH
1 3
R-N= C=N-R
x"

45





is allowed to react with 16, the desired product 12, sodium salt

of the anion and a methylated urea 46 should be formed, Scheme XLV.




- 40 -


Scheme XLV


C+
OO*
H
COONa
16


CH3
R N=C=NR
+
X-

45


N P
0
12
+
CH3 0 1
R N- C-NR
46


Syntheses of methylated carbodiimide are presently being investigated.
The second approach utilizes precursor 14, the synthesis of 3-lactam.
This is an attractive route in that the amine 44 has been synthesized.
Thus, base hydrolysis followed by acidification to give the P-amino
Scheme XLVI


0I ) OH" 0,(T
2) H2 v
H2N B H H2N" H
Br COOEt Br COOH


41


cc,

0
H _Brr
0
48


41




41 -






acid 4_ and treatment with a carbodiimide under appropriate reaction

conditions should give the 3-bromo-azetidinone 48. Subsequent treat-

ment of 43 with a strong base, but poor nucleophile, might give the

1-azabicyclo-[1.1.0]-butane-2-one system 12, Scheme XLVI.












CHAPTER II


ATTEMPTED SYNTHESIS OF A BENZO-2-AZIRINE


INTRODUCTION

Considerable attention has been given to the chemistry of small

strained heterocyclic ring systems. The 2-azirine ring system 49

is one that has received considerable attention. A large number of


VH
XN

H
49



22
recent attempts have been directed toward its synthesis, but the

system has neither been isolated nor trapped. This ring system is of

theoretical interest since, if planar, it is a cyclic conjugated
23
structure containing 4TT electrons. Huckel's rule23 predicts anti-

aromatic character. Since 1-azirines are well known, it does not

seem reasonable to attribute the non-existence of 2-azirines ex-

clusively to strain energy. The instability of the 2-azirine system

could probably be attributed to an unfavorable electronic property


- 42 -




-43,-


that exists within this molecule. The aim of this research was to

synthesize the related benzo-2-azirine system (50).



C |N-R


50



The strategy selected was to synthesize a benzo-2-azirine (50)

via a Retro-Diels-Alder reaction, Scheme XLVII.

Scheme XLV I


A


NR 52
50 52


A derivative of N-aziridinyl-(9, 10-anthrylene)-cyclohexa-3, 5-diene

(51) was selected so that formation of benzo-2-azirine (0) would

also yield anthracene (52) as a by-product and thus provide the

driving force in this synthesis.




-44-


Benzopropene (53), which results from fusion of cyclopropene







53




to a benzene ring is the parent and most highly strained member of

the benzocycloalkene series. 4 The strain energy has been estimated
25
to be at least 45.5 kcal/mole greater than cyclopropane.25 Nonphoto-

chemical synthesis of benzocyclopropenes resulted from the work of

Vogel, Grimme and Korte.26 Pyrolysis of 1:1 adducts 54 of 1, 6-

methano[lO]-annulene with dimethyl acetylenedicarboxylate gave benzene-

cyclopropene (53) in 45% yield, Scheme XLVIII.

Scheme XLVIII


O400C


MeOOC-


r+ j'>COOMe
Kj--C 0ACOOMe


53


54




- 45 -


While this work was in progress, a related Retro-Diels-Alder
1 27
approach was published. Klarner and Vogel attempted to prepare an

antiaromatic benzo-2-oxirene (56) which resulted in the isolation of

a rearrangement product 5Z, Scheme XLIX. They concluded that isomeri-

zation of 55 to 51 constituted a suprafacial 1, 5-sigatropic shift

which is symmetry allowed.

Scheme XLIX






56

50-100C

N C 00
NC% < 0

NCC
55NC%


57



PROPOSED PLAN

The precursor 1, 2, 4, 5-(9, lO-anthrylene)-cycluhexadiene (58)

was chosen to initiate the synthesis of the derivative of N-aziridinyl-

(1, 0lO-anthrylene)-cyclohexa-3, 5-diene (51). If 58 could be syn-

thesized, selective addition of azide to the more strained double

bond could give the bridged triazoline 59, Scheme L.





















Scheme L









N3R Q


58 59




Whereas unactivated olefins are sluggish toward aryl-azides, strained

bicyclic systems, on the contrary, are particularly reactive.28 The

triazoline 59 could easily be converted to the bridged aziridine 60

either thermally or photochemically, Scheme LI.










Scheme LI











R N-R
N lhv or




59 60




The bridged aziridine 60 could then be brominated to give the di-

bromo-addition product 61 or could be treated with N-bromosuccinimide

(NBS) to give the allylic brominated product 62, Scheme LII.

Scheme LI I


60


- 47 -




- 48 -


Bromination of unsaturated aziridines has been accomplished at low

temperature by Paquetteand Kuhla.29 Successful synthesis of 61J or

62 and subsequent treatment with base might give the desired pro-

duct 51, Scheme LIII.

Scheme LIIIl





61


N-R

61 Base .Tv



6 2>51














The synthesis of precursor 58 from the anhydride 63 was planned

by either electrolytic or oxidative bisdecarboxylation of 6. or the

diacid 64, Scheme LIV. Bisdecarboxylation and azide addition are two

key steps in this proposed synthesis. A model compound was chosen to




- 49 -


Scheme LIV















Elect. or

Pb(OAc)4


58


64


investigate the problems involved and to find appropriate reaction

conditions by which precursor 58 and bridged aziridine 60 might be

synthesized. The model compound chosen was anthracene 9, 10-U, P-

succinic anhydride (65.).


63




- 50 -


65


DISCUSSION

Anhydride 65 was synthesized according to the published pro-

cedure of Bachmann and Kioetzel, Scheme LV, by the reaction of

Scheme LV


52


0 0
+uio


0
66


A
C6H6


65




- 51 -


anthracene (52) and maleic anhydride (66). The anhydride 65 was

then converted to the disodium salt 67 and dicarboxylic acid 68.

Electrolytic bisdecarboxylation of 665, 67 and 68 gave 11, 12-

etheno-9, 10-dihydroanthracene (69) in 25 30% yield. Oxidative bis-

decarboxylation with lead tetraacetate of 65 and 68 gave approximately

the same results, Scheme LVI. Isolated products obtained from the

Scheme LVI


Elect, or

Pb(OAc)4


68




- 52 -


electrolytic method were cleaner and did not require further puri-

fication. Of significance in the oxidative method is lactone forma-

tion in bridged compounds containing proximate double bonds, Scheme LVII.

Scheme LVII









COOH Pb(OAC)4
COOH O 0
O 0







It is reported that in the oxidative bisdecarboxylation, lactones are

formed. 3 The electrolytic method is usually favored for bridged bi-

cyclic ring systems.

Following the successful bisdecarboxylation of 6 and its deri-

vatives 67 and 68, the 1, 3-dipolar cycloaddition reaction of a-

methoxyphenyl azide (70) warranted investigation. The selection of

azide 70 was based on the following factors: 1, 3-dipolar cyclo-

addition reaction of aryl azides has been characterized and its
32
mechanism confirmed by Huisgen ; the methoxy group in an nmr spectrum





- 53 -


identifies the azide additions, and; the reactivity of azides with

deactivated alkenes has been shown to increase with electron donating
33
groups. The addition of p-methoxyphenyl azide to II, 12-etheno-9,

10-dihydroanthracene gave the triazoline 71 in 57% yield. Photolysis

of the triazoline 71 with a sun lamp gave the expected aziridine 72

in 50% yield, Scheme LVIII.

Scheme LVIII



_OMe


H P
N H




OMe
69 70 71l




OMe



hv "
Acetone




- 54 -


Synthesis of the anhydride 63 began with the preparation of 11,

12-dicarbomethoxy-9, 10-dihydroanthracene (73) according to the pro-
34
cedure of Diels and Alder, Scheme LIX. Saponification followed by

Scheme LIX


COOMe


MeOOC

{J) + MeOOCC=CCOOMe c


52


neutralization to the diacid 74 and subsequent heating with acetic

anhydride gave the unsaturated anhydride 75 in quantitative yield,

Scheme LX. According to the published procedures of Diels and

Scheme LX


NaOH
HCI


Ac2O


74.


75




- 55 -


Friedrichsen35, anhydride 63 was synthesized and isolated in 95%

yield by reacting 75 with butadiene, Scheme LXI.

Scheme LXI


75


1O0C
C6H6


63


Bisdecarboxylation of anhydride 63 with both oxidative and electro-

lytic methods was not successful. Only starting material was recovered,

Scheme LXII. The anhydride 63 was then converted to the disodium

Scheme LXII


Elect, or Pb(OAc)4


63


No Reaction




- 56 -


salt 76. Acidification of the disodium salt 76 did not give the

expected dicarboxylic acid 64, but instead regenerated the anhydride

63. Electrolysis of the disodium salt 76, Scheme LXIII, also gave

Scheme LXIII


HCI


63 NaOH


Elect.


63


the anhydride rather than the expected diene 58. Tetramethyl succinic

anhydride 36(7Z) is formed by the hydrolysis of the diester with hydro-
37
bromic acid. Dialkyl maleic acids exist only in the form of their

anhydrides (78, R = methyl, ethyl, or phenyl) which are formed spon-




- 57 -


78


taneously upon acidification of aqueous solutions of the salts of the

acids.

An alternative approach to the synthesis of precursor 58 is to

synthesize the isomeric anhydride 79. Bisdecarboxylation of 79 or


79

its dicarboxylic acid 80, Scheme LXIV, might give the desired pre-

Scheme LXIV



COOH
HOOC I :\


Elect.


58




- 58 -


cursor 58.

The synthesis of anhydride 729 began with the preparation of

anthracene 9, 10-endo-a, p-succinic anhydride (a), and subsequent

reduction with lithium aluminum hydride in THF.38 The resulting

diol 81 was converted to the ditosylate 82, Scheme LXV, and

Scheme LXV


65 LAH


TsCI


82


thereafter, synthesized in good yield by the reaction of anthracene

(52) with cis-1, 4-dihydroxy-2-butene,39 Scheme LXVI. The ditosylate 82

Scheme LXVI


H20H 1850C


(CHOH


52





- 59 -


was then treated with 7% sodium hydroxide to give dimethylene-9,

10-ethanoanthracene (84) and a by-product ether 83, Scheme LXVII.

Scheme LXVII


82 7%NaOH


84


83


Separation of 84 from 83 by column chromatography and subsequent re-

action of 84 with maleic anhydride (66) illustrated in Scheme LXVIII

Scheme LXVIII


A


0

+ 0
0
66




- 60 -


40
gave the desired precursor 79 in 86% yield.

The diene 58 was unobtainable via bisdecarboxylation of an-

hydride 79 and triptycene (85) was isolated in low yield, Scheme

LXIX.

Scheme LXIX


58


79


Elect.


Bisdecarboxylation of the diacid was then investigated. The anhydride

79, Scheme LXX, was treated with aqueous sodium hydroxide and aci-

Scheme LXX


I) NaOH
2) HCI


80




- 61 -


fiction gave the dicarboxylic acid 80 in 92% yield.

Scheme LXXI shows oxidative and electrolytic bisdecarboxylation

Scheme LXXI







COOH
HOOC

Elect. or
Q Pb(OAc)4 Q


80 85







which gave triptycene (85) in low yield. Triptycene could have been

formed by one of two pathways: bisdecarboxylation to give the diene

58 and subsequent oxidation at the anode surface, or, stepwise de-

carboxylation of one carboxyl group to give a double bond conjugated

with the first, followed by decarboxylation of the second carboxyl

group to give 85.

In the hope that ester groups might stabilize the diene system,

compound 86 was chosen for synthesis. The Diels-Alder reaction of

dimethylacetylene dicarboxylate with 11, 12-dimethylene-9, lO-ethano-9,




- 62 -


MeOOC






86


1-dihydroanthracene (84), Scheme LXXII, gave 42% yield of 86. The

Scheme LXXII


+ MeOOCC^CCOOMe


diene derivative 86 was then treated with k-methoxyphenyl azide, in

a Carius tube for seven days at 80 0C. The resultant triazoline 87,

Scheme LXXIII, was isolated in 71% yield.


Z 40




- 63 -


Scheme LXXIII


MaOO
EtOAc
A .


At 100C products 88, 89, and anthracene (52) were separated using


Me lOK-N=N- _Ome

88 Q
89

column chromatography. The Retro-Diels-Alder by-product 20 was not

detected in the reaction mixture.


MeOOC
MeOOCa


0M
OMe
90


N3

+ 0
OMe

70


87




- 64 -


0
Photolysis of triazoline 87 with a sun lamp in acetone at 25 C

gave the desired aziridine 91, Scheme LXXIV, in 81% yield. The nmr

Scheme LXXIV


MeO


COOMe


hv
Acetone


spectra showed interesting changes of the diene 86 to the triazoline

87 and finally to the bridged aziridine 2j. The three absorptions

of interest were the aromatic protons, the bridgehead protons and ithe

methyl ester protons. In diene 86 the aromatic region showed a

symmetrical absorption of 8 protons, a singlet for the bridgehead

protons, and a singlet for the 6 protons of the two methyl ester

groups. In the triazoline 87 the aromatic region became quite complex




- 65 -


as it increased to 12 protons with the bridgehead and methyl esters

protons appearing as two very close singlets. On photolysis of the

isolated aziridine 91 the aromatic region separated into two por-

tions, an unsymmetric 7-proton multiple and a 4-proton A-B quartet

that was shielded. The bridgehead and the methyl ester protons

appeared as singlets with the bridgehead protons being slightly

more shielded with essentially no change in the ester groups.

Bromination reactions of aziridine 91 were then investigated.

The addition of bromine gave substitution products as depicted by

nmr and mass spectroscopy and was not further pursued. It is re-

ported that bromination of p-methoxytoluene with N-bromosuccimide

in carbon tetrachloride with benzoyl peroxide as the radical initia-
41
tor gave 65% yield of p-methoxybenzyl bromide, Scheme LXXV.

Scheme LXXV





CH3 CH2Br


f3 + NBS CC 4N
OH ABzW0P.
OCH3




- 66 -


Allylic bromination of 21 was then investigated. The reaction of 91

with N-bromosuccimide and benzoyl peroxide did not give the desired

product 92, Scheme LXXVI. Apparently, the two bromine atoms had

Scheme LXXVI


MeOOC


92


91 NBS, CC4
Bz2z0

MeOO0


1dOMe











Br2
e A'L-OMe


93


substituted on the aromatic ring, based on nmr and mass spectral

analysis. The exact substitution pattern was undetermined. It

appeared that the ester groups might have deactivated the allylic





- 67 -


position and that the most reactive site within the molecule 91

was the aromatic ring with the methoxy group substituent.

In an effort to facilitate allylic bromination, compound 94

was selected. The single conjugated ester group would probably

still stabilize the diene. Also, by having only one ester group,

one allylic position remains essentially unchanged. It is re-

ported that 1-carbethoxycyclohexene is brominated in the 3-position

rather than the 6-position, with N-bromosuccimide and benzoyl
42
peroxide. If aziridine 94 can be synthesized, allylic bromin-

ation may occur at the most active allylic position.




COOEt








94







The synthesis of 94 began with the isolation of 95 in 74% yield,

Scheme LXXVII, from the reaction of 11, 12-dimethylene-9, 10-etheno-

9, 10-dihydroanthracene (84) and ethyl propiolate. The nmr spectrum




- 68 -


Scheme LXXVII


94 + HC=C COOEt


of 25 showed no proton absorption in the vinyl region as expected.

The bridgehead protons appeared as two close singlets at 4.72 and

4.77. R-Methoxyphenyl azide (70) was then added to 95. The expected

triazoline isomers96 and 97 were shown to be present based on an nmr





CEOOEt -O- Me
EtOOC,_,_, vOMe -,4,


97


96




- 69 -


spectrum of the reaction mixture. The bridge protons region

changed from two singlets to a complex multiple. The methoxy

protons were also present in addition to some residual azide.

There was strong absorption in the vinyl region, suggestive of

bridgehead protons on triptycene derivatives. Since the triazoline

isomers give the same aziridine 94, photolysis of the reaction

mixture with subsequent separation by column chromatography was





COOEt








94





pursued. The desired product 94 was not obtained. Only the tripty-

cene derivative 98 and residual starting materials were isolated.

Characterization of 98 was accomplished by nmr and high resolution

mass spectroscopy. The product isolated from the reaction of 95

with NBS, Scheme LXVIII, showed identical spectral properties to 48.

A number of diene systems have been shown to aromatize with NBS.43
A number of diene systems have been shown to aromatize with NBS.




- 70 -


Scheme LXXVIII








COOEt COOEt



M NBS
Q O C C14
^ Bz202

95 98







An attempt was then made to add the azide 70 to anhydride 79.

If the triazoline 29 could have been formed and subsequent photolysis

gave the aziridine 100, oxidative or electrolytic bisdecarboxylation

might give the desired unsaturated aziridine 101, Scheme LXXIX.

Anhydride 79 and azide 70 were heated at 100C in a Carius tube for

seven days. Triazoline 99 was present according to nmr spectro-

scopy. The spectrum of the triazoline showed the methoxy protons

at 3.77 and two singlets for the bridgehead protons. Purification

and further characterization was quite difficult. Photolysis of the




- 71 -


Scheme LXXIX





N3

+ 0 1 A
OMe

70


99


, M e


hv


Elect.


100


crude triazoline 99 was successful as depicted by nmr spectroscopy,
but purification problems were again encountered. The separation of
the aziridine 100 from other components of the mixture was achieved
in a crude form by fractional crystallization. Hydrolysis of the




- 72 -


anhydride 100 was also noted during recrystallization. In order to

eliminate these problems, the diacid 80 was converted to diester

102, Scheme LXXX, in 91% yield. The diester 102 was treated with

Scheme LXXX


MeOO'


H H
MeOH


80


102


R-methoxyphenyl azide (70) in a Carius tube at 100 0C for four days,

Scheme LXXXI. Although other products were formed, the triazoline




- 73 -


Scheme LXXXI








COOMe O
N3 MeOOC a O3

102 + W EOAc 4

0 Me

70
-103













could be separated in good yield using column chromatography. It

was later found that a decrease in temperature from 100 0C to 80 0C,

and an increase in reaction time from four to seven days, increased

the yield of triazoline 103 and decreased the by-products previously

observed. Column chromatography was not required for isolation of

the triazoline. The triazoline 103 was then photolized to give the




- 74 -


desired aziridine 104 in 93% yield, Scheme LXXXII. The aziridine
Scheme LXXXII


Me004


103


vOrMe


hv
Acetone


104


was characterized by mass spectral analysis and its nmr spectrum

showed close similarity to 91.

Saponification of 104_ was finally accomplished, Scheme LXXXIII,

Scheme LXXXIII



COONa
NaOOy< K^sOMe

104 NaOH NaOOOMe
Diglyme


105





- 75 -


by the reaction of 10% sodium hydroxide in aqueous diglyme solution.

Infrared spectroscopy supported the disodium salt structure 105.

Further characterization of the salt 105 was difficult due to its

solubility properties and acid sensitive functions. Attempts were

made to esterify the disodium salt 105 by acidification at low

temperature with 5% perchloric acid, Scheme LXXXIV. Aziridines

Scheme LXXXIV


105


HC104 c
OOC


106










have been shown to be stable under these conditions. Esterification

of the diacid 106 with diazomethane gave a mixture of products

but not the expected diester 104, Scheme LXXXV. Ring opening





- 76 -


Scheme LXXXV


MeOOI


CH2N2 .
Et2 //


prior to the esterification would probably have justified these results.

Electrolytic bisdecarboxylation of the disodium salt 105, Scheme

LXXXVI, also resulted in a complex mixture. The desired diene 101

Scheme LXXXVI





Elect. _OM e

105 E c .


I01


106


104





- 77 -


was not obtained. These results could be attributed to the aziridine

being unstable under electrolytic conditions.


SUMMARY AND CONCLUSIONS

Diene 58 was chosen because it would have a minimum number of

functional groups after the azide addition, but attempted synthesis

resulted in aromatization to triptycene. Stabilization of diene 86

and 95 with ester groups was successful. Azide addition to diene

86 and subsequent photolysis of the resulting triazoline 87 gave

the desired aziridine 91. Azide addition of 95 resulted in aroma-

tization to the triptycene derivative 98. Aromatic substitution oc-

curred on allylic bromination of 9J.. Purification problems of azide

addition to the anhydride 79 were eliminated by converting the an-

hydride to the diester 102. Addition of the azide and subsequent

photolysis gave the aziridine 104. Saponification of 104 followed

by bisdecarboxylation of the disodium salt resulted in a complex

mixture. It is suggested that an aziridine such as 107 be synthe-

sized with a deactivated phenyl or alkyl as the R group. If the X

groups are removable by base, the diene 51 might be synthesized.


107














CHAPTER III


EXPERIMENTAL


General

Melting points were determined on a Thomas-Hoover Unimelt

Capillary melting point apparatus and are uncorrected.

Infrared spectra were recorded on a Perkin-Elmer 137 or Beck-

mann IR-IO spectrophotometer with absorptions reported in recipro-
-l
cal centimeters (cm ). All nuclear magnetic resonance spectra

(nmr) were obtained on a Varian A60-A spectrometer. Chemical

shifts of nmnr spectra run in organic solvents are reported in

ppmfW) downfield from internal standard tetramethylsilane. Low

resolution mass spectra were determined on a Hitachi model RMU-6E

mass spectrometer. High resolution accurate mass spectra were

determined on a AEI MS-30 double beam mass spectrometer. Micro-

analyses were obtained from Atlanta Microlab, Inc., Atlanta,

Georgia.

Separation by column chromatography was conducted using Fisher

Adsorption alumina (A-540, 80-200 mesh and Baker Silica Gel). De-

activated alumina were prepared by adding the desired amount of


- 78 -




- 79 -


water (by weight percent) to the alumina and shaking until no lumps

were visible. Silca gel was used directly and with no previous

treatment. Solvent evaporations were carried out using a Buchler

rotary evaporator in vacuo (water aspirator) and by using a Buchi

Rotaryvapor-R in vacuo (pumps).

Ethyl a-hydroxy-a-(9-fluorenyl acetate) (22)

Zinc metal (19.6 g., 0.300 g. atom) was placed in dried 1-liter

three-necked flask equipped with a dropping funnel, condenser, and

a mechanical stirrer. Fluorenone (50.0 g., 0.259 mole) and ethyl

bromoacetate (45.0 g., 0.269 mole) were added to the dropping funnel,

approximately one-third of the solution added and heated to reflux.

A few crystals of iodine were added to initiate the reaction and the

addition was continued at a rate to maintain reflux. After refluxing

for an additional hour, the reaction was terminated, cooled and poured

into cold 10% sulfuric acid. The benzene layer was separated, washed

with water and 5% sodium bicarbonate. The aqueous solution was ex-

tracted twice with benzene, the benzene layer washed with water,

5% sodium bicarbonate and combined with the first extract. The

solution was dried over anhydrous magnesium sulfate, filtered and

used directly in the next step. A small sample was taken for spectral
-I -l
determination; ir (neat) cm 3320 (OH); 1730 cm (C= 0, ester);

nmr (DCC13); 0.97 (t, 3, J = 7 Hz); 2.80 (s, 2); 3.95 (q, 2, J = 7 Hz);-,

4.22 (broad 5, 1); 7.28 7.58 (m, 8).




- 80 -


Ethyl fluorenylidene acetate ( )10

Toluensulfonic acid (1.00 g.) was added to the benzene solution

and refluxed until 4.6 ml. of water was collected (Dean-Stark trap).

The reaction was allowed to cool to room temperature and then evapor-

ated to a yellow solid. The yellow solid was crystallized from

ethanol (95%) to give ethyl fluorenylidene acetate (63.3 g., 91%)

long yellow needles; mp.76-77 C.

Ethyl azidoformate

The title compound was prepared according to the published pro-

44
cedure of Forster and Fierz.

Attempted synthesis of 1,2-dicarbothoxy-3-spiro-(9-fluorenyl) aziridine

Ethyl fluorenylideneacetate (1.00 g., 4.0 mmole) was dissolved

in methylene chloride. Ethyl azidoformate (0.559 g., 0.0049 mole)

was added, and the infrared spectrum taken. The reaction was allowed

to stand at room temperature. Infrared spectrum was taken after one

month, three months, six months, and one year but showed no change.

Only starting materials were recovered as determined by infrared and

nmr spectroscopy.

Ethyl a-bromo--(9-bromofluorenyl) acetate (24)

The title compound was prepared according to the procedure of

Gilchrist and Rees. i1




- 81 -


Reaction of ethyl a-bromo-a-(9-bromofluorenyl) acetate with ammonia

Ethyl a-bromo-ca-(9-bromofluorenyl) acetate (1.00 g., 2.44 mmoles)

was dissolved in 5 ml. of absolute ethanol. Concentrated aqueous

ammonia (5 ml.) was added and the reaction stirred for eight hours.

Distilled water (25 ml.) was then added, the resultant solution

extracted with ether and dried over anhydrous magnesium sulfate.

Filtration and evaporation gave a product identical in spectral

properties to that of a-bromofluorenylideneacetate as prepared by

Gilchrist and Rees.

-Bromofluorenylideneacetate (25)

The title compound was prepared according to the procedure of
11
Gilchrist and Rees.

Attempted reaction of a-bromofluorenylideneacetate with ammonia

cz-bromofluorenylideneacetate (100 mg., 0.304 mmole) was dissolved

in 6 ml. of absolute ethanol. Concentrated aqueous ammonia (10 ml.)

was added and the reaction stirred at room temperature for 5 days.

Distilled water (10 ml.) was added and the resultant solution extracted

with ether. The ether extract was dried over anhydrous magnesium

sulfate. Filtration and evaporation gave only starting material as

determined by nmr spectoscopy.

Ethyl a-bromo-a-(9-isocyanatofluorenyl) acetate (26)

Ethyl a-bromo-ca-(9-bromnofluorenyl) acetate (5.00 g., 0.0122 mole)

was dissolved in 100 ml. of anhydrous diethyl ether. Freshly prepared





- 82 -


4 5
silver cyanate45 (2.00 g., 0.0133 mole) was then added and the re-

action mixture stirred for twenty-four hours at room temperature.

The reaction mixture was filtered through Celite 540 to give a

yellow solution which was evaporated to dryness to give a deep
-l
yellow oil. (3.80 g., 83.7%); ir (neat) cm1 2247 (N = C = 0).

Ethyl-a-bromo-c-(9-carbethoxyaminofluorenyl) acetate (2B)

Ethyl o-bromo-Q-(9-isocyanatofluorenyl) acetate (3.72 g., 0.01

mole) was warmed with absolute ethanol and allowed to cool. The

white solid was filtered and recrystallized from ethanol (95%)

giving ethyl a-bromo-a-(9-carbethoxyaminofluorenyl) acetate: (3.96 g.,
0 -1
98%); mp. 112-114C; ir (K B2) cm 3300 (N-H); 1740 (C = 0); 1680

(C = 0); nmr (CC14)W 0.98 (q, 6, J = 8 Hz); 3.87 (q, 4, 5 = 8 Hz);

4.92 (s, 1); 5.90 (broad) (s, 1); 7.07-7.97 (m, 7).

Anal. Calcd for C20 H20 NO4 B C; 57.43; H, 4.82; N, 3.35
Found = C; 57.46; H, 4.85; N, 3.35

Ethyl-[2-ethoxy-5-spiro-(9-fluorenyl)-oxazoline] acetate (31)

Absolute ethanol (50 ml.) was placed in a 100-ml. dry round-

bottomed flask equipped with a reflux condenser and magnetic stirrer.

Sodium (0.090 g., 0.00391 g. atoms) was added and the reaction

mixture was allowed to stir at room temperature until all the sodium

had reacted. Ethyl a-bromo-a-(9-carbethoxyaminofluorenyl) acetate

(1.25 g., 0.00299 mole) was added and refluxed for six and one-half

hours. The resultant orange solution was evaporated to dryness,




- 83 -


water added, and extracted with ether. The ether extract was washed

with 10% sodium bicarbonate and dried over anhydrous magnesium sul-

fate. The ether extract was filtered and evaporated to give a deep

yellow oil. Recrystallization from petroleum ether (60-110) gave

colorless crystals of Ethyl-[2-ethoxy-(4-fluorenyl)-oxazoline] acetate

(0.806 g., 80%): mp.-88-90C; ir (KBr) cm- 1740 (C = 0); 1660 (C=N);

nmr (CCI4) )f 0.55 (t,3, J=6 Hz); 1.28 (t,3, J=6 Hz); 3.57 (q,2, J=6 Hz)-,

4.27 (q,2, J=6 Hz); 5.07 (s,l); 7.15-7.60 (m,8); mass spectrum; Found:

m/e 337.1329 (calcd. for C20H1904N: m/e 337.1313Y.

4-Carbethoxy-5-spiro-(9-fluorenyl )-2-oxazolidone (32)

Ethyl ca-bromo-c-(9-carbethoxyaminofluorenyl) acetate (1.02 g.,

0.00236 mole) was heated in a sealed tube at 200C for ten minutes.

The sample was cooled and recrystallized from benzene to give color-

less crystals of 4-carbethoxy-5-spiro-(9-fluorenyl)-2-oxazolidone

(0.757 g., 100%):mp.219-220C; ir (KBr) cm"1 3240(N-H) i1770 (C=O),

1750 (C=O); nmr (D6 MSO) f 0.60 (t,3,5 = 7Hz); 3.10 (broad s,l);

3.63 (q,2,J=7Hz); 5.37 (5,1); 7.28-7.90 (m,8).

m/e (calculated for C18H15 04N) = 309.1000

Found = 309.1042
Reaction of Ethyl -[2-ethoxy-5-spiro-(9-fluorenyl)-oxazoline acetate
with hydrobromic acid

Ethyl-[2-ethoxy-5-spiro-(9-fluorenyl)-oxazoline] acetate (60 mg.,

0.178 mmole) was added to diethyl ether (20 ml.) previously saturated





- 84 -


with HBr. The reaction was allowed to stir at room temperature for

one hour. Evaporation and recrystallization from benzene gave a

product (45 mg., 82%) showing identical physical and spectral pro-

perties to those of 4-carbethoxy-5-spiro-(9-f I uorenyl )-2oxazol done.

4-Methyl-5-spiro-(9-fluorenyl )-2-oxazol idone (36)

Ethyl-Gc-bromo-Q-(9-carbethoxyami nofluorenyl) acetate (1.00 g.,

2.39 mmoles) was refluxed for two and one-half hours in alcoholic

potassium hydroxide (5.0 g. in 50 ml. of 95% ethanol). The reaction

mixture was allowed to cool to room temperature and evaporated to

dryness. Water was then added and extracted with ether. The ether

layer was washed with water and dried over anhydrous magnesium sul-

fate. Filtration and removal of solvent (rotary evaporator) gave a

light yellow residue. Recrystallization from benzene and petroleum

ether (80-110 C) gave 4-methyl-5-spiro-(9-fluorenyl)-2-oxazolidone
o -l
(0.220 g., 37%) white crystals; mp. 160-161C. ir (KBr) cm 3325

(N-H; broad); 1735 (C=O, strong), nmr (DCCI ) c6 0.93 (d,3,J=7Hz);

4.98 (q,l,J=7Hz); 5.42 (s,l,broad); 7.27-7.73 (m,8);

m/e (calculated for C16H13 02N) = 251.0945

Found = 251.0926

9-Ami nof uorene (LOP)

9-Amninofluorene hydroxychloride (2.00 g., 9.22 mmoles) was

dissolved in 100 ml. of distilled water. Sodium hydroxide (15%)




- 85 -


was added until the solution was basic and then an additional 15 ml.

excess was added. A white precipitate formed and was extracted with

diethyl ether (150 ml.; 3 x 50 ml.). The ether extract was washed

twice with water and dried over anhydrous magnesium sulfate. After

filtering, evaporation of solvent gave 9-amino-fluorene (1.60 g., 96%)

a bright yellow solid; mp. 121 C. nmr (DCC1 ) c3 1.68(s,2); 4.72

(s,l); 7.15-7.83 (m,8).

9-Carbethoxyimni nof I uorene

This compound was prepared according to the method of Deyrup and
46
Gill. Into a 250-ml. round-bottomed flask equipped with a magnetic

stirrer, Dean-Stark trap and a reflux condenser was placed activated
47l
manganese dioxide (1.38 g., 0.0158 mole) in 100 ml. of benzene. The

mixture was refluxed for 12 hours. 9--Carbethoxyaminofluorene (0.500 g.,

0.00198 mole) was then added and the reaction mixture was then allowed

to cool to room temperature, filtered through Celite-545. The yellow

solution was evaporated to dryness to give a yellow oil. Re-

crystallization from petroleum ether (60-110) gave 9-carbethoxy-

iminofluorene (0.200 g., 40%) a bright yellow solid; mp. 70-72 C.
-1
ir (KBr) cmr 1700 (C=O); 1680 (C=N),

nmr (CC]4) cf 1.40 (t,3,5=7Hz); 4.37 (q,2,J=7Hz); 6.95-7.66 (m,8).

m/e (calculated for C16H13NO2) = 251.0945

Found = 251.0956





- 86 -


9-Carbethoxyaminofluorene (4W)

The title compound was prepared according to the procedure of

Neish.17

9-Carbethoxyiminofluorene (3J)

Fluorenylideneimine (0.500 g., 0.00279 mole) was dissolved in

dry benzene and triethyl amine (1.00 ml.) added. Ethyl chloroformate

(0.303 g., 0.00279 mole) was added slowly and the reaction stirred

at room temperature for twenty-four hours. The reaction was then

filtered and evaporated to dryness. Recrystallization from benzene

and petroleum ether (20-40) gave 9-carbethoxyiminofluorene (0.376, 54%)

of yellow crystals; mp. 70-71. Spectral properties were the same as

those synthesized in the first part.

Fluorenylideneimine (42)

The title compound was prepared by the procedure of Harris,

Harriman and Wheeler.48

Methyl c-bromo-o-(9-carbethoxyaminofluorenyl) acetate (29)

The title compound was prepared by the same procedure as ethyl

ca-bromo-&-(9-carbethoxyaminofluorenyl) acetate: mp. 127-128.5 C.
-1
ir (KBr) cm1 3300 (N-H); 1740 (C=O); 1690 (C=O);

nmr (CC4) cr 0.98 (t,3,J=7Hz); 3.50 (s,3); 3.92 (q,2,J=7Hz);

4.93 (s,l); 6.00 (s,l, broad); 7.17-7.97 (m,8).




- 87 -


Reaction of Methyl C-bromo-o-(9-carbethoxyaminofluorenyl) acetate
with alcoholic potassium hydroxide

Methyl o-bromno-a-(9-carbethoxyaminofluorenyl acetate was

treated under the same conditions and its ethyl derivative. Only

9-fluorenone, in 20% yield, was isolated from the reaction.

Reaction of 9-Carbethoxyiminofluorene with alcoholic potassium
hydroxide

9-Carbethoxyiminofluorene (0.200 g., 0.000797 mole) was added

to alcoholic solution (1.00 g., KOH in 10 ml. of 95% ethanol) and

refluxed for two and one-half hours. On cooling, the brown mixture

was evaporated to dryness, water added and extracted with ether.

The ether extract was washed with water and dried over anhydrous

magnesium sulfate. Filtration and removal of solvent left a deep

yellow oil. The nmr spectrum of this material was identical to

that of 9-fluorenone.

Attempted Reaction of 9-Carbethoxyiminofluorene with Benzoyl Peroxide

9-Carbethoxyiminofluorene (50 mg., 0.0199 mmole) and a catalytic

amount of benzoyl peroxide were added to a dry 25 ml. round-bottomed

flask equipped with a reflux condenser and a drying tube. The

apparatus was flushed with nitrogen and chlorobenzene (5 ml.) added.

The reaction was refluxed for two and one-half hours, cooled, and

evaporated. Only starting material was isolated from the reaction.




- 88 -


Attempted Reaction of 9-Carbethoxyiminofluorene with Ditertbutyl
Peroxide

9-Carbethoxyiminofluorene (50 mg., 0.199 mmole), chlorobenzene

(5.0 ml.) and tert-butyl peroxide (1.0 ml.) was placed in a Carius

tube and heated at 100 0C for thirty hours. The solution was cooled

and evaporated to give a yellow. residue. Only starting material

was isolated as determined by rnr spectroscopy.

Ethyl a-bromo-a-(9-aminofluorenyl) acetate (4)

Ethyl Q-bromo-a-(9-isocyanatofluorenyl) acetate (3.83 g.,

0.0129 mole) was dissolved in 25 ml. of acetone and 20 ml. of hydro-

iodic acid (48%) was added. The solution was allowed to stir for

four hours at room temperature. The dark solution was extracted

first with ether. The aqueous layer was made basic with 10% sodium

hydroxide and extracted three times with ether. On drying (anhydrous

magnesium sulfate), filtering and evaporating gave a light yellow oil

of ethyl a-bromo-a-(9-aminofluorenyl) acetate (2.57 g., 72%).
-l
ir (neat) cm1 3400 (N-H); 1720 (C=O);

nmr (CCI4) c 0.95 (t,3,J=7Hz); 2.25 (s,2); 3.92 (q,2,J=7Hz);

4.48 (s,l); 7.08-7.87 (m,8).

Ethyl 2-spiro-(9-fluorenyl) aziridine carboxylate (L0)

Ethyl a-bromo-o-(9-aminofluorenyl) acetate (5.85 g., 0.0169 mole)

was dissolved in 25 ml. of absolute ethanol. Triethyl amine (25 ml.)

was added and the reaction stirred at room temperature for three days.




- 89 -


The reaction mixture was evaporated to dryness to give a light yellow

solid. Water was then added and the aqueous mixture extracted with

ether. The ether extract was washed once with water and dried over

anhydrous magnesium sulfate. After filtering and removal of solvent

the residue, a light yellow oil, was recrystallized from 95% ethanol

to give white crystals of 2-carbethoxy-3-spiro-(9-fluorenyl) aziridine

(4.40 g., 98%); mp. 118-120C; ir (KBr) cm-1 3448 (N-H); 1739 (C=0);

nmr (DCCI3 ) c 1.08 (t,3,J=7Hz); 2.58 (broad) (d,l,J=9Hz); 3.43 (broad)

(d,l,J=9Hz); 4.13 (q,2,J=7Hz); 7.00-7.77 (m,8).

Anal. Calcd for C7 H 5NO : C, 76.96; H, 5.70; N, 5.28

Found: C, 76.82; H, 5.77; N, 5.25

Sodium 2-spiro-(9-fluorenyl)-aziridinecarboxylate (O6)

Ethyl 2-spiro-(9-fluorenyl)-aziridinecarboxylate (2.00 g.,

0.00755 moles) was dissolved in 50 ml. of 95% ethanol and sodium

hydroxide (8.0 ml. of 1.0 M, 0.0080 mole) was added. The reaction

was allowed to stir for one hour in which the salt precipitate, the

white solid was filtered, washed with ether and dried under vacuum

to give sodium 2-spiro-(9-fluorenyl)-aziridinecarboxylate (1.96 g.,

100%) as a white powder. A small amount of the sodium salt was re-

crystallized from water (mp. 154-156 decomposition turning red),

which was identified by spectral properties.




- 90 -


Reaction ot Sodium 2-spiro-(9-fluorenyl) aziridine carboxylate
with Thionyl Chloride (Attempted)

This procedure was patterned after that of Deyrup and Clough.

Into a dried three-necked flask equipped with a magnetic

stirrer, inlet and outlet tubes for a nitrogen atmosphere, and

a rubber septrum was added a 57% sodium hydride suspension (0.509 g.,

0.012 mole). The sodium hydride was washed three times and dry

tetrahydrofuran (10 ml.) was added to the reaction flask. Sodium

2-spiro-(9-fluorenyl)-aziridinecarboxylate (0.266 g., 0.0010 mole)

was added and then thionyl chloride (0.071 ml., 0.0010 mole). The

reaction turned yellow immediately and was stirred at room temper-

ature for one hour and twenty-five minutes. The reaction mixture

was filtered through Celite 540 and evaporated to give deep yellow

residue. Analysis of this residue by nmr showed no desired products

had been formed.

Anthracene-9, 10-endo-a, .P-succinic anhydride (5)

The title compound was prepared according to the procedure
49
of Bachmann and Kloetzel.

Disodium 9, 10-endo-c, p-succinate (L7)

Anthracene 9, 10-endo-a, P-succinic anhydride (2.09 g., 0.075

mole) and sodium hydroxide (4.0 g., 0.1 mole) was dissolved in 50%

ethanol and refluxed for two hours. The solution was cooled, evapor-

ated and then dried under vacuum to give a quantitative yield of di-




- 91 -


sodium 9, 10-endo-a, 3-succinate. The product was identified by ir

and nmr spectroscopy.

Anthracene-9, 10-endo-a, P-succinic acid (68)

Anthracene-9, 10-endo-a, p-succinic anhydride (5.00 g., 0.0181

mole) was refluxed in water (100 ml.) for two hours. White crystals

precipitated as the solution cooled. After filtration and drying

anthracene-9, 10-endo-a, p-succinic acid (4.92 g., 99%) was obtained.



Electrolytic Bisdecarboxylation (General Method)

The electrolysis was carried out by a procedure similar to that

50 51 52 53
used by Corey Plieninger Sims and Whitesides52 and Dauben53

The electrolysis apparatus was constructed from a 200 ml. tall-

form beaker that was water-jacketed, two electrodes of platinum gauze

and a mechanical stirrer. The coolant, water, circulated through

the reaction jacket through a copper coil immersed in an ice bath.

The temperature was maintained automatically at 20 C with a control

device composed of a thermometer, immersed into the constructed cell,

a relay and peristalic pump. A mechanical stirrer rotated the

cylindrical platinum gauze anode inside the cylindrical cathode,

both of which were inside the 200 ml. reaction vessel. A volta-

meter and ampmeter were added to the circuit to monitor the electrol-

ysis. Power was supplied by a Lambda (Model LA 20-05 BM-505) con-




Full Text
T
OI
I I T
T
ot
T
01 *N
O'* I ) YUi O t O'* 07 O'*


- 37 -
Scheme XL I I. This structure is supported from spectral analysis.
Scheme XL I I
20 16
Sodium 2-spiro-(9-f1uorenyl) aziridine (16) was treated with
thionyl chloride following the procedure of Deyrup and Clough.' On
work-up no products could be identified by nmr spectroscopy. It
appeared that thionyl chloride had caused total destruction of the
molecule. The use of alternative reaction conditions at low temper
atures using different proton scavengers were without success.
21
Tomalia studied the reaction of some N-unsubstituted aziri-
dines with thionyl chloride, Scheme XL III. He found that by react
ing equimolar amounts of aziridines and triethyl amine with thionyl


- 6 -
Table 1
Ring Strain in Three-Membered Rings
Compound Strain Energy (kcal/mole)
Cyclopropane 27-5
Methylenecyclopropane 41.0
Cyclopropene 55-0
An equivalent or greater increase in the strain energy of the azabi-
cyclo-[1.1.0]-butane-2-one system was expected but perhaps not to the
extent that it would make the synthesis impossible or greater than
the isolated cyclopropene (55-1 kcal/mole).
In order to stabilize the strained ring system, appropriate R^
and R^ groups on the azabicyclo-[1.1.0]-butane-2-one system were
sought. Many ring opening reactions of aziridine may be formulated
as substitutions involving attack of a nucleophile at the aziridine
carbon atom. It seemed reasonable that steric protection of this
carbon atom with large groups would aid in the stabilization of this
ring system. In other highly strained systems such as a-lactones"
6
and a-lactams> tertiary butyl groups have been used with great
success and were considered here. Selection of R^ and R^ groups
which would destabilize positive charge at this carbon should inhibit
ring opening. The fluorenyl group seemed to suit these criteria.
Its derivative, 1-azab¡cyclo-[l.1.0]-butane-2-one J_2 was chosen
for synthesis.


102 -
1, 2-[9> 10-anthrylene]-cyclohexene-cis-4, 5-dicarboxyl ic anhydri de (79)
11, 12-D¡methylene-9, ]0-dihydro-9, 1O-ethanoanthracene (5<00 g.,
0.0217 mole), maleic anhydride (2.13 g*> 0.0217 mole) and benzene
(150 ml.) were refluxed for twenty-four hours. During the first hour
the color of the solution changed to bright yellow which later became
colorless towards the end of the reaction. Upon cooling to room
temperature, the product crystallized as white needles. Filtration
and drying gave 1, 2-[9, 10-anthry1 ene]-cyclohexene-cis-4, 5dicarboxy-
lic anhydride (5*62 g., 79%)' mp. 249-25lC.
In large scale preparation, the ether <83, and diene 84 were
not separated but were reacted directly with maleic anhydride. Thus,
a diene-ether mixture (17-7 g.), ratios of 2.8 as estimated from an
nmr spectrum, maleic anhydride (16.2 g., 0.166 mole) and benzene
(300 ml.) were refluxed for twenty-four hours. The solution was
allowed to cool to room temperature wherein the product crystallized.
Filtration and drying gave (14.4 g., 80%) of the desired product.
The filtrate which still contained a small amount of the anhydride
84 and ether 83., as determined from an nmr spectrum, was discarded.
1> 2-[9, 10-anthry1 ene]-cyclohexene-cis-4, 5~d?carboxyl?c acid (801
1> 2-[9, 10-anthry1 ene]-cyclohexene-cis-4, 5~dicarboxylic an
hydride (10.00 g., 0.030 mole) and 1.0 M sodium hydroxide (100 ml.)
were refluxed for three hours. The solution was cooled, extracted
40


106 -
4,5-Pimethyl-\3, 10-O-Benzenoanthracene] dicarboxylate (8g)
4, 5-Pimethy1 -[1,2,4,5-(9> 10-anthrylene) cyclohexad¡ene] d¡-
carboxylate (100 mg., 0.269 mmole), N-bromosuccinamide (43 mg.,
0.0269 mmole) and carbon tetrachloride (10 ml.) were refluxed for
two hours. The reaction mixture was cooled, filtered, and the
filtrate evaporated to dryness. The colorless residue was re
crystallized from methanol to colorless crystals of 4, 5-dimethyl-
[9, 10-0-benzenoanthracene] dicarboxyl ate (0.059 g-> 43%) : mp.
184-185C.
nmr (CCI4)cf3.73 (s,6); 5-37 (s,2); 6.68-7.45 (m,8); 7-63 (s,2).
m/e (calculated for ^24^184^ = ^70.1204
Found = 370-1194
4, 5~01 methyl -[4,5-(9, 10-anthry1 ene)-cyclohexene-N-(p-methoxy-
phenyl)-!, 2-aziridine] dicarboxyl ate (91)
Into a three-necked round-bottom flask (200 ml.) equipped with
a cold finger, magnetic stirrer, immersion thermometer, and an out
let tube for gas collection by the downward displacement of water,
was added thiazoline (2.30 g., 4.10 mmole) and acetone (80 ml.).
The completely dissolved triazoline was cooled to 20 C by the auto
matic temperature control device used in the electrolysis cell. It
was then irradiated for five hours with a sun lamp. The total volume
of nitrogen gas evolved was 85 ml. The solvent was evaporated to


In a final effort to explore the mechanism, some substituent
reactions were investigated. These data are summarized in Table II.
Table I 1
Substituent Reactions of a-Bromo Carbamates
R
Solvent
Yield (/0)
Et
EtOH
20
20
Me
EtOH
20
20
Me
Me OH
0
2
As shown earlier, the 2-oxazolidone and fluorene are produced in equa
amounts. Substituting a mathoxy in the carbamate portion of the
molecule using ethanol as the solvent produced no change in the yield
of products. This showed that transesterification was quite rapid.
However, changing the solvent to methanol did not give the expected
product 43, but instead gave only 9-fluorenone (23), Scheme XXXIX.


- 40 -
Scheme XLV
Syntheses of methylated carbodiimide are presently being investigated.
The second approach utilizes precursor J_4, the synthesis of 3-lactam.
This is an attractive route in that the amine 44 has been synthesized.
Thus, base hydrolysis followed by acidification to give the (3-amino
Scheme XLVI
12


No. 5
t*
M
VO
i


- 88 -
Attempted Reaction of 9-Carbethoxyiminof1uorene with Ditertbutyl
Peroxide
9-Carbethoxyiminof1uorene (50 mg., 0.199 mmole), chlorobenzene
(5*0 ml.) and tert-butyl peroxide (1.0 ml.) was placed in a Carius
tube and heated at 100C for thirty hours. The solution was cooled
and evaporated to give a yellow residue. Only starting material
was isolated as determined by renr spectroscopy.
Ethyl a-bromo-a-(9-aminof1uoreny1) acetate (^i)
Ethyl Q-bromo-G-(9-¡socyanatofluoreny1) acetate (3.83 g.,
0.0129 mole) was dissolved in 25 ml. of acetone and 20 ml. of hydro-
iodic acid (48%) was added. The solution was allowed to stir for
four hours at room temperature. The dark solution was extracted
first with ether. The aqueous layer was made basic with 10% sodium
hydroxide and extracted three times with ether. On drying (anhydrous
magnesium sulfate), filtering and evaporating gave a light yellow oil
of ethyl a-bromo-Q-(9-aminof1uoreny1) acetate (2.57 g., 72%).
ir (neat) cm"' 3400 (N-H); 1720 (C=0);
nmr (CCl^) cf 0.95 (t ,3, J=7Hz) , 2.25 (s,2); 3-92 (q,2, J=7Hz)*,
4.48 (s, 1); 7.08-7.87 (m,8).
Ethyl 2-spiro-(9~fluoreny1) aziridine carboxylate (20)
Ethyl G-bromo-G-(9-aminof1uoreny1) acetate (5.85 g., 0.0169 mole)
was dissolved in 25 ml. of absolute ethanol. Triethyl amine (25 ml.)
was added and the reaction stirred at room temperature for three days.


- 91 -
sodium 9 10-endo-a, (3-succinate. The product was identified by ir
and nmr spectroscopy.
Anthracene-9, 10-endo-a, (3-succinic acid (68)
Anthracene-9j 10-endo-a, ¡3-succinic anhydride (5-00 g., 0.0181
mole) was refluxed in water (100 ml.) for two hours. White crystals
precipitated as the solution cooled. After filtration and drying
anthracene-9j 10-endo-a, (3-succinic acid (4.92 g., 99%) was obtained.
Electrolytic Bisdecarboxylation (General Method)
The electrolysis was carried out by a procedure similar to that
50 51 52 53
used by Corey Plieninger Sims and Whitesides and Dauben
The electrolysis apparatus was constructed from a 200 ml. ta11-
form beaker that was water-jacketed, two electrodes of platinum gauze
and a mechanical stirrer. The coolant, water, circulated through
the reaction jacket through a copper coil immersed in an ice bath.
The temperature was maintained automatically at 20C with a control
device composed of a thermometer, immersed into the constructed cell,
a relay and peristalic pump. A mechanical stirrer rotated the
cylindrical platinum gauze anode inside the cylindrical cathode,
both of which were inside the 200 ml. reaction vessel. A volta
meter and ampmeter were added to the circuit to monitor the electrol
ysis. Power was supplied by a Lambda (Model LA 20-05 BM-505) con-


- 30 -
formate utilizing the published procedure of Neish. Oxidation of
18
4]_with activated MnO^ according to the procedure of Deyrup and Gill
gave 9-carbethoxyiminof1uorene (37) ¡n acceptable yield, Scheme XXXIV.
Scheme XXXIV
In a second method, 9-iminofluorene (42) was synthesized from
ammonia and 9-fluorene (23) at 165C, Scheme XXXV. Subsequent re-
Scheme XXXV
action of ¡mine 42 with ethyl chloroformate gave the desired 9-carbo-
thoxyiminof1uorene 37


Scheme XXV
tube. Hassner and coworkers'^ have shown that the pyrolysis of methyl
N-(trans-2-iodocyclohexyl) carbamate (33) gives a 2-oxazolidone 34
melting at 55 56 C, Scheme XXVI. The reported melting point for
Scheme XXVI
33
34


THE SYNTHESIS OF SPIRO AND BRIDGED AZIRIDINES
BY
Emmett S. McCaski11, Jr.
A DISSERTATION PRESENTED TO THE GRADUATE
COUNCIL OF THE UNIVERSITY OF FLORIDA IN PARTIAL
FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1974


- 46 -
Whereas unactivated olefins are sluggish toward aryl-azides, strained
28
bicyclic systems, on the contrary, are particularly reactive. The
triazoline jjfj culd easily be converted to the bridged aziridine 60
either thermally or photochemically, Scheme LI.


- 15 -
Scheme XV
Br COOEt
25
compound prepared by Gilchrist and Rees.'* Further reaction of 2
with ammonia was unsuccessful, Scheme XVI. It is evident in this
Scheme XVI
OcO
Br ^COOEt
25


- 52 -
electrolytic method were cleaner and did not require further puri
fication. Of significance in the oxidative method is lactone forma
tion in bridged compounds containing proximate double bonds, Scheme LVII.
Scheme LVI I
It is reported that in the oxidative bisdecarboxylation, lactones are
cyclic ring systems.
Following the successful bisdecarboxylation of 6jj and its deri
vatives Sj_ and 68, the 1, 3-dipolar cycloaddition reaction of j>-
methoxyphenyl azide (70) warranted investigation. The selection of
azide 0 was based on the following factors: 1, 3-dipolar cyclo
addition reaction of aryl azides has been characterized and its
32
mechanism confirmed by Huisgen ; the methoxy group in an nmr spectrum


- 17 -
Scheme XVIII
(depending on the quality of silver cyanate). As expected, 26 was
not the only product. Since both bromines could be displaced by cy
anate ion, it was speculated that the other isomer 7J_ would also
be present. There was no advantage in separating these isomers be-
H
COOEt
27
cause ring closure of either isomer would give the same desired aziri-
dine precursor. One other product, ethyl f1uoreny1 idine acetate (21)
was present in the reaction mixture. Even though the ester 21 was
not isolated, the nmr spectrum showed a vinyl proton at 6.63cf and an
aromatic proton at 8.92cf situated in the deshielding cone of the
OCX)


- 104 -
Triptycene [9, 10-0-Benzenoanthracene1 (§5)
Triptycene was prepared according to the published procedure of
P. 58
Fieser.
Oxidative Bisdecarboxylation of 1, 2-[9, 10-anthrylene]-cyclohexene-
cis-4, 5~dicarboxyl ate anhydride with lead tetraacetate
I, 2-[9, 10-anthrylene]-cyclohexene-cis-4, 5-8icarboxylic acid
(0.500 g., 0.00145 mole), lead tetraacetate (1.00 g., 0.00226 mole)
and dry pyridine (5 ml.) were placed in a 50 ml. round-bottomed flask
and bisdecarboxylated according to the general method described pre
viously. After work-up triptycene (0.143 g., 35%) was obtained.
Characterization was determined from ir, nmr spectrum and mp. which
were identical to the tryptycene prepared by Bartlett and coworkers.^
4, 5-Dimethyl-[l,2,4,5-(9>10-anthrylene)-cyclohexadiene] dicarboxy-
late (86)
II, 12-Dimethylene-9, 10-dihydro-9, 10-ethanoanthracene (4.80 g.,
0.0209 mole), dimethyl acetylene dicarboxylate (4.00 g., 0.0282 mole)
and carbon tetrachloride (40 ml.) were stirred at room temperature
for four days. The solution was evaporated to dryness and anhydrous
methanol (150 ml.) added to it and then heated to boiling. The in
soluble material was filtered off, and the filtrate evaporated to
a crystalline residue. Recrystal 1ization from anhydrous methanol
gave 4, 5-bimethy1 -[1,2,4,5-(9, 10-anthrylene)-cyclohexadiene] di
carboxylate (3.25 g., 42%): mp. 180-182C.




- 61 -
f¡cation gave the dicarboxylic acid 80 in 92% yield.
Scheme LXXI shows oxidative and electrolytic bisdecarboxy1 at ion
Scheme LXXI
COOH
Elect, or
Pb(0Ac)4
which gave triptycene (85) in low yield. Triptycene could have been
formed by one of two pathways: bisdecarboxy1 at ion to give the diene
58 and subsequent oxidation at the anode surface, or, stepwise de
carboxylation of one carboxyl group to give a double bond conjugated
with the first, followed by decarboxylation of the second carboxyl
group to give 8.
In the hope that ester groups might stabilize the diene system,
compound 86 was chosen for synthesis. The Diels-Alder reaction of
dimethylacetylene dicarboxyl ate with 11, 12-dimethylene-9, 10-ethano-9,


in an oil bath at 80C for seven days. The dark brown solution
crystallized on cooling. The solid was transferred to a filter
funnel and washed with a few ml. of carbon tetrachloride. Re
crystallization from anhydrous methanol gave 4, 5_d¡methyl-[(9, 10-
2 1
anthrylene)-cyclohexane-l, 2-1 '-(p-methoxypheny1)-A triazonine]
dicarboxylate (4.0 g., 57%) mp. 194-195C.
¡r (KBr) cm 1740 (C=0, esters)
nmr (DCCl^)cf 1.17-1.70 (broad, m,2); 2.33-2.82 (broad, m,4);
3.48 (s,3); 3-52 (s,3); 3-78 (s,3); 4.48 (s,1); 4.57 (s,1);
6.70-7.45 (m,12).
m/e = 495 (523-28)
4, 5-Dimethyl-[1, 2-(9, 10-anthrylene)-cyclohexene] dicarboxylate (102)
1, 2-(9,10-anthry1ene)-cyclohexene-cis-4, 5dicarboxylic acid
(11.0 g., 0.0318 mole) was refluxed in anhydrous methanol (200 ml.)
containing concentrated sulfuric acid (2.0 ml.) for five hours.
Some white solid precipitated on cooling and was collected by filtra
tion. The filtrate was evaporated to dryness, and dissolved in ether.
The ether extract was washed with 5% sodium carbonate and water, and
then dried over anhydrous magnesium sulfate. The ether solution was
filtered, evaporated to give a colorless residue. The two fractions
were combined and recrystallized from methanol to give 11.8 g. (91%)
f 4, 5-dimethyl-[1, 2-(9, 10-anthrylene)-cyclohexene] dicarboxylate


- 56 -
salt _76. Acidification of the disodium salt 76 did not give the
expected dicarboxylic acid 64, but instead regenerated the anhydride
63. Electrolysis of the disodium salt Scheme LX Ml, also gave
Scheme LX 1 I 1
63
the anhydride rather than the expected diene £8_. Tetramethyl succinic
36
anhydride (77) is formed by the hydrolysis of the diester with hydro-
37
bromic acid. Dialkyl maleic acids exist only in the form of their
anhydrides (78, R = methyl, ethyl, or phenyl) which are formed spon-


- 5 -
The purpose of this study was to synthesize a stable 1-aza-
b¡cyclo-[1.1.0]-butane-2-one, establish the intermediate of this
reaction and to investigate the chemistry of this new system.
DISCUSSION
In an effort to select a derivative of a 1-azabicyclo-[1.1.0]-
butane-2-one system (11) that would be stable, strain energies and
II
synthetic routes for stable azabicyclobutanes, aziridines and aziri-
dinones were considered. The stability of the azabicyclobutane ring
2
has been recently demonstrated by Hortman and coworkers. They syn
thesized and isolated 3-phenyl-1-azabicyclo-[1.1.0]-butane. An estim
ation of the increase in strain energy for introducing a carbonyl
group into the I-azabicyclo-[I.1.0]-butane ring system seemed reason
able. The corresponding values of strain energies for cyclopropane
and the aziridine ring are similar (26.9 and 27-5 kcal /mole"5). Wiberg
has shown that the introduction of a trigonal carbon into a three-
membered ring results in approximately 13 kcal/mole additional strain
energy (Table 1).


Benzopropene (53), which results from fusion of cyclopropene
to a benzene ring is the parent and most highly strained member of
24
the benzocycloalkene series. The strain energy has been estimated
25
to be at least 45-5 kcal/mole greater than cyclopropane. Nonphoto
chemical synthesis of benzocyclopropenes resulted from the work of
26
Vogel, Grimme and Korte. Pyrolysis of 1:1 adducts 4 of 1, 6-
methano[10]-annulene with dimethyl acetylenedicarboxyl ate gave benzene-
cyclopropene (53) in 45% yield, Scheme XLVIII.
Scheme XLVIII
400C
+
aCOOMe
COOMe
53


- 86 -
9-Carbethoxyam¡nof1uorene (4J )
The title compound was prepared according to the procedure of
Neish.1 ^
9-Carbethoxyiminof1uorene ()
FIuoreny1ideneimine (0.500 g., 0.00279 mole) was dissolved in
dry benzene and triethyl amine (1.00 ml.) added. Ethyl chloroformate
(0.303 g., 0.00279 mole) was added slowly and the reaction stirred
at room temperature for twenty-four hours. The reaction was then
filtered and evaporated to dryness. Recrystallization from benzene
and petroleum ether (20-40) gave 9-carbethoxyiminofluorene (0.376, 54%)
of yellow crystals; mp. 70-71- Spectral properties were the same as
those synthesized in the first part.
FIuorenylideneimine (42)
The title compound was prepared by the procedure of Harris,
48
Harriman and Wheeler.
Methyl Obromo-C-(9-carbethoxyami nof 1 uoreny 1) acetate (29)
The title compound was prepared by the same procedure as ethyl
a-bromo-Q-(9-carbethoxyaminof1uorenyl) acetate: mp. 127-128.5C.
ir (KBr) cm"1 3300 (N-H); 1740 (C=0); 1690 (C=0);
nmr (CCl^) cf O.98 (t,3,J=7Hz); 3-50 (s,3); 3-92 (q,2,J=7Hz);
4.93 (s,l); 6.00 (s, 1, broad); 7.17-7-97 (m,8).


- 70 -
Scheme LXXVII I
An attempt was then made to add the azide _70 to anhydride 79
If the triazoline 9 could have been formed and subsequent photolysis
gave the aziridine J_00, oxidative or electrolytic bisdecarboxylation
might give the desired unsaturated aziridine 101, Scheme LXXIX.
Anhydride J3 an<^ azide _70 were heated at 100C in a Carius tube for
seven days. Triazoline ^2. was present according to nmr spectro
scopy. The spectrum of the triazoline showed the methoxy protons
at 3*77 and two singlets for the bridgehead protons. Purification
and further characterization was quite difficult. Photolysis of the


Ib
case, that ammonia is strong as a base to form the intermediate, but
not nucleophilic enough to give ring closure to the aziridine.
Another synthetic approach to the aziridine precursor 19 en-
tails the nucleophilic displacement of a bromide by cyanate to give
the Dromo-isocyanate, Scheme XVII. This bromo-isocyanate can react
Scheme XVI I
9-9-
Br Br
OCN
I
C
i
N
II
C
I
0
C
I
Br
ROH
I
"9
NH
C-0
l
0
R
Base
with alcohol to give a bromo-carbamate. Subsequent cyclization with
a base can give the N-substituted aziridine. The dibromo ester 24
was then treated with silver cyanate, Scheme XVIII. The product 26
was isolated as deep yellow oil in yields that varied from 70 85%


BIBLIOGRAPHY
1. J. A. Deyrup and S. C. Clough, J. Amer. Chem. Soc. 9J_, 4590 (1969)*
2. A. G. Hortman and D. A. Robertson, Jj_ Amer. Chem. Soc., 89, 5974
(1967); A. G. Hortman and J. E. Martinelli, Tetrahedron Letters,
6205 (1968).
3. J. D. Cox, Tetrahedron, 19, 1175 (1963).
4. K. B. Wiberg and R. A. Fenoglio, J. Amer. Chem. Soc., 90, 3395
(1968).
5. J. E. Leffer and R. G. Zepp, J. Amer. Chem. Soc., 92, 3713 (1970).
6. J. C. Sheehan and J. H. Beesen, J. Amer. Chem. Soc., 89, 362 (1967).
7. I. Lengyel and J. C. Sheehan, Angew. Chem. Internat. Ed., 1, 25
(1968).
8. R. Huisgen, G. Szeimier and L. Mbius, Chem. Ber., 99, 475 (1965)
9- W. Lwowski and T. Mattingly, Jr., J. Amer. Chem. Soc., 87, 1947
(1965).
10. A. Sieglitz and H. Jossay, Ber., 54, 2133 (1921).
11. T. L. Gilchrist and C. W. Rees, J. Chem., Soc., (C), 779 (1968).
12. N. H. Cromwell, R. E. Bamburg and J. L. Adelfang, J. Amer. Chem.
Soc., 82, 4241 (I960).
13- 0. C. Dermer and G. E. Ham, "Ethylenimine and Other Aziridines,11
Academic Press, New York, N. Y., 1367> ? 53.
14. E. Katchalsky and D. Ben Ishai, J. Org. Chem., 15, 1667 (1950).
15. A. Hassner, M. E. Lorker, and C. Heathcock, ^ Org. Chem. Soc.,
2, 540 (1967).
16. M. Mousseron, F. Winternitz, Canet. Bull. Chem., France, 737 (1953)-
- 125 -


- 98 -
150 ml. of 10% water-pyr¡dine with 1.9 ml. of triethylamine was unsuc
cessful. The solid did not dissolve upon heating, but instead changed
to a soapy-like suspension. Even though the reaction medium was he
terogeneous, an attempt was made to proceed with the electrolysis at
a potential of 80 volts. Due to the low initial amperage of 0.05 to
0.01 amps, the reaction was terminated.
A second attempt to bisdecarboxy1 ate this disodium salt was made
using water as the solvent, 4, 5~[9> 10-anthylene cyclohexene-cis-1,
2-disodium carboxylate (2.00 g., 0.00513 mole) was dissolved in 100 ml.
of water and electrolyzed at a potential of 20 volts. Initial amper
age was 1.24 amps which was decreased to 0.10 amps after six hours.
After work-up, 4, 5-[9> 10-anthrylene]-cyclohexene-cis-l, 2-dicarboxylic
anhydride was obtained and characterized by spectral analysis.
Attempted Synthesis of 4, 5"[9, 10-anthrylene]-cyclohexene-cis-l,
2-dicarboxylic acid
4, 5-[9, 10-anthrylene]-cyclohexene-cis-1, 2-disodium carboxylate
(100 mg., 0.256 mmole) was dissolved in 3 ml. of water; three drops
of 10% hydrochloric acid were added; thereafter, a white precipitate
formed immediately. Water (7*0 ml.) was then added, the white
solid filtered, and dried to a quantitative yield of 4, 5~[9, 10-
anthylene cyclohexene]-c?s-1, 2-discarboxy1ic acid as characterized
by spectral analysis.


12
Scheme X
4- N3-C-OEt ch2ci2
'COOEt
R.T.
yr.
No Reaction
21
The reaction was monitored with infrared spectroscopy at one-,three-,
six-jand twelve-month intervals. After one-year reaction time, only
starting materials were recovered. The reaction was terminated. The
unreactivity of this alkene may be attributed to the deactivation of
the double bond by the ester group.
Bromination of the unsaturated ester 2J_ according to the published
procedures of Gilchrist and Rees'* gave ethyl Q-bromo-a-(9-bromo-
fluorenyl) acetate (24), Scheme XI.
Scheme XI


CHAPTER I I I
EXPERIMENTAL
General
Melting points were determined on a Thomas-Hoover Unimelt
Capillary melting point apparatus and are uncorrected.
Infrared spectra were recorded on a Perkin-Elmer 137 or Beck
mann IR-10 spectrophotometer with absorptions reported in recipro
cal centimeters (cm ^). All nuclear magnetic resonance spectra
(nmr) were obtained on a Varan A60-A spectrometer. Chemical
shifts of nmr spectra run in organic solvents are reported in
ppmfcf) downfield from internal standard tetramethy1silane. Low
resolution mass spectra were determined on a Hitachi model RMU-6E
mass spectrometer. High rosolution accurate mass spectra were
determined on a AEI MS-30 double beam mass spectrometer. Micro
analyses were obtained from Atlanta Microlab, Inc., Atlanta,
Georgia.
Separation by column chromatography was conducted using Fisher
Adsorption alumina (A-540, 80-200 mesh and Baker Silica Gel). De
activated alumina were prepared by adding the desired amount of
- 78 -


- 32 -
It was found that displacement was on the hydrogen attached to the
carbon bearing the primary and secondary alcohols. Ethers have also
20
been shown to react with alkenes under radical conditions, Scheme
XXXV1 I.
Scheme XXXVI I
CH2(0CH3)2
The reaction of 9-carbethoxyiminof1uorene (37) with benzoyl peroxide
and tert-butyl peroxides under similar reaction conditions were un
successful and only starting material was recovered, Scheme XXXVI II.
Scheme XXXVI I I
t-6u0)2
No Reaction


- 107 -
give a light tan crystalline solid. Recrystallization from methanol
gave the aziridine (1-76 g., 81%) as colorless crystals: mp. 194-
196C.
nmr (DCC1 ) cf 2.43-3.17 (m,4); 3.48 (s,6); 3.60 (s,3); 4.38 (s,3);
6.28-6.72 (AB,4); 6.87-7-40 (m,8).
m/e (calculated for C^H^O^N) = 493.1888
Found = 493-1898
Attempted allylic Bromination of 4, 5dimethyl-[4,5-(9, 10-anthry1 ene)
cyclohexene-N-(p-methoxypheny1)-l, 2-aziridine] dicarboxylate
Into a 50 ml. round-bottomed flask equipped with a magnetic
stirrer and condenser protected with a drying tube, was placed
4, 5-dimethyl-[4, 5 (9, 10-anthrylene)-cyclohexene-N-(p-methoxyphenyl)-l,
2-aziridine] dicarboxylate (100 mg., 0.203 mmole), No-bromosuccinamide
(36 mg., 0.203 mmole) and benzoyl peroxide (47 mg., 0.203 mmole). Dry
carbon tetrachloride (10 ml.) was added and the reaction mixture re
fluxed for two hours and then filtered. The filtrate was evaporated
to dryness to give a colorless cystalline solid (41 mg.): mp. 191193C.
nmr (DCCl^) cT 2.78 (broad, m,2); 3.17 (broad, m,2); 3*55 (s,6);
3.67 (s,3); 4.48 (s,2); 6.53 (m,2); 6.67-7.38 (broad, m,8); mass
spectrum; m/e 65I, 571 (651-80).
4-Ethyl-[9, 10-anthrylene)-cyclohexadiene] carboxylate (95)
11, 12-Dimethylene-9, 10-dihydro-9, 10-ethanoanthracene (5-00 g.,


was
- 51 -
anthracene (52) and maleic anhydride (66). The anhydride 65.
then converted to the disodium salt 67. and dicarboxyl ic acid 68.
Electrolytic bisdecarboxy1 ation of 6, 6 and 68 gave 11, 12-
etheno-9, 10-dihydroanthracene (69.) in 25 30% yield. Oxidative bis-
decarboxylation with lead tetraacetate of 65 and 68 gave approximately
the same results, Scheme LVI. Isolated products obtained from the
Scheme LVI


- 68 -
Scheme LXXVI I
of 25 showed no proton absorption in the vinyl region as expected.
The bridgehead protons appeared as two close singlets at 4.72 and
4.77* £-Methoxypheny1 azide (0) was then added to 25* The expected
triazoline isomers96 and 2 were shown to be present based on an nmr
97


Page
4-Carbethoxy-5-spiro-(9-fluorenyl)-2-oxazolidone (32) .... 83
Reaction of Ethy1 -[2-ethoxy-5-spiro-(9-f1uoreny1)-
oxazoline acetate with hydrobromic acid 83
4-Methyl-5-spiro-(9-f1uoreny1)-2-oxazolidone (36) 84
9-Aminof 1 uorene (40) 84
9-Carbethoxyiminof1uorene (37) 85
9-Carbethoxyaminofluorene (41) 86
9-Carbethoxyiminof 1 uorene (37) 86
FIuoreny1ideneimine (42) 86
Methyl a-bromo-a-(9-carbethoxyaminof1uorenyl) acetate (29) 86
Reaction of Methyl a-bromo-a-(9-carbethoxyamino-
fluorenyl) acetate with alcoholic potassium
hydroxide 87
Reaction of 9-Carbethoxyiminofluorene with alcoholic
potassium hydroxide 87
Attempted Reaction of 9-Carbethoxyiminofluorene
with Benzoyl Peroxide 87
Attempted Reaction of 9-Carbethoxyiminof1uorene
with Ditertbutyl Peroxide 88
Ethyl a-bromo-a-(9-arninof 1 uorenyl) acetate (44) 88
Ethyl 2-spiro-(9-f1uoreny1) aziridine carboxylate (20) ... 88
Sodium 2-spiro-(9-fluorenyl)-aziridinecarboxylate (]_6) ... 89
Reaction of Sodium 2-spiro-(9-f1uoreny1) aziridine
carboxylate with Thionvl Chloride (Attempted) 90
Anthracene-9, 10-endo-a, p-succinic anhydride (65) 90
Disodium 9, 10-endo-a, p-succinate (6]) 90
Anthracene-9> 10-endo-a, p-succinic acid (68) 91
Electrolytic B i sdecarboxy 1 at ion (General Method) 91
Bisdecarboxy1 at ion with Lead Tetraacetate (General) 92
Electrolytic Bisdecarboxy1 at ion of anthracene-9, 10-
endo-a, p-succinic anhydride 93
Electrolytic Bisdecarboxy1 ation of disodium 9> 10-
endo-a, p-succinate 93
Electrolytic Bisdecarboxy1 at ion of 9> 10-endo-a,
p-succinic acid 93
Bisdecarboxy1 at ion of 9> 10-endo-a, p-succinic acid
with Lead Tetraacetate 94
jD-Methoxypheny 1 azide (70) 94
I-(p-Methoxyphenyl )~9, 10-ethanoanthracene
triazol ine (1) 95
N-(p-Methoxyphenyl)-9, 10-ethanoanthracene aziridine (72) 95
9, 10-di hydro-9, 10-ethencanthracer.e-11 12-di-
carboxyl ic acid (74) 95
v


- 92 -
stant voltage power supply with a capability of providing up to 110
volts (dc).
Procedure
The typical reaction process was followed wherein the dicar
boxyl ic acid, anhydride, or disodium salt (1.00 g.-2.00 g.) to be
bisdecarboxylated was dissolved in a 10% aqueous pyridine solution
(100 ml.) containing 1.25 ml. of triethyl amine. The electrolysis
was carried out at a voltage that ranged from 20 to 80 volts with
an initial current of 0.8 1.0 amps. After five to eight hours,
the current dropped to less than 0.2 amps and the electrolysis was
terminated. The product was isolated by extraction of the dark
colored pyridine solution with pentane or diethyl ether. The ex
tract was washed with dilute acid and dried over anhydrous magnesium
sulfate. Filtration and evaporation of the solvent afforded the
alkene in good yield.
Bisdecarboxylation with Lead Tetraacetate (General)
This procedure was carried out similar to that of Cimarusti and
54
Wolinsky.
Pyridine (10 ml./g. of acid), purified by distillation from barium
oxide, was placed in a round-bottom flask equipped with a magnetic
stirrer, condenser, and drying tube. Oxygen was bubbled through the
stirred liquid at room temperature for 15 minutes. The diacid or


i
carbonyl group of the ester.
The major product 26 was characterized by conversion to the
carbamate, Scheme XIX. Warming the isocyanate 26 in the presence
Scheme XIX
of ethanol for a few minutes gave ethyl Q'-bromo-G- (9-carbethoxy amino-
fluorenyl) acetate (28) in excellent yield. The carbamate 28 was
characterized by elementary analysis, nmr and ir spectroscopy and
mass spectral analysis. The structure of isomer 26^ is supported
by both chemical and mass spectral data. As demonstrated earlier,
a bromine atan substituted on the beta position of dibromo ester 24
should dehydrohalogenate quite easily. Thus, if the major product
is 28, this isomer should not dehydrohalogenate under these condi
tions. The carbamate 28 was treated with triethyl amine in benzene,
Scheme XX.


2
was obtained by reduction of the azetidinone 4 with zinc to give
1-tert-buty 1-2-azeti d i none () in 41% yield. Azetidinone was
synthesized from 3-tert-butylaminopropronic acid (6), and thionyl
chloride, Scheme II.
Scheme I I
4
Zn
EtOH
H
-Bu N(CH2)2COOH
6


- 62 -
COOMe
1-dihydroanthracene (84), Scheme LXXII, gave 42% yield of 86. The
Scheme LXX11
diene derivative 86 was then treated with j5-methoxypheny1 azide, in
a Carius tube for seven days at 80C. The resultant triazoline 87,
Scheme LXXIM, was isolated in 71% yield.


- 31 -
The reaction of 9-carbethoxyf1uorene 3J_ under the above con
ditions did not give the desired 2-oxazolidone 36* The only product
isolated was 9-fluorenone (23) in 20% yield, Scheme XXXVI.
Scheme XXXVI
Urry and coworkers have studied the free radical reactions of
alcohols with alkenes. The radical chain process involved the formation
OH
RCHpOH -h CH5=CHR t-BuO)2 R-C-CH,CH?R
H
of alkyoxy radicals and subsequent attack on the alkene by the radical.
OH
R CH-ch2CHR
rch2oh + ch2 chr


112 -
appearing as a colorless crystalline solid: mp. 139-14lC.
ir (KBr) cm ^ 1724 (C=0, esters)
nmr (CCI^) cf 2.38-2.95 (broad, m,6); 3-30 (s,6); 4.60 (s,2);
6.67-7*27 (m,8).
m/e (calculated for ^24^*22^4^ = 374.1517
Found = 374.1544
4, 5-Dimethy 1 £9, 10-anthry1 ene-cyclohexane-N-(p-methoxyphenyl)-l,
2-aziridine] dicarboxylate (LQA)
The triazoline (2.00 g., 0.00382 mole) was irradiated under the
same conditions as the unsaturated derivative. The product isolated
was 4, 5-dimethy1 -[9> 10-anthry1ene-cyclohexane-N-(p-methoxyphenyl)-l,
2-aziridine] dicarboxylate (1.76 g., 93%): mp. 150-151C.
i r
nmr (DCC1^) cf 1.83-2.33 (broad, m,2); 2.50-2.80 (broad, m,4);
3.33 (s,6); 3.67 (s,3); 4.35 (s,2); 6.33-6.82 (AB,4); 6.85-
7.40 (m,8).
m/e (calculated for C H 0 N) = 495-2044
31 29 5
Found = 495.2055
Disodium [9, 10-anthrylenecyclohexene-N-(p-methoxyphenyl )-l, 2-aziri-
dine] dicarboxylate (105)
4, 5-0imethyl-[9, 10-anthrylenecyclohexane-N-(p-methoxyphenyl-1,
2-aziridine] dicarboxylate (I.50 g., 3-03 mmole) was refluxed for two
hours in aqueous diglyme containing 10% sodium hydroxide. The solution


- 66 -
Allylic bromination of £J_ was then investigated. The reaction of 2_L
with N-bromosuccimide and benzoyl peroxide did not give the desired
product 2, Scheme LXXVI. Apparently, the two bromine atoms had
Scheme LXXV I
COOMe
substituted on the aromatic ring, based on nmr and mass spectral
analysis. The exact substitution pattern was undetermined. It
appeared that the ester groups might have deactivated the allylic


- 72 -
anhydride 100 was also noted during recrystallization. In order to
eliminate these problems, the diacid 80 was converted to diester
102, Scheme LXXX, in 91% yield. The diester J_02 was treated with
Scheme LXXX
COOMe
£-methoxypheny1 azide (70)
in a Carius tube at 100 C for four days,
Scheme LXXXI. Although other products were formed, the triazoline


- H3 -
was allowed to cool, evaporated to give a white precipitate. The
white solid was filtered, washed with ether and dried to give a
quantitative yield of disodium [9, 10-anthrylenecyclohexene-N-
(p-methoxypheny1)-l, 2-aziridine] dicarboxyl ate. The product was
identified by ir and nmr spectroscopy.
Attempted esterification of disodium [9, 10-anthrylenecyclohexene-N-
(p-methoxyphenyi )-l 2-aziridine] di carboxyl ate
Disodium [9, 10-anthylenecyclohexene-N-(p-methoxyphenyl)-l,
2-aziridine] dicarboxyl ate (0.50 g., 0.99 mmole) was dissolved in
10 ml. of distilled water and 25 ml. of ether added. The two
phase solution was cooled to 0C and acidified with 5% HCIO^.
Ether (10 ml.) previously saturated with CH^t^ was added and the
solution was allowed to stand at room temperature for four hours.
The solution was evaporated and closed with CCl^. A mixture of
products was obtained as shown by nmr spectroscopy.
Electrolytic Bisdecarboxylation of disodium [9, 10-anthylenecyclo-
hexene-N-(p-methoxyphenyl)-l, 2-aziridine] dicarboxylate
Disodium (9, 10-anthylenecyclohexene-N-(p-methoxyphenyl)-l,
2-aziridine] dicarboxylate (1.00 g., 1.98 mmole) was electrolyzed at
25 V for five hours. The initial current was 0.70 amps and de
creased to 0.2 amps after five hours. After work-up, analysis by
nmr spectroscopy showed no desired product being formed.



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- 73 -
Scheme LXXXI
could be separated in good yield using column chromatography. It
was later found that a decrease in temperature from 100C to 80C,
and an increase in reaction time from four to seven days, increased
the yield of triazoline 103 and decreased the by-products previously
observed. Column chromatography was not required for isolation of
the triazoline. The triazoline 103 was then photo]¡zed to give the


- 82 -
45
silver cyanate (2.00 g., 0.0133 mole) was then added and the re
action mixture stirred for twenty-four hours at room temperature.
The reaction mixture was filtered through Celite 540 to give a
yellow solution which was evaporated to dryness to give a deep
yellow oil. (3.80 g. 83*7%); it (neat) cm 1 2247 (N = C = 0).
Ethyl -obromo-a-(9-carbethoxyami nofl uorenyl ) acetate (28)
Ethyl Orbromo-Q-(9-isocyanatof1uorenyl) acetate (3.72 g., 0.01
mole) was warmed with absolute ethanol and allowed to cool. The
white solid was filtered and recrystallized from ethanol (95%)
giving ethyl a-bromo-o-(9-carbethoxyaminofluorenyl) acetate: (3-96 g.,
98%); mp. 112-114C; ir (K B2) cm"1 3300 (N-H); 1740 (C = 0); 1680
(C = 0); nmr (CCl^cf O.98 (q, 6, J = 8 Hz); 3.87 (q, 4, 5 = 8 Hz);
4.92 (s, 1); 5.90 (broad) (s, 1); 7.07-7-97 (m, 7).
Anal. Caled for Con H NO. B C; 57-43; H, 4.82; N, 3-35
20 20 4 r
Found = C; 57-46; H, 4.85; N, 3-35
Ethyl-[2-ethoxy-5~spiro-(9~fluorenyl)-oxazoline] acetate (31)
Absolute ethanol (50 ml.) was placed in a 100-ml. dry round-
bottomed flask equipped with a reflux condenser and magnetic stirrer.
Sodium (0.090 g., 0.00391 g. atoms) was added and the reaction
mixture was allowed to stir at room temperature until all the sodium
had reacted. Ethyl a-bromo-0-(9-carbethoxyaminofluorenyl) acetate
(1.25 g., 0.00299 mole) was added and refluxed for six and one-half
hours. The resultant orange solution was evaporated to dryness,


10 -
Seemingly the most feasible way to obtain N-substituted spiro-
aziridines ^9 would be to react ethyl azidoformate with ethyl
f1uorenylidene acetate (2J), Scheme VIII. Huisgen, Szeimier and
Scheme VIII
Mifoius have studied the addition reaction of aryl azides to a, f3-un-
saturated esters and nitriles. Aryl azides could not be used here due
to the difficult removal of aryl group. The reaction of ethyl azido-
9
formate with alkenes has been studied by Lwowski and Mattingly. Even
though no examples of a, (3-unsaturated esters were given, success with
other azides warranted investigation.


- 93 -
anhydride and lead tetraacetate were added and the flask heated
with an oil bath to 65C while the stirring continued. Evolution
of carbon dioxide began after a few minutes and was usually
completed after an additional 10 minutes. The dark solution was
allowed to cool to room temperature, triethylene glycol (2 ml.)
and water were added and the resulting mixture was extracted with
pentane or diethyl ether. The extract was washed with dilute acid,
water, and then dried over anhydrous magnesium sulfate. Filtration
and evaporation of the solvent gave the olefin in good yield.
Electrolytic Bisdecarboxylation of anthracene-9, 10-endo-a,
3-succinic anhydride
Anthracene-9, 10-endo-a, 3-succinic anhydride (2.07 g., 0.0075
mole) was electrolized to give 9, 10-dihydro-9, 10-dihydro-9, 10-
ethenoanthracene (0.42 g., 27%). Recrystallization of this product
from ethanol gave colorless white fine needles, mp. 117_119C.
Electrolytic Bisdecarboxylation of disodium 9, 10-endo-a, 3-
succi nate
Disodium 9, 10-endo-a, 3-succinate (2.5 g., J.5 mmole) was
electrolized to give 9, 10-dihydro-9, 10-ethenoanthracene (0.44 g.,
29%): mp. 117-119C.
Electrolytic Bisdecarboxylation of 9, 10-endo-g, 3-succinic acid
Anthracene 9, 10-endo-a, 3-succinic acid (2.21 g., 7.5 mmole)
was electrolized to give 9, 10-dihydro-9, 10-ethenoanthracene (0.42
g., 27%): mp. 117-119C.


- 50 -
DISCUSSION
Anhydride 6 was synthesized according to the published pro-
30
cedure of Bachmann and Kloetzel Scheme LV, by the reaction of
Scheme LV
A
w
0
66
65
c6h6


- 94 -
Bisdecarboxylation of 9 10-endo-Q, p-succinic acid with Lead
Tetraacetate
9, 10-Endo-a, p-succinic acid (1.00 g., 0.0037 mole) was de-
carboxylated in 10 ml. of pyridine at 50-55C. Work-up consisted
of the addition of dilute nitric acid to the solution followed by
extraction with diethyl ether. The ether was washed with 10%
Ma2^3^2^ and dried over anhydrous magnesium sulfate. Filtration
and evaporation of the solvent gave 9> IO-dihydro-9 10-ethenoanthra-
cene (0.25 9 33%): mp. 1171SC.
p-Hethoxyphenylazide (70)
The procedure was similar to that of Smith and Boyer^ in their
preparation of p-nitrophenylazide.
Distilled water (200 ml.) and concentrated hydrochloric acid
(100 ml.) were added to a 3~liter three-necked flask and cooled with
an ice bath to 0C. p-Anisidine (50.0 g., 0.407 mole) previously
recrystallized from water was added slowly with a temperature mainten
ance of 0 to 5C. The amine hydrochloride salt precipitated immediately.
It was diazotized by the slow addition of sodium nitrite (30.0 g.,
0.435 mole) dissolved in distilled water (100 ml.). The reaction
mixture now purple in color was allowed to stir one additional hour.
A temperature range of 0 to 5C was maintained while sodium azide (26.5 g.,
0.408 mole) dissolved in water (100 ml.) was slowly added. The azide
precipitated immediately as a bright yellow solid. The reaction was


- 67 -
position and that the most reactive site within the molecule S]_
was the aromatic ring with the methoxy group substituent.
In an effort to facilitate allylic bromination, compound
was selected. The single conjugated ester group would probably
still stabilize the diene. Also, by having only one ester group,
one allylic position remains essentially unchanged. It is re
ported that 1-carbethoxycyclohexene is brominated in the 3-position
rather than the 6-position, with N-bromosuccimide and benzoyl
42
peroxide. If aziridine 4 can be synthesized, allylic bromin
ation may occur at the most active allylic position.
COOEt
94
The synthesis of 94 began with the isolation of ¡n 74% yield,
Scheme LXXVII, from the reaction of 11, 12-dimethylene-9> 10-etheno-
9, 1O-dihydroanthracene (84) and ethyl propiolate. The nmr spectrum


- 97 -
4, 5-[9, 1O-anthrylene]-cyclohexene-cis-1, 2-dicarboxylic anhydride (63)
35
Using a procedure similar to Diels and Friedrichsen 9, 10-
ethenoanthracene carboxylic anhydride (8.00 g., 0.0292 mole) and
benzene (30 ml.) were placed in a Carius tube and cooled to 0C.
Butadiene (1.58 g., 0.0029 mole) was transferred from a cylinder
through a gas dispersion tube to the Carius tube which was capped,
allowed to stand at room temperature for one hour and then heated
for three days at 100C. On cooling to room temperature the Carius
tube mixture was transferred to an Erlenmeyer flask and recrystal
lized from acetic anhydride. Filtration and drying under vacuum
gave colorless crystals of 4, 5~[9> 10-anthrylene]-cyclohexene-cis-1,
2-dicarboxylic anhydride (9-1 g., 95%): mp* 210-211C.
Attempted Electrolytic Bisdecarboxy1 ation of 4, 5-[9> 10-anthrylene]-
cyclohexene-cis-1, 2-dicarboxylic anhydride
4, 5-[9, 10-anthrylene]-cyclohexene-cis-l, 2-dicarboxylic
anhydride (2.4 g., 0.0075 mole) was electrolized at 80 volts for six
hours. The amperage decreased during the electrolysis from 0.86 to
0.20 amps. The color of the reaction solution changed from colorless
to dark brown over a six-hour period. On work-up and isolation, the
product was shown by spectral analysis to be starting material.
Attempted Electrolytic Bisdecarboxylation of 4, 5~[9, 10-anthrylene]-
cyclohexene-cis-1, 2-disodium carboxylate
An attempt to dissolve 4, 5~[9> 10-anthrylene]-cyclohexene-cis-1,
2-disodium carboxylate (2.92 g., 0.0075 mole) in a solution containing


No. I
in


- 23 -
from the mono-N-substituted urethan apparently favors three-membered
ring formation. The second factor relates to leaving groups effect
iveness. The formation of azir¡dines are facilitated by very effect
ive leaving groups such as tosylate and mesylate. The examples
studied also involved trans groups on six-membered rings. The dis
tinguishing factors between the two pathways may be more complicated
and need further investigation.
14
Katchalsky and Ben Ishai have shown that p-halocarbamates
may be converted to 2-oxazoli dones by pyrolysis at 120 to 200C,
Scheme XXIV.
Scheme XXIV
Heating the carbamate 2% at 200C for five minutes gave the
expected 2-oxazolidone 2, Scheme XXV. The by-product, ethyl
bromide, could be detected when the reaction was conducted in a Carius


101
according to the procedure of Meek and Stacy.
Meso-2, 3-[9, 10-anthrylene)-l, 4-butane-di-p-toluenesulfonate
(63-0 g., 0.110 mole) was heated under reflux in 7% ethanolic sodium
hydroxide (840 ml.) for thirteen hours. During the first few hours
the color of the solution changed to a bright yellow. Towards the
end of the reaction the solution was tan in color. It was allowed to
cool to room temperature and then poured over ice, filtered, and dried
to give 27.8 g. of two products, namely, 11, 12-dimethylene-9, 10 di
hydro-9, 10-ethanoanthracene and 9, 10, 11, 12, 13, l4-hexahydro-9>
10(31,41)-furanothracene in an approximately 2:1 ratio as determined
from nmr spectrum.
A portion of this material (16.0 g.) was chromatographed by
placing it on an alumina column. Elution with petroleum ether
(60 -I10C) gave 9-54 g. of 11, 12-Dimethyl-9, 10-dihydro-9, 10-
ethanoanthracene. Crystallization from ethanol gave sparkling white
needles: mp. 151-152C.
For characterization purposes a small amount of the ether was
eluted with methanol from the column. In other cases the ether was
discarded along with the chromatographic materials. Evaporation of
the solvent gave a white solid which on recrystallization from
acetonitrile melted at 179_180C.


- 45 -
While this work was in progress, a related Retro-Diels-Alder
H 27
approach was published. Klarner and Vogel attempted to prepare an
antiaromatic benzo-2-ox¡rene (56) which resulted in the isolation of
a rearrangement product 57. Scheme XLIX. They concluded that isomeri
zation of 5 to constituted a suprafacial 1, 5-sigatropic shift
which is symmetry allowed.
Scheme XL IX
PROPOSED PLAN
The precursor 1, 2, 4, 5~(9> 10-anthrylene)-cyclohexadiene (58)
was chosen to initiate the synthesis of the derivative of N-aziri diny1 -
(1, 10-anthrylene)-cyclohexa-3, 5-diene (5I). If 58 could be syn
thesized, selective addition of azide to the more strained double
bond could give the bridged triazoline 59, Scheme L.


- 48 -
Bromlnation of unsaturated aziridines has been accomplished at low
29
temperature by Paquetteand Kuhla. Successful synthesis of 6J_ or
62 and subsequent treatment with base might give the desired pro-
duct jjj_, Scheme LI II.
Scheme LI I I
The synthesis of precursor 58_ from the anhydride 6 was planned
by either electrolytic or oxidative bisdecarboxylation of 6 or the
diacid 64, Scheme LIV. Bisdecarboxylation and azide addition are two
key steps in this proposed synthesis. A model compound was chosen to



The synthesis of precursor |9 began with the preparation of
ethyl f1uoreny1idene acetate (2J) according to the procedure of
Sieglitz and Jossay. ^ Ethyl Ct-hydroxy-O (9-f 1 uoreny 1) acetate (22)
was prepared from 9~fluorenone (23) and ethyl bromoacetate in a Re-
formatsky reaction, Scheme IX. The product was not isolated but
Scheme IX
HOTs
C6H6
A
UPO
\COOEt
21
dehydrated by a catalytic amount of toluensulfonic acid to give ethyl
f 1 uorenyl idene acetate (2_1) in an overall yield of 91%.r
Ethyl azidoformate was allowed to react with ethyl fluoreny1idene
acetate (2j) in methylene chloride, Scheme X.


- 90 -
Reaction ot Sodium 2-spiro-(9-f1uoreny1) aziridine carboxylate
with Thionyl Chloride (Attempted)
This procedure was patterned after that of Deyrup and Clough.
Into a dried three-necked flask equipped with a magnetic
stirrer, inlet and outlet tubes for a nitrogen atmosphere, and
a rubber septrum was added a 57% sodium hydride suspension (0.509 g.,
0.012 mole). The sodium hydride was washed three times and dry
tetrahydrofuran (10 ml.) was added to the reaction flask. Sodium
2-spiro-(9~f1uoreny1)-aziridinecarboxylate (0.266 g., 0.0010 mole)
was added and then thionyl chloride (0.071 ml., 0.0010 mole). The
reaction turned yellow immediately and was stirred at room temper
ature for one hour and twenty-five minutes. The reaction mixture
was filtered through Cel¡te 540 and evaporated to give deep yellow
residue. Analysis of this residue by nmr showed no desired products
had been formed.
Anthracene-9, 10-endo-a, fi-succinic anhydride (6-5)
The title compound was prepared according to the procedure
49
of Bachmann and Kloetzel.
Disodium 9, 10-endo-Q, (3-succinate J62)
Anthracene 9, 10-endo-a, pi-succinic anhydride (2.09 g., 0.075
mole) and sodium hydroxide (4.0 g., 0.1 mole) was dissolved in 50%
ethanol and refluxed for two hours. The solution was cooled, evapor
ated and then dried under vacuum to give a quantitative yield of di-


- 8 -
The first precursor J3. would require synthesis of the spiro-
aziridine and ring closure of the a-lactam ring under appropriate
reaction conditions. The second precursor J_4 would necessitate
synthesis of a f3-lactam with a suitable leaving group in the 3-posi-
tion followed by elimination of HX to give the bicyclic product 12.
The third precursor JJj would require preparation of an Q-lactam
followed by ring closure of the aziridine to give the product J_2.
Precursor JJj was eliminated on the basis of work by Lengyel and
Sheehan^ who have shown that the greater the steric requirements of
the substituents on N and on C-3, the easier the preparation and
purification of the a-lactam. This has been attributed to greater
thermal stability and lower reactivity towards nucleophiles. N-un-
substituted a-lactams have not been synthesized to date. If the
sodium or lithium salts of J_6 could be synthesized, Scheme VI,
reaction with thionyl chloride might produce the desired product 12.
If nucleophilic attack by Cl occurs prior to deprotonation, the
Scheme VI
12


Reaction of ethyl g-bromo-g-(9-bromof1uoreny1) acetate with ammonia
Ethyl a-bromo-g-(9-bromof1uoreny1) acetate (1.00 g., 2.44 mmoles)
was dissolved in 5 ml. of absolute ethanol. Concentrated aqueous
ammonia (5 ml.) was added and the reaction stirred for eight hours.
Distilled water (25 ml.) was then added, the resultant solution
extracted with ether and dried over anhydrous magnesium sulfate.
Filtration and evaporation gave a product identical in spectral
properties to that of a-bromof1uoreny1ideneacetate as prepared by
Gilchrist and Rees.
g-Bromofluorenylideneacetate (?_5)
The title compound was prepared according to the procedure of
Gilchrist and Rees.^
Attempted reaction of a-bromof1uorenylideneacetate with ammonia
a-bromof1uoreny1ideneacetate (100 mg., 0.304 mmole) was dissolved
in 6 ml. of absolute ethanol. Concentrated aqueous ammonia (10 ml.)
was added and the reaction stirred at room temperature for 5 days.
Distilled water (10 ml.) was added and the resultant solution extracted
with ether. The ether extract was dried over anhydrous magnesium
sulfate. Filtration and evaporation gave only starting material as
determined by nmr spectoscopy.
Ethyl a-bromo-a-(9-isocyanatof1uoreny1) acetate (26)
Ethyl g-bromo-g-(9-bromof1uorenyl) acetate (5.00 g., 0.0122 mole)
was dissolved in 100 ml. of anhydrous diethyl ether. Freshly prepared


Page
Attempted allylic Bromination of 4, 5-dimethyl-
[4, 5-(9, 10-anthrylene) cyclohexene-N-(p-
methoxypheny1)-l, 2-aziridine] dicarboxylate 107
4-Ethyl-[9, 10-anthry1 ene)-cyclohexadiene]
carboxyl ate (95) .. 107
Attempted addition of p-methoxy azide to 4-Ethyl-
[1,2,4,5-(9j 10-anthrylene) cyclohexadiene]
carboxyl ate 108
4-Carbethoxy-triptycene (9§) 109
1, 2-(9, 10-anthrylene)-cyclohexane-l-p-methoxy-
phenylA2 triazoline-cis-4, 5-dicarboxyl ic
anhydride (99) 109
Photolysis of 1, 2-(9, 10-anthry1ene)-cyclohexane-
1-p-methoxypheny1 A2 triazoline-cis-4, 5~
dicarboxylic anhydride 110
4, 5~0imethy1 -[(9j 10-anthry1ene)-cyclohexane-1,
2-1 1 (p-methoxyphenyl) triazoline] di
carboxylate (103) 110
4, 5-Dimethyl-[1, 2-(9, 10-anthrylene)-cyclo-
hexene] dicarboxylate (102) Ill
4, 5-Oimethyl-[9j 10-anthrylene-cyclohexane-N-
(p-methoxyphenyl)-l, 2-aziridine] dicarboxylate (104) 112
Disodium [9, 10-anthry1enecyclohexene-N-(p-methoxy-
phenyl)-l, 2-aziridine] dicarboxylate (105) 112
Attempted esterification of disodium [9, 10-anthry-
1enecyclohexene-N-(p-methoxypheny1)-1, 2-aziri
dine] dicarboxylate 113
Electrolytic Bisdecarboxylation of disodium [9, 10-
anthylenecyclohexene-N-(p-methoxypheny])-l,
2-aziridine] dicarboxylate 113
APPENDIX 114
BIBLIOGRAPHY 125
v ¡ i
BIOGRAPHICAL SKETCH
129


- 39 -
Scheme XL IV
RCOOH RNH2 + R N=C=N R
O H
ii n
R-C-N-R
H 9 H
R N-C-N R
aziridines are unstable to acid, the free acid derivative of ]6_ can
not be generated. If, however, the carbodiimide could be activated
so that the first step is no longer acid dependent, a similar reaction
may occur with tha aziridinium salt J_6. An ideal reagent would be
a methylated carbodiimide 4jj. If the methylated carbodiimide 4
CH,
i 3
R N=T cNR
+ -
X
45
is allowed to react with JjS, the desired product 12, sodium salt
of the anion and a methylated urea 46 should be formed, Scheme XLV.


- 103 -
once with diethylether and acidified with 6 M hydrochloride acid.
The white precipitate was collected by filtration and dried to give
a quantitative yield of 1, 2-[9, 10-anthrylene]-cyclohexene-cis-4,
5-dicarboxylic acid; mp. 210-212C.
ir (KBr) cm"1 3225 (broad OH)*, 1739, 1695 (C=0);
nmr (D^-acetone) cf 2.60-3.18 (broad m,6); 4.92 (s,2); 6.80-
7.42 (m,8).
m/e (calculated for C H o0.) = 346.1204
22 I o 4
Found = 346,1226
Electrolytic Bisdecarboxy1 at ion of 1, 2-[9, 10-anthrylene]-cyclohexene-
cis-4, 5~d?carboxylic anhydride
1, 2-[9, 10-anthrylene]-cyclohexene-cis-4, 5~dicarboxylic anhydride
(1.00 g., 0.00305 mole), was electrolized for six hours at a potential
of 80 volts. The initial amperage was 0.6 amps. When the amperage
decreased to 0.2 amps, the reaction was terminated. On work-up the
product isolated was triptycene (0.86 g., 12%) as characterized from
ir, nmr spectra and mp. which were identical to that of triptycene
as prepared by Bartlett and coworkers.^
Electrolytic Bisdecarboxylation of 1, 2-[9, 10-anthry1 ene]cyclohexene-
cis-4, 5di carboxyl i c acid
I, 2-[9, 10-anthrylene]-cyclohexene-cis-4, 5_dicarboxylic acid
(0-975 g*, 0.00282 mole) was electrolyzed for three hours at a poten
tial of 40 volts. On work-up only pure triptycene was obtained.


- 76 -
Scheme LXXXV
prior to the esterification would probably have justified these results.
Electrolytic bisdecarboxylation of the disodium salt 105, Scheme
LXXXVI, also resulted in a complex mixture. The desired diene 101
Scheme LXXXVI
101


- 9 -
result should be _18^ Proper treatment of J_8 with a strong non-
nucleophilic base should give the desired product 12.
In an attempt to synthesize precursor J_3, two spiroaziridines,
19 and 2(3, were chosen. Either one of these sp i roaz i r i di nes could
De treated with strong base to produce the desired precursor 16,
Scheme VII.
Scheme VI I
^ONa


- 47 -
Scheme LI
The bridged aziridine 6£ could then be brominated to give the di
bromo-addition product 6J_ or could be treated with N-bromosuccinimide
(NBS) to give the allylic brominated product (x2, Scheme Lll.
Scheme LI I
62


- 77 -
was not obtained. These results could be attributed to the aziridine
being unstable under electrolytic conditions.
SUMMARY AND CONCLUSIONS
Diene 8 was chosen because it would have a minimum number of
functional groups after the azide addition, but attempted synthesis
resulted in aromatization to triptycene. Stabilization of diene 8j6
and with ester groups was successful. Azide addition to diene
86 and subsequent photolysis of the resulting triazoline 8]_ gave
the desired aziridine . Azide addition of resulted in aroma
tization to the triptycene derivative 8. Aromatic substitution oc
curred on allylic bromination of . Purification problems of azide
addition to the anhydride were eliminated by converting the an
hydride to the diester 102. Addition of the azide and subsequent
photolysis gave the aziridine 104. Saponification of followed
by bisdecarboxylation of the disodium salt resulted in a complex
mixture. It is suggested that an aziridine such as 107 be synthe
sized with a deactivated phenyl or alkyl as the R group. If the X
removable by base, the diene might be synthesized.
groups are


- 105 -
ir (KBr), nmr (DCC1 ) c£ 3-23 (s,4); 3-67 (s,6)*, 4.75 (s,2);
6.78-7.30 (m,8).
m/e (calculated for ^24^20^4^ = ^72.1360
Found = 372.1358
4, 5Dimethy1 -[4, 5_(9> 10-anthry1ene)-cyclohexene-1, 2-1 -(p-methoxy-
phenyl-Zl^-triazoline] dicarboxylate (87)
4, 5-Oimethyl-[I,2,4,5-(9> 10-anthrylene)-cyclohexadiene] d¡-
carboxylate (1.00 g., 2.7 mmole), p-methoxyphenylazide (0.402 g.,
0.0027 mole) and ethyl acetate were placed in a Carius tube and
heated in an oil bath at 80C for four days. The dark solution
crystallized on cooling to room temperature. The solid was trans
ferred to a funnel and washed with a few ml. of carbon tetrachloride
to give a light tan crystalline solid of 4, 5-dimethyl-[4, 5(9> 10-
2
anthrylene)-cyclohexene-l, 2-1 -(p-methoxypheny1 A -triazoline
carboxylate (0.99 g., 71%): mp. 200-202C. Recrystallization from
benzene did not change the melting point.
nmr (DCCI ) 1.60-2.3/m,2 3.00-3.40 (m,2); 3.45 (s,3);
3.66 (s,3); 3-72 (s,3); 4.50 (s,1); 4.60 (s,l); 6.71-7-41 (m,12).
Anal. Caled for C^H^O^: C, 71-34; H, 5-22; N, 8.06; C, 71-18;
H, 5-28; N, 8.18
m/e = 493 (521-28)


Scheme XXXIX
29
23
Since the carbamate 28^ did not give ring closure to the desired
azir¡dine hydrolysis of the isocyanate to the amine was attempted
Treatment with an appropriate base could possibly cause ring closure
of a-amino-p-bromo derivative to the spiroaziridine 20. Hydrolysis


Page
Dimethyl 9, 10dihydro-9, 1O-ethenoanthracene 11
12d i carboxyl ate (73) 96
9, 10-dihydro-9, 1O-ethenoanthracene carboxylic
anhydride (75) 96
4, 5t9, 10-anthry1 ene]-cyclohexene-cis-1, 2-di-
carboxyl ic anhydride (63) 97
Attempted Electrolytic Bisdecarboxy1 at ion of 4,
5-[9, 10-anthrylene]-cyclohexene-cis-1, 2-di
carboxyl ic anhydride 97
Attempted Electrolytic Bisdecarboxylation of 4,
5-[9, 10-anthry1 ene]-cyclohexene-cis-1, 2-di
sodium carboxylate 97
Attempted Synthesis of 4, 5~[9, 10-anthrylene]-
cyclohexene-cis-1, 2-dicarboxylic acid 98
Attempted Electrolytic Bisdecarboxylation of 4,
5- [9, 10-anthrylene-cyclohexene-cis-l, 2-di
carboxyl ic anhydride with Lead Tetraacetate 99
Meso-2, 3-[9, 10-anthrylene]-1, 4-butanediol (8J ) 99
Meso-2, 3-[9, 10-anthrylene]-1, 4-butane-di-p-
tol uene-sul fonate (82) 100
11, 12 Dimethyl-9, 10-dihydro-9, 1O-ethanoanthracene .. 100
1, 2-[9, 10-anthrylene]-cyclohexene-cis-4, 5-di-
carboxylic anhydride (79) 102
1, 2-[9, 10-anthrylene]-cyclohexene-cis-4, 5~8i-
carboxylic acid (§0) 102
Electrolytic Bisdecarboxylation of 1, 2 [9, 10-
anthrylene] -cycl ohexene-ci s-4, 5-dicarboxylic
anhydride 103
Electrolytic Bisdecarboxylation of 1, 2-[9, 10-
anthrylene] -cyclohexene-ci s-4, 5_8¡carboxylic acid 103
Triptycene [9, 10-0-Benzenoanthracene (85) 104
Oxidative Bisdecarboxylation of 1, 2-[9, 10-anthry-
lene]-cyclohexene-cis-4, 5~8icarboxylate anhydride
with lead tetraacetate 104
4, 5-Dimethyl-[1,2,4,5-(9,10-anthrylene)-cyclo-
hexadiene] dicarboxylate (6) 104
4, 5-0imethy1 -[4, 5-(9, 10-anthrylene)-cyclohexane-l,
2-1 -(p-methoxyphenyl A^-tr iazol i ne] dicarboxylate ($.7) 105
4, 5-Oimethy1 -[9, 1O-o-Benzenoanthracene] di-
carboxylate (89) 1 06
4, 5-0imethyl-[4, 5~(9, 10-anthrylene)-cyclohexene-
N-(p-methoxypheny1)-l, 2-aziridine] dicarboxylate (21)106


Scheme LXXIX
crude triazoline 99. was successful as depicted by nmr spectroscopy,
but purification problems were again encountered. The separation of
the aziridine 100 from other components of the mixture was achieved
in a crude form by fractional crystallization. Hydrolysis of the


-128-
55- P. A. S. Smith and J. H. Boyer, "Org. Synthesis Col 1. Vol. IV,
John Wiley and Sons, New York, N. Y., 1943 P* 75-
56. K. Kitohonoki, Tetrahedron Letters, 1059 (1965)
57. P. D. Bartlett, M. J. Ryan and Saul G. Cohen, Amer. Chem.
Soc., 64, 264-9 (1942).
58.L. F. Fieser,"Organic Experiments," D. C. Heath Co., Boston, Mass.,
1964, p. 152.


BIOGRAPHICAL SKETCH
Emmett Scott McCaski11, Jr., is a native of the State of Missis
sippi. He attended the public schools until transferring to Tougaloo
Preparatory School near Jackson, Mississippi, where he completed his
high school education.
Mr. McCaski11 began his college career at Tougaloo Southern
Christian College. He later transferred to Alcorn A & M College,
Norman, Mississippi where he received a Bachelor of Science degree
in Chemistry. Thereafter, he entered the Graduate School of Fisk Uni
versity, Nashville, Tennessee, where, in 1961, he received a Master
of Science degree in Organic Chemistry.
The author has worked as an Assistant Professor in Chemistry
at Mississippi Valley State College, Itta Bena, Mississippi, as a
science teacher in the Alachua County Public Schools, Gainesville,
Florida, and as a Research Assistant in the Department of Medicine,
University of Florida, Gainesville, Florida.
In August 1971 > Mr. McCaski11 enrolled in the Graduate School
of the University of Florida where, until the present time, he has
pursued his work toward the degree of Doctor of Philosophy. During
his graduate study, both teaching and research assistantships were
held.
129 -


- 49 -
Scheme LIV
investigate the problems involved and to find appropriate reaction
conditions by which precursor 8 and bridged aziridine 6£ might be
synthesized. The model compound chosen was anthracene 9> 10-a, (3-
succinic anhydride (65)


- 53 -
identifies the azide additions, and; the reactivity of azides with
deactivated alkenes has been shown to increase with electron donating
3 3
groups. The addition of £-methoxyphenyl azide to 11, 12-etheno-9,
10-dihydroanthracene gave the triazoline 71 in 57% yield. Photolysis
of the triazoline 71 with a sun lamp gave the expected aziridine 2
in 50% yield, Scheme LV1I I.
Scheme LVI I I
72


- 38 -
Scheme XL I I I
V7 + Et3N
N
H
so2ci2
- I5C
CCI4
0

S-CI
25oC Cl ch2ch2 N-S->0
chloride at reduced temperatures it was possible to trap and character
ize the new class of aziridine derivatives, 1 -(aziridine) sulfinyl
chlorides. When these compounds stood at room temperature for several
hours, 2-chloro-N-suIfiny1 ethylamine was isolated. Although none of
these derivatives were isolated, this does suggest that there is
probably an attack of the thionyl chloride on the nitrogen which
changed the reaction path.
CONCLUSION
Although the 1-azabicyclo-[1.1.0]-butane-2-one was not syn
thesized there are at least two approaches which might warrant future
study. The first is the ring closure of the a-lactam ring. Since
the synthesis of this ring involves the formation of a N-C bond and
removal of an OH group in J_6, this is closely related to the syn
thesis of peptide with carbodiimide derivatives, Scheme XLIV. Since


- 7 -
Ring closures from precursors J_3., Jj+ and JMj were considered for
the synthesis of ]_2, Scheme V.
Scheme V


CHAPTER I
ATTEMPTED SYNTHESIS OF A 1 -AZAB I CYCLO- [ 1 1.0] B LITAN E-2-ONE
INTRODUCTION
A previous investigation by Deyrup and Clough^ led to the dis
covery that certain aziridine derivatives undergo ring expansion to
3-chloro-2-azetidi none (Jj.
Their work began when an attempt to synthesize a 2-aziridine-carbonyl
chloride (_2) resulted in a new path to the 3-halo-2-azetidinone system,
Scheme I. Thus, when the lithium or sodium salt of 1-tert-buty1-2-
aziridine carboxylate (3.) was treated with thionyl chloride or oxalyl
chloride in the presence of excess sodium hydride, the resultant pro
duct was 1-tert-buty1-3-chloro-2-azetidinone (4) in 33% yield. Struct
ure proof of this azetidinone 4 was based on ir and nmr spectroscopy,
elemental and mass spectral analysis. Further proof of the structure
1
%


- 54 -
Synthesis of the anhydride 6 began with the preparation of 1 1,
12-dicarbomethoxy-9, 1O-dihydroanthracene (73) according to the pro-
34
cedure of Diels and Alder, Scheme L1X. Saponification followed by
Scheme LIX
neutralization to the diacid 74 and subsequent heating with acetic
anhydride gave the unsaturated anhydride in quantitative yield,
Scheme LX. According to the published procedures of Diels and
Scheme LX
74
75


-108-
0.0217 mole), ethyl propiolate (4.2o g., 0.0435 mole) and benzene
(40 ml.) were heated in a Cari us tube on a steam cone for twenty-
four hours. The solution was transferred to a flask and evaporated
to dryness to give a light yellow crystalline solid. Recrystalliza
tion from ethanol gave 5*25 g. (74%) of 4-ethyl-[1,2,4,5(9> 10-an-
thrylene)-cyclohexadiene] carboxylate as a colorless crystalline
solid: mp. 182-182.5C.
ir (KBr) cm 1699 (C=0, ester)
nmr (DCC1 ) cf 1.18 (t,3,J=7Hz); 3.10 (m,4); 4.12 (d,2,J=7Hz);
4.72 (s,1); 4.77 (s,1); 6.85-7-42 (m,9).
m/e (calculated for C__rl Q_) = 323.1453
23 20 2
Found 323.1456
Attempted addition of p-methoxy azide to 4-Ethy1 -[1,2,4,5(9, 10-
anthrylene) eyelohexadiene] carboxylate
4-Ethyl-[1,2,4,5-(9, 10-anthry1 ene) cyclohexadiene] carboxylate
(0.500 g., 0.0152 mole), p-methoxypheny1azide (0.453 g., 3-04 mmole)
and purified ethyl acetate (0.5 ml.) was heated in a Carius tube
o
at 100 C for seventy-two hours. The dark solution was evaporated
to a black residue which was chromatographed in si lea gel packed in
petroleum ether (20-40). The first fraction eluted from the column
was a mixture of anthracene and unreacted p-methoxypheny1 azide. The
identity of these two products was confirmed by nmr spectroscopy.


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.
Dr. Herman Baers
Assoc. Professor of Clinical Microbiology
This dissertation was submitted to the Department of Chemistry in the
College of Arts and Sciences and to the Graduate Council, and was
accepted as partial fulfillment of the requirements for the degree of
Doctor of Philosophy.
December, \3~¡h
Dean, Graduate School


22
It has been shown that cyclization of N-(2-substituted alkyl)-carboxy-
amide may proceed by two pathways, Scheme XXIII. The first pathway
Scheme XXIII
-9
C-
HN-COOR
Strong
>
Base
C=0
h
0 R
2)
1
C-
C
1
/;
H-N
^C0
1
0
I
R
yields a 1-acyl aziridine and the second leads to the formation of
oxazolines.
Instances in which aziridines are formed rather than oxazolines
13
have been attributed mainly to two factors. Decreased resonance
stabilization of the anion resulting from the removal of a proton


- 59 -
was then treated with 7% sodium hydroxide to give dimethylene-9,
1O-ethanoanthracene (84) and a by-product ether 83, Scheme LXVII.
Scheme LXVII
Separation of 84 from 83, by column chromatography and subsequent re
action of 84 with maleic anhydride (66) illustrated in Scheme LXVIII
Scheme LXVI I I


1


LIST OF TABLES
Table
I
I I
Page
Ring Strain in Three-Membered Rings 6
Substituent Reactions of a-Bromo Carbamates 33
VI i i


20 -
c=o
I
OMe
30
no peaks between 405 and 238 mass units, this fragment probably was
formed as depicted in Scheme XX.
Scheme XXI
m/e = 405 m/e = 238
Ring closures of 2(j and _28 to the aziridine with ethoxide
in ethanol were attempted. The expected aziridine 29. was not ob-


- 75 -
by the reaction of 10% sodium hydroxide in aqueous diglyme solution.
Infrared spectroscopy supported the disodium salt structure 105
Further characterization of the salt 105 was difficult due to its
solubility properties and acid sensitive functions. Attempts were
made to esterify the disodium salt 105 by acidification at low
temperature with 5% perchloric acid, Scheme LXXXIV. Aziridines
Scheme LXXXIV
HCIO4
0c
COOH
have been shown to be stable under these conditions. Esterification
of the diacid J_06 with diazomethane gave a mixture of products
but not the expected diester 104, Scheme LXXXV. Ring opening


OI
T
T
ot
O'l
T
T
L ON
v* i. *) wa o t
-|i r, i"
-


- 95 -
then allowed to stir overnight. Filtration, recrystallization
from ethonol (95%) and drying gave bright yellow plates of £-
methoxypheny1azi de (51-0 g., 84%): mp. 34-35 C.
2
1 -(p-Methoxyphenyl)~9, 10-ethanoanthracene A triazoline (j_[)
\
9, 10-di hydro-9, 10.-ethanoanthracene (0.430 g., 0.00210 mole)
and p-methoxypheny1 azide (0.317 9*, 0.00213 mole), both in ethyl
acetate (6 ml.), were refluxed for twenty-eight hours. The re
sultant brown solution was cooled and evaporated to give a dark
oil. Crystallization from benzene gave 1 -(p-methoxypheny1)-9.
1 0-ethanoanthracene triazoline (0.42 g. 57%): nip. 1 58 160C;
nmr (DCC^) 0^3.80 (5,3); 4.20-5*40 (m,4); 6.60-7-50 (m,12).
N-(p-methoxypheny1)-9, 10-ethanoanthracene aziridine (72)
1 -(p-Methoxyphenyl)-9, 10-ethanoanthracene triazoline
(0.410 g., 0.00116 mole) was dissolved in dry acetone (30 ml.)
and irradiated for three hours with a sun lamp. Evaporation of the
solvent and recrystallization from methanol-chloroform solution gave
N-(p-methoxypheny1)-9, 10-ethanoanthracene aziridine (0.188 g., 50%)
mp. 185-188C; nmr (DCC^) cf 2.67 (2,m); 3-55 (s,3); 4.58 (m,2);
6.63 (s,4); 6.88-7-37 (m,8). The above compound showed similar
chemical shifts of 9, 10-ethanoanthracene aziridine as prepared by
Ki tohonoki.^
9, 10-dihydro-9, 10-ethenoanthracene-l1, 12-dicarboxy1ic acid (741
Dimethyl 9, IO-dihydro-9, 10-ethenoanthracene-11, 12-dicarboxy-


- 64 -
Photolysis of triazoline 82 with a sun lamp in acetone at 25 C
gave the desired aziridine 2J_, Scheme LXXIV, in 81% yield. The nmr
Scheme LXXIV
87
COOMe
spectra showed interesting changes of the diene 86_ to the triazoline
87 and finally to the bridged aziridine 9J_- The three absorptions
of interest were the aromatic protons, the bridgehead protons and the
methyl ester protons. In diene £36 the aromatic region showed a
symmetrical absorption of 8 protons, a singlet for the bridgehead
protons, and a singlet for the 6 protons of the two methyl ester
groups. In the triazoline 82 the aromatic region became quite complex


CHAPTER I I
ATTEMPTED SYNTHESIS OF A BENZ0-2-AZIRINE
INTRODUCTION
Considerable attention has been given to the chemistry of small
strained heterocyclic ring systems. The 2-azirine ring system 49
is one that has received considerable attention. A large number of
recent attempts have been directed toward its synthesis, but the
system has neither been isolated nor trapped. This ring system is of
theoretical interest since, if planar, it is a cyclic conjugated
structure containing 4 TT electrons. Huckel's rule predicts anti
aromatic character. Since 1-azirines are well known, it does not
seem reasonable to attribute the non-existence of 2-azirines ex
clusively to strain energy. The instability of the 2-azirine system
could probably be attributed to an unfavorable electronic property
- 42 -


- 85 -
was added until the solution was basic and then an additional 15 ml.
excess was added. A white precipitate formed and was extracted with
diethyl ether (150 ml.; 3 x 50 ml.). The ether extract was washed
twice with water and dried over anhydrous magnesium sulfate. After
filtering, evaporation of solvent gave 9~amino-f1uorene (1.60 g., 96%)
a bright yellow solid; mp. 121 C. nmr (DCCl^) cf 1.68(s,2); 4.72
(s,1); 7.15-7.83 (m,8).
9-CarbethoxyTni nof 1 uorene
This compound was prepared according to the method of Deyrup and
k6
Gill. Into a 250-ml. round-bottomed flask equipped with a magnetic
stirrer, Dean-Stark trap and a reflux condenser was placed activated
4 7
manganese dioxide (1.38 g., 0.0158 mole) in 100 ml. of benzene. The
mixture was refluxed for 12 hours. 9"Carbethoxyam¡nof1uorene (0.500 g.,
O.OOI98 mole) was then added and the reaction mixture was then allowed
to cool to room temperature, filtered through Celite-545. The yellow
solution was evaporated to dryness to give a yellow oil. Re
crystallization from petroleum ether (60-110) gave 9-carbethoxy-
iminofluorene (0.200 g., 40%) a bright yellow solid; mp. 70-72C.
ir (KBr) cm"1 1700 (C=0); 1680 (C=N),
nmr (CCl^) cT 1.40 (t,3,5=7Hz); 4.37 (q,2,J=7Hz); 6.95-7-66 (m,8).
m/e (calculated for C .H NOj = 251.0945
I o 13 2
Found =251.0956


- 26 -
Scheme XXVII i
viously saturated with dry HBr. The isolated product was the 2-oxa-
zolidone 32, Scheme XXXIX. These results support the reaction inter-
Scheme XXXIX
mediate 3 proposed by Hassner and coworkers.
16
Hassner and other workers have synthesized a large number of
aziridines by cyclization of iodocarbamates with a base, Scheme XXX.


- 60 -
gave the desired precursor 9 in 86% yield.
The diene 8 was unobtainable via bisdecarboxylation of an
hydride _79 and triptycene (8) was isolated in low yield, Scheme
LXIX.
Scheme LXIX
58
Bisdecarboxylation of the diacid was then investigated. The anhydride
79 Scheme LXX, was treated with aqueous sodium hydroxide and aci-
Scheme LXX


- 89 -
The reaction mixture was evaporated to dryness to give a light yellow
solid. Water was then added and the aqueous mixture extracted with
ether. The ether extract was washed once with water and dried over
anhydrous magnesium sulfate. After filtering and removal of solvent
the residue, a light yellow oil, was recrystallized from 95% ethanol
to give white crystals of 2-carbethoxy-3-spiro-(9-f1uoreny1) aziridine
(4.40 g., 98%); mp. 118-120C; ir (KBr) cm"' 3448 (N-H); 1739 (C=0);
nmr (DCCl^)cf 1.08 (t,3,J=7Hz); 2.58 (broad) (d,l,J=9Hz); 3*43 (broad)
(d,l,J=9Hz)i 4.13 (q,2,J=7Hz); 7.00-7.77 (m,8).
Anal. Caled for C H N02: c> 76.96; H, 5.70; N, 5.28
Found: C, 76.82; H, 5-77; N, 5-25
Sodium 2-sp?ro-(9-fluorenyl)-aziridinecarboxy1 ate (16)
Ethyl 2-spiro-(9-f1uoreny1)-aziridinecarboxylate (2.00 g.,
0.00755 moles) was dissolved in 50 ml. of 95% ethanol and sodium
hydroxide (8.0 ml. of 1.0 M, 0.0080 mole) was added. The reaction
was allowed to stir for one hour in which the salt precipitate, the
white solid was filtered, washed with ether and dried under vacuum
to give sodium 2-spiro-(9-f1uoreny1)-aziridinecarboxy1 ate (1.96 g.,
100%) as a white powder. A small amount of the sodium salt was re
crystallized from water (mp. 154-156 decomposition turning red),
which was identified by spectral properties.


130 -
Mr. McCaski11 is married to the former Cornelia Ann Brown.
He has three daughters, Gevelyn, E'mett and Mettlyn.


-109-
The second fraction eluted from the column was a colorless solid
(mp. 133-135C) identified as 4-carbethoxy-triptycene.
nmr (CCl^) of 1.20 (t,3); 4.17 (q,2); 5-30 (s,2); 6.70-7-42 (m,8);
7-55 (m,1); 7-60 (m,l); 7-95 (m,l).
Further elution for the column with chloroform gave unidentifiable
products.
4-Carbethoxy-triptycene (98)
4-Ethyl -[1,2,4,5(9> 10-anthrylene) cyclohexadiene] carboxylate
(200 mg., 0.610 mmole), N-bromosuccinamide (109 mg., 0.610 mmole),
a catalytic amount of benzoyl peroxide and carbon tetrachloride (5 ml.)
were refluxed for two hours. The reaction mixture was cooled, filtered
#
and the filtrate evaporated to dryness to give a light yellow residue.
Recrystallization from ethanol gave 4-carbethoxytriptycene (0.186 g.,
94%): mp. 134-136C.
nmr (CC14> of 1.20 (t,3); 4.17 (q,2); 5-30 (s,2); 6.70-7-42 (m,8);
7-55 (m,l); 7-60 (m,l); 7-95 (m,l).
1, 2-(9, 10-anthrylene)-cyclohexane-l-p-methoxyphenyl Za triazoline-
cis-4, 5dicarboxylic anhydride (99)
1, 2-(9, 10-anthry1ene)-cyclohexene-cis-4, 5_dicarboxylic an
hydride (6.60 g., 0.0201 mole), p-methoxyphenylazide (6.00 g., 0.0402
mole), and purified ethyl acetate were refluxed for seven days. The
dark solution was evaporated to dryness to give a dark brown residue.


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
Phi 1osophy.
Dr. J. A. Deyrup, Chairman
Professor of Chemistry
I certify that 1 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
Phi 1osophy.
Dr. George B. Butler
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
Phi 1osophy.
Dr. William R. Dolbier, Jr. x
Assoc. Professor of Chemistry
1 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
Phi 1osophy.
Dr. William Weltner^
Professor of Chemistry


- 3 -
The ring expansion was of both mechanistic and synthetic inter
est. The similar behavior of thionyl chloride and oxalyl chloride
with the aziridinium salts suggested that in both reactions a common
intermediate is present and opposes intermediates such as ]_ or 8.
A symmetrical carbonium-type intermediate can also be overruled
since the reaction was found to be stereospecific, Scheme III.
Scheme I 1 I
R
Ri
Xt<
N
t-Bu
0
C-ONa
w
Cl
(CO Cl2)2
H-
R-
\
t-Bu
(a) R = ay R] = H
(b) R = H; Rj = CH3
(a) R = CH3; R] = H
(b) R = H; R] = CH3


100 -
glistening white needles melting at 223-224C.
Meso-2, 3-[9, 10-anthrylene]-l, 4-butanediol was also prepared
by heating anthracene (10 g., 0.563 mole) and cis-2-butene-l, 4 diol
o
in a hydrogenation bottle for twenty-four hours at 180-185 C. The
light brown liquid was cooled to give a white solid which was filtered,
washed with water and then crystallized from methanol to give 126 g.
(84%) of the product. Spectral analysis of this product was identical
to that of meso-2, 3-[9> 10-anthrylene]-1, 4-butanediol.
OO
Meso-2, 3-[9, 10-anthrylene]-l, 4-butane-di-p-toluene-sulfonate (82)
Meso-2, 3-[9, 10-anthrylene]-l, 4-butanediol (50 g., 0.188 mole)
was dissolved in dry pyridine (500 ml.) which had been distilled from
barium oxide. This solution was cooled and maintained at 0C with a
salt-ice bath. p-Toluene sulfonyl chloride (76.2 g., 0.400 mole) was
added and stirred until it dissolved. The solution was refrigerated
for forty-eight hours. The precipitated product was filtered, the
filtrate poured over ice and the mixture allowed to stand at room
temperature until the ice melted. The solid was filtered, combined
with the first fraction and the recrystallized from acetonitrile to
give meso-2, 3-[9, 10-anthrylene]-1, 4-butane-di-p-toluene-sulfonate
(99 g., 93%): mp. 185-187C.
11, 12 Dimethyl-9, 10-dihydro-9, 10-ethanoanthracene (84)
11, 12 Dimethyl-9, 10-dihydro-9, 10-ethanoanthracene was prepared


Copyright by
Emmett
. McCaski11, Jr.
1974


- 28 -
were made to investigate in detail its mechanism. Anionic and cationic
rearrangements were considered but do not reasonably explain these re
sults. As a working model a radical mechanism was proposed because
alkyloxy radicals are stable intermediates and account for the pro
ducts, Scheme XXXII.
Scheme XXXI I


J.-.i
a.o
7.0
4.0
4.0
PPM (1)
4.0
No. 9
i,..i i-.li--,t I ,i i ,i i I ii i
a.o a.o i.o o
t1
ro
OJ


- 58 -
cursor 8.
The synthesis of anhydride 2. began with the preparation of
anthracene 9, 10-endo-Q, p-succinic anhydride (65), and subsequent
oO
reduction with lithium aluminum hydride in THF. The resulting
38
diol 8_1_ was converted to the ditosylate 8_2, Scheme LXV, and
Scheme LXV
thereafter, synthesized in good yield by the reaction of anthracene
39
(52) with cis-1, 4-dihydroxy-2-butene, Scheme LXVI. The ditosylate 82_
Scheme LXVI


110 -
Cyclohexane was then added, the mixture heated to give a tan solid,
which was filtered and dried. Attempts to recrystallize this pro
duct were unsuccessful. An nmr spectrum was taken on this sample:
(DCC13) cf 1.67 (broad, 2); 2.75-3-16 (broad, m,4); 3-80 (s,3);
4.50 (s,1); 6.67-7.45 (m,12).
This sample was used without further purification.
Photolysis of 1, 2-(9, 10-anthrylene)-cyclohexane-l-p-methoxyphenyl-
triazol?ne-cis-4, 5~dicarboxylic anhydride
The triazoline (2.00 g., 4.19 mmole) was placed in a dried 200 ml.
round-bottomed flask equipped with a condenser, protected with a dry
ing tube, and magnetic stirrer. Dried acetone (50 ml.) was added
and the resulting solution irradiated for eight hours. The solvent
was evaporated to dryness to give a brown residue, which was heated
in cyclohexane to give 1-54 (82%) of a tan solid. Numerous attempts
to recrystallize this solid were unsuccessful. Even though the nmr
spectrum on this crude sample showed the expected chemical shifts
of the desired aziridine, impurities in this sample made it impossible
to characterize.
4, 5-Oimethy1 -[(9> 10-anthrylene)-cyclohexane-1, 2-1 1 (p-methoxy
phenyl ) A ^ triazoline] dicarboxyl ate (LQi)
4, 5-0imethyl-[l, 2-(9, 10-anthry1ene)-cyclohexene]-dicarboxyl ate
(5.00 g., 0.0134 mole), p-methoxyphenyl azide (3.00 g., 0.0201 mole)
and ethyl acetate (5*0 ml.) were placed in a Carius tube and heated


- 13 -
Synthesis of the unsubstituted spiroaziridine 20^ was attempted
by the reaction of ammonia with a, p-dibromo ester 24, Scheme XII.
This approach was patterned after a series of papers by Cromwell and
Scheme XI I
coworkers which dealt with the reaction of a, p-dibromo ketones with
ammonia, primary and secondary amines, Scheme XIII.
Scheme XIII
9 ,
R-CH-CH-C R +
II rv
Br Br
RNH,


- 43 v
that exists within this molecule. The aim of this research was to
synthesize the related benzo-2-azirine system (50).
50
The strategy selected was to synthesize a benzo-2-azirine (50)
via a Retro-Diels-Alder reaction, Scheme XLVII.
Scheme XLVI I
A derivative of N-aziridiny1 -(9, 10-anthrylene)-cyclohexa-3, 5~diene
(51) was selected so that formation of benzo-2-azirine (50) would
also yield anthracene (52) as a by-product and thus provide the
driving force in this synthesis.


- 19 -
Scheme XX
OOP
ft
Etc' fir'COOEt
N(Et)3
No Reaction
28
Only starting material was recovered.
MeO-C-N
COOEt
29
A high resolution mass spectrum of methoxy derivative 23 showed at
base peak at 238 (m/e calculated = 238.0867; found 238.0879)*
Structure 30 may be assigned to this fragment. Since there are


- 29 -
In this proposed mechanism, hydroxide ion first abstracts the proton
from the amide nitrogen to give 9-carbethoxy¡minof1uorene (37) The
resulting anion is probably destroyed under reaction conditions.
The intermediate reacts further in an oxidative or radical chain
process to give radical 8 which cyclizes to 39. and subsequent
hydrogen abstraction gives the product 36.- Because the reaction
conditions were strongly basic, radical scavengers could not be used
to confirm the radical process. In order to investigate the mechanism
of this reaction 9-carbethoxyiminof 1 uorene /.was synthesized and
subjected to free radical initiators.
9-Carbethoxy imi nof 1 uorene was synthesized by two methods.
The first method was the synthesis of 9-(carbethoxyamino) fluorene 41,
Scheme XXXIII, by the reaction of 9-aminof1uorene 40 with ethyl chloro-
Scheme XXXI I I
41


Abstract of Dissertation Presented to the Graduate Council
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
THE SYNTHESIS OF SPIRO AND BRIDGED AZIRIDINES
By
Emmett S. McCaskill, Jr.
December, 197^
Chairman: James A. Deyrup
Major Department: Chemistry
Attempts were made to synthesize a stable 1-azabicyclo-[1.1.0]-
butane-2-one system, and confirm this proposed intermediate in the
aziridine-azetidinone ring expansion. Although the 1-azabicyclo-
[1.1.0]-butane-2-one system was not synthesized, this research re
sulted in corroboration of the oxazoline-oxazolidone interconversion,
a new cyclization of 3-halo-carbamates and the synthesis of a spiro-
(9-fluorenyl)-aziridine. An explanation of these results is pre
sented.
Attempts were also made to synthesize a benzo-2-azir¡dine system
by a Retro-Diels-Alder reaction. This involved the synthesis of a
N-aziridinyl-(9, 10-anthrylene)-cyclohexa-3, 5_diene derivative.
Realizing the importance of synthesizing this compound, the synthesis
of bridged aziridines was pursued initially. We were successful in
obtaining three precursors. The results of this work are discussed.
i x


- 96 -
late (96 g., 0.300 mole) was refluxed for three hours in methanolic
sodium hydroxide. The reaction mixture was evaporated to give the
disodium salt which, thereafter, was dissolved in water. The re
sultant solution was acidified with 10% hydrochloric acid to give
a white precipitate. Filtration and drying gave 3, 10-ethenoanthra-
cene-11, 12-dI carboxylic acid (71.0 g., 81%): mp. 248-250C.
34
Dimethyl 3, 10-dihydro-9, 10-ethenoanthracene 11, 12-dicarboxyl ate (73)
Anthracene (50.0 g., 0.281 mole) and dimethyl acetylene di-
carboxylate (40.0 g., 0.281 mole) were heated in an Erlenmeyer
flask (1-liter) on a hot plate until a brown solution was formed.
On cooling to room temperature, a light tan solid v/as formed. Re-
crystallization from absolute methanol gave 9> 10-dihydro-9, 10-
ethenoanthracene-11, 12-dicarboxyl ate (87 g., 91%) as colorless
crystals: mp. 160161C.
34
9, 10-dihydro-9, 10-ethenoanthracene carboxylic anhydride (7R)
Acetic anhydride (30 ml.) was poured into an Erlenmeyer flask
(250 ml.) and heated to boiling. 9 10-dihydro-9, 10-ethenoanthra-
cene dicarboxylic acid (10.0 g., 0.0342 mole) was added slowly and
heated for a few minutes until dissolved. The solution was then
allowed to cool to room temperature followed by refrigeration over
night. The colorless crystals were collected and dried to give 9>
10-ethenoanthracene carboxylic anhydride in quantitative yield:
mp. 247-249C.


- 57 -
taneously upon acidification of aqueous solutions of the salts of the
acids.
An alternative approach to the synthesis of precursor 3 is to
synthesize the isomeric anhydride 79.. Bisdecarboxylation of ]%_ or
its dicarboxylic acid 8£, Scheme LXIV, might give the desired pre-
Scheme LX I V
HOOC
COOH
Elect.
>
80
58


- 35 -
of bromo-isocyanate 26. with 47% hydroiodic acid gave the desired
bromo-amine 44 in 50% yield, Scheme XL. This bromo-amine 44 isolated
Scheme XL
as a colorless oil. The structure is supported by ir and nmr spectro
scopy.
The cyclization of the a-amino-O(9-bromof1uorenyl) acetate (44)
was finally accomplished. The reaction of 44 with triethyl amine at
room temperature using ethanol as the solvent gave ethyl-2-spiro-
(9-f1uorenyl) aziridine carboxylate (20) as white crystals in 98%
yield, Scheme XLI. This structure is supported by ir, nmr, and mass
spectral analysis. The nmr spectrum was interesting and merits some
comment. The N-H proton appeared at 2.58cf as a broad doublet
(J=9Hz). The proton on C-3 appeared at 3.43 cT also as a broad doublet


17.
W. J. P. Neish, Rec. Tran. Chem. 69> 207 (1950).
J. A. Deyrup and J. C. Gill, Synthes ¡ s, 34 (1974).
18.
19.
20.
21.
22.
23.
24.
25-
26.
27.
28.
29.
30.
W. H. Urry, F. W. Stacey, 0. 0. Juvelard and C. H. McDonnell,
J. Amer. Chem. Soc., 75, 250 (1954); W. H. Urry, F. W. Stacey,
E. S. Huyser and 0. 0. Juvelard, J. Amer. Chem. Soc., 76,
450 (1954).
f|. ^S^Kharasch, J. Kuderman and W. Kudenberg, J. Org. Chem. 18, 1225
D. A. Tomalia, Tetrahedron Letters, 2559 (1967).
E. M. Burgess, R. Carithers and L. McCullough, J. Amer. Chem.
Soc., 90 1923 (I968); F. W. Fowler and A. Hassner, J. Amer.
Chem Soc., 90 2875 (1968); J. A. Deyrup and G. R. Stevenson,
J. C. Chabala and V. L. Pascucci, Tetrahedron Letters, 3591 (1972).
R. Breslow, Angew. Chem., J_, 567 (1968); A. Streitweiser, "Mole
cular Orbital Theory for Organic Chenii st, John Wiley and Sons,
Inc., New York, N. Y., 1961.
Brian Halton, Chem. Rev. 22 H3 (1973).
E. F. U1lman and E. Buncel1, J^ Amer. Chem. Soc., 85, 2106 (1963).
E. Vogel, W. Grimme and S. Korte, Tetrahedron Letters, 3625 (I965).
F. Klarner and E. Vogel, Angew. Chem. Internat. Ed., T2, 840 (1973).
K. Alder, H. Drieger and H. Weiss, Ber., 88, 144 (1955).
L. A. Paquette and D. E. Kuhla, Tetrahedron Letters, 4517 (1967)-
W. E. Bachmann and M. C. Kloetzel, J. Amer. Chem. Soc., 60, 481
(1938).
31. K. Alder and S. Schneider, Ann., 524 (1936).
32. R. Huisgen, Anger. Chem., Int. Ed., Engl., 2, 633 (1963).
33. R. Huisgen, G. Szeimies, and L. Mobius, Chem. Ber., 100, 2494 (I967).
34. C. Diels and K. Alder, Ann., 486, 191 (1931).


- 14 -
The reaction has been shown to proceed not by initial displacement
but by elimination to give the Q-bromo-G!-|3-unsaturated ketone.
Scheme XIV. The a-amino-p-bromo ketone obtained by the Michael
Scheme XIV
I! /
R-CH-CH-C-R
i i
Br Br
nh3
0
ii /
R-CH=CC-R
l
Br
NH2 Br
addition of the nitrogeneous base with Ct-bromo-O-p-unsaturated ketone,
cyclizes to the aziridine. Dibrcmides of a, p-unsaturated acids and
their derivatives were shown to follow the same course of reaction.
Reactions of dibromo ester 24 with liquid ammonia for eight
hours did not give the expected aziridine 20. Instead, ethyl
a-bromof1uoreny1idene acetate (25) was isolated, Scheme XV. This
product had physical and spectral properties identical to those of a


No. 6
y
120


TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS
LIST OF TABLES viii
i x
ABSTRACT
CHAPTER I Attempted Synthesis of a 1-azabicyclo-[1.1.0]-
butane-2-one 1
Introduction 1
Discussion 5
Conclusion 38
II Attempted Synthesis of a Benzo-2-Azirine 42
Introduction 42
Proposed Plan 45
Discussion 50
Summary and Conclusions 77
111 Experimental 78
General 78
Ethyl ohydroxy-a-(9~f 1 uoreny 1 acetate) (22.) 79
Ethyl fluoreny 1 idene acetate (2J ) 80
Ethyl azidoformate 80
Attempted synthesis of 1,2-dicarbothoxy-3-spiro- 80
(fluorenyl) aziridine
Ethyl obromo-o (9-bromofl uoreny 1) acetate (4).... 80
Reaction of ethyl a-bromo-a-(9-bromofluoreny1)
acetate with ammonia 81
O-Bromof1uoreny1ideneacetate (5) 81
Attempted reaction of a-bromof1uoreny1ideneacetate
wi th ammon i a 81
Ethyl a-bromo-o(9-isocyanatof 1 uorenyl) acetate (2£) 81
Ethy1-a-bromo-a- (9-carbethoxyaminof1uorenyl)
acetate (2§) 82
Ethyl -[-ethoxy-5-spiro-(9-f1uorenyl) oxazoline]
acetate (3J) 82


117
o


- 87 -
Reaction of Methyl G-bromo-a-(9-carbethoxyaminof1uorenyl) acetate
with alcoholic potassium hydroxide
Methyl Q-bromo-a- (9-carbethoxyaminofluorenyl acetate was
treated under the same conditions and its ethyl derivative. Only
9-fluorenone, in 20% yield, was isolated from the reaction.
Reaction of 9Carbethoxyiminofluorene with alcoholic potassium
hydroxide
9-Carbethoxyiminof1uorene (0.200 g., 0.000797 mole) was added
to alcoholic solution (1.00 g., K0H in 10 ml. of 95% ethanol) and
refluxed for two and one-half hours. On cooling, the brown mixture
was evaporated to dryness, water added and extracted with ether.
The ether extract was washed with water and dried over anhydrous
magnesium sulfate. Filtration and removal of solvent left a deep
yellow oil. The nmr spectrum of this material was identical to
that of 9fluorenone.
Attempted Reaction of 9-Carbethoxyiminof1uorene with Benzoyl Peroxide
9-Carbethoxyiminofluorene (50 mg., 0.0199 mmole) and a catalytic
amount of benzoyl peroxide were added to a dry 25 ml. round-bottomed
flask equipped with a reflux condenser and a drying tube. The
apparatus was flushed with nitrogen and chlorobenzene (5 ml.) added.
The reaction was refluxed for two and one-half hours, cooled, and
evaporated. Only starting material was isolated from the reaction.


acid 41_ and treatment with a carbodiimide under appropriate reaction
conditions should give the 3-bromo-azetidinone 43. Subsequent treat
ment of 43 with a strong base, but poor nucleophile, might give the
1-azabicyclo-[1.1.0]-butane-2-one system J_2, Scheme XLVI.


- 99 -
Attempted Electrolytic Bisdecarboxy1 at ion of 4, 5~[S, 10-anthry-
lene-cyclohexene-cis-1, 2-dicarboxylic anhydride with Lead Tetra-
acetate
4, 5-[9, 10-anthrylene]-cyclohexene-cis-1, 2-dicarboxylic
anhydride (1.00 g., 0.00305 mole) was treated with lead tetra
acetate (1.35 g.> 0.00305 mole) using the general procedure for
oxidative bisdecarboxylation. After work-up of the product was
shown by nmr spectroscopy to be starting material.
Meso-2, 3 [9 IQ-anthrylene]-!, 4-butanediol (8j)
38
This procedure was similar to that of Walborsky. Lithium
aluminum hydride (6.00 g.., O.I58 mole) and dried tetrahydrofuran
were added to a 1-liter, three-necked round-bottom flask equipped
with a mechanical stirrer, a reflux condenser, a nitrogen inlet and
outlet and a pressure-equalizing addition funnel. Anthracene 9
10-endo-a, p-succinic and anhydride (25-0 g., 0.0091 mole) dissolved
in dried tetrahydrofuran (285 ml.)were placed in the addition funnel
and added at a rate to maintain reflux. After the addition, the re
action was refluxed for an additional two hours. The reaction was
then quenched by the addition of water (8.0 ml.), 15% sodium hydroxide
(8 ml.) and again water (24 ml.) which precipitated the salts. The
resulting mixture was filtered, and the filtrate evaporated to dry
ness to give meso-2, 3- [9, 10-anthrylene]-], 4-butanediol (23.7 g.,
98%) as a colorless solid. Recrystallization from methonal gave


- 74 -
desired aziridine 104 in 93% yield, Scheme LXXX i I. The aziridine
Scheme LXXXII
was characterized by mass spectral analysis and its nmr spectrum
showed close similarity to 91-
Saponification of 104 was finally accomplished, Scheme LXXXII I,
Scheme LXXXII I
105


- 80 -
Ethyl f1uorenylidene acetate ( 21 )
Toluensulfonic acid (1.00 g.) was added to the benzene solution
and refluxed until 4.6 ml. of water was collected (Dean-Stark trap).
The reaction was allowed to cool to room temperature and then evapor
ated to a yellow solid. The yellow solid was crystallized from
ethanol (95%) to give ethyl fluorenylidene acetate (63.3 g., 91%)
o
long yellow needles; mp. 76-77 C.
Ethyl azidoformate
The title compound was prepared according to the published pro-
44
cedure of Forster and Fierz.
Attempted synthesis of 1,2-dicarbothoxy-3-spiro-(9-fluorenyl) aziridine
Ethyl f1uorenylideneacetate (1.00 g., 4.0 mmole) was dissolved
in methylene chloride. Ethyl azidoformate' (0.559 g., 0.0049 mole)
was added, and the infrared spectrum taken. The reaction was allowed
to stand at room temperature. Infrared spectrum was taken after one
month, three months, six months, and one year but showed no change.
Only starting materials were recovered as determined by infrared and
nmr spectroscopy.
Ethyl g-bromo-o-(9-bromofluorenyl) acetate (£4)
The title compound was prepared according to the procedure of
1 1
Gilchrist and Rees.


APPENDIX: Spectra


- 79 -
water (by weight percent) to the alumina and shaking until no lumps
were visible. Silca gel was used directly and with no previous
treatment. Solvent evaporations were carried out using a Buchler
rotary evaporator in vacuo (water aspirator) and by using a Buchi
Rotaryvapor-R J_n vacuo (pumps).
Ethyl a-hydroxy-Q-(9-fluorenyl acetate) (22)
Zinc metal (19-6 g., 0.300 g. atom) was placed in dried 1-liter
three-necked flask equipped with a dropping funnel, condenser, and
a mechanical stirrer. Fluorenone (50.0 g., 0.259 mole) and ethyl
bromoacetate (45*0 g., 0.269 mole) were added to the dropping funnel,
approximately one-third of the solution added and heated to reflux.
A few crystals of iodine were added to initiate the reaction and the
addition was continued at a rate to maintain reflux. After refluxing
for an additional hour, the reaction was terminated, cooled and poured
into cold 10% sulfuric acid. The benzene layer was separated, washed
with water and 5% sodium bicarbonate. The aqueous solution was ex
tracted twice with benzene, the benzene layer washed with water,
5% sodium bicarbonate and combined with the first extract. The
solution was dried over anhydrous magnesium sulfate, filtered and
used directly in the next step. A small sample was taken for spectral
determination; ir (neat) cm 3320 (OH); 1730 cm (C = 0, ester);
nmr (DCCI3). 0.97 (t, 3, J = 7 Hz). 2.80 (s, 2); 3-95 (q, 2, J = 7 Hz);
4.22 (broad 5, 0; 7-28 7-58 (m, 8).


- 55 -
35
Friedrichsen anhydr¡de 63. was synthesized and isolated in 95%
yield by react i ng _7 wi th butadiene, Scheme LXI.
Scheme LXI
Bisdecarboxylation of anhydride 63 with both oxidative and electro
lytic methods was not successful. Only starting material was recovered,
Scheme LX 11. The anhydride 63. was then converted to the disodium
Scheme LX 1 I
Elect, or Pb(OAc)4
2e
63
No Reaction


- 83 -
water added, and extracted with ether. The ether extract was washed
with 10% sodium bicarbonate and dried over anhydrous magnesium sul
fate. The ether extract was filtered and evaporated to give a deep
yellow oil. Recrystallization from petroleum ether (60-110) gave
colorless crystals of Ethyl-[2-ethoxy-(4-f1uorenyl)-oxazoline] acetate
(0.806 g., 80%): mp. 88-90C; ir (KBr) cm"' 17^0 (C = 0); 1660 (C=N);
nmr (CCl^) ^0.55 (t,3, J=6 Hz); 1.28 (t,3, J=6 Hz); 3-57 (q,2, J=6 Hz)-,
4.27 (q2, J=6 Hz); 5-07 (s,l); 7-15-7.60 (m,8); mass spectrum; Found;
m/e 337-1329 (caled, for c2oH194N: m^e 337-1313^
4-Carbethoxy-5-spiro-(9-f1uorenyl)-2-oxazolidone (32)
Ethyl a-bromo-o(9-carbethoxyaminof1uorenyl) acetate (1.02 g.,
0.00236 mole) was heated in a sealed tube at 200C for ten minutes.
The sample was cooled and recrystallized from benzene to give color
less crystals of 4-carbethoxy~5-spiro-(9-f1uorenyl)-2-oxazolidone
(0.757 g., 100%): mp. 219-220C; ir (KBr) cm"1 3240 (N-H). 1770 (C=0),
1750 (C=0); nmr (D^SO) cT 0.60 (t,3,5 = 7Hz); 3-10 (broad s,l);
3.63 (q,2,J=7Hz)-, 5-37 (5,1); 7-28-7-90 (m,8).
m/e (calculated for C _H 0.N) = 309-1000
I o 15^
Found = 309.1042
Reaction of Ethyl-[2-ethoxy-5-sp¡ro-(9-f1uorenyl)-oxazoline acetate
with hydrobromic acid
Ethyl-[2-ethoxy-5-spiro-(9-f1uoreny1)-oxazoline] acetate (60 mg.,
O.I78 mmole) was added to diethyl ether (20 ml.) previously saturated


Scheme XL I
(J=9Hz). On addition of D^O the 2.58cf resonance disappeared and the
doublet at 3.43cf collapsed to a singlet. This last result elegantly
supports the assigned structure of the spi roazi r idine 20_.
Following the synthesis of the spiroaziridine 2£ as discussed
above, an attempt was made to convert 2_0 to the sodium salt according
to the reaction conditiuns of Deyrup and Clough' with the intent of
obtaining the 1-azabicyclo-[1.1.0]-butane-2-one following subsequent
reaction with thionyl chloride.
Ethyl 2-spiro-(9-f1uoreny1)-aziridine carboxylate (20) was
refluxed in aqueous alcoholic sodium hydroxide for one hour. The
sodium salt _T6 was isolated as a white powder in quantitative yield,


- 25 -
/ j o
cis-cydo-hexano[b]-2~oxazol ¡done (3ft) is 55 C; the isomeric trans-
o 1 5
cyclohexano[b]-2-oxazolidone melts at 110 C This reaction
establishes the fact that an inversion of the iodine-bearing
carbon is involved in the pyrolytic conversion of iodo-carbamate
to 2-oxazoli dones and with this evidence Hassner proposed the follow
ing mechanism, Scheme XXVII. If this mechanism is correct, it
Scheme XXVI I
34
should be possible to convert a 2-oxazoline to a 2-oxazolidone with
the addition of HBr under anhydrous conditions, Scheme XXVIII. This
conversion was then carried out with 2-oxazoline 3J_ in ether pre-


ACKNOWLEDGEMENTS
Several people made significant contributions at appropriate
stages of this study. Working with Dr. James A. Deyrup was a
stimulating intellectual experience. Jim Gill, Bill Szabo and
George Kuta are thanked for their assistance and contributions
of ideas. My graduate committee members, Drs. Butler, Dolbier,
Weltner and Baers were an immense help in their critique of this
research. The several versions of this dissertation were effi
ciently and insightfully typed by Gerda Covell.
The gestation period of this doctoral study was quite a
sacrifice for my family. I am grateful to my children who, young
as they are, tried to understand it all. I would be remiss if
I did not thank my wife's parents, George and Evelyn Brown and
my parents, Emmett and Rosie McCaski11, for their concern and
support. I am grateful for my wife's understanding throughout
these years. For this, it is a pleasure to be able, at last, to
dedicate this dissertation to all members of my family.


No. 8
122


- 84 -
with HBr. The reaction was allowed to stir at room temperature for
one hour. Evaporation and recrystallization from benzene gave a
product (45 mg., 82%) showing identical physical and spectral pro
perties to those of 4-carbethoxy-5-sp¡ro-(9-f1uoreny1)-2oxazolidone.
4-Methyl-5-spiro-(9-f1uoreny1)-2-oxazolidone (36)
Ethyl-Ct-bromo-a-(9-carbethoxyami nofl uoreny 1 ) acetate (1.00 g. ,
2.39 mmoles) was refluxed for two and one-half hours in alcoholic
potassium hydroxide (5.0 g. in 50 ml. of 95% ethanol). The reaction
mixture was allowed to cool to room temperature and evaporated to
dryness. Water was then added and extracted with ether. The ether
layer was washed with water and dried over anhydrous magnesium sul
fate. Filtration and removal of solvent (rotary evaporator) gave a
light yellow residue. Recrystallization from benzene and petroleum
ether (80-110C) gave 4-methyl-5-spiro-(9-f1uorenyl)-2-oxazol¡done
(0.220 g., 37%) white crystals; mp. 160161C. ir (KBr) cm 3325
(N-H; broad)*, 1735 (C=0, strong), nmr (DCC1 ^) cf 0.93 (d,3,J=7Hz);
4.98 (q,l,J=7Hz); 5.42 (s,1,broad); 7.27-7-73 (m,8);
m/e (calculated for C^^^02N) = 251.0945
Found = 251.0926
9-Aminofluorene (40)
9-Aminofluorene hydroxychlor ide (2.00 g., 9.22 mmoles) was
dissolved in 100 ml. of distilled water. Sodium hydroxide (15%)


- 4 -
An appropriate mechanism, Scheme IV, capable of explaining these
results is the initial formation of the 2-aziridinecarbonyl chloride
(). Interaction of the unshared electron pair on the annular nitro
gen and the carbonyl carbon results in the formation of a 1-azabicyclo-
[1.1.0]-butane-2-one cation (10). This strained bicyclic ion 10
proposed as the intermediate for this reaction gave 1-tert-buty1-3-
chloro-2-azetidone (4) by a stereospecific attack by chloride ion.
Scheme IV
t-Bu
3
0
C-ONa
jt-Bu
l
Cl
t-Bu
44--C-XI
0
Cl^p
t-Bu
10
4


- 65 -
as it increased to 12 protons with the bridgehead and methyl esters
protons appearing as two very close singlets. On photolysis of the
isolated aziridine 21 the aromatic region separated into two por
tions, an unsymmetric 7-proton multiplet and a 4-proton A-B quartet
that was shielded. The bridgehead and the methyl ester protons
appeared as singlets with the bridgehead protons being slightly
more shielded with essentially no change in the ester groups.
Bromination reactions of aziridine 21 were then investigated.
The addition of bromine gave substitution products as depicted by
nmr and mass spectroscopy and was not further pursued. It is re
ported that bromination of £-methoxytoluene with N-bromosuccimide
in carbon tetrachloride with benzoyl peroxide as the radical initia-
41
tor gave 65% yield of £-methoxybenzy1 bromide, Scheme LXXV.
Scheme LXXV


- 69 -
spectrum of the reaction mixture. The bridge protons region
changed from two singlets to a complex multiplet. The methoxy
protons were also present in addition to some residual azide.
There was strong absorption in the vinyl region, suggestive of
bridgehead protons on triptycene derivatives. Since the triazoline
isomers give the same aziridine 94, photolysis of the reaction
mixture with subsequent separation by column chromatography was
COOEt
94
pursued. The desired product 9k was not obtained. Only the tripty
cene derivative %8_ and residual starting materials were isolated.
Characterization of 8 was accomplished by nmr and high resolution
mass spectroscopy. The product isolated from the reaction of
with NBS, Scheme LXVIII, showed identical spectral properties to 48.
43
A number of diene systems have been shown to aromatize with NBS.


- 27 -
Scheme XXX
Treatment of carbamate 28^ under similar condi
the expected aziridine 20. Instead, 2-oxazol
fluorenone 23. were isolated, each in 20%yiel
Scheme XXXI
tions did not give
idone 6 and 9~
d, Scheme XXXI.
aq NaOH
H
EtOOC N
+ 23
28
36
This reaction was quite unique in that the total process involved the
formation of a carbon-carbon bond on a carbon which contains a nitrogen
atom. Since this reaction has potential synthetic utility, attempts


35- 0- Diels and W. Friedrichsen, Ann., 513 145 (1934).
36. K. Auwers and V. Meyer, Ber., 23, 101 (1890).
37- R. Anschutz, Ann., 254, 168 (1889)*
38. H. M. Walborsky, Helv. Chim. Acta, 36, 1251 (1953).
39. H. Krzikalla, E. Woldan, and 0. Dornheim, Ger. Pat. 736,024;
Chem. Abstr., 8, 46205 (1944).
40. J. S. Meek and R. D. Stacy, J. Org. Chem., 26, 300 (1961).
41. G. S. Misra and J. S. Shukla, J. Ind. Chem. Soc., 23, 277 (1951).
42. R. Grewe and I. Hinrichs, Ber., 97 443 (1964).
43. J. P. Wibaut and F. A. Haak, Rec. Trau. Chim., 69, 1387 (1950).
44. M. 0. Forster and H. E. Fierz, J. Chem. Soc., 91 81 (5908).
45. A. Hassner and C. Heathcock, J. Org. Chem., 30 1751 (1965).
46. J. A. Deyrup and J. C. Gill, Synthesis, 4 (1974).
47. E. R. Pratt, T. P. McGovern, J. Org. Chem. 29, 1540 (1964).
48. G. Harris, B. Harriman and K. Wheeler, J. Amer. Chem. Soc., 68,
846 (1946).
49. W. E Bachmann and M. C. Kloetzel, J. Amer. Chem. Soc., 60, 481,
(1938).
50. E. J. Corey, J. Amer. Chem. Soc., 85, 165 (1963).
51. H. Plieninger, Chem. Ber., 100, 2427 (1967).
52. J. J. Sims and T. Whites ides, Tetrahedron Letters, 5'17 (1968).
53- H. J. Dauben, Jr. and H. H. Westberg, Tetrahedron Letters, 5123
(1968).
54. C. M. Cimarusti and J. Wolinsky, J. Amer. Chem. Soc., 90, 113
(1968).


- I
tained, but a 2-oxazoline 3J_ was isolated in 80% yield, Scheme XXII.
Scheme XX I I
0- CN
EtO'
EtOH
COOEt
26
28
EtO
uco
EtO-^-N^i
0 COOEt
31
19


- 63 -
Scheme LXXI I I
At
100C
products 88, 89, and anthracene (2) were separated using
OMe
88
column chromatography. The Retro
detected in the reaction mixture.
Diels-Alder by-product was not
90