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Structure and reactivity in the heterotropilidene series and other studies

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Title:
Structure and reactivity in the heterotropilidene series and other studies
Creator:
White, Robert Merrifield, 1945-
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Language:
English
Physical Description:
xvi, 215 leaves. : ; 28 cm.

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Subjects / Keywords:
Chlorides ( jstor )
Ethanol ( jstor )
Ethers ( jstor )
Hydrogen ( jstor )
Ions ( jstor )
Mass spectra ( jstor )
Mass spectroscopy ( jstor )
Phenyls ( jstor )
Protons ( jstor )
Sodium ( jstor )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Heterotropilidene ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis -- University of Florida.
Bibliography:
Bibliography: leaves 211-214.
General Note:
Typescript.
General Note:
Vita.

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University of Florida
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University of Florida
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Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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Full Text


Structure and Reactivity in the Heterotropilidene
Series and Other Studies
By
ROBERT MERRIFIELD WHITE
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
1972


Ck
DEDICATION
This dissertation is dedicated to all of the people, places,
animals, and things which have made the past four years a
worthwhile experience in Life.


ACKNOWLEDGEMENTS
The author wishes to thank his research director, Prof.
Merle A. Battiste, for excellent guidance on this project,
helpful discussions, and, most of all, moral support when
it was needed. The author would also like to thank the Palenik
Group, especially M. Mathew, for the generous use of their
x-ray facilities and cheerful help on structure 67; Dr. R.W.
King for the computer solutions of the NMR spectra of com
pounds 79 and 80; and Dr. R. -Rehburg for samples of com
pounds 2, 3, 10, and 11 and the excellent groundwork done
on the project before the author took over.
The author also wishes to recognize and thank The
Ghetto, Alpha Chi Sigma and its members, especially S.R.,
S.W., P.F.E., J.H., M.K., H.J., and R.K.; 1743, SCL, L$N,
T.E.H., The Zoo, The Rat, R.W.C.V., C.C.V., R.L., Huntsville,
Nashville, and all of the other people, places, animals, and
tilings whose sheer volume space does, not permit mention of
but which have made the past four years more than just a
pure academic experience.
The author also wishes to thank his wife, Ann, for
providing moral support when it was needed and his son,
Robbie, for being so patient these past four years.
ii i


"I remember when this whole thing began
No talk of God then we called you a man."
Jesus Christ Superstar, 1970
iv


PREFACE
As part of a general study of the Diels-Alder reaction
of tetrazines with alkenes, it was discovered independently
in 1966 by Sauer and Heinrichs,1 and Battiste and Barton2
that sym-triphenylcyclopropene reacts with 3,6-diphenyl-
1, 2,4,5-tetrazine (1) at 20 to 78 to produce a yellow com
pound (2) C35H26N2 which, on heating (100 or greater),
isomerizes to an almost colorless compound (3) which, on
further heating (230), decomposes into benzonitrile and svm-
tetraphenylpyrrole. The results of both investigations are
summarized in Scheme 1.
Scheme 1
Sauer was of the opinion that 2 is in the diazanor-
caradiene form, 1,2,5,6,7-pentapheny1-3,4-diazabicyclo[4.1 .0] -
hepta-2,4-diene (4). Battiste, however, argued that 2 should
be described as 3,4,S,6,7-pentapheny1-5H-1,2-diazepine (5).


H
0 H
0
0
N=N
0
0
4
5
Both Sauer and Battiste agreed that 2,5-diphenyl-3,4-
diazabicyclo[4.1.0]hepta-2,4-diene (6)123 and 2,5,7-
triphenyl -3,4-diazabicyclo[4.1.0]hepta-2,4-diene (7)4 and
other diazanorcaradienes with no phenyls at C-l and C-6
exist exclusively in the diazanorcaradiene form at room
temperature.
Sauer based his argument for 4 on the fact that the UV
spectrum of 2 is quite similar to that of 6 even though
Maier3 had previously shown that substituents in the 1- and
6-positions imposed steric restrictions on the phenyls in
the 2- and 5-positions causing a hypsochromic shift in the
ultraviolet. Thus, there was some doubt as to whether the
UV of 4 and the UV of 6 could be compared.
Battiste suggested that the low-field position of the
only non-aromatic absorption in the NMR spectrum of 2
indicated an allylic type signal rather than a cyclopropyl
type signal. Battiste also felt that the phenyls in the 1-
and 6-positions would facilitate the disrctatory opening of
the initially formed 4 to give a diazacycloheptatriene
system.
vi


Sauer proposed that product 3 is the result of dis-
rotatory ring opening of 4 to give the 5H-diazepine 5 or one
of its hydrogen-shifted (except to nitrogen) products. Again
Sauer based his arguments on the UV spectrum of 3,citing
extended conjugation as being responsible for the spectrum.
On the basis of its facile conversion to tetraphenyl-
pyrrole and benzonitrile, Battiste tentatively proposed the
bicyclic structure 8 for isomer 3.
8
The reaction of dimethyl 1, 2,4,5-tetrazine-3,6-dicar-
boxylate (9) with sym-triphenylcyclopropene gives products
10 and 11 which are analogous to 2 and 3 above. Since the
product 11 shows non equivalent ester methyls in the NMR,
Sauer5 assigned to it the structure 12.
12
vi 1


It was shown by Rehburg and Battiste6 that mixtures of
pyrroles are obtained from diaza species similar to 3 or 11
when the tetrazine has substituted phenyls, methyls,or
carbomethoxy groups attached to it as illustrated below in
Scheme 2.
Scheme 2
At the time this work was initiated, it still was not
known definitely whether 2 existed as diazanorcaradiene or
5H-diazepine, nor had the structure of 3 been established.
Also, no mechanistic details on the conversion of 2 to 3
were available. Chapter I deals in some detail with the
structures of 2 and 3 and the mechanism of the thermal
isomerization of 2 to 3.
When this investigation was begun, the aromaticity and
stability of the cycloheptatrienylium or tropylium cation
(13) were well known.73 Also, the aromaticity of cyclo-
heptatrienone or tropone (14) was well-documented.78
vi 11


*
0 o'
13 14
By contrast, the analogous 1,2-diazacycloheptatrieny-
lium cation (15) was a complete unknown at the beginning of
this work. Only one 1,2-diazatropone derivative, 16, had
been reported.9 In acid, 16 did not protonate on oxygen to
form the aromatic dibenzohydroxydiazatropylium cation, but,
rather, it protonated on nitrogen to form an amine salt as
illustrated in Scheme 3.
H
Scheme 3
Since at the beginning of this -investigation it was
thought that compounds such as 2 existed in the open 5H-
diazepine form, the possibility of synthesizing the diaza
IX


analogs of the tropylium cation and tropone appeared to be
a feasible project. The diazatropylium cation-diazatropone
problem will be dealt with in Chapter IV.
Also, the tetrazines which are used in the synthesis of
many of the diazanorcaradienes and diazepines present them
selves as an interesting heteroaromatic series. The spec
tral properties of some of the more interesting members of
this series will be examined in some detail along with
members of related aromatic systems in Chapter III.
x


>
TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
PREFACE . v
LIST OF TABLES xii
LIST OF FIGURES xiii
ABSTRACT xv
Chapter
I.THE DIAZANORCARADIENE-DIAZEPINE REARRANGEMENT. 1
Results and Discussion 1
II.MASS SPECTRAL CORRELATIONS 44
Introduction 44
Results and Discussion 46
III.CYCLOPROPYL CONJUGATION IN HETEROAROMATIC
SYSTEMS 8 0
Cyclopropyl Conjugation 80
Synthesis 83
Dicyclopropyltetrazine and Dicyclopropyl-
pyridazine The Ground State 90
Dicyclopropyltetrazine and Dicyclopropyl-
pyridazine The Excited State 112
IV.. THE DIAZATROPYLIUM CATION AND DIAZATROPONE ... 130
Attempted Syntheses of 1,2-Diazatropylium
Cations 130
Attempted Syntheses of 1,2-Diazatropone 150
V.EXPERIMENTAL 159
REFERENCES 211
BIOGRAPHICAL SKETCH 215
xi


fe
LIST OF TABLES
Table Page
IKinetic Parameters for the Thermal Isomeriz
ation of 2 to 3 3
IIBond Distances and Their Estimated Standard
Deviations in Diazepine 67 37
IIIBond Angles and Their Estimated Standard
Deviations in Diazepine 67 38
IVRelative Intensities for Important Mass Spectral
Fragmentations of Diazanorcaradienes 48
VThermal Decomposition Data for Some 4H-
Diazepines 51
VIChemical Shift Data for Tetrazine 79 and
Pyridazine 80 88
VII Magnetic Coupling Data for 79, 80, 85 and 86 .... 89
VIIIChemical Shift Data for iso-Propyl and Cyclo-
propyl Aromatic Compounds Ill
IX Principal Absorbances for Some Tetrazines 114
X Principal Absorbances for Some Pyridazines 115
XI Proton Assignments for 96 134
xii


s
LIST OF FIGURES
Figure Page
1 NMR spectrum of unknown 49 in CDC13 25
2 NMR spectrum of unknown 49 in d5-pyridine 28
3 ORTEP generated diagram of 3,7-bis (4-bromo -
phenyl)-4-(4-methylpheny1)-5,6-diphenyl-4H-
1, 2-diazepine (67) 41
4 Mass spectrum of 1, 2,5,6,7-pentaphenyl-3,4 -
diazabicyclo[4.1.0]hepta-2,4-diene (2) 56
5 Mass spectrum of 2,5-bis (4-bromophenyl)- 7-
(4-methylpheny1)-l,6-diphenyl-3,4-diazabicyclo-
[4.1.0]hepta-2,4-diene (66) 60
6 Mass spectrum of 3,4,5,6,7-pentaphenyl-4H-1,2 -
diazepine (3) 65
7 Mass spectrum of 3,7-bis(4-bromophenyl)-4 -
(4-methylpheny1)-5,6-diphenyl-4H-1,2-
diazepine (67) 69
8 Mass spectrum of dimethyl 1,6,7 tr.iphenyl 3,4 -
diazabicyclo[4.1.0]hepta-2,4-diene-2,5-
dicarboxylate (10) 74
9 Mass spectrum of 7-(4-methylphenyl)-l,2,5,6-
tetrapheny1-3,4-diazabicyclo[4.1.0]hepta-2,4-
diene (68) 77
10 NMR spectrum of 3,6-dicyclopropyl-1,2,4,5-
tetrazine (79) in CDC13 at NMR probe temperature
(40) 94
11 NMR spectrum of 3,6-dicyclopropyl-1,2,4,5 -
tetrazine (79) in CDC13 at -10 96
12 NMR spectrum of 3,6-dicyclopropy1 -1,2,4,5 -
tetrazine (79) in CDC13 at -30 98
13 NMR spectrum of 3,6-dicyclopropyl-1,2,4,5 -
tetrazine (79) in CDC13 at -60 100
14 NMR spectrum of 3,6-dicyclopropy1 -1 2,4,5 -
tetrazine (79) in diphenyl ether at NMR probe
temperature (40) 102
xii i


Page
fe
Figure
15 NMR spectrum of 3,6-dicyclopropylpyridazine
(80) in CDC13 at 42.5 104
16 NMR spectrum of 3,6-dicyclopropylpyridazine
(80) in CDC13 at -5.5 106
17 NMR spectrum of 3,6-dicyclopropylpyridazine
(80) in CDC13 at -59.0 108
18 Visible spectrum of 3,6-dicyclopropyl-
1,2,4,5-tetrazine (79) in ethanol 119
19 Visible spectrum of 3,6-dicyclopropyl -
1,2,4,5-tetrazine (79) in cyclohexane 121
20 UV spectrum of 3,6-dicyclopropyl-1,2,4,5 -
tetrazine (79) in ethanol 123
21 UV spectrum of 3,6-dicyclopropyl-1,2,4,5-
tetrazine (79) in cyclohexane 125
22 UV spectrum of 3,6-dicyclopropylpyridazine
(80) in ethanol 127
23 UV spectrum of 3,6-dicyc]opropy]pyridazine
(80) in cyclohexane 129
24 NMR spectrum of 3,5,7-tripheny]-4H-1,2-diazepine
hydrofluoroborate (99) in TFA/CDC13 at 17.0 .... 141
25 NMR spectrum of 3,5,7-triphenyl-4H-1,2-diazepine
hydrofluoroborate (99) in TFA/CDC13 at 1.5 143
26 NMR spectrum of 3,5,7-triphenyl-4H-1,2-diazepine
hydrofluoroborate (99) in TFA/CDC13 at -18.5 ... 145
27 UV spectrum of unknown 102 149
28 UV spectrum of 4,5-dipheny1-5,6-dicarbomethoxy-
1- (1,2-diphenylcyclopropen-3-yl)-1,4-dihydro-
pyridazine-4 aldehyde (104) 154
xiv


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
STRUCTURE AND REACTIVITY IN THE HETEROTROPILIDENE
SERIES AND OTHER STUDIES
By
Robert Merrifield White
March, 1972
Chairman: M.A. Battiste
Major Department: Chemistry
It has been found that.the reaction between sym-tri-
phenylcyclopropene and 3,6-dipheny1 -1,2,4,5-tetrazine pro
duces 1,2,5,6,7-pentapheny1-3,4-diazabicyclo[4.1.0]hepta-
2,4-diene or pentaphenyldiazanorcaradiene which, on heating,
isomerizes to 3,4,5,6,7-pentaphenyl-4H-1,2-diazepine as
determined by x-ray studies. It has been demonstrated
conclusively that pentaphenyldiazanorcaradiene rearranges to
the 4H-diazepine via a carbon-shift rather than a hydrogen-
shift mechanism. The exact mechanism of the carbon shift
was not determined. Preliminary work on the decomposition
of 4H-diazepines into pyrroles and benzonitriles has also
been done.
2,5-Dipheny1 -1,3,4-thiadiazole has been isolated in low
yield in the synthesis of 3,6-dipheny1-1,4-dihydro-1,2,4,5-
tetrazine from sulfur, ethanol, hydrazine hydrate, and
benzonitrile.
xv


In the heteroaromatic series, it has been demonstrated
that cyclopropyl conjugation is present in the highly
interesting 3,6-dicyclopropy1-1,2,4,5-tetrazine and, as
anticipated, to a lesser extent, in 3,6-dicyclopropyl -
pyridazine in both the ground and excited states.
Attempts at synthesizing the diaza analogs of tropone
and the tropylium cation by standard methods met with no
success. However, some interesting rearrangements and new
compounds were observed.
xvi


CHAPTER I
THE DIAZANORCARADIENE-DIAZEPINE REARRANGEMENT
Results and Discussion
The first step taken in dissecting and analyzing the
thermal conversion of 2 to 3 outlined in Scheme 1 was to
determine the structure of compound 3. The structure of
3 was attacked using x-ray spectroscopy. It was decided
to employ the heavy atom technique by reacting sym-tri-
phenylcyclopropene with the then unknown 3,6-bis (4-iodo-
phenyl)-1,2,4,5-tetrazine (17) at elevated temperatures
to give directly 3 with two phenyl rings carrying iodine
atoms.
Since classical methods of synthesizing 17 had failed
previously,6 the recently developed method of Abdel-Rahman
et a_l. 1 0 was used to produce the yellow dihydroderivative
of 17 which was then oxidized to the deep purple 17.
Unfortunately, 17 was contaminated with what is tentatively
identified as 2,5-bis(4-iodopheny1)-1,3,4-thiadiazole (18)
(see Chapter III) which was very difficult to remove due
to the gross insolubility of both 17 and 18. The thia
diazole 18 could be separated from 17 only by chromato
graphy over basic alumina with boiling xylene which tended
to completely decompose the tetrazine 17 unless it was
rapidly eluted from the column.
1


2
Reaction of 17, either chromatographed or crude, with
sym-triphenyl cyclopropene in refluxing xylene gave the
desired substituted 3 without isolation of the intermediate
substituted 2. The x-ray analysis11 of the iodine-
substituted 3 showed that it has the 4H-diazepine structure
19.
N N
19
Obviously, the above described conversion of 10 to 11
should proceed in a manner analogous to the 2 to 3 conver
sion and product 11 should have the 4H-diazepine structure
20 rather than structure 12 as assigned by Sauer.
N N
20
At least formally, the conversion of 2 to 3 may be con
1 2
sidered as two concerted suprafacial 1,5-hydrogen shifts
from the open form of 2 as shown below in Scheme 4.


3
Scheme 4
The kinetics of the thermal isomerization of 2 to 3
were followed by NMR at 150 and 140. Good first-order
kinetics were observed and the resulting kinetic para
meters are given in Table I. The energy of activation (E )
a.
was found to be 33.4 kcal/mole. The kinetics indicated that
the reaction is unimolecular and supported the mechanism
of Scheme 4.
Table I
Kinetic Parameters for the Thermal Isomerization of 2 to 3
temp. (C) k (sec *) AH* (kcal/mole) AS* (cal/mole-deg)
150.0 2.93 x 10"5 32.6 -3.14
140.0 1.07 x 10'5 32.6 -3.24
Taking the premise that two concerted 1,5-hydrogen
shifts were responsible for the conversion of 2 to 3, it
appeared of considerable mechanistic interest to examine
some systems in which the cyclopropane ring of the diaza-
norcaradiene does not carry three phenyl rings as in 2.
Two such systems are 21 and 22, which are simply 2 and 10
without a phenyl on the methylene carbon (C-7).


4
N-N
N-N
21
22
Both 21 and 22 are readily synthesized by the cyclo
addition of 1,2-diphenylcyclopropene13 with 1 and 9 respec
tively. The resulting adducts are bright yellow crystalline
compounds whose spectral and analytical properties define
their structure as that of the norcaradiene valence
tautomer.
The aromatic region of the NMR spectrum of 21 shows two
multiplets centered at t2.18 and 2.80 integrating in the
ratio 4:6 and a spike at 3.16 which accounts for ten pro
tons. The lower field aromatic multiplet is assigned to
the ortho protons of the phenyl rings attached to the
azine linkage. Deshielding of these ortho protons by the
electron-withdrawing and diamagnetically deshielding azine
linkage is assumed. The higher field multiplet is assigned
to the further removed meta and para protons of the phenyls
at C-2 and C-4. The ten-proton spike which is at higher
field than either multiplet accounts for the phenyls
attached to the cyclopropane ring. The two methylene (C-7)
protons, which are especially important for structural
identification, appear as two widely separated


5
sharp doublets at t6.31 (J = 5.5 Hz) and 8.68 (J = 5.5 Hz).
That the methylene protons appear as two doublets could be
accounted for by a diazacycloheptatriene which is frozen
in a non-inverting conformation, but the chemical shift
of both protons is more indicative of cyclopropyl than
allylic protons. The higher field doublet is assigned to
the endo proton which is shielded to some extent by the
azine linkage. The lower field doublet is assigned to
the exo proton which is deshielded by the phenyl rings
attached to the cyclopropyl ring (vide infra).
At about this time preliminary x-ray crystallographic
results by Fritchie14 revealed that 23 indeed exists in the
diazanorcaradiene form rather than the diazacyclophepta-
triene form. A notable result of Fritchie's investigation
of 23 was that the cyclopropyl hydrogen occupies the exo
position and lies in the deshielding region of the phenyls
at C-l and C-6. Thus, in assigning only non-aromatic
proton as allylic rather than cyclopropyl on the basis of
chemical shift, Battiste2 was in error due to unforeseen
diamagnetic deshielding effects.
23


6
Heating 21 in pyridine caused noticeable broadening of
the NMR doublets at temperatures as low as about 90. The
signals for both methylene protons completely disappeared
at 150. Although time averaging of the two methylene
protons was apparently occurring via ring inversion, no
time-averaged singlet for a rapidly inverting diazanorcara-
diene could ever be observed presumably due to decomposition
(vide infra). Also, no signal for rearranged 21 could be
found.
On heating to as high as about 190 in either d5-nitro-
benzene or napthalene, decomposition of 21 to an unidenti
fied red oil was observed. Further heating converted the
red oil to a yellow oil which could not be identified
after chromatography and spectral analysis.
Compound 22 showed temperature-dependent NMR behavior
similar to that exhibited by other diazanorcaradienes, such
as 24, with ester groups in the 2- and 5-positions.15 At
-3.5 the molecule is frozen in a non-exchanging form which
shows the expected NMR spectrum for the diazanorcaradiene
structure. The phenyls attached to the cyclopropane ring
show the expected ten-proton spike at t2.95. The ester
methyls, which are magnetically equivalent, appear as a
singlet at t6.35. Again, as in the NMR spectrum of 21,
the cyclopropyl protons show up as two widely separated
doublets at t6.37 (J = 5.7 Hz) and 9.0 (J = 5.7 Hz). Warm
ing the NMR solution of 22 to 37 causes complete disappear
ance of the cyclopropyl signals. The cyclopropyl doublets


7
coalesce at about 24 which is indicative of the phenyls
actually inhibiting the opening of the diazanorcaradiene
to the 5H-diazepine as the system 24 reported by Binsch and
Sauer15 coalesces at between 5 and 16.
N-N'
24
An attempt at thermally isomerizing 22 in refluxing
dioxane only produced small amounts of what is assumed to
be dimethyl 1,6-diphenyl 3,4-diazabicyclo[4.1.0]hept-2-en-
5-ol-2,5-dicarboxylate (25) mainly on the basis of its NMR
spectrum.
The NMR spectrum of 25 shows the expected broad singlet
at t1.15 for the N-H proton, two multiplets centered at
2.95 and 3.6 integrating 8:2 for the ten aromatic protons,
a broad singlet for hydroxyl proton at 4.75, sharp singlets
at 5.58 and 6.18 for the nonequivalent methyl protons, and
an AB-quartet centered at 6.78 (J = 12.5 Hz) for the cyclo
propyl protons.
No attempt was made at assigning the stereochemistry of
25. The mass spectrum of 25 gives the correct molecular
weight (364) but the cracking pattern in no way resembles
the mass spectral cracking pattern produced by the precursor
22. In the mass spectrometer one might have expected the
parent ion of 25 to lose a molecule of water to yield the


8
parent ion of 22, but apparently other processes are com
petitive with loss of water and, hence, the cracking pattern
of 25 does not resemble that of 22. The addition of water
across the carbon-nitrogen double bond of diazanorcaradienes
is well-documented.516 An attempt at an authentic synthe
sis of 25 was apparently a failure for unknown reasons.
Since of the two systems, 21 and 22, 22 should have
shown the greater propensity for rearrangement6 but did not
rearrange, no attempt other than the high temperature NMR
work was made at thermally isomerizing 21.
The thermal behavior of the simplest diazanorcaradiene,
6, which is 2 with no phenyls on the cyclopropyl carbons,
was also investigated. Refluxing 6 in xylene for 18 hours
produced nothing but tar and starting material.
Another system, 2,5,7 triphenyl-3,4-diazabicyclo [4.1.0]
hepta-2,4-diene (7), was examined. Refluxing in dioxane
for 132 hours yielded nothing but unidentifiable resin.
26
If 7 had rearranged to a 4H-diazepine via two concerted
1,5-hydrogen shifts, it would have rearranged to the known
26.17 Diazepine 26 was found to be stable under the condi
tions used in the attempted rearrangement of 7.


9
From the above results it was concluded that three
phenyls on the cyclopropane ring were necessary before a
diazanorcaradiene will rearrange to a 4H-diazepine. How
ever, it was still a mystery as to why systems 6, 7, 21,
and 22 did not rearrange to at least some small extent
if the rearrangement was taking place by way of a hydro
gen shift mechanism.
Upon closer examination of the systems which do rearrange
and those which do not, it was noted that in the systems
which rearrange there is a phenyl ring over the azine link
age. Thus, 2 is 1,2,5,6-tetrapheny1-endo-7-phenyl-3,4-
diazabicyclo[4.1.0]hepta-2,4-diene as shown in structure 27.
The compound 7 has the requisite phenyl in the 7-position,
but this phenyl is exo to the azine linkage as shown in
structure 23 since, in the absence of steric interaction
from substituents in the 1- and 6-positions, the phenyl
at C-7 prefers the exo position.
0
27
The above observations led
perhaps the rearrangement is of
to the hypothesis that
the Cope ([3,3] sigmatropic)


10
type involving the endo-7-phenyl as illustrated in Scheme
5.
Scheme 5
To test the idea of the Cope mechanism, the synthesis
of 2,5,7,7-tetraphenyl- 3,4 -diazabicyclo[4.1.0]hepta-2,4-
diene (29) was attempted since this system would have the
requisite endo- 7-phenyl but no phenyls in the 1- and 6-
positions. Rearrangement of 29 by the pathway depicted in
Scheme 5 would lead to the diazepine 30.
The NMR spectrum of 30 should show an aromatic multiplet
with the previously described deshielding of the ortho
protons of the phenyl at C-7. The ortho protons of the
phenyl at C-3 probably would not show any deshielding as
the phenyls at C-4 would impose steric restrictions forcing
the C-3 phenyl out of the plane of the azine linkage. The


11
H
30
vinylic protons should appear as an AB-quartet. The mass
spectrum of 30 should also be similar to that for 29 with
loss of benzonitrile as the base peak (see Chapter II).
During their investigation of the diazanorcaradiene 7,
Amiet and Johns4 reported that 7 could be synthesized in
low yield (7%) from trains -1, 2 dibenzoyl 3-phenylcyclo-
propane (31) only by heating with hydrazine in ethanol for
long periods of time, whereas the cis isomer of 31 reacted
rapidly and almost quantitatively at room temperature. In
the present investigation it was found that 7 could be
produced in satisfactory yield (55.1%) from 31 at room
temperature if a catalytic amount of sodium hydroxide was
added to the mixture of 31 and hydrazine in ethanol. Pre
sumably, the observed increase in yield is due to a rapidly
established base-catalyzed cis-trans equilibration as shown
in Scheme 6.
-h20
7
Scheme 6


12
In view of the above observation, the synthesis of 29
was attempted by reaction of the known trans-1,2-dibenzoyl-
3,3-diphenylcyclopropane (32)18 with hydrazine in the
presence of sodium hydroxide in ethanol. At room tempera
ture in ethanol, 32 and hydrazine in the presence of sodium
hydroxide showed no signs of reaction, i.e. no yellow color
or precipitate. On refluxing, the reaction mixture developed
a yellow coloration but then turned colorless again. The
colorless crystals isolated from the reaction mixture at
this point were not the desired 29, but an isomer C29H22N2
as determined from the mass spectrum and elemental analysis.
In the aromatic region, the NMR spectrum of this iso
meric compound 33 showed a multiplet centered at t2.01
accounting for two protons and a multiplet at 2.8 account
ing for nineteen protons indicating only one phenyl with
ortho protons deshielded by an azine or otherwise electron-
withdrawing group. The only other feature of the spectrum
was a slightly broadened singlet at t4.31. Mostly on the
basis of the above NMR evidence the compound was identified
as 3,6-dipheny1-4-benzhydrylpyridazine (33).
The phenyl in the 6-position is relatively free to
assume coplanarity with the pyridazine ring, thus account
ing for the pair of deshielded ortho protons. However, the
phenyl in the 3-position is sterically crowded by the bulky
benzhydryl group in the 4-position which inhibits coplan-
anty with the pyridazine ring and, thus, all five protons
of the 3-phenyl are at approximately the same chemical


13
shift. The lone pyridazine ring proton is assumed to be
masked by the higher field multiplet. The singlet at x4.31
is accounted for by the benzhydryl proton. The fact that
in the mass spectrum of 33 the parent ion is base peak is
in accord with a pyridazine carrying aromatic substituents.
Due to the development of a transient yellow color
during the formation of 33, it was not clear whether 29 is
initially formed and then converted into 33 under the influ
ence of base (Scheme 7) or 32 was transformed via a base-
catalyzed ring-opening reaction into 2-benzhydry1-1,4 -
diphenylbut-cis- 2-ene-l ,4-dione which would then react with
hydrazine to form 33 (Scheme 8).
Scheme 7


14
Scheme 8
When 29 was finally synthesized at a later date, it
was found to be insensitive to refluxing ethanolic sodium
hydroxide in the time interval necessary for the formation
of 33. Thus, it appears that a pathway similar to that in
Scheme 8 is in operation in the formation of 33 from 32.
The failure to obtain 29 by the simple route above
forced the adoption of a more elaborate synthetic scheme.
The scheme chosen was similar to that developed by Maier3
and is outlined below (Scheme 9) for this particular system.


15
Scheme 9
The known 3418 was synthesized in good yield (611)
from diphenyldiazomethane19 and commercial maleic anhydride
simply by mixing the two reactants in benzene. The litera
ture method1820 calls for mixing the two components and
refluxing in benzene.
Presumably due to polymerization, treatment of a ben
zene solution of 34 with anhydrous aluminum chloride only
resulted in the formation of yellow, aqueous bicarbonate
soluble resin.
Addition of a benzene solution of 34 to anhydrous
aluminum chloride in benzene yielded 77.7% of a compound
tentatively identified as 3,3-diphenyl-trans-2-benzoylcyclo-
propanecarboxylic acid (37). Although the compound did not
give a correct elemental analysis, it did give a correct
mass spectral molecular weight (342) and, while the compound


16
was fairly insoluble, it gave an NMR spectrum which showed
only aromatic protons and an AB-quartet centered at x6.06.
The approximate coupling constant of 6 Hz for the AB-quartet
suggested the trans assignment for 37.21 When 29 was
subsequently obtained, its AB-quartet for the cyclopropyl
protons showed a coupling constant of 8.0 Hz which is indica
tive of a cis configuration.21
While the synthesis of 29 was in progress, a companion
effort was directed towards the synthesis of more compli
cated, but just as physically useful systems such as 40 and
43. At first these systems appeared to be more readily
accessible than 29. The proposed synthetic routes are out
lined below in Schemes 10 and 11. The requisite 2,3-dibenz-
oylbicyclo[2.2.1]hepta-2,5-diene (38)22 and 1,2-dibenzoylcy-
clohexa-1,4 diene (41)23 were known and easily obtained on
the multigram scale.
38
39
40
Scheme 10


17
Scheme 11
Unfortunately, both 38 and 41 were very unreactive
towards diphenyldiazomethane. On stirring for 24 days,
38 decolorized a solution of diphenyldiazomethane but
workup of the colorless material caused decomposition to
a purple substance which further decomposed to brown tar.
Refluxing 41 in benzene with a large excess of diphenyl
diazomethane gave rise to copious amounts of a material
which is assumed to be benzophenone azine. Presumably the
low reactivity of 38 and 41 towards diphenyldiazomethane is
due to the cis arrangement of the benzoyl groups on the .
double bond in both cases. This factor lias been noted
previously.2 4
In an effort to bypass the critical synthetic inter
mediates 35 and 36 of Scheme 9, an attempt was made at the
synthesis of 44 which, it was hoped, would add two moles of
phenyllithium to produce 29.


18
O
o
44
On treatment with hydrazine 3,3-dipheny1-cis-cyclopro-
panedicarboxylic acid18 (45) was found to yield only water-
soluble material which, on addition of mineral acid,
regenerated 45. Presumably the water-soluble material is
the hydrazine salt of the acid rather than the hydrazide or
the desired 44.
Attempted addition of diphenyldiazomethane to maleic
hydrazide25 gave no identifiable products.
On refluxing the anhydride 34 with hydrazine in ethanol
for 60 hours, a new crystalline substance is produced. The
NMR spectrum, mass spectrum, and elemental analysis agreed
with structure 44 but, unfortunately, the spectra also
agreed with structure 46. The infrared, which shows a doub
let rather than a singlet in the N-H stretch region, indi
cates that structure 46 is probably the better choice.
NH
2
46


19
Cyclic bisamide 44 or its isomer 46 gave no identifiable
products on attempted addition of phenyllithium under a
variety of conditions.
As a last resort, addition of phenylmagnesium bromide
to the anhydride 34 was attempted with success. Equimolar
quantities of the Grignard reagent and 34 produced 35 in
low yield (6.9%) when the reaction was carried out at room
temperature. Slightly better yields and cleaner product
were obtained either by adding the Grignard reagent to 34
in toluene at dry ice temperatures or by use of the diphenyl
cadmium reagent.
Besides giving the correct molecular weight and elementa
analysis, the ketoacid 35 gave the expected NMR spectrum.
In the aromatic region, there is a low-field multiplet cen
tered at tl.9 integrating for two protons and a higher-
field multiplet centered at 2.6 integrating for thirteen
protons. The xl.9 multiplet is assumed to be due to the
ortho protons of the benzoyl phenyl. The x2.6 multiplet
accounts for the remaining aromatic protons. The expected
AB-quartet at x6.48 integrates for .two protons. The coup
ling constant of 8.0 Hz is that to be expected for cis
protons on a cyclopropyl ring of this sort.21 Ketoacid
35 also shows a carboxylic acid proton as a very broad,
almost undetectable singlet at about x-1.4.
The infrared (KBr pellet) of 35 shows no strong absorb
ance for hydroxyl as would be expected for a carboxylic acid
hydroxyl. The carbonyl stretch of 55 is at 1730 cm 1 which


20
is more typical of a lactone than a free carboxylic acid.
The above is in accord with the observation that ketoacids
similar3 to 35 usually exist exclusively in a pseudo acid
form (structure 47) in the solid state.
In solution, ketoacids such as 35 tend to form an equi
librium between free acid and psuedo acid.3
35
:0
47
On melting, 35 evolves carbon dioxide to yield some tar
and the known 1,4,4-triphenylbut-3-en-1-one (48). 2 6 The
melting point and infrared carbonyl absorption were in close
agreement with that reported.26
The previously unreported NMR spectrum for 48 fits the
compound well. The aromatic region shows a two-proton mul-
tiplet centered at t2.17 and a thirteen-proton multiplet
centered at 2.7. As with 35 (vide, supra), the two aromatic
multiplets respectively account for the ortho protons of
the phenyl attached to the carbonyl and the remaining aro
matic protons. The remaining portion of the spectrum shows
the expected vinylic triplet at t3.59 (J = 7.0 Hz) integrat
ing for one proton and the expected methylene doublet at
6.21 (J = 7.0 Hz) integrating for two protons.


21
Stirring a solution of 35 and hydrazine hydrate in
ethanol for 24 hours gave the desired 2,7,7-triphenyl-5 -
keto-3,4-diazabicyclo[4.1.0]hept-2-ene (36) as a white
crystalline precipitate. Even though 36 gave a correct
mass spectral molecular weight (338) an acceptable ele
mental analysis could not be obtained. The analysis
suggested the presence of a-half mole of water of crystal
lization. The infrared spectrum showed the expected
carbonyl stretch3 at 1670 cm 1.
Although fairly insoluble, an NMR spectrum of 36 could
be obtained. The amide proton appeared as a broad absorb
ance at xl.9. As expected, the ortho protons of the phenyl
ring attached to the carbon-nitrogen double bond appeared
as a distinct multiplet at about x2.0, with the remaining
aromatic protons appearing at higher field (2.40 3.16).
The two cyclopropyl protons appeared as the expected AB-
quartet at x6.88 (J^g = 8.0 Hz). The upfield half of the
quartet is split again into a pair of doublets by coupling
with the ande proton Oy (JBN Hz> = Hz).


22
The coupling between Hg and finds precedent in the
literature27 and is not unexpected, especially when, upon
examination of a molecular model of 36, it is found that
Hg and fit nicely into the well-known "W" pattern.28
There is no coupling between and as determined from
an HA-100 spectrum.
Addition of phenyl1ithium to 56 proceeded smoothly
producing 29 in moderate yield (47.2%). Diazanorcaradiene
29 analyzed correctly and gave a correct mass spectral
molecular weight (398) in addition to a reasonable frag
mentation pattern.
In the aromatic region, the NMR spectrum of 29 dis
played a four-proton multiplet centered at rl.8, a six-
proton multiplet centered at 2.5, and two five-proton
singlets at 2.71 and 3.03. Presumably the lower field
nultiplet is due to the ortho protons of the phenyls on
the deshielding azine linkage while the higher field
multiplet again accounts for the remaining protons on the
2- and 4-phenyls. It is assumed that the higher field


23
aromatic singlet is due to the cyclopropyl phenyl over the
slightly shielding region of the azine linkage while the
lower field aromatic singlet is due to the other unshielded
cyclopropyl phenyl. The only other feature of the NMR
spectrum of 29 is a sharp singlet at t6.58 integrating for
two protons. The singlet is due to the now equivalent
cyclopropyl protons.
Chemical evidence for structure 29 was provided by its
acid-catalyzed conversion into pyridazine 33 which had been
previously characterized.
In refluxing xylene over a 24-hour period, 29 gives rise
to a new, colorless, unknown isomer 49 which does not show
the properties usually exhibited by 4H-diazepines even
though it analyzes correctly and gives the correct molecu
lar weight of 398.
The mass spectrum of 49 is completely different from
that of 29. The parent ion is base peak rather than the
parent minus benzonitrile ion which is only 3.5% of base
peak. The mass spectrum of 49 is quite featureless except
for peaks at 597 (21%) and 321 (14%).
The NMR spectrum of 49 is also quite featureless dis
playing, as illustrated in Figure 1, only N-H at t0.18 and
aromatic multiplets centered at 2.7 and 3.2. The three NMR
signals integrated for one, fifteen, and six protons respec
tively. That the signal at t0.18 is due to hydrogen
attached to nitrogen was proved by deuterium exchange with
heavy water which readily destroyed this signal.


Figure 1.
NMR spectrum of unknown 49 in CDC13


3 0 4 0 5.0 PPM ir) 6.0 7.0 8.0 9.0
25


26
Changing the NMR solvent from deuteriochloroform to
d5-pyridine altered the spectrum drastically as shown in
Figure 2, but gave no new information. Unchanged 49 could
be recovered after dissolution in pyridine.
Infrared and UV spectra gave no further useful informa
tion as to the identity of 49.
It was fairly obvious that 49 was not the desired 4H-
diazepine 30. The possibilities left for 49 were all
C29H22N2 isomers which would show the observed spectro
scopic properties of 49 and have a reasonable mechanistic
route for their formation.
The first possibility chosen for 49 was structure 50
which is shown along with a possible mechanism (Scheme 12)
[1,5]
0 0
H
50
Scheme 12


Figure 2. NMR spectrum of unknown 49 in d5-pyridine
4


7.0 3_0 4^ 5.0 Pm(T) 6.0 7X) 8^0 9J)
28


29
Structure 50 would fit the spectroscopic data if one
assumes sufficient deshielding of the vinylic and aliphatic
protons for them to appear in the aromatic region of the
NMR. However, 50 is a dihydropyridazine and, on the basis
of previous work,29 should readily oxidize to the fully aro
matic pyridazine.
Oxidation of 49 with potassium dichromate in aqueous
acetic acid gave only some tar and a 41.31 recovery of start
ing material. Extensive chromatography produced no more
material.
Oxidation of 49 with 1,2-dichloro-5,6-dicyano-1,4-
benzoquinone (DDQ) gave only dark green, difficultly soluble
material which, on chromatography over basic alumina,
yielded 87% recovered starting material which showed no
peak in the mass spectrum for 49 minus two hydrogens.
At this point it became fairly obvious that 49 does
not possess a dihydropyridazine structure or any other
structure which could be easily oxidized.
The next structure considered was structure 51 shown
below in Scheme 13.


30
29
0
0
0
0
51
Scheme 13
There is no chemical evidence for or against 51. Once
again one must assume sufficient deshielding of the vinylic
proton to place it in the aromatic region in the NMR.
Other spectroscopic data do not really speak for or against
structure 51.
In the series 52 53 and 54,3 0 the proton on the
pyrazole nitrogen appears in the NMR spectrum at 613.3,
10, and 7.22 as a broad singlet whose position is con
centration dependent. The position of the N-H proton
of 49 is at about 69.8.


31
55 56
For the two compounds 55 and 56, 31 the UV spectra
respectively consist of X = 256 nm (e = 33100) and
* 1 max v
X = 250 nm (e = 15100). The UV maximum of 49 is at
237 nm (e = 28400) with inflections at 255 and 298 nm.
Possibly, steric interactions among the two phenyls and the
phenylstyryl group of 51 would cause a hypsochromic shift.
Since 49 was not the desired 4H-diazepine 30 and since
49 could not be identified, other means to determine the
mechanism of the diazanorcaradiene-diazepine isomerization
were sought.
The most direct and reasonable approach to this question
involved resorting to a suitably labeled system which was
known to rearrange and whose rearrangment product could be


32
identified by x-ray methods. The diazanorcaradiene 57 was
chosen as an appropriate system for study.
0
C6H4 -]D-Br
6HtP-R
H
C 6H 4 -Br
Scheme 14
As outlined in Scheme 14, the 4H-diazepine 59 would
result if 57 underwent electrocyclic ring opening to the
corresponding 5H-diazepine followed by two consecutive supra-
facial concerted 1,5-hydrogen shifts (path B) as illustrated
previously in Scheme 4 for diazanorcaradiene 2.
The diazepine 58 could arise in several ways. First,
58 could result from the Cope-type mechanism previously
illustrated in Scheme 5 for the diazanorcaradiene 2. Also,
58 can arise by a Berson-Willzott Bones rearrangement3 2
whereby C-7 of structure 57 "walks" around the six-membered
ring to produce a 2,3-diazabicyclo[4.1.0]hepta-2,4-diene 60
which is unstable and opens up to the 4H-diazepine as
depicted in Scheme 15.


33
H
CeHu -p_-R
C6H4-L-Br 58
60
Scheme 15
The first step of Scheme 15 is concerted if the movement
of C-7 occurs with retention at C-7 as shown in structure 61
since this is a [1,5] sigmatropic change.12
INI
0
C6H4 -p_-Br
61
Other nonconcerted mechanisms similar to the Bones
rearrangement may also be envisioned. One such mechanism
involving a dipolar (or diradical) intermediate is given in
Scheme 16.
H C 6 H 4 _p__ R
0
0
57 -fe p-Br-C6H4 ^ C6H4-p_-Br fe 60 58
N-N'
Scheme 16


34
For the synthesis of 57, the problem reduces to the
preparation of triphenylcyclopropene with only the 3-phenyl
substituted with a group which can be observed by x-ray,
e.g. halogen, small aliphatic groups, etc. The above means
that no synthesis in which all three cyclopropeny1 carbons
become equivalent chemically is satisfactory. Thus, synthe
ses of sym-triphenylcyclopropene such as that developed by
Battiste are unsatisfactory.29
Recently, it was demonstrated by Longone and Stehouwer13
that hydride ion can be added to the known diphenylcyclopro-
penyl cation to give exclusively 1,2-diphenylcyclopropene in
high yield. Thus, it was reasoned that an appropriately sub
stituted phenylmagnesium bromide could be added to the same
cation to give the desired substituted triphenylcyclopropene.
As a first attempt, ¡3-chlorophenylmagnesium bromide was
added to diphenylcyclopropeny1 perchlorate to produce, after
chromatography, a colorless solid whose NMR spectrum showed
only a singlet at x6.79 (sym-triphenylcyclopropene x6.833)
and an aromatic multiplet. However, the aromatic multiplet
integrated much too high and the compound tended to discolor
even in the absence of air and light. It was assumed that
the desired 3-(4-chlorophenyl)-1,2-diphenylcyclopropene (62)
had been obtained, but it could not be purified.
The same reaction as above was repeated with p^-tolyl-
magnesium bromide. Good, clean product was obtained only
if the cation was added to the solution of the Grignard
reagent slowly. Rapid addition caused production of resinous


35
conglomerations which discolored the final product-as in
the case of cyclopropene 62.
The 3-(4-methylphenyl)- 1,2-diphenylcyclopropene (63)
characterized as expected. Besides giving a correct ele
mental analysis, 63 displayed the right mass spectral molecu
lar weight (282). The NMR spectrum of 63 showed the expected
aromatic multiplet centered at x2.64 integrating for fourteen
protons and two singlets at 6.83 and 7.76 integrating for
one and three protons respectively. The x6.83 signal is
typical for a triphenylcyclopropene cyclopropeny1 proton as
was mentioned above. The x7.76 signal is, of course, due to
the methyl group.
If the Grignard reagent had added so as to give the
isomeric cyclopropene 64, a one-proton singlet at ca.
x2.634 rather than 6.83 would have been anticipated.
The infrared spectrum of 63 displayed the typical
cyclopropene carbon-carbon double bond stretch at 1830 cm 1
(sym-triphenylcyclopropene 1820 cm 1 34). The UV spectrum
of 63 was also very useful as it showed the maxima charac
teristic of a sym-triphenylcyclopropene at 332.5 nm


36
(e = 23000), 315 nm ( e = 28000), 305 run (s, z = 22000),
302 nm (infl.) and 228 nm (a = 32000). For comparison,
the UV spectrum of sym-triphenyleyelopropene itself in
ethanol consists of maxima at 330 nm (e = 24200), 313 nm
(e = 29000), and 228 nm (e = 30600).3 5
Cycloaddition of 63 with 3,6-bis(4-bromophenyl)-
1,2,4,5-tetrazine (65)6 produced the expected 2,5-bis-
(4-bromopheny1)- 7 -(4-methylphenyl)-1,6-diphenyl -3,4-
diazabicycio[4.1.0]hepta-2,4-diene (66). The diazanorcara-
diene analyzed correctly and gave a correct mass spectral
molecular weight (644) The diazanorcaradiene also gave a
reasonable mass spectral fragmentation pattern which is
discussed in Chapter II.
The NMR spectrum of 66 simply consisted of a twenty-
two-proton aromatic multiplet centered at t2.93, a one-
proton singlet at 5.03 for the cyclopropyl proton, and a
three-proton singlet at 7.83 for the methyl group. For
comparison purposes, the cyclopropyl proton of the analogous
diazanorcaradiene 2 appears at t4.98.2
The thermal rearrangement of 66 in refluxing xylene
proceeded more rapidly than was anticipated and, as a
result, a much lower yield of the 4H-diazepine was obtained
than was expected due to decomposition. Presumably, the
methyl group of the substituted phenyl aids in the decompo
sition of the 4H-diazepine 67 to the corresponding pyrroles
and benzonitriles. Diazepine 67 gave the anticipated analyti
cal and spectral data as recorded in the Experimental Sec
tion (Chapter V) .


37
Table II
Bond Distances and Their Estimated Standard Deviations
Diazepine 67
Atoms
Distance (A)
e. s d.
Br (1)
C(E4)
1.91
0.01
C(E4)
C(E5)
1.38
0.01
C(E5)
C(E6)
1.40
0.01
C(E6)
C (El)
1.37
0.01
C (El)
C(E2)
1.39
0.01
C(E2)
C(E3)
1.38
0.01
C(E3)
C(E4)
1.37
0.01
C (El)
C (5)
1.50
0.01
C (5)
N (1)
1.31
0.01
N (1)
N (2)
1.39
0.01
N ( 2)
C(l)
1.29
0.01
C (1)
C (Al)
1.47
0.01
C (Al)
C(A2)
1.40
0.01
C(A2)
C (A3)
1.38
0.01
C (A3)
C(A4)
1.37
0.01
C(A4)
Br (2)
1.91
0.01
C(A4)
C (A5)
1.36
0.01
C(A5)
C(A6)
1.41
0.01
C(A6)
C (Al)
1.39
0.01
C(l)
C (2)
1.52
0.01
C (2)
C(B1)
1.53
0.01
C(B1)
C(B2)
1.39
0.01
C(B2)
C(B3)
1.43
0.01
C(B3)
C (B4)
1.37
0.01
C(B4)
C (Me)
1.54
0.01
C(B4)
C(B5)
1.41
0.01
C(B5)
C(B6)
1.37
0.01
C(B6)
C(B1)
1.40
0.01
C (2)
C (3)
1.52
0.01
C (3)
C(C1)
1.50
0.01
C(C1)
C(C2)
1.40
0.01
C(C2)
C(C3)
1.41
0.01
C(C3)
C(C4)
1.38
0.01
C(C4)
C (C 5 )
1.36
0.01
C(C5)
C(C6)
1.42
0.01
C(C6)
C(C1)
1.38
0.01
C (3)
C (4)
1.34
0.01
C (4)
C(D1)
1.48
0.01
C(D1)
C(D2)
1.42.
0.01
C(D2)
C(D5)
1.40
0.01
C(D5)
C(D4)
1.40
0.01
C(D4)
C(D5)
1.43
0.01
C(D5)
C(D6)
1.40
0.01
C(D6)
C(D1)
1.39
0.01
C (4)
C ( 5)
1.48
0.01
£
estimated
standard deviation.
in


C(4) C C3)
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OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO l/l
0'0'O^Q\0\sJvjs]NjsjN]vjC\^UiC'0'G'ssls]0'sJ0\,^Js]0'0'0'Cn(/i0'0\0N0'0'vjNj0\0\Q\viLni Q-.
V CM
CO
Bond Angles and Their Estimated Standard Deviations in
Diazepine 67


39
- Table TIT
(continued)
Atoms
Angle (deg.)
e.s.d.
C(C1)
C ( C 2 )
C ( C 3 )
120.2
0.7
C(C2)
C(C3)
C(C4)
119.3
0.8
C(C3)
C(C4)
C(C5)
121.0
0.8
C(C4)
C(C5)
C(C6)
120.5
0.7
C(C5)
C(C6)
C(C1)
119.1
0.7
C(C6)
C(C1)
C(C2)
119.8
0.6
C (3)
C(C1)
C (C 2)
120.3
0.6
C (3)
c (Cl)
C(C6)
119.9
0.6
C (3)
C (4)
C (5)
120.7
0.6
C (5)
C (4)
C (Dl)
114.0
0.5
C (3)
C (4)
C (Dl)
125.3
0.6
C (4)
C (Dl)
C(D2)
121.5
0.6
C (4)
C(D1)
C(D6)
120.7
0.6
C(D1)
C(D2)
C(D5)
121.5
0.7
C(D2)
C (D3)
C(D4)
118.8
0.7
C(D3)
C(D4)
C(D5)
121.3
0.8
C(D4)
C(D5)
C (D6)
117.8
0.7
C(D5)
C(D6)
C (Dl)
122.9
0.7
C(D6)
C (Dl)
C(D2)
117.7
0.6
estimated standard deviation.
The x-ray analysis of 67, which is described in the
Experimental Section, revealed that the rearrangement of 66
follows path A given in Scheme 14 above. An ORTEP-generated
model of 67 is shown in Figure 3. A table of bond lengths
is given in Table 2 and a table of bond angles is given in
Table 3.
At this point, all that can be said in the absence of
further data is that diazanorcaradienes containing one phenyl
on each cyclopropyl position rearrange to 4H-diazepines by
one of the mechanisms discussed above involving movement of
an entire carbon rather than hydrogen shifts. Once again a
system whose rearrangement appeared to be simple on the
surface turned out to be quite complex on closer examination.


Figure 3. ORTEP-generated diagram of 3,7-bis(4-bromopheny1)-4-(4-methylpheny1)-5,6-
diphenyl-4H-1,2-diazepine (67)


p


42
In connection with the further reaction of the diazepine
systems to produce pyrroles and benzonitriles, some ground
work on the mechanism of this fragmentation was carried out.
As was mentioned at the beginning of the chapter,
diazepines which result from the high temperature reaction
of sym-triphenylcyclopropene and tetrazines substituted
with groups other than unsubstituted phenyl decompose at
high temperatures into mixtures of pyrroles and benzoni
triles as shown in Scheme 2. Thus, in an as yet unspeci
fied manner (see Chapter II), not only the groups originally
on the tetrazine ring but also the 1- and 2-positions of the
cyclopropene become involved in the diazepine decomposition.
It was also of interest to ascertain whether or not the
4-phenyl of the diazepine also becomes involved in the
decomposition. Toward this end 1,2,5,6-tetraphenyl-7-
(4-methylpheny1)-3,4-diazabicyclo[4.1.0]hepta-2,4-diene
(68) was prepared. Diazanorcaradiene 68 showed the
expected properties which, as demonstrated in the Experi
mental Section, are quite similar to those for 66.
When 68 was decomposed in the injector port of an
analytical gas chromatograph with the column at such a
temperature that benzonitrile and £-tolunitrile are
separable, jo-tolunitrile was detected and identified
solely on the basis of its relative retention time. The
results are summarized in Scheme 17. It should be stressed
that these results on the decomposition of 68, while excit
ing, are still only tentative.


43
68
CH-
69
pyrroles
Scheme 17


CHAPTER II
MASS SPECTRAL CORRELATIONS
Introduction
The frequent observation that mass spectral and thermal
behavior closely parallel each other for certain compounds
is one of the more intriguing aspects of mass spectrometry.36
It will be the main purpose of this chapter to demonstrate
briefly that the thermolytic reactions of Scheme 2 in
Chapter I are correlated by the mass spectral behavior of
the diazanorcaradienes which rearrange to 4H-diazepines and
to attempt to enlighten the mechanism of the 4H-diazepine
decomposition.
As shown in Scheme 2, the thermolysis of diazepines
such as 70 yields two pyrroles, benzonitrile, and acetoni
trile. In the absence of further data, such conversions
NN
3
70
may be rationalized generally as in Scheme 18.
44


45
r = co2ch3
" C113
= E-H3C-C6H4
Scheme 18


46
Results and Discussion
The most obvious mass spectral feature of the diaza-
norcaradienes which undergo thermal rearrangement is their
marked similarity to the mass spectra of their respective
4H-diazepines. As examples, the mass spectra of diazanor-
caradienes 2 and 66 are plotted in Figures 4 and 6. The
mass spectra of the corresponding 4H-diazepines 3 and 67
are given in Figures 5 and 7 respectively. Except for the
intensities of some peaks, the mass spectra of 2 and 3 and
of 66 and 67 are almost superimposable.
From the above one can arrive at one of three conclu
sions the parent ion of the diazanorcaradiene rapidly
rearranges to the parent ion of the respective 4H-diaze-
pine, the parent ion of the 4H-diazepine isomerizes to the
parent ion of its precursor diazanorcaradiene, or both the
diazanorcaradiene and 4H-diazepine parent ions convert into
a common intermediate which gives rise to the observed
fragmentation pattern.
The mass spectra of all diazanorcaradienes examined,
whether they have been observed to rearrange or not, show
several similar fragmentations as illustrated in Scheme 19.
Table IV gives the intensities for the observed fragmenta
tions of the diazanorcaradienes studied. In those diaza-
norcaradienes not bearing carbomethoxy or methyl groups in
the 2- and 4-positions, loss of benzonitrile or substituted
benzonitrile is base peak. All diazanorcaradienes, regard
less of substitution or ability to rearrange, show a fairly


47
intense (2 to 99% of base peak) peak for parent ion (mT)
minus nitrogen. Corresponding to this loss of nitrogen
11
denotes metastable for this fragmentation
Scheme 19
peak is a flat-top metastable peak which indicates that the
nitrogen is lost from the parent ion with the release of a
small amount of kinetic energy.37
From the above observation that the mass spectra of 4H-
diazepines resemble the general diazanorcaradiene mass
spectrum, it is tempting to assume that in the mass spectro
meter 4H-diazepines derived from diazanorcaradienes revert
to their precusor diazanorcaradienes or an ion common to


Table IV
Relative Intensities for Important Mass Spectral Fragmentations of Diazanorcaradienes1
Diazanorcaradiene
-H
-n2
-R'CN
-RCN
2
R=0, R'=0, R"=0b
16%C
99%d
100%
e
71
R=£-I-CeH4, R'=0, R"=0b
7%
41%
4 2 % £
100%
72
R=CH3, R'=0, R"=0b,g
2 8 %h
39%
4%
100%
10
R=C02CH3, R'=0, R"=0b
11%
51%
33%
66%h1
22
R=C02CH3, R =0, R"=H^
16%
2%
5%
20%k
21
R=0, R'=0, R"=H^
8%
37%
100%
_e
7
R=0, R'=H, R"=0^fl
9%
20%
100%
4%
68
R=0, R'=0, R"=p-H3C-C6H4S
5%
33%
100%
e
^responding 4H-diazepine will be
the same
to -3% unless
otherwise
noted.
See Table V below for thermal data on this compound or a related compound. Diazepine
is 11%. Diazepine is 66%.
4H-diazepine not available.
'Same as loss of R'CN. Diazepine is 29%.
Corresponding
1Base peak
See text for a discussion of this intensity,
m/e 291. ^Does not rearrange to a 4H-diazepine. kBase peak m/e 346 (parent ion).
In
the isomeric diazepine
100%.
26
1 7
the listed fragmentations are respectively 13%, 5%, and


49
both. This would lend some credence to the first step of
Scheme 18. However, the mass spectra of diazepine 26 and
diazanorcaradiene 7 are also quite similar even though, as
demonstrated in Chapter I, thermally 7 does not isomerize
to 26. It has also been shown that apparently 26 does not
decompose into pyrroles and benzonitrile on thermolysis.38
Thus, in the absence of further information, all that can be
said about the diaza species which give rise to pyrroles on
thermal decomposition of 4H-diazepines derived from diaza-
norcaradienes is that the mechanism of Scheme 18 or
something similar is not precluded by mass spectral
observations.
Although the mass spectra of rearrangeable diazanorcara-
dienes and, of course, the corresponding 4H-diazepines give
no real information on the mechanism of diazepine decomposi
tion to pyrroles, for the most part the mass spectra do
follow the thermal decomposition process quite closely.
The thermal decomposition data for the four diazepines
that have been studied6 are tabulated in Table V. The mass
spectra of the four diazepines or closely related compounds
are given in Table IV.
All diazepines formed from the rearrangement of diazanor-
caradienes show intense mass spectral peaks for pyrroles
formed by electron-impact-induced decomposition of mT. At
least as far as low-resolution mass is concerned, the
pyrroles formed in the mass spectrometer correspond to those
formed by the thermal process of Scheme 18. The base peak


50
in the mass spectrometer is always mT minus benzonitrile or
substituted benzonitrile except when the azine linkage is
substituted with carbomethoxy or methyl groups. It will be
noted that thermally 3,7-bis (jd-tolyl) 4,5,6-triphenyl 4H-
1,2-diazepine (73), which is related to 71 decomposes into
an approximately equimolar mixture of pyrroles resulting
from loss of benzonitrile and j>-tolunitrile. In the mass
spectrometer diazepine 71 loses approximately three times as
much £-iodobenzonitrile as benzonitrile. The above facts
may be rationalized by considering that thermally 73 (or 71)
can lose nitriles RCN and R'CN only from bicyclic forms
similar to 8 (see Preface and Scheme 18), whereas in the
mass spectrometer the diazepine can lose RCN from the open
form or the bicyclic form but can lose R'CN only by isomeriz-
ing through the bicyclic form. It will be again noted that
the diazepine 26 does not result from the thermal isomeriza
tion of a diazanorcaradiene nor has it been possible to
thermally decompose it into benzonitrile and pyrrole, but
yet, in the mass spectrometer, loss of benzonitrile is base
peak.


51
Table V
Thermal Decomposition Data for Some 4H-Diazepines
6
Diazepine
-0CN
-RCNa
3
11
73
70
b
1001
>98%
49%
67%
c
d
O
R is the group originally on the 3- and 7-positions
of unidentified liquid (not benzonitrile or D-tolu-
nitrile) was detected in this decomposition.
The mass spectra of diazepine 11 and its related
diazanorcaradiene 10 (Figure 8) show 71% and 65% peaks for,
respectively, loss of methyl cyanoformate and loss of
benzonitrile from the parent ion. The base peak corres
ponds to what may be formally described as the decarboxyla
tion product of the pyrrole formed by loss of benzonitrile
from the parent ion as depicted in Scheme 20. Thermally,
diazepine 11 converts exclusively into dimethyl 3,4-
diphenylpyrrole-2,5 dicarboxyl ate, which is the end result
of loss of benzonitrile from 11.6 Again the loss of methyl
cyanoformate from the parent ion of 11 may be due to
fragmentation from the open diazepine form as opposed to


52
E
CH
3
m/e 438
m/e 335
m/e 291
E = C02CH3
Scheme 20
fragmentation from a bicyclic form and thus have no thermal
analogy.
In the mass spectrum of the diazanorcaradiene related
to 70 (72), loss of acetonitrile from the parent ion is base
peak but loss of benzonitrile from the parent ion gives only
a 3% peak! Thermally the diazanorcaradiene 72 converts into
70 only with difficulty relative to cases where the diaza
norcaradiene azine linkage is substituted with phenyls or
carbomethoxy groups. Also with difficulty, 70 thermally
converts into a 2.17:1 molar mixture of, respectively,
2,5-dimethyl-5,4-diphenylpyrrole and 1-methy1-2,3,4-tri-
phenylpyrrole.6 Thus, thermally, loss of benzonitrile is
the predominant pathway. The combination of the loss of
acetonitrile from the unrearranged form of the diazanor
caradiene 72 in the mass spectrometer and the difficulty
with which the diazanorcaradiene rearranges to 70 may be
used to rationalize the unusually low abundance of the loss
of benzonitrile from the parent ion in the mass spectrum


53
of the diazanorcaradiene 72. At the time of this writing
no mass spectrum of 70 was available.
As a further complication to the diazepine decomposi
tion problem, it was shown tentatively in Chapter I that,
on thermolysis, diazanorcaradiene 68 presumably reacting
via diazepine 69 yields tolunitrile in addition to the
expected benzonitrile.
The mass spectrum of 68 shows a peak for the loss of
tolunitrile from the parent ion as depicted in Figure 9.
The loss of tolunitrile from the parent ion is supported by
a metastable peak but, unfortunately, the metastable can
also be accounted for by loss of methyl from the parent
minus benzonitrile ion. A similar problem arises in the
interpretation of the mass spectrum of diazanorcaradiene
66 and its related diazepine 67 (Figures 6 and 7).
In closing this chapter it will be noted that the
mass spectra of all diazanorcaradienes and diazepines
examined show a P-1 peak of 5-28% intensity (see Table IV).
In all cases except when the azine linkage is substituted
with methyl groups the P-1 intensity is only 5-16%. It is
assumed that the hydrogen lost is the one at C-7 in
diazanorcaradienes and C-4 in diazepines except when the
azine linkage is substituted with methyl groups, which opens
the possibility of loss of hydrogen from one of the methyl
groups to form an ion such as 74.


54
0 H
CH
2
N=N
74
Although some of the driving force for loss of a
hydrogen radical from the parent ion is conversion from the
odd-electron mT to the even electron P-1 ion, perhaps
another driving force may be formation of the aromatic
diazatropylium cation 75. It is noteworthy that in the
mass spectrum of cycloheptatriene, which is known to
easily convert into the aromatic tropylium cation, base
peak is loss of hydrogen radical.39 The diazatropylium
problem will be discussed more fully in Chapter IV.
R
N-N
75


Figure 4.
Mass spectrum of 1,2,5,6,7-pentapheny1-3,4-diazabicyclo[4.1.0] hepta-
2,4-diene (2)


Ease-Peak
230 210 100 170 150 130 110 90 70 50 30
Mas G
(-n
ON


Base Peak
Fig. 4 continued


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Fig
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Figure 5. Mass spectrum of 2,5-bis(4-bromopheny1)- 7-(4-methylpheny1)-1
3,4-diazabicyclo[4.1.0]hepta-2,4-diene (66)
, 6 -diphenyl -


Base Peak
Mass
ON
o


Peak
Fig. 5 continued
61


Peak
Mass
ON
K)
Fig. 5 continued


Base Peak
660 640
Mass
cn
Fig. 5
continued


Figure 6.
Mass spectrum of 3,4,5,6,7-pentapheny1-4H-1,2-diazepine (3)


Base Peak
O'
Ln


430 410 390 370 350 330 310 290 270 250 230
Mass
Fig. 6 continued
ON
ON


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Mass
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Fig
6 continued


Figure 7. Mass spectrum of 3,7-bis(4-bromopheny1)-4-(4-methylphenyl)-5,6-dipheny1-
4H-1,2-diazepine (67)


Base Peak
ON
SP


Base Peak
OP
O
Fig. 7 continued


Base Peak
Mass
"vj
-
Fig. 7 continued


660 640 -o
Fig
7 continued
Mass


Figure 8. Mass spectrum of dimethyl 1,6,7-tripheny1 3,4-diazabicyclo[4.1.0]hepta-
2,4-diene-2,5-dicarboxylate (10)


Base Peak
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H3C02C-^/) C02CH3
Mass
4^.


Ease Peak
Lr
Fig. 8 continued


Figure 9. Mass spectrum of 7-(4-methylphenyl)-1,2,5,6-tetrapheny1-3,4-diazabicyclo-
[4.1.0]hepta-2,4-diene (68)


Ease Peak
230 210 190 170 150 130 110 90 70 50 30
Mass


Ease Peak
Fig. 9 continued


Base Teak
Fig
9 continued


CHAPTER III
CYCLOPROPYL CONJUGATION IN HETEROAROMATIC SYSTEMS
Cyclopropyl Conjugation
The phenomenon of cyclopropyl conjugation is quite well
known1+0 and has been extensively investigated in both 'the
ground state and excited state of many molecules.
Closs and Klinger41 observed that with decreasing
temperature the ortho protons in cyclopropylbenzenes show
increased shielding. The increased shielding was attributed
to increased population of the bisected, electronically
favorable conformation 76.
Electron diffraction42 and infrared spectroscopy43
also have been employed to detect cyclopropyl conjugation
in unsaturated molecules which are in their ground state.
Kosower and Ito44 found that the excited states of
ketones are stabilized by the presence of a cyclopropyl
ring alpha to the carbonyl carbon if the geometry is correct.
In ketone 77 the geometry is correct for cyclopropyl
80


81
conjugation as the cyclopropyl ring is in the bisected
configuration. The geometry is far from ideal in ketone
78. Interaction in the excited state was found to lower
the excited state of 77 by 7-8 kcal/mole relative to the
excited state of 78.
As a general rule, it has been found that, in the
absence of geometric factors, weak cyclopropyl conjugation
is a consequence of poor electron-withdrawing ability of
the unsaturated group to which the cyclopropane ring is
attached.45 In other words, the greater the electron
demand of the molecule to which the cyclopropane ring is
attached, the greater will be the conjugation of the cyclo
propane ring with that molecule. Also, it has been shown
that the extent of cyclopropyl conjugation is a function
of geometry only if the group interacting with the cyclo
propane ring is sufficiently electron-withdrawing.45
The compounds to be investigated, 3,6 dicyclopropyl-
1,2,4,5-tetrazine (79) and 3,6-dicyclopropylpyridazine
(80), are both similar to monocyclopropylbenzene studied
by Closs and Klinger41
in that the cyclopropyl rings are


82
both bonded to an aromatic six-membered ring. There are
definite interesting differences though.
Tetrazine 79 contains four nitrogens in the aromatic
ring which, accordingly, should enhance cyclopropyl conjuga
tion with the tetrazine ring due to the great electron-
withdrawing power of the tetrazine ring. Also, unlike
cyclopropylbenzene, the tetrazine ring of 79 carries no
hydrogens and, thus, there are negligible steric factors.
The only complication is that, assuming the dicyclopropyl-
tetrazine is completely in the bisected form, two conforma
tions are possible which may complicate the NMR spectrum
of 79. The top view of the hypothetically possible syn and
anti conformations is illustrated below as structures 81 and
82 respectively.
H H H
The pyridazine 80 should exhibit cyclopropyl conjuga
tion similar to that of tetrazine 79 but reduced somewhat
due to replacement of two nitrogens by less electron-
withdrawing C-H groups i.e. the conjugation in 80 should be
intermediate between that of cyclopropylbenzene and
tetrazine 79. Also, in the case of 80, steric effects again


83
are operative as in cyclopropylbenzene since the pyridazine
ring has a hydrogen in both the 4- and 5-positions. Assum
ing the bisected form for 80 the syn rotamer 83 should be
favored over the syn rotamer with both cyclopropyl methylene
functions interacting with the hydrogens of the pyridazine
ring or either of the trans rotamers.
H
H
H
H
83
Synthesis
The synthesis developed by Abdel-Rahman eit al. 10 is
only one of the many synthetic schemes known for the forma
tion of dihydrotetrazines which can be oxidized to their
respective £-tetrazines.46k7 The synthesis is quite simple
in that it involves merely refluxing a mixture of hydrazine
hydrate, a nitrile, flowers of sulfur, and ethanol for a
period of one to three hours. As an example, use of benzoni-
trile in the Abdel-Rahman synthesis yields 851 dihydro-3,6-
dipheny1-1,2,4,5-tetrazine. Aromatic nitriles generally
produce dihydrodiaryltetrazines in high yield, whereas alkyl
nitriles give only low yields of the respective dihydro
dial kyltetrazines.


Full Text

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FILES



Structure and Reactivity in the Heterotropilidene
Series and Other Studies
By
ROBERT MERRIFIELD WHITE
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
1972

«k
DEDICATION
This dissertation is dedicated to all of the people, places,
animals, and things which have made the past four years a
worthwhile experience in Life.

ACKNOWLEDGEMENTS
The author wishes to thank his research director, Prof.
Merle A. Battiste, for excellent guidance on this project,
helpful discussions, and, most of all, moral support when
it was needed. The author would also like to thank the Palenik
Group, especially M. Mathew, for the generous use of their
x-ray facilities and cheerful help on structure 67; Dr. R.W.
King for the computer solutions of the NMR spectra of com¬
pounds 79 and 80; and Dr. R. -Rehburg for samples of com¬
pounds 2, 3, 10, and 11 and the excellent groundwork done
on the project before the author took over.
The author also wishes to recognize and thank The
Ghetto, Alpha Chi Sigma and its members, especially S.R.,
S.W., P.F.E., J.H., M.K., H.J., and R.K.; 1743, SCL, L$N,
T.E.H., The Zoo, The Rat, R.W.C.V., C.C.V., R.L., Huntsville,
Nashville, and all of the other people, places, animals, and
tilings whose sheer volume space does, not permit mention of
but which have made the past four years more than just a
pure academic experience.
The author also wishes to thank his wife, Ann, for
providing moral support when it was needed and his son,
Robbie, for being so patient these past four years.
in

"I remember when this whole thing began
No talk of God then - we called you a man."
Jesus Christ Superstar, 1970
IV

PREFACE
As part of a general study of the Diels-Alder reaction
of tetrazines with alkenes, it was discovered independently
in 1966 by Sauer and Heinrichs,1 and Battiste and Barton2
that sym-triphenylcyclopropene reacts with 3,6-diphenyl-
1, 2,4,5-tetrazine (1) at 20 to 78° to produce a yellow com¬
pound (2) C35H26N2 which, on heating (100° or greater),
isomerizes to an almost colorless compound (3) which, on
further heating (230°), decomposes into benzonitrile and svm-
tetraphenylpyrrole. The results of both investigations are
summarized in Scheme 1.
Scheme 1
Sauer was of the opinion that 2 is in the diazanor-
caradiene form, 1,2,5,6,7-pentapheny1-3,4-diazabicyclo[4.1 .0] -
hepta-2,4-diene (4). Battiste, however, argued that 2 should
be described as 3,4,S,6,7-pentapheny1-5H-1,2-diazepine (5).

H
0 H
0
0
N=N
0
0
4
5
Both Sauer and Battiste agreed that 2,5-diphenyl-3,4-
diazabicyclo[4.1.0]hepta-2,4-diene (6)1’2’3 and 2,5,7-
triphenyl - 3 , 4 - diazabicyclo [4 . 1 . 0] hepta- 2 , 4 -diene (7)4 and
other diazanorcaradienes with no phenyls at C-l and C-6
exist exclusively in the diazanorcaradiene form at room
temperature.
Sauer based his argument for 4 on the fact that the UV
spectrum of 2 is quite similar to that of 6 even though
Maier3 had previously shown that substituents in the 1- and
6-positions imposed steric restrictions on the phenyls in
the 2- and 5-positions causing a hypsochromic shift in the
ultraviolet. Thus, there was some doubt as to whether the
UV of 4 and the UV of 6 could be compared.
Battiste suggested that the low-field position of the
only non-aromatic absorption in the NMR spectrum of 2
indicated an allylic type signal rather than a cyclopropyl
type signal. Battiste also felt that the phenyls in the 1-
and 6-positions would facilitate the disrctatory opening of
the initially formed 4 to give a diazacycloheptatriene
system.
vi

Sauer proposed that product 3 is the result of dis-
rotatory ring opening of 4 to give the 5H-diazepine 5 or one
of its hydrogen-shifted (except to nitrogen) products. Again
Sauer based his arguments on the UV spectrum of 3,citing
extended conjugation as being responsible for the spectrum.
On the basis of its facile conversion to tetraphenyl-
pyrrole and benzonitrile, Battiste tentatively proposed the
bicyclic structure 8 for isomer 3.
8
The reaction of dimethyl 1, 2,4,5-tetrazine-3,6-dicar-
boxylate (9) with sym-triphenylcyclopropene gives products
10 and 11 which are analogous to 2 and 3 above. Since the
product 11 shows non equivalent ester methyls in the NMR,
Sauer5 assigned to it the structure 12.
12
vi 1

It was shown by Rehburg and Battiste6 that mixtures of
pyrroles are obtained from diaza species similar to 3 or 11
when the tetrazine has substituted phenyls, methyls,or
carbomethoxy groups attached to it as illustrated below in
Scheme 2.
Scheme 2
At the time this work was initiated, it still was not
known definitely whether 2 existed as diazanorcaradiene or
5H-diazepine, nor had the structure of 3 been established.
Also, no mechanistic details on the conversion of 2 to 3
were available. Chapter I deals in some detail with the
structures of 2 and 3 and the mechanism of the thermal
isomerization of 2 to 3.
When this investigation was begun, the aromaticity and
stability of the cycloheptatrienylium or tropylium cation
(13) were well known.7’3 Also, the aromaticity of cyclo¬
heptatr ienone or tropone (14) was well-documented.7’8
vi 11

*
0 o'
13 14
By contrast, the analogous 1,2-diazacycloheptatrieny-
lium cation (15) was a complete unknown at the beginning of
this work. Only one 1,2-diazatropone derivative, 16, had
been reported.9 In acid, 16 did not protonate on oxygen to
form the aromatic dibenzohydroxydiazatropylium cation, but,
rather, it protonated on nitrogen to form an amine salt as
illustrated in Scheme 3.
H
Scheme 3
Since at the beginning of this -investigation it was
thought that compounds such as 2 existed in the open 5H-
diazepine form, the possibility of synthesizing the diaza
IX

analogs of the tropylium cation and tropone appeared to be
a feasible project. The diazatropylium cation-diazatropone
problem will be dealt with in Chapter IV.
Also, the tetrazines which are used in the synthesis of
many of the diazanorcaradienes and diazepines present them¬
selves as an interesting heteroaromatic series. The spec¬
tral properties of some of the more interesting members of
this series will be examined in some detail along with
members of related aromatic systems in Chapter III.
x

€>
TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
PREFACE .• v
LIST OF TABLES xii
LIST OF FIGURES xiii
ABSTRACT xv
Chapter
I.THE DIAZANORCARADIENE-DIAZEPINE REARRANGEMENT. 1
Results and Discussion 1
II.MASS SPECTRAL CORRELATIONS 44
Introduction 44
Results and Discussion 46
III.CYCLOPROPYL CONJUGATION IN HETEROAROMATIC
SYSTEMS 8 0
Cyclopropyl Conjugation 80
Synthesis 83
Dicyclopropyltetrazine and Dicyclopropyl-
pyridazine - The Ground State 90
Dicyclopropyltetrazine and Dicyclopropyl-
pyridazine - The Excited State 112
IV.. THE DIAZATROPYLIUM CATION AND DIAZATROPONE ... 130
Attempted Syntheses of 1,2-Diazatropylium
Cations ’ 130
Attempted Syntheses of 1,2-Diazatropone . 150
V.EXPERIMENTAL 159
REFERENCES 211
BIOGRAPHICAL SKETCH 215
xi

LIST OF TABLES
Table Page
IKinetic Parameters for the Thermal Isomeriz¬
ation of 2 to 3 3
IIBond Distances and Their Estimated Standard
Deviations in Diazepine 67 37
IIIBond Angles and Their Estimated Standard
Deviations in Diazepine 67 38
IVRelative Intensities for Important Mass Spectral
Fragmentations of Diazanorcaradienes 48
VThermal Decomposition Data for Some 4H-
Diazepines 51
VIChemical Shift Data for Tetrazine 79 and
Pyridazine 80 88
VII Magnetic Coupling Data for 79, 80, 85 and 86 .... 89
VIIIChemical Shift Data for iso-Propyl and Cyclo-
propyl Aromatic Compounds Ill
IX Principal Absorbances for Some Tetrazines 114
X Principal Absorbances for Some Pyridazines 115
XI Proton Assignments for 96 134
xii

%
LIST OF FIGURES
Figure Page
1 NMR spectrum of unknown 49 in CDC13 25
2 NMR spectrum of unknown 49 in d5-pyridine 28
3 ORTEP generated diagram of 3,7-bis (4-bromo -
phenyl)-4-(4-methylpheny1)-5,6-diphenyl-4H-
1, 2-diazepine (67) 41
4 Mass spectrum of 1, 2,5,6,7-pentaphenyl-3,4 -
diazabicyclo[4.1.0]hepta-2,4-diene (2) 56
5 Mass spectrum of 2,5-bis (4-bromophenyl)- 7-
(4-methylpheny1)-l,6-diphenyl-3,4-diazabicyclo-
[4.1.0]hepta-2,4-diene (66) 60
6 Mass spectrum of 3,4,5,6,7-pentaphenyl-4H-1,2 -
diazepine (3) 65
7 Mass spectrum of 3,7-bis(4-bromophenyl)-4 -
(4-methylpheny1)-5,6-diphenyl-4H-1,2-
diazepine (67) 69
8 Mass spectrum of dimethyl 1,6,7 - tr.iphenyl - 3,4 -
diazabicyclo[4.1.0]hepta-2,4-diene-2,5-
dicarboxylate (10) 74
9 Mass spectrum of 7-(4-methylphenyl)-1,2,5,6-
tetrapheny1-3,4-diazabicyclo[4.1.0]hepta-2,4-
diene (68) 77
10 NMR spectrum of 3,6-dicyclopropyl -1, 2,4,5-
tetrazine (79) in CDC13 at NMR probe temperature
(40°) ' 94
11 NMR spectrum of 3,6-dicyclopropyl-1,2,4,5 -
tetrazine (79) in CDC13 at -10° 96
12 NMR spectrum of 3,6-dicyclopropy1 -1,2,4,5-
tetrazine (79) in CDC13 at -30° 98
13 NMR spectrum of 3,6-dicyclop’ropyl-1,2,4,5 -
tetrazine (79) in CDC13 at -60° 100
14 NMR spectrum of 3,6-dicyclopropy1 -1,2,4,5-
tetrazine (79) in diphenyl ether at NMR probe
temperature (40°) 102
xii i

Page
fe
Figure
15 NMR spectrum of 3,6-dicyclopropylpyridazine
(80) in CDC13 at 42.5° 104
16 NMR spectrum of 3,6-dicyclopropylpyridazine
(80) in CDC13 at -5.5° 106
17 NMR spectrum of 3,6-dicyclopropylpyridazine
(80) in CDC13 at -59.0° 108
18 Visible spectrum of 3,6-dicyclopropyl-
1,2,4,5-tetrazine (79) in ethanol 119
19 Visible spectrum of 3,6-dicyclopropyl -
1,2,4,5-tetrazine (79) in cyclohexane 121
20 UV spectrum of 3,6-dicyclopropyl-1,2,4,5 -
tetrazine (79) in ethanol 123
21 UV spectrum of 3,6-dicyclopropyl-1,2,4,5-
tetrazine (79) in cyclohexane 125
22 UV spectrum of 3,6-dicyclopropylpyridazine
(80) in ethanol 127
23 UV spectrum of 3,6-dicyc]opropy]pyridazine
(80) in cyclohexane 129
24 NMR spectrum of 3,5,7-tripheny]-4H-1,2-diazepine
hydrofluoroborate (99) in TFA/CDC13 at 17.0° .... 141
25 NMR spectrum of 3,5,7-triphenyl-4H-1,2-diazepine
hydrofluoroborate (99) in TFA/CDC13 at 1.5° 143
26 NMR spectrum of 3,5,7-triphenyl-4H-1,2-diazepine
hydrofluoroborate (99) in TFA/CDC13 at -18.5° ... 145
27 UV spectrum of unknown 102 149
28 UV spectrum of 4,5-dipheny1-5,6-dicarbomethoxy-
1- (1,2-diphenylcyclopropen-3-yl)-1,4-dihydro-
pyridazine-4 - aldehyde (104) 154
xiv

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
STRUCTURE AND REACTIVITY IN THE HETEROTROPILIDENE
SERIES AND OTHER STUDIES
By
Robert Merrifield White
March, 1972
Chairman: M.A. Battiste
Major Department: Chemistry
It has been found that.the reaction between sym-tri-
phenylcyclopropene and 3,6-dipheny1 -1,2,4,5-tetrazine pro¬
duces 1,2,5,6,7-pentapheny1-3,4-diazabicyclo[4.1.0]hepta-
2,4-diene or pentaphenyldiazanorcaradiene which, on heating,
isomerizes to 3,4,5,6,7-pentaphenyl-4H-1,2-diazepine as
determined by x-ray studies. It has been demonstrated
conclusively that pentaphenyldiazanorcaradiene rearranges to
the 4H-diazepine via a carbon-shift rather than a hydrogen-
shift mechanism. The exact mechanism of the carbon shift
was not determined. Preliminary work on the decomposition
of 4H-diazepines into pyrroles and benzonitriles has also
been done.
2,5-Dipheny1 -1,3,4-thiadiazole has been isolated in low
yield in the synthesis of 3,6-dipheny1-1,4-dihydro-1,2,4,5-
tetrazine from sulfur, ethanol, hydrazine hydrate, and
benzonitrile.
xv

In the heteroaromatic series, it has been demonstrated
that cyclopropyl conjugation is present in the highly
interesting 3,6-dicyclopropy1-1,2,4,5-tetrazine and, as
anticipated, to a lesser extent, in 3,6-dicyclopropyl -
pyridazine in both the ground and excited states.
Attempts at synthesizing the diaza analogs of tropone
and the tropylium cation by standard methods met with no
success. However, some interesting rearrangements and new
compounds were observed.
xvi

CHAPTER I
THE DIAZANORCARADIENE-DIAZEPINE REARRANGEMENT
Results and Discussion
The first step taken in dissecting and analyzing the
thermal conversion of 2 to 3 outlined in Scheme 1 was to
determine the structure of compound 3. The structure of
3 was attacked using x-ray spectroscopy. It was decided
to employ the heavy atom technique by reacting sym-tri-
phenylcyclopropene with the then unknown 3,6-bis (4-iodo-
phenyl)-1,2,4,5-tetrazine (17) at elevated temperatures
to give directly 3 with two phenyl rings carrying iodine
atoms.
Since classical methods of synthesizing 17 had failed
previously,6 the recently developed method of Abdel-Rahman
et a_l. 1 0 was used to produce the yellow dihydroderivative
of 17 which was then oxidized to the deep purple 17.
Unfortunately, 17 was contaminated with what is tentatively
identified as 2,5-bis(4-iodopheny1)-1,3,4-thiadiazole (18)
(see Chapter III) which was very difficult to remove due
to the gross insolubility of both 17 and 18. The thia¬
diazole 18 could be separated from 17 only by chromato¬
graphy over basic alumina with boiling xylene which tended
to completely decompose the tetrazine 17 unless it was
rapidly eluted from the column.
1

2
Reaction of 17, either chromatographed or crude, with
sym-triphenyl cyclopropene in refluxing xylene gave the
desired substituted 3 without isolation of the intermediate
substituted 2. The x-ray analysis11 of the iodine-
substituted 3 showed that it has the 4H-diazepine structure
19.
N —N
19
Obviously, the above described conversion of 10 to 11
should proceed in a manner analogous to the 2 to 3 conver¬
sion and product 11 should have the 4H-diazepine structure
20 rather than structure 12 as assigned by Sauer.
N —N
20
At least formally, the conversion of 2 to 3 may be con¬
1 2
sidered as two concerted suprafacial 1,5-hydrogen shifts
from the open form of 2 as shown below in Scheme 4.

3
Scheme 4
The kinetics of the thermal isomerization of 2 to 3
were followed by NMR at 150 and 140°. Good first-order
kinetics were observed and the resulting kinetic para¬
meters are given in Table I. The energy of activation (E )
a.
was found to be 33.4 kcal/mole. The kinetics indicated that
the reaction is unimolecular and supported the mechanism
of Scheme 4.
Table I
Kinetic Parameters for the Thermal Isomerization of 2 to 3
temp. (°C) k (sec *) AH* (kcal/mole) AS* (cal/mole-deg)
150.0 2.93 x 10"5 32.6 -3.14
140.0 1.07 x 10'5 32.6 -3.24
Taking the premise that two concerted 1,5-hydrogen
shifts were responsible for the conversion of 2 to 3, it
appeared of considerable mechanistic interest to examine
some systems in which the cyclopropane ring of the diaza-
norcaradiene does not carry three phenyl rings as in 2.
Two such systems are 21 and 22, which are simply 2 and 10
without a phenyl on the methylene carbon (C-7).

4
N-N
N-N
21
22
Both 21 and 22 are readily synthesized by the cyclo¬
addition of 1,2-diphenylcyclopropene13 with 1 and 9 respec¬
tively. The resulting adducts are bright yellow crystalline
compounds whose spectral and analytical properties define
their structure as that of the norcaradiene valence
tautomer.
The aromatic region of the NMR spectrum of 21 shows two
multiplets centered at t2.18 and 2.80 integrating in the
ratio 4:6 and a spike at 3.16 which accounts for ten pro¬
tons. The lower field aromatic multiplet is assigned to
the ortho protons of the phenyl rings attached to the
azine linkage. Deshielding of these ortho protons by the
electron-withdrawing and diamagnetically deshielding azine
linkage is assumed. The higher field multiplet is assigned
to the further removed meta and para protons of the phenyls
at C-2 and C-4. The ten-proton spike which is at higher
field than either multiplet accounts for the phenyls
attached to the cyclopropane ring. The two methylene (C-7)
protons, which are especially important for structural
identification, appear as two widely separated

5
sharp doublets at t6.31 (J = 5.5 Hz) and 8.68 (J = 5.5 Hz).
That the methylene protons appear as two doublets could be
accounted for by a diazacycloheptatriene which is frozen
in a non-inverting conformation, but the chemical shift
of both protons is more indicative of cyclopropyl than
allylic protons. The higher field doublet is assigned to
the endo proton which is shielded to some extent by the
azine linkage. The lower field doublet is assigned to
the exo proton which is deshielded by the phenyl rings
attached to the cyclopropyl ring (vide infra).
At about this time preliminary x-ray crystallographic
results by Fritchie14 revealed that 23 indeed exists in the
diazanorcaradiene form rather than the diazacyclophepta-
triene form. A notable result of Fritchie's investigation
of 23 was that the cyclopropyl hydrogen occupies the exo
position and lies in the deshielding region of the phenyls
at C-l and C-6. Thus, in assigning only non-aromatic
proton as allylic rather than cyclopropyl on the basis of
chemical shift, Battiste2 was in error due to unforeseen
diamagnetic deshielding effects.
23

6
Heating 21 in pyridine caused noticeable broadening of
the NMR doublets at temperatures as low as about 90°. The
signals for both methylene protons completely disappeared
at 150°. Although time - averaging of the two methylene
protons was apparently occurring via ring inversion, no
time-averaged singlet for a rapidly inverting diazanorcara-
diene could ever be observed presumably due to decomposition
(vide infra). Also, no signal for rearranged 21 could be
found.
On heating to as high as about 190° in either d5-nitro-
benzene or napthalene, decomposition of 21 to an unidenti¬
fied red oil was observed. Further heating converted the
red oil to a yellow oil which could not be identified
after chromatography and spectral analysis.
Compound 22 showed temperature-dependent NMR behavior
similar to that exhibited by other diazanorcaradienes, such
as 24, with ester groups in the 2- and 5-positions.15 At
-3.5° the molecule is frozen in a non-exchanging form which
shows the expected NMR spectrum for the diazanorcaradiene
structure. The phenyls attached to the cyclopropane ring
show the expected ten-proton spike at t2.95. The ester
methyls, which are magnetically equivalent, appear as a
singlet at t6.35. Again, as in the NMR spectrum of 21,
the cyclopropyl protons show up as two widely separated
doublets at t6.37 (J = 5.7 Hz) and 9.0 (J = 5.7 Hz). Warm¬
ing the NMR solution of 22 to 37° causes complete disappear¬
ance of the cyclopropyl signals. The cyclopropyl doublets

7
coalesce at about 24° which is indicative of the phenyls
actually inhibiting the opening of the diazanorcaradiene
to the 5H-diazepine as the system 24 reported by Binsch and
Sauer15 coalesces at between 5 and 16°.
N-N'
24
An attempt at thermally isomerizing 22 in refluxing
dioxane only produced small amounts of what is assumed to
be dimethyl 1,6-diphenyl - 3,4-diazabicyclo[4.1.0]hept-2-en-
5-ol-2,5-dicarboxylate (25) mainly on the basis of its NMR
spectrum.
The NMR spectrum of 25 shows the expected broad singlet
at t1.15 for the N-H proton, two multiplets centered at
2.95 and 3.6 integrating 8:2 for the ten aromatic protons,
a broad singlet for hydroxyl proton at 4.75, sharp singlets
at 5.58 and 6.18 for the nonequivalent methyl protons, and
an AB-quartet centered at 6.78 (J = 12.5 Hz) for the cyclo¬
propyl protons.
No attempt was made at assigning the stereochemistry of
25. The mass spectrum of 25 gives the correct molecular
weight (364) but the cracking pattern in no way resembles
the mass spectral cracking pattern produced by the precursor
22. In the mass spectrometer one might have expected the
parent ion of 25 to lose a molecule of water to yield the

8
parent ion of 22, but apparently other processes are com¬
petitive with loss of water and, hence, the cracking pattern
of 25 does not resemble that of 22. The addition of water
across the carbon-nitrogen double bond of diazanorcaradienes
is well-documented.5’16 An attempt at an authentic synthe¬
sis of 25 was apparently a failure for unknown reasons.
Since of the two systems, 21 and 22, 22 should have
shown the greater propensity for rearrangement6 but did not
rearrange, no attempt other than the high temperature NMR
work was made at thermally isomerizing 21.
The thermal behavior of the simplest diazanorcaradiene,
6, which is 2 with no phenyls on the cyclopropyl carbons,
was also investigated. Refluxing 6 in xylene for 18 hours
produced nothing but tar and starting material.
Another system, 2,5,7 - triphenyl-3,4-diazabicyclo [4.1.0]
hepta-2,4-diene (7), was examined. Refluxing in dioxane
for 132 hours yielded nothing but unidentifiable resin.
26
If 7 had rearranged to a 4H-diazepine via two concerted
1,5-hydrogen shifts, it would have rearranged to the known
26.17 Diazepine 26 was found to be stable under the condi¬
tions used in the attempted rearrangement of 7.

9
From the above results it was concluded that three
phenyls on the cyclopropane ring were necessary before a
diazanorcaradiene will rearrange to a 4H-diazepine. How¬
ever, it was still a mystery as to why systems 6, 7, 21,
and 22 did not rearrange to at least some small extent
if the rearrangement was taking place by way of a hydro¬
gen shift mechanism.
Upon closer examination of the systems which do rearrange
and those which do not, it was noted that in the systems
which rearrange there is a phenyl ring over the azine link¬
age. Thus, 2 is 1,2,5,6-tetrapheny1-endo-7-phenyl-3,4-
diazabicyclo[4.1.0]hepta-2,4-diene as shown in structure 27.
The compound 7 has the requisite phenyl in the 7-position,
but this phenyl is exo to the azine linkage as shown in
structure 23 since, in the absence of steric interaction
from substituents in the 1- and 6-positions, the phenyl
at C-7 prefers the exo position.
0
27
The above observations led
perhaps the rearrangement is of
to the hypothesis that
the Cope ([3,3] sigmatropic)

10
type involving the endo-7-phenyl as illustrated in Scheme
5.
Scheme 5
To test the idea of the Cope mechanism, the synthesis
of 2,5,7,7-tetraphenyl- 3,4 -diazabicyclo[4.1.0]hepta-2,4-
diene (29) was attempted since this system would have the
requisite endo- 7-phenyl but no phenyls in the 1- and 6-
positions. Rearrangement of 29 by the pathway depicted in
Scheme 5 would lead to the diazepine 30.
The NMR spectrum of 30 should show an aromatic multiplet
with the previously described deshielding of the ortho
protons of the phenyl at C-7. The ortho protons of the
phenyl at C-3 probably would not show any deshielding as
the phenyls at C-4 would impose steric restrictions forcing
the C-3 phenyl out of the plane of the azine linkage. The

11
H
30
vinylic protons should appear as an AB-quartet. The mass
spectrum of 30 should also be similar to that for 29 with
loss of benzonitrile as the base peak (see Chapter II).
During their investigation of the diazanorcaradiene 7,
Amiet and Johns4 reported that 7 could be synthesized in
low yield (7%) from trains -1, 2 - dibenzoyl - 3-phenylcyclo-
propane (31) only by heating with hydrazine in ethanol for
long periods of time, whereas the cis isomer of 31 reacted
rapidly and almost quantitatively at room temperature. In
the present investigation it was found that 7 could be
produced in satisfactory yield (55.1%) from 31 at room
temperature if a catalytic amount of sodium hydroxide was
added to the mixture of 31 and hydrazine in ethanol. Pre¬
sumably, the observed increase in yield is due to a rapidly
established base-catalyzed cis-trans equilibration as shown
in Scheme 6.
Ü2ÍW
-h2o
7
Scheme 6

12
In view of the above observation, the synthesis of 29
was attempted by reaction of the known trans-1,2-dibenzoyl-
3,3-diphenylcyclopropane (32)18 with hydrazine in the
presence of sodium hydroxide in ethanol. At room tempera¬
ture in ethanol, 32 and hydrazine in the presence of sodium
hydroxide showed no signs of reaction, i.e. no yellow color
or precipitate. On refluxing, the reaction mixture developed
a yellow coloration but then turned colorless again. The
colorless crystals isolated from the reaction mixture at
this point were not the desired 29, but an isomer C29H22N2
as determined from the mass spectrum and elemental analysis.
In the aromatic region, the NMR spectrum of this iso¬
meric compound 33 showed a multiplet centered at t2.01
accounting for two protons and a multiplet at 2.8 account¬
ing for nineteen protons indicating only one phenyl with
ortho protons deshielded by an azine or otherwise electron-
withdrawing group. The only other feature of the spectrum
was a slightly broadened singlet at t4.31. Mostly on the
basis of the above NMR evidence the compound was identified
as 3,6-diphenyl-4-benzhydrylpyridaz.ine (33).
The phenyl in the 6-position is relatively free to
assume coplanarity with the pyridazine ring, thus account¬
ing for the pair of deshielded ortho protons. However, the
phenyl in the 3-position is sterically crowded by the bulky
benzhydryl group in the 4-position which inhibits coplan-
anty with the pyridazine ring and, thus, all five protons
of the 3-phenyl are at approximately the same chemical

13
shift. The lone pyridazine ring proton is assumed to be
masked by the higher field multiplet. The singlet at x4.31
is accounted for by the benzhydryl proton. The fact that
in the mass spectrum of 33 the parent ion is base peak is
in accord with a pyridazine carrying aromatic substituents.
Due to the development of a transient yellow color
during the formation of 33, it was not clear whether 29 is
initially formed and then converted into 33 under the influ¬
ence of base (Scheme 7) or 32 was transformed via a base-
catalyzed ring-opening reaction into 2-benzhydry1-1,4 -
diphenylbut-cis- 2-ene-l ,4-dione which would then react with
hydrazine to form 33 (Scheme 8).
Scheme 7

14
Scheme 8
When 29 was finally synthesized at a later date, it
was found to be insensitive to refluxing ethanolic sodium
hydroxide in the time interval necessary for the formation
of 33. Thus, it appears that a pathway similar to that in
Scheme 8 is in operation in the formation of 33 from 32.
The failure to obtain 29 by the simple route above
forced the adoption of a more elaborate synthetic scheme.
The scheme chosen was similar to that developed by Maier3
and is outlined below (Scheme 9) for this particular system.

15
Scheme 9
The known 3418 was synthesized in good yield (611)
from diphenyldiazomethane19 and commercial maleic anhydride
simply by mixing the two reactants in benzene. The litera¬
ture method18’20 calls for mixing the two components and
refluxing in benzene.
Presumably due to polymerization, treatment of a ben¬
zene solution of 34 with anhydrous aluminum chloride only
resulted in the formation of yellow, aqueous bicarbonate
soluble resin.
Addition of a benzene solution of 34 to anhydrous
aluminum chloride in benzene yielded 77.7% of a compound
tentatively identified as 3,3-diphenyl-trans-2-benzoylcyclo-
propanecarboxylic acid (37). Although the compound did not
give a correct elemental analysis, it did give a correct
mass spectral molecular weight (342) and, while the compound

16
was fairly insoluble, it gave an NMR spectrum which showed
only aromatic protons and an AB-quartet centered at x6.06.
The approximate coupling constant of 6 Hz for the AB-quartet
suggested the trans assignment for 37.21 When 29 was
subsequently obtained, its AB-quartet for the cyclopropyl
protons showed a coupling constant of 8.0 Hz which is indica¬
tive of a cis configuration.21
While the synthesis of 29 was in progress, a companion
effort was directed towards the synthesis of more compli¬
cated, but just as physically useful systems such as 40 and
43. At first these systems appeared to be more readily
accessible than 29. The proposed synthetic routes are out¬
lined below in Schemes 10 and 11. The requisite 2,3-dibenz-
oylbicyclo[2.2.1]hepta-2,5-diene (38)22 and 1,2-dibenzoylcy-
clohexa-1,4 - diene (41)23 were known and easily obtained on
the multigram scale.
38
39
40
Scheme 10

17
Scheme 11
Unfortunately, both 38 and 41 were very unreactive
towards diphenyldiazomethane. On stirring for 24 days,
38 decolorized a solution of diphenyldiazomethane but
workup of the colorless material caused decomposition to
a purple substance which further decomposed to brown tar.
Refluxing 41 in benzene with a large excess of diphenyl¬
diazomethane gave rise to copious amounts of a material
which is assumed to be benzophenone azine. Presumably the
low reactivity of 38 and 41 towards diphenyldiazomethane is
due to the cis arrangement of the benzoyl groups on the .
double bond in both cases. This factor lias been noted
previously.2 4
In an effort to bypass the critical synthetic inter¬
mediates 35 and 36 of Scheme 9, an attempt was made at the
synthesis of 44 which, it was hoped, would add two moles of
phenyllithium to produce 29.

18
O
o
44
On treatment with hydrazine 3,3-dipheny1-cis-cyclopro-
panedicarboxylic acid18 (45) was found to yield only water-
soluble material which, on addition of mineral acid,
regenerated 45. Presumably the water-soluble material is
the hydrazine salt of the acid rather than the hydrazide or
the desired 44.
Attempted addition of diphenyldiazomethane to maleic
hydrazide25 gave no identifiable products.
On refluxing the anhydride 34 with hydrazine in ethanol
for 60 hours, a new crystalline substance is produced. The
NMR spectrum, mass spectrum, and elemental analysis agreed
with structure 44 but, unfortunately, the spectra also
agreed with structure 46. The infrared, which shows a doub¬
let rather than a singlet in the N-H stretch region, indi¬
cates that structure 46 is probably the better choice.
NH
2
46

19
Cyclic bisamide 44 or its isomer 46 gave no identifiable
products on attempted addition of phenyllithium under a
variety of conditions.
As a last resort, addition of phenylmagnesium bromide
to the anhydride 34 was attempted with success. Equimolar
quantities of the Grignard reagent and 34 produced 35 in
low yield (6.9%) when the reaction was carried out at room
temperature. Slightly better yields and cleaner product
were obtained either by adding the Grignard reagent to 34
in toluene at dry ice temperatures or by use of the diphenyl
cadmium reagent.
Besides giving the correct molecular weight and elementa
analysis, the ketoacid 35 gave the expected NMR spectrum.
In the aromatic region, there is a low-field multiplet cen¬
tered at tl.9 integrating for two protons and a higher-
field multiplet centered at 2.6 integrating for thirteen
protons. The xl.9 multiplet is assumed to be due to the
ortho protons of the benzoyl phenyl. The x2.6 multiplet
accounts for the remaining aromatic protons. The expected
AB-quartet at x6.48 integrates for .two protons. The coup¬
ling constant of 8.0 Hz is that to be expected for cis
protons on a cyclopropyl ring of this sort.21 Ketoacid
35 also shows a carboxylic acid proton as a very broad,
almost undetectable singlet at about x-1.4.
The infrared (KBr pellet) of 35 shows no strong absorb¬
ance for hydroxyl as would be expected for a carboxylic acid
hydroxyl. The carbonyl stretch of 55 is at 1730 cm 1 which

20
is more typical of a lactone than a free carboxylic acid.
The above is in accord with the observation that ketoacids
similar3 to 35 usually exist exclusively in a pseudo acid
form (structure 47) in the solid state.
In solution, ketoacids such as 35 tend to form an equi¬
librium between free acid and psuedo acid.3
35
:0
47
On melting, 35 evolves carbon dioxide to yield some tar
and the known 1,4,4-triphenylbut-3-en-1-one (48). 2 6 The
melting point and infrared carbonyl absorption were in close
agreement with that reported.26
The previously unreported NMR spectrum for 48 fits the
compound well. The aromatic region shows a two-proton mul-
tiplet centered at t2.17 and a thirteen-proton multiplet
centered at 2.7. As with 35 (vide, supra), the two aromatic
multiplets respectively account for the ortho protons of
the phenyl attached to the carbonyl and the remaining aro¬
matic protons. The remaining portion of the spectrum shows
the expected vinylic triplet at t3.59 (J = 7.0 Hz) integrat¬
ing for one proton and the expected methylene doublet at
6.21 (J = 7.0 Hz) integrating for two protons.

21
Stirring a solution of 35 and hydrazine hydrate in
ethanol for 24 hours gave the desired 2,7,7-triphenyl-5 -
keto-3,4-diazabicyclo[4.1.0]hept-2-ene (36) as a white
crystalline precipitate. Even though 36 gave a correct
mass spectral molecular weight (338) , an acceptable ele¬
mental analysis could not be obtained. The analysis
suggested the presence of a-half mole of water of crystal¬
lization. The infrared spectrum showed the expected
carbonyl stretch3 at 1670 cm 1.
Although fairly insoluble, an NMR spectrum of 36 could
be obtained. The amide proton appeared as a broad absorb¬
ance at xl.9. As expected, the ortho protons of the phenyl
ring attached to the carbon-nitrogen double bond appeared
as a distinct multiplet at about x2.0, with the remaining
aromatic protons appearing at higher field (2.40 - 3.16).
The two cyclopropyl protons appeared as the expected AB-
quartet at x6.88 (J^g = 8.0 Hz). The upfield half of the
quartet is split again into a pair of doublets by coupling
with the anúde proton (HN) (JBN Hz> = Hz).

22
The coupling between Hg and finds precedent in the
literature27 and is not unexpected, especially when, upon
examination of a molecular model of 36, it is found that
Hg and fit nicely into the well-known "W" pattern.28
There is no coupling between and as determined from
an HA-100 spectrum.
Addition of phenyl1ithium to 56 proceeded smoothly
producing 29 in moderate yield (47.2%). Diazanorcaradiene
29 analyzed correctly and gave a correct mass spectral
molecular weight (398) in addition to a reasonable frag¬
mentation pattern.
In the aromatic region, the NMR spectrum of 29 dis¬
played a four-proton multiplet centered at rl.8, a six-
proton multiplet centered at 2.5, and two five-proton
singlets at 2.71 and 3.03. Presumably the lower field
nultiplet is due to the ortho protons of the phenyls on
the deshielding azine linkage while the higher field
multiplet again accounts for the remaining protons on the
2- and 4-phenyls. It is assumed that the higher field

23
aromatic singlet is due to the cyclopropyl phenyl over the
slightly shielding region of the azine linkage while the
lower field aromatic singlet is due to the other unshielded
cyclopropyl phenyl. The only other feature of the NMR
spectrum of 29 is a sharp singlet at t6.58 integrating for
two protons. The singlet is due to the now equivalent
cyclopropyl protons.
Chemical evidence for structure 29 was provided by its
acid-catalyzed conversion into pyridazine 33 which had been
previously characterized.
In refluxing xylene over a 24-hour period, 29 gives rise
to a new, colorless, unknown isomer 49 which does not show
the properties usually exhibited by 4H-diazepines even
though it analyzes correctly and gives the correct molecu¬
lar weight of 398.
The mass spectrum of 49 is completely different from
that of 29. The parent ion is base peak rather than the
parent minus benzonitrile ion which is only 3.5% of base
peak. The mass spectrum of 49 is quite featureless except
for peaks at 397 (21%) and 321 (14%).
The NMR spectrum of 49 is also quite featureless dis¬
playing, as illustrated in Figure 1, only N-H at t0.18 and
aromatic multiplets centered at 2.7 and 3.2. The three NMR
signals integrated for one, fifteen, and six protons respec¬
tively. That the signal at t0.18 is due to hydrogen
attached to nitrogen was proved by deuterium exchange with
heavy water which readily destroyed this signal.

Figure 1.
NMR spectrum of unknown 49 in CDC13

3 0 4 0 5.0 PPM ir) 6.0 7.0 8.0 9.0
25
??M .¿i

26
Changing the NMR solvent from deuteriochloroform to
d5-pyridine altered the spectrum drastically as shown in
Figure 2, but gave no new information. Unchanged 49 could
be recovered after dissolution in pyridine.
Infrared and UV spectra gave no further useful informa
tion as to the identity of 49.
It was fairly obvious that 49 was not the desired 4H-
diazepine 30. The possibilities left for 49 were all
C29H22N2 isomers which would show the observed spectro¬
scopic properties of 49 and have a reasonable mechanistic
route for their formation.
The first possibility chosen for 49 was structure 50
which is shown along with a possible mechanism (Scheme 12)
29 £?-•— 0
[1,5]
7
0 0
H
50
Scheme 12

Figure 2. NMR spectrum of unknown 49 in d5-pyridine
4

t'O
oo

29
Structure 50 would fit the spectroscopic data if one
assumes sufficient deshielding of the vinylic and aliphatic
protons for them to appear in the aromatic region of the
NMR. However, 50 is a dihydropyridazine and, on the basis
of previous work,29 should readily oxidize to the fully aro¬
matic pyridazine.
Oxidation of 49 with potassium dichromate in aqueous
acetic acid gave only some tar and a 41.31 recovery of start¬
ing material. Extensive chromatography produced no more
material.
Oxidation of 49 with 1,2-dichloro-5,6-dicyano-1,4-
benzoquinone (DDQ) gave only dark green, difficultly soluble
material which, on chromatography over basic alumina,
yielded 87% recovered starting material which showed no
peak in the mass spectrum for 49 minus two hydrogens.
At this point it became fairly obvious that 49 does
not possess a dihydropyridazine structure or any other
structure which could be easily oxidized.
The next structure considered was structure 51 shown
below in Scheme 13.

30
29
51
Scheme 13
There is no chemical evidence for or against 51. Once
again one must assume sufficient deshielding of the vinylic
proton to place it in the aromatic region in the NMR.
Other spectroscopic data do not really speak for or against
structure 51.
In the series 52 , 53 , and 54 , 3 0 the proton on the
pyrazole nitrogen appears in the NMR spectrum at 613.3,
10, and 7.22 as a broad singlet whose position is con¬
centration dependent. The position of the N-H proton
of 49 is at about 69.8.

31
55 56
For the two compounds 55 and 56, 31 the UV spectra
respectively consist of X = 256 nm (e = 33100) and
* 1 max v
X = 250 nm (e = 15100). The UV maximum of 49 is at
237 nm (e = 28400) with inflections at 255 and 298 nm.
Possibly, steric interactions among the two phenyls and the
phenylstyryl group of 51 would cause a hypsochromic shift.
Since 49 was not the desired 4H-diazepine 30 and since
49 could not be identified, other means to determine the
mechanism of the diazanorcaradiene-diazepine isomerization
were sought.
The most direct and reasonable approach to this question
involved resorting to a suitably labeled system which was
known to rearrange and whose rearrangment product could be

32
identified by x-ray methods. The diazanorcaradiene 57 was
chosen as an appropriate system for study.
0
C6H4 -]D-Br
6HtP-R
H
C 6H 4 -Br
Scheme 14
As outlined in Scheme 14, the 4H-diazepine 59 would
result if 57 underwent electrocyclic ring opening to the
corresponding 5H-diazepine followed by two consecutive supra-
facial concerted 1,5-hydrogen shifts (path B) as illustrated
previously in Scheme 4 for diazanorcaradiene 2.
The diazepine 58 could arise in several ways. First,
58 could result from the Cope-type mechanism previously
illustrated in Scheme 5 for the diazanorcaradiene 2. Also,
58 can arise by a Berson-Willzott Bones rearrangement3 2
whereby C-7 of structure 57 "walks" around the six-membered
ring to produce a 2,3-diazabicyclo[4.1.0]hepta-2,4-diene 60
which is unstable and opens up to the 4H-diazepine as
depicted in Scheme 15.

33
H
CeHu -p_-R
C6H4-p_-Br 58
60
Scheme 15
The first step of Scheme 15 is concerted if the movement
of C-7 occurs with retention at C-7 as shown in structure 61
since this is a [1,5] sigmatropic change.12
INI
0
C6H4 -p_-Br
61
Other nonconcerted mechanisms similar to the Bones
rearrangement may also be envisioned. One such mechanism
involving a dipolar (or diradical) intermediate is given in
Scheme 16.
H C 6 H 4 _p__ R
0 \t>
0
57 -fe— p-Br-C6H4 “—^ Cs^-EL-Br —fe— 60 —58
N-N'
Scheme 16

34
For the synthesis of 57, the problem reduces to the
preparation of triphenylcyclopropene with only the 3-phenyl
substituted with a group which can be observed by x-ray,
e.g. halogen, small aliphatic groups, etc. The above means
that no synthesis in which all three cyclopropeny1 carbons
become equivalent chemically is satisfactory. Thus, synthe¬
ses of sym-triphenylcyclopropene such as that developed by
Battiste are unsatisfactory.29
Recently, it was demonstrated by Longone and Stehouwer13
that hydride ion can be added to the known diphenylcyclopro-
penyl cation to give exclusively 1,2-diphenylcyclopropene in
high yield. Thus, it was reasoned that an appropriately sub¬
stituted phenylmagnesium bromide could be added to the same
cation to give the desired substituted triphenylcyclopropene.
As a first attempt, ¡5-chlorophenylmagnesium bromide was
added to diphenylcyclopropeny1 perchlorate to produce, after
chromatography, a colorless solid whose NMR spectrum showed
only a singlet at x6.79 (sym-triphenylcyclopropene - x6.833)
and an aromatic multiplet. However, the aromatic multiplet
integrated much too high and the compound tended to discolor
even in the absence of air and light. It was assumed that
the desired 3-(4-chlorophenyl)-1,2-diphenylcyclopropene (62)
had been obtained, but it could not be purified.
The same reaction as above was repeated with j^-tolyl-
magnesium bromide. Good, clean product was obtained only
if the cation was added to the solution of the Grignard
reagent slowly. Rapid addition caused production of resinous

35
conglomerations which discolored the final product-as in
the case of cyclopropene 62.
The 3-(4-methylpheny1)- 1,2-diphenylcyclopropene (63)
characterized as expected. Besides giving a correct ele¬
mental analysis, 63 displayed the right mass spectral molecu¬
lar weight (282). The NMR spectrum of 63 showed the expected
aromatic multiplet centered at x2.64 integrating for fourteen
protons and two singlets at 6.83 and 7.76 integrating for
one and three protons respectively. The x6.83 signal is
typical for a triphenylcyclopropene cyclopropeny1 proton as
was mentioned above. The x7.76 signal is, of course, due to
the methyl group.
If the Grignard reagent had added so as to give the
isomeric cyclopropene 64, a one-proton singlet at ca.
x2.634 rather than 6.83 would have been anticipated.
The infrared spectrum of 63 displayed the typical
cyclopropene carbon-carbon double bond stretch at 1830 cm 1
(sym-triphenylcyclopropene - 1820 cm 1 34). The UV spectrum
of 63 was also very useful as it showed the maxima charac¬
teristic of a sym-triphenylcyclopropene at 332.5 nm

36
(e = 23000), 315 nm (e = 28000), 305 run (s, z = 22000),
302 nm (infl.)» and 228 nm (e = 32000). For comparison,
the UV spectrum of sym-triphenylcyclopropene itself in
ethanol consists of maxima at 330 nm (e = 24200), 313 nm
(e = 29000), and 228 nm (e = 30600).3 5
Cycloaddition of 63 with 3,6-bis(4-bromophenyl)-
1,2,4,5-tetrazine (65)6 produced the expected 2,5-bis-
(4-bromopheny1)- 7 -(4-methylphenyl)-1,6-diphenyl -3,4-
diazabicycio[4.1.0]hepta-2,4-diene (66). The diazanorcara-
diene analyzed correctly and gave a correct mass spectral
molecular weight (644) . The diazanorcaradiene also gave a
reasonable mass spectral fragmentation pattern which is
discussed in Chapter II.
The NMR spectrum of 66 simply consisted of a twenty-
two-proton aromatic multiplet centered at t2.93, a one-
proton singlet at 5.03 for the cyclopropyl proton, and a
three-proton singlet at 7.83 for the methyl group. For
comparison purposes, the cyclopropyl proton of the analogous
diazanorcaradiene 2 appears at t4.98.2
The thermal rearrangement of 66 in refluxing xylene
proceeded more rapidly than was anticipated and, as a
result, a much lower yield of the 4H-diazepine was obtained
than was expected due to decomposition. Presumably, the
methyl group of the substituted phenyl aids in the decompo¬
sition of the 4H-diazepine 67 to the corresponding pyrroles
and benzonitriles. Diazepine 67 gave the anticipated analyti¬
cal and spectral data as recorded in the Experimental Sec¬
tion (Chapter V) .

37
Table II
Bond Distances and Their Estimated Standard Deviations
Diazepine 67
Atoms
Distance (A)
e. s . d.
Br (1)
C(E4)
1.91
0.01
C(E4)
C(E5)
1.38
0.01
C(E5)
C(E6)
1.40
0.01
C(E6)
C (El)
1.37
0.01
C (El)
C(E2)
1.39
0.01
C(E2)
C(E3)
1.38
0.01
C(E3)
C(E4)
1.37
0.01
C (El)
C (5)
1.50
0.01
C (5)
N (1)
1.31
0.01
N (1)
N (2)
1.39
0.01
N (2)
C(l)
1.29
0.01
C(l)
C(A1)
1.47
0.01
C(A1)
C(A2)
1.40
0.01
C(A2)
C (A3)
1.38
0.01
C (A3)
C(A4)
1.37
0.01
C(A4)
Br (2)
1.91
0.01
C(A4)
C (A5)
1.36
0.01
C(A5)
C(A6)
1.41
0.01
C(A6)
C(A1)
1.39
0.01
C(l)
C (2)
1.52
0.01
C (2)
C(B1)
1.53
0.01
C(B1)
C(B2)
1.39
0.01
C(B2)
C(B3)
1.43
0.01
C(B3)
C (B4)
1.37
0.01
C(B4)
C (Me)
1.54
0.01
C(B4)
C(B5)
1.41
0.01
C(B5)
C(B6)
1.37
0.01
C(B6)
C(B1)
1.40
0.01
C (2)
C (3)
1.52
0.01
C (3)
C(C1)
1.50
0.01
C(C1)
C(C2)
1.40
0.01
C(C2)
C(C3)
1.41
0.01
C(C3)
C(C4)
1.38
0.01
C(C4)
C (C 5 )
1.36
0.01
C(C5)
C(C6)
1.42
0.01
C(C6)
C(C1)
1.38
0.01
C (3)
C (4)
1.34
0.01
C (4)
C(D1)
1.48
0.01
C(D1)
C(D2)
1.42.
0.01
C(D2)
C(D5)
1.40
0.01
C(D5)
C(D4)
1.40
0.01
C(D4)
C(D5)
1.43
0.01
C(D5)
C(D6)
1.40
0.01
C(D6)
C(D1)
1.39
0.01
C (4)
C ( 5)
1.48
0.01
£
estimated
standard deviation.
in

C(4) C C3)
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3

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n-p‘f)tdwwwwbdw2wwwww>>>>>/--1 k> tni—1■ tn tm m tm tn tn tn tn tn tn tri
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K)K>4—‘4—‘Kit—‘fOfOl—‘I—‘COI—'Nil—>!—‘ON44—‘4—‘Nil—‘4—‘COI—‘I—‘t'Jt'Ot'JI—‘CObOl—*tNJI—1t'J4-‘t'OI-'t'J4-‘t'OI—‘4-41—>
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OHOOOCO(00-P>v]HNOHONlC»(OK)(00'ONMO'OWOl010W4í>W'JvJO'0\vlUDNCOWMUiOO
D-*
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OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO (/)
0\0'^O0'0'v]*sjsjNj^vj^Q\0\Ln0>0'0'sslN]0\^J0'v]'sj0'0'0'(/i(/iQ\0N0N0'C''s]Nj0\0'Q'^JCnLn Q-.
V CM
oo
Bond Angles and Their Estimated Standard Deviations in
Diazepine 67

39
^ Table TIT
(continued)
Atoms
Angle (deg.)
e.s.d.
C(C1)
C(CZ)
C ( C 3 )
120.2
0.7
C(C2)
C(C3)
C(C4)
119.3
0.8
C(C3)
C(C4)
C(C5)
121.0
0.8
C(C4)
C(C5)
C(C6)
120.5
0.7
C(C5)
C(C6)
C(C1)
119.1
0.7
C(C6)
C(C1)
C(C2)
119.8
0.6
C (3)
C(C1)
C (C 2)
120.3
0.6
C (3)
C(C1)
C(C6)
119.9
0.6
C (3)
C (4)
C (5)
120.7
0.6
C (5)
C (4)
C (Dl)
114.0
0.5
C (3)
C (4)
C (Dl)
125.3
0.6
C (4)
C (Dl)
C(D2)
121.5
0.6
C (4)
C(D1)
C(D6)
120.7
0.6
C(D1)
C(D2)
C(D5)
121.5
0.7
C(D2)
C (D5)
C(D4)
118.8
0.7
C(D3)
C(D4)
C(D5)
121.3
0.8
C(D4)
C(D5)
C(D6)
117.8
0.7
C(D5)
C(D6)
C (Dl)
122.9
0.7
C(D6)
C (Dl)
C(D2)
117.7
0.6
estimated standard deviation.
The x-ray analysis of 67, which is described in the
Experimental Section, revealed that the rearrangement of 66
follows path A given in Scheme 14 above. An ORTEP-generated
model of 67 is shown in Figure 3. A table of bond lengths
is given in Table 2 and a table of bond angles is given in
Table 3.
At this point, all that can be said in the absence of
further data is that diazanorcaradienes containing one phenyl
on each cyclopropyl position rearrange to 4H-diazepines by
one of the mechanisms discussed above involving movement of
an entire carbon rather than hydrogen shifts. Once again a
system whose rearrangement appeared to be simple on the
surface turned out to be quite complex on closer examination.

Figure 3. ORTEP-generated diagram of 3,7-bis(4-bromopheny1)-4-(4-methylpheny1)-5,6-
diphenyl-4H-1,2-diazepine (67)

■p»

42
In connection with the further reaction of the diazepine
systems to produce pyrroles and benzonitriles, some ground¬
work on the mechanism of this fragmentation was carried out.
As was mentioned at the beginning of the chapter,
diazepines which result from the high temperature reaction
of sym-triphenylcyclopropene and tetrazines substituted
with groups other than unsubstituted phenyl decompose at
high temperatures into mixtures of pyrroles and benzoni¬
triles as shown in Scheme 2. Thus, in an as yet unspeci¬
fied manner (see Chapter II), not only the groups originally
on the tetrazine ring but also the 1- and 2-positions of the
cyclopropene become involved in the diazepine decomposition.
It was also of interest to ascertain whether or not the
4-phenyl of the diazepine also becomes involved in the
decomposition. Toward this end 1,2,5,6-tetraphenyl-7-
(4-methylpheny1)-3,4-diazabicyclo[4.1.0]hepta-2,4-diene
(68) was prepared. Diazanorcaradiene 68 showed the
expected properties which, as demonstrated in the Experi¬
mental Section, are quite similar to those for 66.
When 68 was decomposed in the injector port of an
analytical gas chromatograph with the column at such a
temperature that benzonitrile and £-tolunitrile are
separable, p-tolunitrile was detected and identified
solely on the basis of its relative retention time. The
results are summarized in Scheme 17. It should be stressed
that these results on the decomposition of 68, while excit¬
ing, are still only tentative.

43
pyrroles
Scheme 17

CHAPTER II
MASS SPECTRAL CORRELATIONS
Introduction
The frequent observation that mass spectral and thermal
behavior closely parallel each other for certain compounds
is one of the more intriguing aspects of mass spectrometry.36
It will be the main purpose of this chapter to demonstrate
briefly that the thermolytic reactions of Scheme 2 in
Chapter I are correlated by the mass spectral behavior of
the diazanorcaradienes which rearrange to 4H-diazepines and
to attempt to enlighten the mechanism of the 4H-diazepine
decomposition.
As shown in Scheme 2, the thermolysis of diazepines
such as 70 yields two pyrroles, benzonitrile, and acetoni¬
trile. In the absence of further data, such conversions
N—N
3
70
may be rationalized generally as in Scheme 18.
44

45
r = co2ch3
" C113
= E-H3C-c6h4
Scheme 18

46
Results and Discussion
The most obvious mass spectral feature of the diaza-
norcaradienes which undergo thermal rearrangement is their
marked similarity to the mass spectra of their respective
4H-diazepines. As examples, the mass spectra of diazanor-
caradienes 2 and 66 are plotted in Figures 4 and 6. The
mass spectra of the corresponding 4H-diazepines 3 and 67
are given in Figures 5 and 7 respectively. Except for the
intensities of some peaks, the mass spectra of 2 and 3 and
of 66 and 67 are almost superimposable.
From the above one can arrive at one of three conclu¬
sions - the parent ion of the diazanorcaradiene rapidly
rearranges to the parent ion of the respective 4H-diaze-
pine, the parent ion of the 4H-diazepine isomerizes to the
parent ion of its precursor diazanorcaradiene, or both the
diazanorcaradiene and 4H-diazepine parent ions convert into
a common intermediate which gives rise to the observed
fragmentation pattern.
The mass spectra of all diazanorcaradienes examined,
whether they have been observed to rearrange or not, show
several similar fragmentations as illustrated in Scheme 19.
Table IV gives the intensities for the observed fragmenta¬
tions of the diazanorcaradienes studied. In those diaza-
norcaradienes not bearing carbomethoxy or methyl groups in
the 2- and 4-positions, loss of benzonitrile or substituted
benzonitrile is base peak. All diazanorcaradienes, regard¬
less of substitution or ability to rearrange, show a fairly

47
intense (2 to 99% of base peak) peak for parent ion (mT)
minus nitrogen. Corresponding to this loss of nitrogen
11
denotes metastable for this fragmentation
Scheme 19
peak is a flat-top metastable peak which indicates that the
nitrogen is lost from the parent ion with the release of a
small amount of kinetic energy.37
From the above observation that the mass spectra of 4H-
diazepines resemble the general diazanorcaradiene mass
spectrum, it is tempting to assume that in the mass spectro¬
meter 4H-diazepines derived from diazanorcaradienes revert
to their precusor diazanorcaradienes or an ion common to

Table IV
Relative Intensities for Important Mass Spectral Fragmentations of Diazanorcaradienes1
Diazanorcaradiene
-H
-n2
-R'CN
-RCN
2
R=0, R'=0, R"=0b
16%C
99%d
100%
e
71
R=£-I-CeH4, R’=0, R"=0b
7%
41%
4 2%£
100%
72
R=CH3, R'=0, R"=0b,g
2 8 %h
39%
4%
100%
10
R=C02CH3, R'=0, R"=0b
11%
51%
33%
66%h’1
22
R=C02CH3, R’=0, R"=H^
16%
2%
5%
20%k
21
R=0, R'=0, R"=H^
8%
37%
100%
_e
7
R=0, R'=H, R"=0^jl
9%
20%
100%
4%
68
R=0, R'=0, R"=p-H3C-C6H4S
5%
33%
100%
e
^responding 4H-diazepine will be
the same
to -3% unless
otherwise
noted.
See Table V below for thermal data on this compound or a related compound. Diazepine
is 11%. Diazepine is 66%.
4H-diazepine not available.
'Same as loss of R'CN. Diazepine is 29%.
gCorresponding
1Base peak
See text for a discussion of this intensity,
m/e 291. ^Does not rearrange to a 4H-diazepine. kBase peak m/e 346 (parent ion).
In
the isomeric diazepine
100%.
26
1 7
the listed fragmentations are respectively 13%, 5%, , and

49
both. This would lend some credence to the first step of
Scheme 18. However, the mass spectra of diazepine 26 and
diazanorcaradiene 7 are also quite similar even though, as
demonstrated in Chapter I, thermally 7 does not isomerize
to 26. It has also been shown that apparently 26 does not
decompose into pyrroles and benzonitrile on thermolysis.38
Thus, in the absence of further information, all that can be
said about the diaza species which give rise to pyrroles on
thermal decomposition of 4H-diazepines derived from diaza-
norcaradienes is that the mechanism of Scheme 18 or
something similar is not precluded by mass spectral
observations.
Although the mass spectra of rearrangeable diazanorcara-
dienes and, of course, the corresponding 4H-diazepines give
no real information on the mechanism of diazepine decomposi¬
tion to pyrroles, for the most part the mass spectra do
follow the thermal decomposition process quite closely.
The thermal decomposition data for the four diazepines
that have been studied6 are tabulated in Table V. The mass
spectra of the four diazepines or closely related compounds
are given in Table IV.
All diazepines formed from the rearrangement of diazanor-
caradienes show intense mass spectral peaks for pyrroles
formed by electron-impact-induced decomposition of mT. At
least as far as low-resolution mass is concerned, the
pyrroles formed in the mass spectrometer correspond to those
formed by the thermal process of Scheme 18. The base peak

50
in the mass spectrometer is always mT minus benzonitrile or
substituted benzonitrile except when the azine linkage is
substituted with carbomethoxy or methyl groups. It will be
noted that thermally 3,7-bis (jd-tolyl) - 4,5,6-triphenyl - 4H-
1,2-diazepine (73), which is related to 71 decomposes into
an approximately equimolar mixture of pyrroles resulting
from loss of benzonitrile and j>-tolunitrile. In the mass
spectrometer diazepine 71 loses approximately three times as
much £-iodobenzonitrile as benzonitrile. The above facts
may be rationalized by considering that thermally 73 (or 71)
can lose nitriles RCN and R'CN only from bicyclic forms
similar to 8 (see Preface and Scheme 18),whereas in the
mass spectrometer the diazepine can lose RCN from the open
form or the bicyclic form but can lose R'CN only by isomeriz-
ing through the bicyclic form. It will be again noted that
the diazepine 26 does not result from the thermal isomeriza¬
tion of a diazanorcaradiene nor has it been possible to
thermally decompose it into benzonitrile and pyrrole, but
yet, in the mass spectrometer, loss of benzonitrile is base
peak.

51
Table V
Thermal Decomposition Data for Some 4H-Diazepines
6
Diazepine
-0CN
-RCNa
3
11
73
70
b
1001
>98%
49%
67%
c
d
O
R is the group originally on the 3- and 7-positions
of unidentified liquid (not benzonitrile or n-tolu-
nitrile) was detected in this decomposition.
The mass spectra of diazepine 11 and its related
diazanorcaradiene 10 (Figure 8) show 71% and 65% peaks for,
respectively, loss of methyl cyanoformate and loss of
benzonitrile from the parent ion. The base peak corres¬
ponds to what may be formally described as the decarboxyla¬
tion product of the pyrrole formed by loss of benzonitrile
from the parent ion as depicted in Scheme 20. Thermally,
diazepine 11 converts exclusively into dimethyl 3,4-
diphenylpyrrole-2,5 - dicarboxyl ate, which is the end result
of loss of benzonitrile from 11.6 Again the loss of methyl
cyanoformate from the parent ion of 11 may be due to
fragmentation from the open diazepine form as opposed to

52
E
CH
3
m/e 438
m/e 335
m/e 291
E = C02CH3
Scheme 20
fragmentation from a bicyclic form and thus have no thermal
analogy.
In the mass spectrum of the diazanorcaradiene related
to 70 (72), loss of acetonitrile from the parent ion is base
peak but loss of benzonitrile from the parent ion gives only
a 3% peak! Thermally the diazanorcaradiene 72 converts into
70 only with difficulty relative to cases where the diaza¬
norcaradiene azine linkage is substituted with phenyls or
carbomethoxy groups. Also with difficulty, 70 thermally
converts into a 2.17:1 molar mixture of, respectively,
2,5-dimethyl-5,4-diphenylpyrrole and 1-methy1-2,3,4-tri-
phenylpyrrole.6 Thus, thermally, loss of benzonitrile is
the predominant pathway. The combination of the loss of
acetonitrile from the unrearranged form of the diazanor¬
caradiene 72 in the mass spectrometer and the difficulty
with which the diazanorcaradiene rearranges to 70 may be
used to rationalize the unusually low abundance of the loss
of benzonitrile from the parent ion in the mass spectrum

53
of the diazanorcaradiene 72. At the time of this writing
no mass spectrum of 70 was available.
As a further complication to the diazepine decomposi¬
tion problem, it was shown tentatively in Chapter I that,
on thermolysis, diazanorcaradiene 68 presumably reacting
via diazepine 69 yields tolunitrile in addition to the
expected benzonitrile.
The mass spectrum of 68 shows a peak for the loss of
tolunitrile from the parent ion as depicted in Figure 9.
The loss of tolunitrile from the parent ion is supported by
a metastable peak but, unfortunately, the metastable can
also be accounted for by loss of methyl from the parent
minus benzonitrile ion. A similar problem arises in the
interpretation of the mass spectrum of diazanorcaradiene
66 and its related diazepine 67 (Figures 6 and 7).
In closing this chapter it will be noted that the
mass spectra of all diazanorcaradienes and diazepines
examined show a P-1 peak of 5-28% intensity (see Table IV).
In all cases except when the azine linkage is substituted
with methyl groups the P-1 intensity is only 5-16%. It is
assumed that the hydrogen lost is the one at C-7 in
diazanorcaradienes and C-4 in diazepines except when the
azine linkage is substituted with methyl groups, which opens
the possibility of loss of hydrogen from one of the methyl
groups to form an ion such as 74.

54
Although some of the driving force for loss of a
hydrogen radical from the parent ion is conversion from the
odd-electron M? to the even electron P-1 ion, perhaps
another driving force may be formation of the aromatic
diazatropylium cation 75. It is noteworthy that in the
mass spectrum of cycloheptatriene, which is known to
easily convert into the aromatic tropylium cation, base
peak is loss of hydrogen radical.39 The diazatropylium
problem will be discussed more fully in Chapter IV.
R”

Figure 4.
Mass spectrum of 1,2,5,6,7-pentapheny1-3,4-diazabicyclo[4.1.0] hepta-
2,4-diene (2)

Ease-Peak
230 210 150 170 150 130 110 90 70 50 30
Mass
Ln
ON

Base Peak
Vi
Fig. 4 continued

Base Peak
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Fig. 4 continued

Figure 5. Mass spectrum of 2,5-bis(4-bromopheny1)- 7-(4-methylpheny1)-1
3,4-diazabicyclo[4.1.0]hepta-2,4-diene (66)
, 6 -diphenyl -

Base Peak
Mass
ON
o

Peak
Fig. 5 continued
61

Peak
Fig. 5 continued

660 640
Mass
cn
Fig. 5 continued

Figure 6.
Mass spectrum of 3,4,5,6,7-pentapheny1-4H-1,2-diazepine (3)

Base Peak

430 410 390 370 350 • 330 310 290 270 250 230
Mass
Fig. 6 continued

Fig
6 continued

Figure 7. Mass spectrum of 3,7-bis(4-bromopheny1)-4-(4-methylphenyl)-5,6-dipheny1-
4H-1,2-diazepine (67)

Base Peak
ON
SP

Base Peak
Of'
o
Fig. 7 continued

Base Peak
Mass
Fig. 7 continued

660 640
ro
Fig
7 continued
Maas

Figure 8. Mass spectrum of dimethyl 1,6,7-tripheny1 - 3,4-diazabicyclo[4.1.0]hepta-
2,4-diene-2,5-dicarboxylate (10)

Base Peak
H3CO
C02CH3
Mass

Ease Peak
Fig. 8 continued

Figure 9. Mass spectrum of 7-(4-methylphenyl)-l,2,5,6-tetraphenyl-3,4-diazabicyclo-
[4.1.0]hepta-2,4-diene (68)

Base Peak
230 210 190 170 150 130 110 90 70 50 30
Mass
<3

Ease Peak
Fig. 9 continued

Base Teak
Fig •
9 continued

CHAPTER III
CYCLOPROPYL CONJUGATION IN HETEROAROMATIC SYSTEMS
Cyclopropyl Conjugation
The phenomenon of cyclopropyl conjugation is quite well
known40 and has been extensively investigated in both 'the
ground state and excited state of many molecules.
Closs and Klinger41 observed that with decreasing
temperature the ortho protons in cyclopropylbenzenes show
increased shielding. The increased shielding was attributed
to increased population of the bisected, electronically
favorable conformation 76.
Electron diffraction42 and infrared spectroscopy43
also have been employed to detect cyclopropyl conjugation
in unsaturated molecules which are in their ground state.
Kosower and Ito44 found that the excited states of
ketones are stabilized by the presence of a cyclopropyl
ring alpha to the carbonyl carbon if the geometry is correct.
In ketone 77 the geometry is correct for cyclopropyl
80

81
conjugation as the cyclopropyl ring is in the bisected
configuration. The geometry is far from ideal in ketone
78. Interaction in the excited state was found to lower
the excited state of 77 by 7-8 kcal/mole relative to the
excited state of 78.
As a general rule, it has been found that, in the
absence of geometric factors, weak cyclopropyl conjugation
is a consequence of poor electron-withdrawing ability of
the unsaturated group to which the cyclopropane ring is
attached.45 In other words, the greater the electron
demand of the molecule to which the cyclopropane ring is
attached, the greater will be the conjugation of the cyclo¬
propane ring with that molecule. Also, it has been shown
that the extent of cyclopropyl conjugation is a function
of geometry only if the group interacting with the cyclo¬
propane ring is sufficiently electron-withdrawing.45
The compounds to be investigated, 3,6 - dicyclopropyl-
1,2,4,5-tetrazine (79) and 3,6-dicyclopropylpyridazine
(80) , are both similar to monocyclopropylbenzene studied
by Closs and Klinger41
in that the cyclopropyl rings are

82
both bonded to an aromatic six-membered ring. There are
definite interesting differences though.
Tetrazine 79 contains four nitrogens in the aromatic
ring which, accordingly, should enhance cyclopropyl conjuga¬
tion with the tetrazine ring due to the great electron-
withdrawing power of the tetrazine ring. Also, unlike
cyclopropylbenzene, the tetrazine ring of 79 carries no
hydrogens and, thus, there are negligible steric factors.
The only complication is that, assuming the dicyclopropyl-
tetrazine is completely in the bisected form, two conforma¬
tions are possible which may complicate the NMR spectrum
of 79. The top view of the hypothetically possible syn and
anti conformations is illustrated below as structures 81 and
82 respectively.
H H H
The pyridazine 80 should exhibit cyclopropyl conjuga¬
tion similar to that of tetrazine 79 but reduced somewhat
due to replacement of two nitrogens by less electron-
withdrawing C-H groups i.e. the conjugation in 80 should be
intermediate between that of cyclopropylbenzene and
tetrazine 79. Also, in the case of 80, steric effects again

83
are operative as in cyclopropylbenzene since the pyridazine
ring has a hydrogen in both the 4- and 5-positions. Assum¬
ing the bisected form for 80 the syn rotamer 83 should be
favored over the syn rotamer with both cyclopropyl methylene
functions interacting with the hydrogens of the pyridazine
ring or either of the trans rotamers.
H
H
H
H
83
Synthesis
The synthesis developed by Abdel-Rahman eit al. 10 is
only one of the many synthetic schemes known for the forma¬
tion of dihydrotetrazines which can be oxidized to their
respective £-tetrazines.46 ’47 The synthesis is quite simple
in that it involves merely refluxing a mixture of hydrazine
hydrate, a nitrile, flowers of sulfur, and ethanol for a
period of one to three hours. As an example, use of benzoni-
trile in the Abdel-Rahman synthesis yields 851 dihydro-3,6-
dipheny1-1,2,4,5-tetrazine. Aromatic nitriles generally
produce dihydrodiaryltetrazines in high yield, whereas alkyl
nitriles give only low yields of the respective dihydro¬
dial kyltetrazines.

84
Besides being simple, the Abdel-Rahman synthesis
represents a route to dihydrotetrazines under non-acidic,
non-forcing reaction conditions. Thus, the synthesis is
ideal for preparation of the intriguing 3,6-dicyclopropyl-
1,2,4,5-tetrazine (79) which can be converted into the
equally interesting 3,6-dicyclopropylpyridazine (80) by
kno\'m routes.1
Of itself the Abdel-Rahman synthesis presents an
interesting mechanistic problem. While synthesizing large
quantities of 3,6-dipheny1 -1,2,4,5-tetrazine (1), about a
2.51 isolated yield of the well-known 2,5-diphenyl-1,3,4 -
thiadiazole (84)48 was obtained as a side product in this
work.
No mention of 84 was made by Abdel-Rahman. The only
reported work towards enlightening the mechanism of the
dihydrotetrazine forming reaction was to ascertain that
phenylthiohydrazide, under the reaction conditions, does
not afford dihydrodiphenyltetrazine. Abdel-Rahman found that
under the reaction conditions employed phenylthiohydrazide
reacts to form, not dihydrodiphenyltetrazine, but rather
"something else."10 What the "something else" is was not

85
determined. No spectral or chemical data on the "-something
else" were given.
The mechanistic possibilities for the formation of 84
are quite large and, as yet, uninvestigated. One possible
mechanism involving phenylthiohydrazide is illustrated in
Scheme 21. The freedom of assuming that phenylthiohydrazide
can be formed under the reaction conditions has been taken.
Phenylthiohydrazide is known to react with phenylimidate
ethyl ester hydrochloride in refluxing ethanol49 and with
benzoyl chloride in N-methylpyrrolidinone50 to form 84.
S
//
//
0-C 0-C
NHNH.
NHNH,
H-shift
S
II
0-C
: SH
'<
^ / ^0
NHNH-, v
NHNH.
H - s h i f t
1
84
N2H4
H - s h i f t
/ \ /NHNH9
0-C C
11 7 0
N-NH v
H~S
2 -
,H- shift
HS -S' .NHNH,
c z
\ / V
N-NH
\ / \
0-C
'0
Scheme 21
Using the above-described method of Abdel-Rahman, the
desired 3,6-dicyclopropy1-1,2,4,5-tetrazine (79) was syn¬
thesized in low yield (5.7% by glpc) . The crystalline 79
displayed the expected chemical and spectral properties
given in Chapter V.
At ambient temperatures, the NMR spectrum of 79 in
deuteriochloroform consisted of two multiplets centered

86
at t7.47 and 8.73 integrating for two and eight protons
respectively as illustrated in Figure 10. Since the chemi¬
cal shift and coupling constant data could not be determined
by casual inspection, the data were obtained by computer
analysis by King51 who used the LAOCOON II program modified
for magnetic equivalence (LAMP II). The chemical shift
data are reproduced in Table VI along with the data for
3,6-dicyclopropylpyridazine (80). The coupling constant
data for 79, 80, and the two known cyclopropyl systems, 8552
and 86,53 are given in Table VII. It will be noted that, as
expected, the coupling found in systems 79 and 80 is quite
similar to that found in the three known systems given in
Table VII. The numbering system of structure 87 is used to
identify the cyclopropyl protons. Recognizing that 79 and
H(l)
H(5)
H(3)
87
80 can exist in different rotameric forms was not necessary
for the computer analysis of 79 or 80.
As a model compound for 79, the known 3,6-di-iso-propyl -
1,2,4,5- tetrazine (88)54 was synthesized by the method of
Scheme 22 . 5 5 The spectral properties for 88, which are

87
Ethanol
HC1
N2H4
2. NaN02, H
88
Scheme 22
given in Chapter V, agreed with those in the literature.55
The previously unknown 3,6-dicyclopropylpyridazine
(80) and its model compound 3,6-di-iso-propylpyridazine (89)
were both easily synthesized by reaction of respectively,
79 and 88 with norbornadiene.1 Both crystalline, colorless
compounds displayed the expected spectral properties.
In the aromatic region-, the NMR spectrum of 89 dis¬
played the expected sharp two-proton singlet at x2.59 for
the pyridazine protons. The iso-propyl groups manifested
themselves by the expected septuplet at t6.75 (J = 7.0 Hz)
which integrates for two protons and doublet at 8.65 (J =
7.0 Hz) which integrates for twelve protons. The coupling
constants for 89 are the same as in the known tetrazine 88.
As was anticipated, the iso-propyl methine protons of 89
appeared at higher field than the corresponding protons of
tetrazine 88 (vide infra and Table VIII).
The ambient temperature NMR spectrum of 3,6-dicyclo-
propylpyridazine (80) in deuteriochloroform is given in
Figure 15. The spectrum displays the anticipated two-proton
singlet at t2.92 and, two- and eight-proton multiplets
centered at 8.05 and 9.0 respectively.

88
Table VI
Chemical Shift Data for Tetrazine 79 and Pyridazine 80
Compound
Nucleus
Shifta
Standard
Deviation (Hz)
79
HOI).
-147.35
0.02
H(2,4)
-73.23
0.02
H(3,5)
-76.80
0.02
80
H (1)
-116.99
0.01
H(2,4)
-56.76
0.01
H(3,5)
-63.77
0.01
In Hz downfield from TMS as internal standard using carbon
disulfide as a solvent.
85

89
Table VII
Magnetic Coupling
Data for 79, 80,
85 and 86
Coupling
Standard
Compound
Nuclei
Constant (Hz)
Deviation (Hz)
79
1-2,
1-4
8.30
0.03
1-3,
1-5
4.86
0.03
2-3,
4-5
-4.1
0.2
2-4
9.1
0.6
2-5 ,
3-4
6.8
0.2
3-5
9.7
0.6
80
1-2,
1-4
8.25
0.01
1-3,
1-5
4.83
0.01
2-3,
4-5
-3.95
0.02
2-4
9.2
0.1
2-5,
3-4
6.48
0.02
3-5
9.4
0.1
85s2
1-2,
1-4
8.16
a
1-3,
1-5
4.89
—
2-3,
4-5
-4.49
—
2-4
9.02
—
2-5 ,
3-4
6.22
—
3-5
86a5 3
1-2,
1-4
8.40
a
1-3,
1-5
5.05
—
2-3,
4-5
-4.48
—
2-4
9.31
—
2-5 ,
3-4
6.31
—
3-5
9.36
—
86b5 3
1-2,
1-4
8.25
a
1-3,
1-5
4.80
—
2-3 ,
4-5
-4.88
—
2-4
9.05
—
2-5 ,
3-4
6.89
—
3-5
9.78
—
No standard deviation given.

90
Dicyclopropyltetrazine and Dicyclopropylpyridazine. - The
Ground State
If the cyclopropyl rings of tetrazine 79 and pyridazine
80 are conjugated with the heteroaromatic rings in the
ground states of these molecules, several phenomena should
be observable. Since cyclopropyl conjugation with the
heteroaromatic ring can occur only in the bisected conforma¬
tion (vide supra) , the methine hydrogen of the cyclopropyl
ring should spend more of its time in the deshielding region
of the heteroaromatic ring than it would if the cyclopropyl
ring was able to rotate freely. Thus, the methine proton
should be deshielded relative to freely rotating systems
such as the iso-propyl compounds 88 and 89, excluding the
effects of the groups themselves. The cyclopropyl rings of
79 and 80 should conjugate with the heteroaromatic rings
via such resonance structures as 90. Thus, the methylene
protons of the cyclopropyl rings should show deshielding
due to the charge which is placed on the g-carbons of the
cyclopropyl ring. Lowering the temperature of a solution of
either 79 or 80 should increase the. number of molecules in
the bisected configuration while raising the temperature
should decrease the number of molecules in the bisected
configuration.
+
90

91
As illustrated in Figures 11-13, lowering the tempera¬
ture of a solution of 79 in deuteriochloroform changes the
NMR spectrum of 79 drastically. At -60° the lower field
multiplet appears as what is essentially a pentet at t7.35
(J = 6.6 Hz) and the higher field multiplet shows up as a
doublet at 8.62 (J = 6.6 Hz). The temperature-dependent
spectral changes have been interpreted as being due to H(2)-
H(5) becoming magnetically equivalent thus simplifying the
spectrum.51 It will be noted that the chemical shift of
the methine protons only changes from t7.54 to 7.37 or 0.17
ppm - a shift in the right direction for increased cyclo¬
propyl conjugation but a shift whose magnitude may be
accounted for by changes in solute-solvent interactions.
The simplification of the NMR spectrum of 79 on lowering
the temperature of its deuteriochloroform solution is con-
sistant with increased cyclopropyl conjugation only if it
is assumed that the equivalence of H(2)-H(5) is due only to
increased population of the bisected conformation. Again
the simplification of the NMR spectrum may be accounted for
by assuming changes in solvent-solute interactions.
An NMR spectrum of 79 in diphenyl ether is given in
Figure 14. Although the shape of the multiplets has changed,
the multiplets are still due to the methine and methylene
protons. Heating a solution of 79 in diphenyl ether causes
no change in the NMR spectrum. Especially notable is the
fact that the chemical shift of the methine proton is essen¬
tially unchanged on heating.

92
Figures 15-17 illustrate that the cyclopropyl multi-
plets in the NMR spectrum of 80 are even less affected than
the multiplets of a spectrum of 79 on lowering the tempera¬
ture of a solution of 80. If the simplification of the NMR
spectrum of 79 was due to cyclopropyl conjugation (vide
supra), the fact that simplification of the NMR spectrum of
80 is less pronounced than in the case of 79 is completely
in accord with the supposition that cyclopropyl conjugation
in pyridazine 80 will be less than in tetrazine 79 (vide
supra).
Of interest in the NMR spectra of 80 and its model
compound 3,6-di-iso-propylpyridazine (89) are the pyridazine
protons. The aromatic protons of the cyclopropyl compound
80 are shielded relative to the aromatic protons of the iso -
propyl compound 89 by 0.33 ppm. The shielding of the aro¬
matic protons of 80 may be attributed to either shielding
by the cyclopropyl rings in the bisected conformation when
one or both of the cyclopropyl rings is syn to the aromatic
proton or the aromatic protons may be shielded simply due to
electronic density flowing into the pyridazine ring from the
cyclopropyl rings. It is certainly true that the cyclopropyl
rings exert an electron-withdrawing effect inductively,56
but the resonance effect of cyclopropyl is positive and the
positive resonance effect should overcome the negative induc¬
tive effect. Either of the above effects which cause the
aromatic protons of 80 to be shielded relative to the protons

Figure 10. NMR spectrum of 3,6-dicyclopropy1 -1,2,4,5-tetrazine (79) in CDC13 at NMR
probe temperature (40°)

o
-p.

Figure 11.
NMR spectrum of 3,6-dicyclopropyl-1,2,4,5-tetrazine (79) in CDC13 at -10°

i

Figure 12. NMR spectrum of 3,6-dicyclopropyl-1,2,4,5-tetrazine (79) in CDC13 at -30°

,N-N
CO

Figure 13.
NMR spectrum of 3,6-dicyclopropy1-1,2,4,5-tetrazine (79) in CDC13 at -60°
4

100

Figure 14.
NMR spectrum of 3,6-dicyclopropy1-1,2,4,5-tetrazine (79) in diphenyl
ether at NMR probe temperature (40°)

102

Figure 15. NMR spectrum of 3,6-dicyclopropylpyridazine (80) in CDC13
at 42.5°

104

Figure 16.
NMR spectrum of 3,6-dicyclopropylpyridazine (80) in CDCI3 at -5.5°

2.0 3.0 ' 4.0 5.0 PPM Ir) ' 6.0 7.0 8.0 ' 9.0 10
106

Figure 17. NMR spectrum of 3,6-dicyclopropylpyridazine (80) in CDC13 at -59.0°

103

109
of 89 requires that the cyclopropyl rings of 80 be in the
bisected conformation.
Lowering the temperature of a solution of 80 actually
causes the aromatic protons of 80 to become more deshielded
rather than more shielded. This is in complete accord with
80 assuming a conformation such as 83 in which the aromatic
protons are no longer in the shielding region of the cyclo¬
propyl rings. Again the deshielding of the aromatic protons
may be accounted for by assuming changes in solvent-solute
interactions with decreasing temperature.
Examination of the NMR spectrum of the three iso¬
propyl compounds 88, 89, and 1,4-di-iso-propylbenzene (91)57
reveals that, as anticipated, on transforming from the
carbocyclic 91 to the diazine 89 to the tetrazine 88, a
downfield shift is experienced by both the methine and methyl
protons of the iso-propyl groups. The shift difference (see
Table VIII) on exchange of two C-H moieties for nitrogens
is about 0.30 to 0.47 ppm for the methine protons while the
shift difference for the methyl protons is only about 0.15
ppm. Since, with the exception of a very small hyperconjuga-
tive effect, the iso-propyl groups can be assumed to be
freely rotating, the above shift differences can be attributed
largely to inductive effects produced by the nitrogens which
are more electron-withdrawing than the C-H units.
Examination of the three cyclopropyl compounds 79, 80,
and monocyclopropylbenzene (92) 5 8 reveals the same type of
downfield shift trend as with the iso-propyl compounds above.

110
However, it will first be noted that the shift differences
for the cyclopropyl methine proton are not as great as in
the iso-propy1 series. This anomalous behavior cannot be
explained readily. The important protons in this series
are the ones 3 to the aromatic ring. The fact that these
3-methylene protons show increased deshielding relative to
the methyl protons in the iso -propy1 series is a good indi¬
cation that positive charge is being placed on the 3-carbons
via resonance structures such as 90 which is a good indica¬
tion that the cyclopropyl rings of 79 and 80 are conjugating
with the heteroaromatic ring and providing it with electron
density.
That monocyclopropylbenzene is as valid a model as 1,4-
dicyclopropylbenzene can be shown in two ways. First, a
visual examination of an NMR spectrum of an impure sample
of dicyclopropylbenzene59 shows that the chemical shift of
the methine proton is at about the same shift as the methine
of monocyclopropylbenzene. In both cases the center of the
methine proton multiplet is taken as a good first approxi¬
mation of the chemical shift of the methine proton. The
NMR spectra of the known 2-cyclopropylthiophene and 2,5-
dicyclopropyIthiophene have been reported.60 Using the
above-described center-of-the-multiplet approach, one finds
that the methine proton of 2,5-dicyclopropylthiophene is
actually at lower field than the methine proton of the mono¬
cyclopropy lthiophene .

Table VIII
Chemical Shift Data for iso-Propyl and Cyclopropyl Aromatic Compounds
Compound
Tmethine
At
tch3
At
X = Y =
CHa,b
7.19
0.47
8.79
0.15
X = CH,
Y = Nc
6.72
0.30
8.64
0.16
X = Y =
NC
6.42
/x=x\
8.48
U>N
Vy^
Compound
Tmethine
At
lGHa
Ax
a
TCHb
ATb
X = Y =
CHa,d,e
8.20
0.15
9.32
0.27
9.26
0.32
X = CH,
Y = Nc
8.05
0.51
9.05
0.28
8.94
0.22
X = Y =
NC
7.54
8.78
8.72
aNo solvent given. bRef.
Q
56. In carbon
disulfide.
^Mono cyclopropyl rather
than dicyclopr
opyl. See
text. eRef.
57.
111

112
Dicyclopropyltetrazine and DicyclopropyIpyridazine - The
Excited State
After ascertaining that some cyclopropyl conjugation is
present in the ground states of tetrazine 79 and pyridazine
80, it was of interest to examine the possibility of cyclo¬
propyl conjugation in the excited states of these molecules.
First, however, a discussion of the electronic spectra of
tetrazine, pyridazine, and their simple derivatives is in
order.
Being heteroaromatics tetrazines and pyridazines show
both n+TT* and transitions in their electronic spectra.
The lowest energy n->-Tr* transition of tetrazines is of such
low energy that it occurs in the visible region of the
spectrum imparting a purple color to tetrazines. Since
pyridazines have no absorptions in the visible region, they
are colorless.
Table IX lists the absorbances for ^-tetrazine and sóme
of its simple alkyl and aryl derivatives. Table X lists
the absorbances for pyridazine and its known aliphatic and
aryl derivatives.
As expected, the position of the n->-iT* transition in
dicyclopropyltetrazine 79 is hypsochromically shifted with
respect to other alkyl tetrazines due to the relative
electron-withdrawing power of cyclopropyl relative to
"normal" alkyl groups.56 The n-nr* band of both 79 and 88
shifts hypsochromically on changing from a nonpolar solvent
(cyclohexane) to a polar solvent (ethanol) as expected.61

113
The bands assigned as secondary absorbances ^L^)
in both 79 and 88 shifted bathochromically on changing from
cyclohexane to ethanol as expected.61 Replacement of the
iso -propyl groups of 88 with cyclopropyl groups shifts the
secondary C1!^) band of 88 bathochromically by 41 nm in
ethanol and 39 nm in cyclohexane.
Also the UV spectrum of 79 contains at shorter wave¬
lengths a new band that does not appear in the spectra of
any other alkyl tetrazines. Although this band does not
show the expected shift on solvent change, it is assigned as
the primary band ) of the aromatic tetrazine ring.
This primary band would be the band predicted by
Nishimoto62 to be at 191 nm for s_-tetrazine . The only UV
absorbance displayed by 3,6-diphenyl-1,2,4,5-tetrazine (1)
is assumed to be this f1L ) band on the basis of its inten-
sity. It is also assumed that the C1^^) band of 1 is masked
by the intense (^L ) band.
On comparing 79 and 88, the bathochromic shift of the
secondary band and the appearance of the previously
unobserved (in the alkyl series) primary band, due to
a bathochromic shift of that band, is unambiguous evidence
for cyclopropyl conjugation in the excited state. It will
be noted that in ethanol the (!L ) band of 79 is at 222 nm
while in 1 the same band is at 297 nm which is in accord
with the known pattern of phenyl causing greater bathochromic
shifts than cyclopropyl which in turn causes a bathochromic
shift from the alkyl substituted compound.

114
Table IX
Principa 1 Absorbances for Some Tetrazines
R
Solvent
n->-7T
* (nm)
TT+TT
* (nm)
Hb
cyclohexane
542
(829)
252
(2150)
320
(26)
ch3c
ethanol
538
(560)
274
(3620)
CH 3 b
cyclohexane
562
(832)
273
(3720)
c2n5c
ethanol
540
(500)
273
(3190)
c3h7c
ethanol
542
(470)
275
(2940)
iso-C3H7C
ethanol
545
(470)
273
(3050)
iso-C3H7d
ethanol
544
(460)
273
(2920)
cyclohexane
552
(537)
271
(3020)
Ci iH23C
ethanol
542
(535)
276
(3070)
C3H5d
ethanol
537
(502)
314
(1780)
270
(505)
222
(20100)
cyclohexane
543
(758)
310
(1950)
274
(s, 619)
226
(21700)
C 6 H 5 e
chloroform
545
(500)
300
(60000)
c6h5
ethanol
546
(449)
297
(35700)
aSee Chapte
r V for complete
spectra
of all
compound
s
recorded in
this work i.e.
shoulders and inflections. Als'
see Figures
18-21 for reproductions
of the
spectra
of the
cyclopropyl
compound 79.
Ref. 63.
CRe f.
54. dThis work
eRef. 64.

115
Table X
£
Princip a 1 Absorbances for Some Pyridazines
R
Solvent
n->ir
* (nm)
IT -â–ºIT
* (nm)
Hb
ethanol
313
(303)
246
(1160)
cyclohexane
340
(315)
246
(1300)
iso-C3H7c
ethanol
320
(227)
257
(1650)
cyclohexane
344
(290)
262
(1670)
C 3H 5C
ethanol
317
(s, 248)
278
(1550)
226
(13400)
cyclohexane
• 342
(299)
276
(1330)
225
(14800)
c6h5c
ethanol
279
(29300)
o
See Chapter V for complete spectra of compounds recorded
in this work i.e. shoulders and inflections. See also
Figures 22 and 23 for reproductions of the spectra of the
b c
cyclopropyl compound 80. Ref. 63. This work.
In the pyridazine series again the absorbance assigned
to the n->iT* transition shifts hypso'chromically on changing
the solvent from cyclohexane to ethanol for 80 and 89. Also
the position of the n->-TT* absorbance for the cyclopropyl
derivative, 80, is at shorter wavelength than the correspond¬
ing band for the iso-propyl compound, 89, in accord with the
greater inductive effect of the cyclopropyl rings.

116
As in the case of the tetrazine series the bands
assigned to transitions shift bathochromically on
changing from a nonpolar solvent to a polar one. Again
replacement of the iso-propyl groups by cyclopropyl rings
causes a large bathochromic shift in the original
band (secondary or band) and the appearance of a new,
more intense band (primary or ¡L band). The results
are again interpreted as evidence for cyclopropyl conju¬
gation in the excited state. It will be noted that, as in
the tetrazine series, the (!L ) band of the cyclopropyl
compound 80 lies above the assumed position for the same
band in the iso-propyl compound 89 but below the position
of the same band for 3,6-diphenylpyridazine (93).
On comparing tetrazine 79 and pyridazine 80, it would
appear that cyclopropyl conjugation is less important in 80
than in 79 in the excited state of these molecules as was
anticipated. Using iso-propyl compounds 88 and 89 as model
compounds, it can be seen that the shift difference between
79 and 88 is not the same as the shift difference between
80 and 89. The shift difference between the secondary bands
of tetrazines 79 and 88 is approximately 40 nm while the
corresponding shift difference between the pyridazines 80
and 89 is only about 14 to 21 nm. The results are those
anticipated in view of the results, in the hydrocarbon series.45
No comparison using the primary (!L ) bands of 79 and
80 is possible as the position of the primary band in the

117
corresponding iso-propyl compounds is in the far ultra¬
violet and could not be determined.

Figure 18. Visible spectrum of 3,6-dicyclopropyl-1,2,4,5-tetrazine (79) in ethanol
4

450 nm
500
600
550
650
119

Figure 19. Visible spectrum of 3,6-dicyclopropyl-1,2,4,5-tétrazine (79) in
cyclohexane
«

J I L
J L
i l
4 50 nm
500
1.0
0.8
0.6
0.4
0.2
0.0
550
600
650
121

Figure 20.
o
UV spectrum of 3,6-dicyclopropy1-1,2,4,5-tetrazine (79) in ethanol

4
JL
200 nm
i
250
i
300
A. 3.07
B. 3.07
-4
10 M
10“5 M
Absolute Ethanol

UV spectrum of 3,6-dicyclopropy1-1,2,4,5-tetrazine (79) in
cyclohexane
Figure 21.

200 250 300 350 400
125

Figure 22.
UV spectrum of 3,6-dicyclopropylpyridazine C80) in ethanol*
4

— l.o
4
200 nm
250
300
B. 5.40 x 10-5 M
Absolute Ethanol
400
127

Figure 23. UV spectrum of 3,6-dicyclopropylpyridazine (80) in cyclohexane

200 nm
250
300
1.0
B. 5.28 x 10-5 M
Cyclohexane
0.6

CHAPTER IV
THE DIAZATROPYLIUM CATION AND DIAZATROPONE
As was mentioned in Chapter II, 13 is base peak in the
mass spectrum of cycloheptatriene whereas cations similar to
75 are only a few percent of base peak in the mass spectra
of 4H-1,2-diazepines and 3,4-diazanorcaradienes. Again the
mass spectral behavior of diazanorcaradienes and diazepines
appears to have a strong bearing on the chemistry of these
heterocycles as will be demonstrated by the results of this
chapter.
Attempted Syntheses of 1,2-Diazatropy1ium Cations
There are several varied methods for producing the
carbocyclic tropylium cation.7’8 Only those methods of
direct application to the synthesis of a diazatropylium
cation will be reviewed briefly here.
In 1954 Doering and Knox65 established that the
addition of one mole of bromine to cycloheptatriene yielded
a dibromide which on heating underwent dehydrohalogenation
to yield 15 (bromide gegenion) as illustrated in Scheme 23,
130

131
Br
Br
o
H
13
Scheme 23
The oxidizing agent DDQ is known mechanistically to
operate primarily as a hyride abstractor.66 Reid et al.6 7
utilized the above fact in synthesizing tropylium perchlorate
as depicted in Scheme 24.
CIO
4
Scheme 24
Dauben68 first reported the use of trityl carbonium ion
salts as hydride abstractors in the synthesis of a series of
tropylium perchlorates, fluoroborates, bromides, chlorides,
and iodides. The other reaction product is triphenyl-
methane which is readily soluble in diethyl ether and
easily removed from the ionic, insoluble tropylium salt by
extraction.
On heating, the diazanorcaradiene 6 rapidly undergoes
ring inversion presumably via the open 5H-diazepine form.2’3
It was assumed that on refluxing in benzene enough of this
open form would be present to react with DDQ to form 3,7-
diphenyl-1,2-diazatropylium cation whose gegenion, the DDQ-H

132
anion, could be exchanged for the more suitable perchlorate
anion.
Mixing DDQ and 6 at room temperature in benzene causes
an immediate color change from bright yellow to dark red.
Refluxing the dark red solution leads to a 67.71 yield of
red-black, highly insoluble material (94) which exists as
hard microcrystals. The unknown material 94 has a melting
point which varies from batch to batch.
The analytical and spectral data for 94 were of poor
quality and uniformative. The elemental analysis for 94
did not indicate a 1:1 adduct; but,rather, it indicated that
94 was contaminated with a small amount of benzene. Despite
the fact that 94 analyzed low for both nitrogen and chlorine
(.see Chapter V) , it was assumed that 94 could be best
described as a 1:1 adduct between DDQ and 6. A good, con¬
sistent mass spectrum could never be obtained for 94 and,
even in trifluoroacetic acid (TFA), 94 was not soluble enough
to produce a useful NMR spectrum. The IR spectrum of 94
indicated absorptions for C-H stretch, nitrile (singlet,
2200 cm *), and C=C stretch.
Since DDQ often contains traces of hydrogen chloride
due to reaction with atmospheric water, it was hypothesized
that perhaps 6 converted into the known 3,6-diphenyl-4 -
methylpyridazine (95)3 by acid-catalyzed ring-opening.3
The 95 thus formed might then complex with DDQ to form 94.
However, 95 was found not to react with DDQ under the
conditions used in the formation of 94.

133
The reaction of 94 with sodium borohydride in aceto¬
nitrile produced a new, colorless compound 96 in 26.51 yield.
The mass spectrum of 96 displayed a parent ion at m/e
248 while an elemental analysis indicated that 96 was a
dihydroderivative of 6. The IR spectrum of 96 indicated
the presence of amine hydrogen and a carbon-nitrogen double
bond.
In the aromatic region of the NMR spectrum, 96 displayed
two multiplets centered at t2.25 and 2.68 integrating for
two and eight protons respectively. As in previous cases
(vide supra), the two multiplets are assumed to account for
the ortho protons of the phenyl attached to a carbon-nitrogen
double bond and the remaining protons. The upfield portion
of the NMR spectrum of 96 consisted of a very broad one-
proton singlet at t4.59, a broad one-proton singlet at 5.92,
a three-proton multiplet centered at 7.95, and a one-proton
multiplet centered at 8.95. On the basis of the above spectral
data, 96 is thought to be the product of the sodium boro¬
hydride reduction of 6 which is somehow complexed with
DDQ. The upfield portion of the NMR spectrum of 96 is
assigned as shown in Table XI. The stereochemistry shown
is assigned assuming attack on the carbon-nitrogen double bond
from below the six-membered ring of the diazanorcaradiene 6.
The reduction of one carbon-nitrogen double bond of 6 is
not surprising in view of the results of Heinrichs and
et. al.;5 however, complex hydride reductions of diazanor-
caradienes have not been reported previously.

134
Table XI
Proton Assignments for 96
Proton Assignment
1 17.95 mult.
2 5.92 sing.
3 4.59 sing.
6 7.95 mult.
7a 7.95 mult.
7b 8.95 mult.
Confirming the above conclusions, it was found that 96
is formed quantitatively on reacting 6 with sodium boro-
hydride in acetonitrile. Thus, it seems clear that the
complex 94 contains 6 which has retained its original
structural identity. If the material 95 was merely polymer
or insoluble tar containing 26.51 6, then 6 should have been
easily leached out in TFA (vide supra) and displayed the
characteristic NMR spectrum of 6 in TFA. Protonated 6 in
TFA solution is stable at room temperature for several weeks.
Since the reduction of 94 by borohydride produced only a
26.5?ó yield of 96 and the reduction of 6 by borohydride is
quantitative, there is some question as to whether 94 can be
described accurately as a 1:1 complex between DDQ and 6.
To date, the structure of 94, if it is a pure compound,
is still unknown.

135
The reaction of trityl fluoroborate with 6 at room
temperature did not proceed at any measurable rate. Heating
a mixture of 6 and trityl fluoroborate in acetonitrile
produced nothing but unidentified black tar.
Upon finding that 3 is a 4H-diazepine rather than a
bicyclic compound2 (see Chapter I), it was decided to
attempt a synthesis of 3,4,5,6,7-pentaphenyl-1,2-diaza-
tropylium bromide via a route similar to that used by
Doering and Knox65 in the synthesis of tropylium bromide.
Reaction of 3 with excess bromine in carbon tetra¬
chloride produced a yellow, crystalline material (97) which
was too unstable to obtain anything more than an NMR
spectrum. The NMR spectrum of the yellow 97 consisted of a
two-proton multiplet centered at t2.27, a twenty-three-
proton multiplet centered at 2.86, and a broad one-proton
singlet at 3.95. The NMR spectrum of the precursor 3
shows, in addition to the aromatic multiplet, a broad singlet
at t4.10. On the basis of the previous work of Maier16 and
the NMR spectrum, the yellow 97 was tentatively identified
as the N-bromobromide salt of 3.
No attempt was made to react 3 with trityl cation as,
from previous studies,69 the abstraction of a hydride from
a carbon bonded to a phenyl ring is extremely difficult.
Facile access to large amounts of the recently syn¬
thesized 3,5,7-tripheny1-4H-1,2-diazepine (26)17 gave strong
impetus to an attempt at the synthesis of 3,5,7-triphenyl-
1,2-diazatropylium salts. In view of the reaction of

136
bromine with 3, the method of Doering and Knox65 was not
considered. Rather, the synthetic method of Dauben68 was
deemed to have the greater possibility of success. Although
the 1,3,5-triphenyltropy1ium cation has apparently never
been synthesized, it was assumed that steric effects due to
the 3- and 5-phenyls would not hinder abstraction of a
hydride from 26. It should be noted that the 4-position of
26 has only hydrogen bonded to it.
Reaction of 26 with trityl perchlorate at room tempera¬
ture gave a 30.51 yield of a yellow, crystalline material
(98) which analyzed correctly for the desired diazatropylium
perchlorate salt. However,.the NMR spectrum, which consisted
of a sixteen-proton multiplet centered at t2.27 and a broad
two-proton singlet at 5.70, indicated that two non-aromatic
protons were still present. The IR spectrum of 98 indicated
the presence of hydrogen attached to nitrogen (3100 cm x)
and fluoroborate anion (1100 to 1040 cm x).
Fluoroborate salts are known for their volatility and
ability to be vaporized for mass spectral analysis.70 The
fluoroborate salt 99 was no exception. The mass spectrum of
99 was found to be very similar to the reported17 mass
spectrum for the precursor 26 which is not what would have
been expected had 99 been triphenyldiazatropylium fluorobo¬
rate. A parent ion at m/e 221 rather than the parent ion
found at m/e 222 would have been expected if 99 was the
desired diazatropylium.

137
If the trityl cation had extracted a hydride ion from 26
in forming 99, triphenylmethane should have been present in
the reaction mixture.68 Chromatography of the complex,
highly colored mother liquor from the above reaction yielded
no triphenylmethane.
On mixing a small quantity of 99 with sodium borohydride
in acetonitrile, gas evolved and 26 was regenerated. Pre¬
sumably the gas was hydrogen produced by the reaction of
sodium borohydride with a protonated amine. The diazepine
26 should be regenerated on reaction of the diazatropylium
cation with sodium borohydride but the reaction should
proceed without the evolution of hydrogen.
The above results lead to the conclusion that the
yellow salts isolated in the above reactions were 3,5,7-
triphenyl-4H-1,2-diazepine hydroperchlorate (98) and
3,5,7 - tripheny 1 - 4II-1,2-diazep ine hydrof luoroborate (99).
As a final check on this structural assignment it was found
that reaction of 26 with perchloric acid in acetic anhydride
produced 98 identical in all respects to the 98 produced
above. Perchlorate 98 and fluoroborate 99 are assumed to be
formed by reaction of 26 with the corresponding acid which
results from reaction of the trityl cation with moisture which
inadvertantly enters the reaction vessel.

138
\+ ¿
nN~N
X
H
98 X = C104
99 X = BF4"
The NMR spectrum of 98 and 99 is in good agreement
with the structure assigned. The 6-proton whose NMR
absorbance is at x3.32 in 26 is now shifted into the aromatic
multiplet by resonance structures such as 100 and the
inductive effect of the positive charge on nitrogen. The two
H
100
protons at C-4, which appear as a doublet of doublets in the
neutral 26 due to the rigidity of the diazepine ring,17 now
absorb as a very broad singlet at ambient temperatures since,
for unknown reasons, the diazepine ring is now free to
rapidly ring invert and thus interchange the chemical shifts
of the two protons in the 4-position.

139
At present, it is not known which nitrogen the acidic
proton is bonded to in 98 and 99. The proton attached to
nitrogen is assumed to be exchanging at such a rate that
it cannot be detected by NMR methods.
At the same time 98 and 99 were discovered and
characterized, similar reactions were carried out by Carty.71
Carty, however, assigned 98 and 99 the structure 101, which
is a cyclic eight ir-electron antiaromatic system.
101
Carty71 claimed that the t5.70 signal in the NMR
spectrum was due to two equivalent N-H protons whose signal
was somewhat broadened due to the quadrupole moment of
nitrogen and chemical exchange. The other data obtained in
this work such as the mass spectrum of 99 and the reaction
of 99 with sodium borohydride were explained by a rapid,
allowed 1,5-hydrogen shift from N-l to C-4.
If structure 101 was the true structure for 98 and
99, lowering the temperature of a solution of either 98 or
99 should cause no change in the NMR spectrum of either
of these compounds. On the other hand, if the structures
assigned in this work are correct, the signal at t5.70
should broaden further, disappear, and transform into a

Figure 24. NMR spectrum of 3,5,7-triphenyl-4H-1,2-diazepine hydrofluoroborate (99)
in TFA/CDClj at 17.0°

141

Figure 25. NMR spectrum of 3,5,7-tripheny1-4H-1,2-diazepine hydrofluoroborate (99)
in TFA/CDCla at 1.5°
4

143

NMR spectrum of
3,5,7-tripheny1 -4H-1,2-diazepine hydrofluoroborate (99)
in TFA/CDCls at -18.5°
Figure 26.

145

146
doublet of doublets symmetrically displaced about -the
original 5.70 signal.
As illustrated in Figures 24 through 26, the t5.70
singlet does collapse and two new signals symmetrically
displaced about the original signal appear at about 4.6 and
6.8. Due to crystallization of 99 from the TFA solution at
low temperatures, an NMR spectrum of 99 in a frozen conforma¬
tion could not be obtained. However, the data obtained do
indicate that the structures as assigned in this work are
correct.
In a final attempt at the synthesis of the 3,5,7-tri-
phenyl-1,2-diazatropylium cation equimolar quantities of
26 and DDQ were mixed in benzene at room temperature to give
a very deep red solution. After stirring for about an hour,
the red solution began to deposit colorless needles. As
crystallization proceeded, the red color of the solution
faded. An 88.5% total yield of colorless crystals of unknown
102 was isolated. The colorless crystals tended to yellow
very slightly on isolation.
Elemental analysis and mass spectrometric measurement
indicated that 102 was a 1:1 complex between 26 and DDQ.
The NMR spectrum of 102 was very uninformative as it
displayed only a multiplet at xl.6 - 2.7. Any tropylium-
type protons would have been expected to absorb at around
x0.572 in the absence of any shielding effects from the
phenyl rings bonded to the diazepine ring. The IR spectrum

147
of 102 indicated nitrile (singlet 2200 cm J) and C=C
stretch. Moisture in the potassium bromide mulling agent
prevented the detection of any O-H stretch.
The UV spectrum of 102 (Figure 27) is essentially
the UV spectrum of 2617 with the exception of the new band
at 221 nm and the intensities of the main absorption maxima.
On the basis of the above information, 102 was tenta¬
tively assigned the diazepine structure given below. The
NMR spectrum is explained by assuming that protons at C-4
and C-6 are inductively shifted downfield into the aromatic
region of the spectrum due to both the strongly electron-
withdrawing hydroxydichlorodicyanophenylether group at C-4
and the presumed dipolar character of the diazepine-oxygen
bond at C-4. The UV spectrum is consistent with 102's
similarity to the precursor 26 and the presence of the
hydroxydichlorodicyanopheny1 ether function at C-4 which
may be the cause of the new band at 221 nm. The insolubility
of 102 is not unexpected.
Ar = 4-hydroxy - 2,3-dichloro-4,5-dicyanophenyl
102
From the above studies it would appear that the
hypothetical 1,2-diazatropy1ium cation is either too

Figure 27.
UV spectrum of unknown 102

«
20 0 nm
1
1
250
i
0
1.50 x 10“5 M
Acetonitrile
0.6
0.4
300 350 400
149

150
unstable to be synthesized or so unstable that synthesis
will be difficult and must be approached by methods other
than those employed in this work.
Attempted Syntheses of 1,2-Diazatropone
Among the many known synthetic routes to the carbocyclic
tropone,7 only two were followed in the attempted synthesis
of 1,2-diazatropone. The first method, that of Radlick,73
involved simple oxidation of cycloheptatriene directly to
tropone using selenium dioxide. The second method was
designed after the report of Harmon e_t al.7 4 that pyrolysis
of ditropenyl ether in the presence of moist alumina and
phosphorus pentoxide yielded, by disproportionation, tropone
and cycloheptatriene. Other synthetic routes which lacked
literature precedence were also probed.
Assuming that it would have the best chance of undergo¬
ing oxidation, diazanorcaradiene 22 was treated with selenium
dioxide according to Radlick's73 procedure. No identifiable
product resulted from the attempted oxidation. No attempt
was made at oxidizing the 4H-diazepine 26.
In adapting Harmon's74 synthesis of tropone to a 1,2-
diaza system the reaction sequence of Scheme 25 was employed.
It was assumed the 22 and the 1,2-diazatropone could be
separated by chromatography.

151
Scheme 25
Reaction of two moles of tetrazine 9 with one mole of
ether 103 yielded a mixture of product and unreacted tetra¬
zine which could not be separated easily. Repeating the
reaction using a 1:1 molar ratio of reactants yielded a
bright yellow crystalline compound 104 which gave a mass
spectral molecular weight of 568 and an elemental analysis
consistent with a 1:1 adduct. The UV spectrum of 104
(Figure 2 8) indicated that a diphenyIcyclopropenyl moiety
attached to an electron-withdrawing element or group was
still present. The above data were consistent with
assigning the new compound the diazanorcaradiene structure
105.

152
105
However, both the NMR and IR spectra indicated that the
ester groups of 104 were nonequivalent which is not in
accord with the symmetrical structure 105. Other features
of the NMR spectrum indicated that 104 should be assigned
the structure given below.
104
The NMR spectrum of 104 showed the aldehyde protons as
a sharp one-proton singlet at xl.08, the phenyl protons as
a multiplet in the 1.93 to 3.23 region, and the cyclopropene
proton as a sharp one-proton singlet at 5.32. The non¬
equivalent ester methyls manifest themselves by two sharp
three-proton singlets at t6.42 and 6.52.

Figure 28. UV spectrum of 4,5-dipheny1 - 3,6-dicarbomethoxy-1 -(1,2-diphenylcyclopropen-
3-yl)-l,4-dihydropyridazine-4-aldehyde (104)

250 nm
300
1.0
0.8
°2CH3
2.80 x 10-5 M
Chloroform
350
400
450
154

155
As expected, the mass spectrum of 104 shows no measur¬
able peaks for loss of either benzonitrile or methyl cyano-
formate (see Chapter II). Also, as anticipated, the base
peak is at m/e 191 which can be accounted for by diphenyl-
cyclopropenyl cation formation. There is no peak for diphenyl-
cyclopropenone.
Diesteraldehyde 104 is simply a member of the well-
known dihydropyridazines1 which are yellow when the 3- and
6-positions are substituted with ester groups. The visible
spectrum of 104 displays the expected weak n->-TT* band at
590 nm (e = ^180) while the UV spectrum (Figure 28) is
consistent with a diphenyl-cyclopropeny1 group attached to
an electron-withdrawing element or group.75
Although only two carbonyl stretches could be identi¬
fied in the IR spectrum of 104, it is obvious from the NMR
spectrum that the methyl ester functions are nonequivalent.
The characteristic aldehydic carbon-hydrogen stretches76
were located as two weak bands at 2840 and 2730 cm 1.
That 104 fails to add another mole of the powerful
diene 9 at room temperature is in complete accord with
previous observations.2 Diphenylcyclopropenes with powerful
electron-withdrawing substituents in the 3-position invaria¬
bly exhibit low dieneophilicity. No attempt was made at
reacting 9 with a second mole of tetrazine under forcing
conditions.
Unfortunately, an attempt at completely oxidizing 104
to the fully aromatic, easily synthesized dimethyl

156
4,5-diphenylpyridazine-3,6-dicarboxylate was an apparent
failure.
Although the reáction between 9 and 103 did not produce
the desired bisdiazanorcaradienyl ether or even the equally
desirable diazanorcaradienyldiphenylcyclopropenyl ether 105,
the formation of 104 is of extreme interest.
Mechanistically, the monoadduct 105 is almost certainly
the initial product, but rearrangement by either of the
paths shown in Scheme 26 leads to 104. It should be stressed
at this point that 104 was formed at room temperature and no
heat was ever applied to the reaction mixture.
9 + 103
E
Scheme 26
No evidence for either mechanism exists at the present
time. The similarity between the concerted, allowed
(tt2s + ir2s + 02s)12 mechanism (path a above) and the Cope-
type mechanism proposed in Chapter I should be noted
especially in view of the results of the x-ray study on the
diazanorcaradiene (66)-diazepine (67) system. It should be
pointed out that the ionic mechanism (path b above) is also

157
quite reasonable in view of the known stability of the
diphenylcyclopropenium cation.75 Another mechanism for the
conversion of 105 into 104 involves a concerted, allowed [1,5]
shift of the diphenyIcyclopropenyl group of 105 from oxygen
to nitrogen.
Since the difficulty encountered in attempting to
utilize Scheme 25 could not be bypassed, other synthetic
schemes were considered.
Although diphenylcyclopropenone77 is known to have
aromatic properties, the possibility that it might undergo
the Diels-Alder reaction with the powerful diene 9 was
considered. Unfortunatelyas was anticipated, the attempted
reaction of 9 and diphenylcyclopropenone produced a complex
mixture which seemed to consist mostly of unreacted, impure
diphenylcyclopropenone.
In order to bypass the stability of diphenylcyclopro¬
penone, the aromatic diphenylcyclopropenone was converted
into the known diphenylcyclopropenone ethylene ketal 106.78
Reaction between 9 and 106 was sluggish as expected (vide
supra - 104), and the reaction mixture was again a complex
mixture which defied identification even after chromatography
over basic alumina.
Unfortunately, the synthetic schemes utilized in this
work in the attempted production o.f 1,2-diazatropone have
either failed at such early stages or for such theoretically
sound reasons that nothing concrete can be said about the
stability or ease of production of 1,2-diazatropone.

158
However, in view of the results in the diazatropylium series,
it is felt that diazatropone will also be a relatively
inaccessible system.

CHAPTER V
EXPERIMENTAL
General
All melting points ivere obtained using either a
Thomas-Hoover or Mel-temp melting point apparatus and are
uncorrected. Analytical gas-liquid chromatographic (glpc)
work was done on an Aerograph Hy-Fi Model 600-D equipped
with a hydrogen flame ionization detector. Preparative glpc
work was performed on an Aerograph A-90-P instrument.
Elemental analyses were obtained from Galbraith Laboratories
Peninsular ChemResearch, or Atlantic Microlabs.
Spectra
Mass spectra were obtained on a Perkin-Hitachi RMU-6E
mass spectrometer at 70 ev. Mass spectra are listed by mass
(m/e) unit with the relative intensity in parentheses next
to the mass unit. Unless the mass spectral peak has some
special significance or analytical value, only those peaks
of 101 or greater relative intensity are listed. Where
it was necessary to give a plot of the whole spectrum, the
plots are given as figures as indicated.
Nuclear magnetic resonance (NMR) spectra, unless stated
otherwise, were recorded on either a Varian A-60 or A-60A
instrument. All standard symbols and abbreviations are used
159

160
Ultraviolet (IJV) and visible spectra were obtained using
a Cary Model 15 recording spectrophotometer. UV and visible
absorbances are listed by wavelength (nm) with the molar
extinction coefficient in parentheses next to the wavelength.
Standard abbreviations are used. No molar extinction
coefficient is assigned to inflections.
Infrared (IR) spectra were procured on either a Perkin-
Elmer Model 137 or Model 337 and selected absorbances are
listed by wavenumber (cm 1).
Temperature-Dependent NMR Spectra
All temperature-dependent NMR spectra were recorded on a
Varian A-60A instrument. Except as noted, temperatures greater
than 40° were accurately determined by the chemical shift
difference between the hydroxyl and methylene hydrogens of
ethylene glycol. Except as noted,temperatures lower than
40° were accurately determined from the chemical shift
differance between the hydroxyl and methyl hydrogens of
methanol.
3,6-Bis (4 -iodophenyl)-1,2,4,5-tetrazine (17)
Using the method of Abdel-Rahman et ad. 1 0 20.9 g (91.2
mmoles) of freshly chromatographed (basic alumina) p-iodo-
benzonitrile, 18.2 g (364 mmoles) of hydrazine hydrate,
1.67 g (52.1 mmoles) of flowers of sulfur, and 150 ml of
absolute ethanol were combined to form a dark red mixture
which was refluxed for 2 hours to yield an almost completely
solid, orange mixture. Filtration gave 16.0 g (32.8 mmoles

161
or 71.91) of yellow 1,2-dihydro-3,6-bis (4 - iodopheny 1) -
1,2,4,5 -tetrazine.
To 2.0 g (4.1 mmoles) of the dihydrotetrazine dissolved
in 150 ml of acetone was added excess anhydrous iron trichlor
ide powder. The resulting purple sludge was filtered, washed
with water and dimethyl formamide, and recrystallized from
xylene to give 0.90 g (1.9 mmoles or 451) of 17 as purple
leaflets, mp 308-310° (dec.). Final purification to remove
small amounts of what was later tentatively identified as
2,5-bis (4-iodopheny1)-1,3,4-thiadiazole (18) was accomplished
by rapidly passing the compound in boiling xylene over basic
alumina. If the tetrazine remained in contact with the
alumina too long, the characteristic purple color of the
tetrazine was destroyed indicating total decompostion. The
IR of this tetrazine was very similar to that for the known
3,6 - bis (4-bromopheny1)-1,2,4,5-tetrazine (65) . 6
Mass Spectrum: 487 (1.5%), 486 (8%), 229 (100%), 101
(95%), 75 (23%), 51 (18%).
Infrared (KBr): 2920, 1580, 1495, 1320, 1185, 1057,
1003, 919, 840, 825, 727, 710, 590 cm"1.
3,7-Bis(4-iodopheny1)-4,5,6-triphenyl-4H-l,2-diazepine (19)
A solution of 2.03 g (4.18 mmoles) of unchromatographed
17 in 200 ml of xylene containing 1.23 g (4.59 mmoles) of sym
triphenylcyclopropene29 was refluxed 22 hours with additional
small amounts of the cyclopropene added near the end to
completely remove the red coloration.
The xylene was flash evaporated and the almost colorless

162
residue dissolved in chloroform and filtered. Crystals were
obtained on addition of low-boiling petroleum ether to the
chloroform solution. Final purification was accomplished by
chromatography over silica gel which gave 1.22 g (1.68 mmoles
or 40.31) of very pale green crystals of 19, mp 249.0-249.5°.
Mass Spectrum: 728 (2%), 727 (8%), 726 (211), 699
(151), 698 (3 8%) , 623 (39%), 498 (32%), 497 (100%), 496 (24%),
269 (17%), 268 (19%), 266 (20%), 230 (13%), 150 (50%), 103
(15%), 87 (23%), 86 (36%), 85 (37%), 84 (59%), 60 (15%),
45 (18%).
Analysis for C35H24I2N2:
element calculated found
C 57.87% 57.73%
H 3.32% 3.48%
NMR (CDC13):
t2.25-3.04 multiplet 26H
4.17 br. singlet 1H
Infrared (KBr): 2940, 1595, 1460, 1010, 1000, 828,
770, 745, 713, 700 cm"1.
Kinetics of the Thermal Rearrangement of 1,2,5,6,7-Penta-
phenyl-3,4-diazabicyclo[4.1.0]hepta-2,4-diene (2) to
3,4,5,6,7-Pentaphenyl-4H-1,2-diazepine (3).
Kinetic runs were made at 150.0°C and 140.0°C by follow¬
ing the disappearance of the cyclopropyl absorbance of 2
in the NMR with fluorene as an internal standard.
Kinetic solutions were made up of about 40 mg of 2 and

163
10 mg of fluorene both accurately weighed and dissolved
in the standard amount of d5-nitrobenzene in an NMR tube
which was then sealed with a pressure cap.
Kinetic values for 2 relative to the internal standard
were taken from at least three good integrals. Integrals
which were exceptionally noisy were discarded. The kinetic
parameters were obtained from a least squares plot.
2,5,7-Triphenyl-3,4-diazabicyclo[4.1.0]hepta-2,4-diene (7)
The stirring of 1.27 g (3.90 mmoles) of tra.ns-1,2-
dibenzoyl-3-phenylcyclopropane (31), 90 mg of sodium
hydroxide, and 0.50 ml (10 mmoles) of hydrazine hydrate in
500 ml of absolute ethanol for 72 hours resulted in formation
of a yellow suspended solid. Filtration followed by
recrystallization from 95% ethanol yielded two crops of
bright yellow needles weighing 629 mg and 58.1 mg (total:
2.15 mmoles or 55.11; lit.4: 16%) and melting, respectively,
at 232-233° and 228.5-230° with decomposition (lit.4 mp 235°).
Spectra were in agreement with those reported.4
Thermal Rearrangement of (7)
A 103 mg sample of 7 was refluxed in 7 ml of dioxane for
a total of 132 hours to yield a brown oil which showed no
recognizable absorbances in the NMR. Chromatography over
deactivated alumina gave two yellow bands, the NMR spectra of
which also showed nothing recognizable.

164
Check on the Thermal Stability of the Anticipated Thermal
Rearrangement Product of 7
A 115 mg sample of 3,5,7 - triphenyl-4H-1,2-diazepine
(26) was refluxed for 132 hours in dioxane and the residue
resulting from removal of solvent was recrystallized from
ethanol to yield 73.2 mg (63.7% recovery) of starting
material, mp 189-191°. Another recrystallization raised the
melting point to 191.8-192.5°. The recovered material had
an NMR spectrum identical to that of authentic 26.
Attempted Thermal Rearrangement of 2,5-Diphenyl-3,4-diaza-
bicyclo[4.1.0]hepta-2,4-diene (6)2
A 93.4 mg sample of 62 was refluxed in xylene containing
a few drops of N,N-dimethylaniline as a proton scavenger for
18 hours to yield, after chromatography over silica gel, only
a small amount of tar and an undetermined amount of starting
material. The recovered material gave the same NMR spectrum
as authentic 6.
1,2-Diphenylcyclopropene 13
1,2-Diphenylcyclopropene was prepared by the method of
Longone13 in the reported yield but the product could never
be obtained in completely crystalline form. Spectral
properties agreed with those given by Longone.
Dimethyl 1,6-Diphenyl-3,4-diazabicyclo[4.1.0]-hepta-2,4-
diene-2,5-dicarboxylate (22)
To 619 mg (95% purity assumed from NMR, 3.06 mmoles) of

165
1,2-diphenylcyclopropene in 10 ml methylene chloride was
added slowly a solution of 606 mg (3.06 mmoles) of dimethyl
1,2,4,5-tetrazine-3,6-dicarboxylate (9) in 50 ml of methylene
chloride until a very faint pinkness persisted. Flash
evaporation of the methylene chloride from the now golden
solution and washing with low-boiling petroleum ether
yielded 984 (2.72 mmoles or 90% based on unused tetrazine)
of yellow crystals of 22, mp 192.3-193.0° (dec.). Mixing
diphenylcyclopropene with excess 9 invariably produced an
intractable crystalline mixture.
Low temperature NMR work was done for this compound.
Mass Spectrum: 364 (5%) , 363 (24%) , 362 (100%) , 329
(19%), 277 (35%), 259 (20%), 245 (33%), 212 (31%), 211 (34%),
210 (37%), 115 (13%).
Analysis for C2iHieN204:
element
calculated
found
C
69.60%
69.70%
H
5.01 %
5.18 %
N
7.73%
7.87 %
NMR (CDC13 , -3.
5°C) :
t2.95
singlet
10H
6.35
singlet
6H
6.37
doublet
1H
J= 5.6 Hz
9.0
doublet
1H
J= 5.6 Hz
Infrared (KBr):
2950, 1750,
1540, 1470,
1430, 1330
1210, 1180, 11
00, 830, 790,
775, 700 cm"
i
•

166
Attempted Thermal Rearrangement of (22)
A 150 mg sample of 22 was refluxed in 10 ml of dioxane for
12 hours to yield a brown mixture which, on crystallization
from chloroform-1ight petroleum ether or diethyl ether, gave
a small amount of faintly colored needles, mp 123-123.5°.
This compound is tentatively identified as dimethyl 1,6-
diphenyl - 3,4-diazabicyclo[4.1.0]hept-2-en-4-ol-2,5-dicarboxy-
late (26).
Mass Spectrum: 381 (8%), 380 (21%), 275 (15%), 261 (17%),
260 (64%), 229 (23%), 197 (32%), 192 (16%), 191 (12%), 190
(58%), 188 (20%), 157 (15%), 135 (36%), 134 (18%), 132 (15%),
120 (24%), 105 (100%), 78 (13%), 77 (60%), 52 (15%).
Analysis for C2iH2oN205:
element
calculated
found
66.30%
66.43%
H
5.30%
5.34%
N
7.37%
7.29%
NMR (CDC13) :
T 1.15
br. singlet
1H
2.75-3.18
multiplet
8H
3.5-3.7
multiplet
2H
4.75
br. singlet
1H
6.18
sh. singlet
3H
5.58
sh. singlet
3H
6.78
AB quartet
2H JAB=12.5 Hz
Infrared (KBr):
3350, 3200,
3000, 2900, 1725, 1720,
1500, 1440, 1320, 1300, 1220, 767, 700 cm

167
Dimethyl 1,6-Dipheny1-3,4-diazabicyclo[4.1,0]hepta-2,4-
diene-2,5-dicarboxylate Hydrate (26)
A suspension of 74 mg of 22 in 10 ml of 4:1 water-dioxane
was refluxed for 10 minutes to produce a colorless solution
which was then extracted with chloroform. On concentration
the chloroform solution yielded colorless, gummy crystals
which, after washing with carbon tetrachloride and recrystal¬
lization from chloroform-1ight petroleum ether, melted at
127.7-128.0°. This compound gave an infrared similar to,
but different from, that for the previously isolated 26.
l,2,5,6-Tetraphenyl-3,4-diazabicyclo[4.1.0]hepta-2,4-diene (21)
A chloroform solution of 1,2-diphenylcyclopropene
(339 mg, 94% purity assumed from NMR; 1.66 mmoles) and 3,6-
diphenyl - 1 , 2 , 4 , 5 - tetrazine (1) (412 mg; 1.76 mmoles) was
stirred for eleven days at room temperature. The solvent
was flash evaporated from the still red solution and the
residue chromatographed over basic alumina to yield 120 mg
(0.513 mmoles) recovered tetrazine and 586 mg (1.47 mmoles)
or 99.5% based on recovered tetrazine) bright yellow needles
of 21, mp 207.5-208.0° (dec.).
High temperature NMR work was done on this compound.
The temperatures were not accurately determined.
Mass Spectrum: 401 (2%), 400 (8%), 399 (11%), 398
(26%), 397 (8%), 371 (16%), 370 (37%), 296 (32%), 295 (100%),
294 (28%), 293 (16%), 192 (21%), 190 (30%), 189 (17%), 149
(24%), 103 (36%), 78 (34%).

168
Analysis for C29
H 2 2 N 2 •
element
calculated
found
C
87.40%
87.25%
H
5.57%
5.69%
NMR (CDC13):
x2.0-2.36
multiplet
4H
2.65-2.95
multiplet
6H
3.16
singlet
10H
6.31
doublet
1H
J= 5.5
Hz
8.68
doublet
1H
J= 5.5
Hz
Infrared (KBr):
2990, 1490,
1430, 1330,
1140,
108
1030, 1020, 930
, 785, 715,
700, 695 cm
i
Attempted Preparation of 2,5,7,7-Tetraphenyl-3,4-diazabicyclo-
[4.1.0]hepta-2,4-diene (29)
A solution of 7.508 g (18.68 mmoles) of trans-1,2-
dibenzoyl-3,3-diphenylcyclopropane (32), 1 8 1.84 ml (56.1
mmoles of anhydrous 97% hydrazine and 0.36 g (9.0 mmoles)
of sodium hydroxide in 700 ml of absolute ethanol was
refluxed for 72 hours during which time the mixture initially
turned yellow but at the end was totally colorless. The
solid which resulted on evaporation of solvent was recrystal¬
lized first from chloroform-hexane and then from 95% ethanol
to yield two crops of colorless rhombs weighing a total of
4.85 g (12.2 mmoles or 65.6%). The first crop melted
185.7-186.0°. The compound was identified as 3,6-diphenyl-
4-benzhydrylpyridazine (33) .

169
Mass Spectrum:
400 (5%), 399 (29.9%), 398 (1.00%),
67 (13%) , 65 (13%).
Analysis for C29
H22N2:
element
calculated
found
C
87.40%
87.39%
H
5.57%
5.61%
N
7.03%
6.98%
NMR (CDC13):
Tl.86-2.16
multiplet
2H
2.4-3.23
multip let
19H
4.31
singlet
1H
Infrared (KBr):
2950 , -1575 ,
1490, 1450, 1390, 1190,
10S0, 1030, 1000, 790
, 765, 740,
705, 700 cm'1.
6,6 - Diphenyl - 2,4-diketo-3-oxabicyclo[3.1.0]hexane (54)
To a solution of 5.45 g (55.6 mmoles) of commercial maleic
anhydride in 400 ml of warm benzene was added with magnetic
stirring 11.99 g (61.75 mmoles) of diphenyldiazomethane19 in
a small amount of benzene. On mixing, immediate gas evolution
and decolonization began. After stirring for 12 hours, the
mixture was flash evaporated and the resulting slightly pink
mass was broken up, washed with low-boiling petroleum ether,
and recrystallized from cyclohexane to yield 9.0 g (34 mmoles
or 61%; lit.,20 25.3%) snow-white, fine needles melting at
161.0-161.3° (lit.,20 mp 162°). The NMR spectrum of 34
agreed with that given in the literature.20

170
5,3-Diphenyl-cis-1,2-cyclopropanedicarboxylie Acid (45)18
A mixture of 2.0 g (7.6 mmoles) of 34 and 0.8 g (20
mmoles) of sodium hydroxide in 100 ml of water was stirred at
room temperature for 4 hours, filtered, and acidified to yield
1.9 g (6.7 mmoles or 891) of crystalline 45, mp 201-202°
(effervescence)-(lit.,18 mp 204°). Recrystallization only
served to lower the melting point.
Attempted Preparation of 7,7-Dipheny1 - 2,5-diketo-3,4-diaza-
bicyclo[4.1.0]heptane (44)
A) A solution of 1.6 g (6.0 mmoles) of 45 in 600 ml of
absolute ethanol was stirred for 4 days with 0.90 ml (0.87 g,
17 mmoles) of hydrazine hydrate. After flash evaporation of
the ethanol, there remained a water-soluble substance which,
on acidification, yielded 1.3 g (4.6 mmoles or 77% recovery)
of starting material, mp 199.0-199.5°.
B) A mixture of 1.2 g (10.0 mmoles) of maleic hydrazide25
and 2.04 g (10.5 mmoles) of diphenyldiazomethane19 was
stirred in 250 ml dimethyl formamide for 25 days after which
period the solvent was flash evaporated to yield a gummy
solid which produced nothing identifiable even after
recrystallization from 951 ethanol.
C) A sample of 8.0 g (30 mmoles) of 34 was refluxed in
800 ml of absolute ethanol containing 2.25 ml (46 mmoles) of
hydrazine hydrate for 60 hours. The ethanol was flash
evaporated giving a crude solid which, on crystallization
from a small amount of absolute ethanol, yielded 6.3 g

171
(23 mmoles or 751) of colorless crystals of 44 (or its isomer -
see Chapter I), mp 177.8-178.8°.
Mass Spectrum: 279 (21), 278 (31), 277 (II), 262 (41%),
261 (411), 233 (301), 220 (391), 219 (411), 192 (641), 191
(1001), 190 (141), 189 (281), 165 (381), 115 (171).
Analysis for Ci7Hii+N202:
element
C
H
N
calculated
73.661
5.071
10.071
NMR (CDC13):
found
73.661 73.501
5.081 5.171
10.041
r2.40-2.98
mu1tip let
10H
6.50
br. singlet
2H
6.88
singlet
2H
Infrared (KBr):
3350, 3290,
3050, 1730 1430,
1148, 910, 855, 775, 752, 704, 690, 545 cm
1210 ,
Attempted Preparation of 2,5 , 7,7-Tetrapheny1-3,4-diazabicyclo-
[4.1.0]hepta-2,4-diene (29)
Assuming a 701 yield, 24.8 mmoles of phenyllithium were
synthesized from 493 mg (71 mmoles) of lithium metal and
11.14 g (71 mmoles) of bromobenzene in 60 ml of dry diethyl
ether.
The pheny11ithium solution was added dropwise to a
magnetically stirred solution of 1.40 g (5.02 mmoles) of
44 in 125 ml of dry benzene. A very dark, apparently yellow,
reaction mixture was produced. The dark reaction mixture

172
was extracted with water, filtered, and dried to give an
intractable yellow gum.
Attempted Preparation of exo-3,3-diphenyl-endo-2,4-dibenzoyl-
tricyclo[5.2.1.02,4]oct-6-ene (39)
A mixture of 601 mg (2.00 mmoles) of 2,3-dibenzoylbicyclo-
[2.2.1]hepta-2,5-diene (39)22 and 408 mg (2.10 mmoles) of
diphenyldiazomethane19 was stirred for 24 days in 130 ml of
benzene to produce a faintly yellow solution. Upon evaporation
of solvent and exposure of the residue to the atmosphere, a
deep purple petroleum ether insoluble substance appeared.
On further exposure to the atmosphere, the purple residue
transformed into a brown tarry mass.
Attempted Preparation of 7,7-Diphenyl-1,6-dibenzoylbicyclo-
[4.1.0]hept-3-ene (42)
A solution of 993 mg (3.44 mmoles) of 1,2-dibenzoy1 -
cyclohexa-1,4-diene (41)23 in 125 ml of benzene was combined
with 700 mg (3.61 mmoles) of diphenyldiazomethane19 with no
apparent reaction. After one day of stirring at room
temperature, there was still no perceptible reaction so the
benzene was brought to reflux until all traces of diphenyl¬
diazomethane were gone. The NMR spectrum of this crude
reaction mixture indicated much starting material, but no
signals for the desired product. Additional diphenyl¬
diazomethane merely produced what was assumed to be benzo-
phenone azine.

173
3,3-Diphenyl-2-cis-benzoylcyclopropanecarboxylic Acid (35)
A) Under anhydrous conditions, 9.75 g (73.1 mmoles) of
aluminum chloride were added to 7.9 g (30 mmoles) of 34 in
warm benzene with rapid mechanical stirring. The reaction
was worked up by a procedure developed by Maier.3 This
involved adding the reaction mixture to aqueous hydrochloric
acid, removing the benzene, filtration, dissolution of the
filtrant in aqueous bicarbonate solution, filtration again,
and precipitation of the ketoacid from the filtrate with
mineral acid. The solid obtained in this case was a beige
powder which consisted mostly of yellow, gummy resin.
Different experimental conditions were tried but none
gave the desired compound.
B) Essentially the same reaction as in A) was run
except that 1.601 g (6.061 mmoles) of 34 in 425 ml of dry
benzene were added to 3.30 g (24.8 mmoles) of aluminum chlor¬
ide in 200 ml of dry benzene over a 2-hour period with rapid
mechanical stirring. Using Maier's workup after an
additional 5.5 hours of stirring gave 1.61 g (4.71 mmoles or
77.7%) of a colorless compound, mp 217.8-218.8°, after
recrystallization from chloroform-ligroin. The compound was
tentatively identified as the trans isomer (37) of the
desired compound.
Mass Spectrum: 343 (1.5%), 342 (31), 297 (13%), 265
(20%), 264 (100%), 247 (11%), 221 (10%), 220 (53%), 219
(30%), 218 (13%), 192 (22%), 191 (20%), 189 (23%), 165 (13%),
105 (59%), 77 (12%).

174
Analysis for C23H
1803 :
element
calculated
found
C
80.68%
77.50% 77.59%
H
5.30%
5.07% 5.07%
NMR (CDC13):
xl.75-2.0
multiplet
2.33-2.9
multiplet
5.76
doublet
J = 6 Hz
6.37
doublet
J = 6 Hz
C) Using standard
technique
, 19.4 mmoles phenyl-
magnesium bromide were
prepared
in 25 ml of dry diethyl ether
The ether solution of the Grignard was added to 5.28 g
(20.0 mmoles) of 34 over a period of 30 minutes. After
stirring an additional 90 minutes the reaction mixture was
poured onto 500 ml of ice-water slush and acidified. The
organic solvents were flash evaporated leaving behind a
gummy solid which was stirred overnight with a solution of
1.7 g sodium bicarbonate in 100 ml water.
The bicarbonate solution was filtered and acidified
with concentrated hydrochloric acid to yield after filtration
and recrystallization from ethanol, 470 mg (1.37 mmoles or
6.9%) of 35, mp 187.7-189.0° (effervescence).
An attempt at scaling up the reaction gave less material.
It was later found that the ethanol recrystallization is
wasteful and benzene recrystallization was substituted.
Mass Spectrum: 342 (1%), 298 (16%), 220 (23%), 193

175
(23%) , 192 (13%), 191 (13%), 165 (10%), 105 (21%), 103
(100%), 77 (29%).
Analysis for C2
3H1803:
element
calculated
found
C
80.68%
80.20%
H
5.30%
5.52%
NMR (CDC13) :
Tl.76-2.0
multiplet
2H
2.20-2.97
multiplet
13H
6.48
AB-quartet
2H JAB
-1.4
v. br. singlet
1H
Infrared (KBr): 2940, 2510, 1730, 1630, 1590, 1570,
1460, 1250, 1240, 955, 750, 720, 710, 695, 690 cm'1.
D) Using standard technique, diphenylcadmium was
synthesized from 9.72 g (400 mmoles) of magnesium, 47.1 g
(300 mmoles) of bromobenzene, and 31.2 g (281 mmoles) of
anhydrous cadmium chloride.
The diphenylcadmium was leached from its reaction
mixture with two 100 ml portions of benzene, filtered, and
mixed with 8.98 g (34.0 mmoles) of 34 in 300 ml of benzene
to yield, after standing for 36 hours, a gummy precipitate to
which was added 90g (910 mmoles) of 37% hydrochloric acid
in 500 ml of ice-water slush. The benzene layer yielded
yellow crystals which were stirred overnight with a solution
of 8.4 g (100 mmoles) of sodium bicarbonate in 600 ml of water.
Acidification of the aqueous solution produced very little
of the desired ketoacid as the residue left behind from the

176
bicarbonate wash contained most of the compound. The total
yield was 2.45 g (7.17 mmoles or 21%) of the colorless,
crystalline 35, mp ca. 190° (effervescence).
Analysis for C23H18O3:
element calculated found
C 80.68% 80.48%
H 5.30% 5.43%
E) Phenylmagnesium bromide (39.5 mmoles) was prepared
by standard technique in 75 ml of diethyl ether and added over
45 minutes to 10.4 g (39.4 mmoles) of 34 in 1200 ml of dry
toluene which had been cooled to -68 to -75°. The reaction
mixture was subjected to Maier's workup using 8.6 g (87.3
mmoles) of 37% hydrochloric acid in 500 ml of water and 8.4 g
(100 mmoles) of sodium bicarbonate in 600 ml of water. As in
D), some of the ketoacid did not dissolve in the bicarbonate at
first and had to be dissolved in the bicarbonate solution after
a crystallization from benzene. The total amount of material,
1.494 g (4.37 mmoles or 11.1%) was obtained in two crops,
735 mg and 759 mg, melting at, respectively, 197-198° and
188.5-189.5° (effervescence).
Pyrolysis of 35
A sample of 100 mg (0.292 mmoles) of 35 was heated neat
at about 200° until gas evolution ceased. The brown melt
was recrystallized twice from diethyl ether-light petroleum
ether to yield 14 mg (0.047 mmoles or 16%) of slightly yellow
needles, mp 125.0-125.7°, (lit.,26
mp 126-126.5°). A separate

177
sample was pyrolyzed neat in an NMR tube to give the NMR
spectrum described below. The compound was identified as
1,4,4 - triphenylbut-3-en-1-one (48).
NMR (CDC13):
1330
t2.05-2.31
multiplet
2H
2.42-3.0
multiplet
13H
3.59
triplet
1H
J=7.0
Hz
6.21
doublet
2H
J=7.0
Hz
Infrared (KBr):
2900, 1670 (1
it.26,
1690),
1435
1210, 995, 770,
765, 745, 700
, 695,
68 5 cm
1
2,7,7-Triphenyl-3,4-diazabicyclo[4.1.0]hepta-2-en-5-one (36)
To 4.3 ml (4.3 g, 86 mmoles) of hydrazine hydrate in
400 ml of absolute ethanol was added 2.470 g (7.222 mmoles)
of 35. After stirring for 12 hours a precipitate appeared
and was filtered off after another 24 hours of stirring to
yield 1.77 g (5.22 mmoles or 72.4%) of colorless crystals of
36 mp 244.0-245.0°. An analytical sample was obtained on
recrystallization from etlianol, mp 244.7245.2°.
Mass Spectrum: 339 (5%), 338 (24%), 337 (16%), 235
(39%), 193 (22%), 192 (100%), 191 (28%), 166 (13%), 165
(47%), 115 (12%), 77 (13%).
Analysis for C23H18N2O:
element calculated found
C 81.63% 79.50% 79.63%
H 5.36% 5.71% 5.63%
N
8.28
8.04%

178
Calculated for hemihydrate: C, 79.51%; H, 5.511; N,
8.07%.
NMR (CDC13):
rl. 9
br. singlet
1H
1.95-2.13
multiplet
2H
2.40-3.16
multip let
13H
6.88
AB-quartet*
2H
*The upfield half appears as a doublet of doublets due
to further splitting by the N-H function. Jg^=1.5 Hz and
Jan=0.0 Hz as determined from an HA-100 spectrum.
Infrared (KBr): 3100, 3000, 2850, 1670, 1495, 1445,
1365 , 1320 , 1070 , 775 , 760 ,.705 , 692 cm"1.
2,5,7,7-Tetraphenyl-3,4-diazabicyclo[4.1.0]hepta-2,4-diene (29)
Phenyllithium (9.94 mmoles) prepared from 197 mg
(28.4 mmoles) of lithium and 2.23 g (14.2 mmoles) of bromo-
benzene in 60 ml of dry diethyl ether was added dropwise to
674 mg (1.99 mmoles) of 36 in about 100 ml of freshly distilled
tetrahydrofuran (THF). The transient red color which appeared
as each drop of phenyllithium made contact with the THF
solution remained after about one-fifth of the addition.
The deep red reaction mixture was stirred an additional
30 minutes and then poured onto 500 ml óf ice-water slush
containing 800 mg (13 mmoles) of glacial acetic acid. The
pale yellow compound was extracted -with diethyl ether and
chromatographed over basic alumina to yield 374 mg (0.939
mmoles or 47.2%) of bright yellow, beautiful needles of 29,
mp 227.0-227.5° (dec.).

179
Mass Spectrum:
400 (1%) , 399
(14%), 398
296 (25%), 295 (100%)
, 294 (23%),
193 (22%),
166 (25%).
Analysis for C29
H 2 2 N 2 :
element
calculated
found
C
87.40%
87.44%
H
5.57%
5.58%
N
7.03%
6.93%
NMR (CDC13):
xl.60-2.0
multiplet
4H
2.34-2.7
multiplet
6H
2.71
singlet
6H
3.03
singlet
6H
6.58
singlet
2H
Infrared (KBr):
2940, 1540,
1495, 1450,
705, 690 cm 1.
Acid-catalyzed Rearrangement of 29
A sample of 100 mg of 29 was refluxed 3 hours in 50 ml of
dioxane containing 0.5 ml of 37% hydrochloric acid to yield
a bright yellow solution which, after neutralization, removal
of solvent, and chromatography over basic alumina, yielded
46 mg (46%) of 3,6-diphenyl-4-benzhydrylpyridazine (33) as
proved by NMR. The still colored 33 was recrystallized from
absolute ethanol to give material melting 177.5-179°C (pure
material, 185.7-186.0°).

180
Attempted Base-catalyzed Rearrangement of 29
A mixture of 93 mg of 29 and 19 mg of sodium hydroxide
was refluxed for 75 hours in 25 ml of absolute ethanol to
give a still green, but cloudy mixture which, after filtration
and chromatography over basic alumina, yielded 73 mg (78%
recovery) of 29, mp 231-231.5° (dec.). The NMR spectrum of
the recovered material was identical to that for authentic 29.
Thermal Rearrangement of 29
A) A sample of 100 mg of 29 was refluxed a total of
24 hours in 25 ml of xylene. After flash evaporation of the
xylene and chromatography over basic alumina, 45.1 mg (45.1%)
of faintly colored unknown 49, mp 225.0-225.3° was obtained
B) A sample of 500 mg of 29 was refluxed for 23 hours
in xylene containing a small amount of quinoline as a proton
scavenger to yield 245 mg (81.7%) of 49 on crystallization
from low-boiling petroleum ether.
Compound 49 was found to be unchanged on dissolving
in pyridine. That the signal in the NMR spectrum of this
compound in CDCI3 at t0.18 was due to hydrogen attached to
nitrogen was proved by adding deuterium oxide to the NMR
solution causing the signal to disappear.
Mass Spectrum: 400 (5.5%), 399 (32%), 398 (100%),
397 (14%), 321 (17%), 295 (3.5%).
Analysis for C29H22N2:
element calculated found
c
87.40%
87.34%
87 ,
.37%
H
5.57%
5.65%
5,
,61%
N
7.03%
7.02%
6,
.95%

181
NMR (CDC13) :
x0.18
br. singlet
1H
2.40-2.95
mult ip let
15H
2.95-3.52
multiplet
6H
NMR (d5-pyridine)
:
xl.9-2.3
multiplet
4H
2.3-2.9
multiplet
12H
3.06
singlet
5H
Infrared (KBr):
3100, 2940, 1490,
1140 ,
765, 750, 739, 729, 700, 693 cm'1.
UV (ethanol): 298 (infl.), 255 (infl.), 237 (28400) nm,
Attempted Oxidation of 49
A) A sample of 106 mg (0.266 mmoles) of 49 was dissolved
in about 4 ml of glacial acetic acid and 31.2 mg (0.106 mmoles)
of potassium dichromate in 0.5 ml of water were added. The
resulting orange solution was heated on the steam bath to
give, after 2 hours, a dark green solution. Water was added
to precipitate the organic material which was extracted into
chloroform and chromatographed over basic alumina to yield
mainly tar and 43.8 mg (41.3% recovery) of starting material,
mp 225-226°. The NMR spectrum of the recovered material was
identical to that for authentic 49.
B) A mixture of 75.0 mg (0.188 mmoles) of 49 and 44.7 mg
(0.197 mmoles) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ) was refluxed for 1 hour in benzene to produce a very
dark green, fairly insoluble compound which on chromatography

182
over basic alumina yielded 65 mg (0.16 mmoles or 8.7% recovery)
of starting material, mp 225.5-226.0°. The mass spectrum
of the recovered 49 showed no P-2 peak.
3-(4-chlorophenyl)-1,2-diphenylcyclopropene (62)
To 3.44 mmoles p_-chlorophenylmagnesium bromide in 50 ml
of dry diethyl ether was rapidly added 1.000 g (3.440 mmoles)
of diphenylcyclopropenyl perchlorate. A resinous clump of
brown material appeared immediately. After workup with
saturated aqueous ammonium chloride and removal of solvent,
the brown oil was chromatographed over basic alumina to
yield a colorless, oily solid material which tended to
discolor even in the absence of air and light. As determined
at a later date, the desired material was probably obtained,
but was contaminated with an unknown material which appeared
to be produced by too rapid addition of the cyclopropenyl
cation.
NMR (CDC13) :
t2.20-2.78 multiplet 12H
2.86 singlet 6H
6.79 singlet 1H
3- (4-methylphenyl)-1,2-diphenylcyclopropene (63)
A solid sample of 1.00 g (3.44 mmoles) of diphenyl¬
cyclopropenyl perchlorate was added slowly to a solution of
6.90 mmoles of p_-tolylmagnesium bromide in 50 ml of diethyl
ether under anhydrous conditions. As in the attempted
synthesis of 62, rapid addition tends to produce resinous

183
material which discolors the final product. A mild reflux
is produced on introduction of the cation to the Grignard
reagent. After workup as in the case of 62 and chromato¬
graphy over basic alumina, 451 mg (1.60 mmoles or 46.31) of
colorless, completely crystalline 63 was obtained, mp 103-
105.5°. An analytical sample was obtained on recrystalliz¬
ation from hexane, mp 106.9-107.5°.
Mass Spectrum: 284 (4%), 283 (251), 282 (1001), 281
(19%), 268 (12%), 267 (50%), 266 (11%), 265 (20%).
Analysis for C
2 2H18:
element
calculated
found
C
93.58%
93.52%
H
6.42%
6.41%
NMR (CDC13):
t2.04-3.25
multiplet
14H
6.83
singlet
1H
7.76
singlet
3H
Infrared (KBr): 2940, 1830, 1510, 1490, 1445, 1025,
915, 830, 763, 740, 688 cm'1.
UV: 332.5 (23000), 315 (28000), 305 (s , 22000),
302 (inf1.), 228 (32000) nm.
2,5-Bis(4-bromopheny1)-7-(4-methylpheny1)-1,6-diphenyl - 3,4-
diazabicyclo[4.1.0]hepta- 2,4-diene (66)
A mixture of 451 mg (1.60 mmol'es) of 63 and 659 mg
(1,68 mmoles) of 3,6-bis (4-bromopheny1)-1,2,4,5-tetrazine
(65)5 was refluxed for 55 hours in a 75:25 mixture of xylene-

184
chloroform to yield a wine-red reaction mixture which was
filtered and chromatographed over basic alumina to yield
104 mg (0.265 mmoles) of recovered tetrazine 65 and, after
long vacuum drying at elevated temperature, 777 mg (1.20
mmoles or 84.5% based on recovered tetrazine) of bright
yellow crystals of 66, mp 231.5-
232.0° with si
cation and some decomposition.
Mass Spectrum:
See Chapter
II, Figure 6
Analysis for C3
6H2 6Br2N2:
element
calculated
found
C
66.89%
67.12%
H
4.05%
4.18%
N
4.33%
4.31%
NMR (CDC13):
t2.11-3.75
mu1tiplet
22H
5.03
singlet
1H
7.83
singlet
3H
Infrared (KBr):
3000, 1590
, 1490, 1390,
1010, 835, 725, 695
cm 1 .
Thermal Rearrangemen
t of Diazanorcaradiene 66
A sample of 500
mg of 66 was refluxed in
for 24 hours to give
a very pale
yellow solut
flash evaporated and chromatographed over basic alumina.
Apparent unanticipated decomposition to pyrroles and benzo-
nitriles made purification usually difficult and lowered
the yield of crystalline diazepine 66. Only 130 mg (26%) of 66

185
mp
840
230.8-231.0° were obtained.
Mass
Spec
trum:
See Chapter
II, Fi,
gure 7.
Analysis
for C
3 6 H2 6 hr 2N 2 :
element
calculated
found
C
66.89%
66
.75%
H
4.05%
4
.10%
N
4.33%
4
.37%
NMR
(CDC1
3) :
T 2.36
-3.33
multiplet
22H
4.20
singlet
1H
7.85
singlet
3H
Infr
ared
(KBr)
: 2940, 1580,
1480 ,
1075, 1000, 1010,
820,
805 ,
735,
720, 698 cm-1
X-ray Analysis of Diazepine 67
Crystals of the diazepine suitable for x-ray analysis
were grown either from saturated chloroform-ligroin solutions
or by solvent exchange using chloroform and ligroin. The
diazepine crystallizes as beautiful, clear, almost colorless
rhombs.
From precession photographs of a small crystal mounted
along its diagonal, it was determined that the diazepine
crystallizes in the monoclinic system with space group
(C^h) or Cc(C|p (systematic absences hkl: h+k=2n; hOl:
l=2n; OkO: k=2n).79 The rough cell constants were determined
to be a=25.70 A, b=10.48 A, c=21.37 A, and B=90°10'. A
calculated density of 1.491 g/cm3 assuming eight molecules

186
per unit cell agreed quite well with the experimentally
found value (in carbon tetrachloride-cyclohexane) of
1.468 g/cm3.
A crystal of approximate dimensions 0.207 x 0.275 x
0.25 mm was mounted on a Syntex Autodiffractometer for data
O
collection. Molybdenum K radiation (0.71069 A) was used.
3.
The accurate cell constants with their estimated standard
deviations (e.s.d.) in parentheses next to them were deter-
O
mined by the diffractometer and are as follows: a=25.77 A
(0.01 A), b=10.528 A (0.009 A), c=21.42 A (0.02 A), and 6=
90.25° (0.02°). A total of 3872 reflections was measured by
the 20-0 moving crystal-moving counter method up to 20 = 45°.
After data processing, only 2643 reflections were
considered observed, i.e, not less than 1.30 times their
e.s.d. A Wilson plot80 of the intensity data indicated that
the diazepine probably crystallized with a centric space
group (C2/c).
A sharpened Patterson function81 revealed the positions
of the two bromine atoms thus solving the phase problem.
From a first Fourier series82 on the data using the
known positions of all the bromines, the positions of all
thirty-eight non-hydrogen atoms were found and estimated by
Booth’s83 method bringing the R-value to 34.051% in a
second Fourier series. The same estimating procedure in the
second Fourier brought the R-value down to 20.955%
Further refinement of the structure was accomplished
using full-matrix least squares (FMLSQ) with all atoms

187
isotropic. After one cycle, the R-value dropped to 14.3721.
After one more cycle of isotropic FMLSQ and one cycle of FMLSQ
with only the bromine atoms anisotropic, the R-value dropped
to 8.664% and, with all atoms anisotropic and three cycles of
block diagonal least squares (BDLSQ), the R-value was 7.223%.
From a difference Fourier, the position of each hydrogen
was also found and estimated again by Booth's method. Two
cycles of BDLSQ excluding the hydrogens caused the R-value
to drop to a respectable 5.982%. A final cycle of BDLSQ
including the hydrogens only brought the R-value down to
5.921%, but refined the carbon-hydrogen bond lengths to
O O
acceptable limits (0.89 A to 1.11 A).
An ORTEP drawing of the molecule identified as 3,7-bis-
(4-bromopheny1)-4 -(4-methylpheny1)- 5,6-diphenyl -4H-1,2 -
diazepine (67) is given in Chapter I along with a table of
bond lengths and a table of bond angles and their e.s.d.'s.
7 - (4-Methylpheny1)-1,2,5,6 -tetrapheny1-5,4-diazabicyclo-
[4.1.0]hepta-2,4-diene (68)
A mixture of 201 mg (0.712 mmoles) of impure 63 and
175 mg (0.748 mmoles) of 1 was stirred in 50 ml of chloroform
for 14 days to yield a still purple solution which, on
chromatography over basic alumina, gave 73.5 mg (0.150 mmoles
or 21.1%) of bright yellow needles of 68, mp 212.8-213.0°.
Mass Spectrum:
See Chapter II,
Figure
Analysis for C
3 6 H 2 8 N 2 :
element
calculated
found
C
88.49%
88.38%
H
5.78%
5.85%
N
5.73%
5.62%

188
NMR (CDC13):
xl.95-2.35
multiplet
4H
2.5-3.7
multiplet
20H
5.05
singlet
1H
7.85
singlet
3H
Infrared (KBr):
2940, 2850, 1490,
1440, 1330, 1070,
920, 810, 788, 775, 740, 725, 695 cm'1.
2 , 5-Bis (4 -iodopheny1)-
1,6,7-triphenyl-3
,4-diazabicyclo-
[4.1.0]hepta-2,4-diene
: (71)
A mixture of 604 mg (1.24 mmoles, unchromatographed) of
17 and 367 mg (1.37 mmoles) of sym-triphenylcyclopropene2 9
was refluxed for 12 days in 65 ml of a 10:3 chloroform-xylene
mixture and then stirred at room temperature an additional
44 days in 50 ml of xylene. The resulting orange mixture was
filtered and chromatographed over basic alumina to yield an
undetermined amount of diazanorcaradiene 71 as bright yellow
crystals, mp 223-224°.
Mass Spectrum: 728 (3%), 727 (12%), 726 (27%), 699 (18%),
698 (41%), 624 (14%), 623 (42%), 498 (31%), 497 (100%), 496
(23%), 493 (13%), 370 (13%), 368 (15%), 268 (13%), 267 (12%).
Analysis (crystallization from benzene-ligroin) for
C3 5H2 412N2 :
element
calculated
found
C
57.87%
61.51%
61.61%
H
3.32%
3.97%
3.86%
Calculated assuming inclusion
of 1 mole
of benzene
(C4iH30I2N2): C, 61.21%; H, 3.75%.

189
Analysis (crystallization from chloroform-ligroin)
for
C35H24I2N2•
element
calculated
found
C
57.87%
51
. 77%
H
3.32%
3
.08%
N
3.86%
3
.33%
Calculated assuming inclusion
of 1
mole of chloroform
t25ci
3I2N2): c,
51.12%; H, 2.
98% ;
N, 3.31%.
NMR
(CDC13):
t 2.4 3
singlet
10H
2.5-3.3
multiplet
19H
5.02
singlet
1H
Inf r
ared (KBr):
2950, 1580,
1500 ,
1480, 1500, 1480,
1450, 1390, 1320, 1010, 828, 757, 722, 695 cm \
3,6-Dicyclopropy1-1,2,4,5-tetrazine (79)
A mixture 10.000 g (0.149 moles) of freshly distilled
cyclopropyl cyanide, 45 ml of absolute ethanol, 2.96 g
(9.24 mmoles) of flowers of sulfur, and 30.74 g (0.614 mmoles)
of hydrazine hydrate was refluxed for 2.5 hours giving a
green mixture. The mixture was poured into 800 ml of water
to produce a cloudy suspension which was immediately oxidized
with 10.4 g (0.150 moles) of sodium nitrite and 20 ml of
glacial acetic acid.
The violet, smelly mixture resulting from the sodium
nitrite oxidation was extracted to colorlessness with
methylene chloride. After drying over anhydrous sodium

190
carbonate, the purple methylene chloride layer was concentra¬
ted by distillation through a column packed with glass beads.
Codistillation of the tetrazine was a definite problem.
The concentrated solution was passed through a 3' x
1/4" FFAP on DMCS treated Chrom-P column at 120° to produce
pure, beautiful, violet needles, mp 45,5-46.5° without
decomposition. Yield: 5.7% by glpc using biphenyl as an
internal standard.
Attempts at purifying 79 by passing over SE-30 on
DMCS treated Chrom-P and by high vacuum line manipulation
were only moderately successful. Recrystallization was out
of the question as the compound is apparently soluble in all
organic solvents. As with all aliphatic tetrazines, 79 is
very volatile.
Low temperature NMR work was done on this compound. The
temperatures were determined from dial settings after a
calibration check.
Mass Spectrum: 160 (6%), 101 (6%), 81 (10%), 77 (18%),
(18%), 43 (56%)
Analysis for C
, 41 (53%), 32
e H i o N i, :
(100%) .
element
calculated
found
C
59.24%
58.90%
H
6.21%
5.93%
N
34.55%
34.39%
NMR
(CDC13):
t7.23-7.71
multiplet
2H
8.60-8.86
multiplet
8H

191
NMR (CCU) :
•
x7.25-7.72
multiplet
2H
8.54-8.88
multiplet
8H
NMR (diphenyl ether):
t7.35-7.95
multiplet
2H
8.58-9.25
multiplet
8H
Infrared (film)
: 2940, 1440,
1345, 1240, 1100, 1060,
915, 890, 820,
690 cm 1.
UV and Visible
(cyclohexane):
568 (550), 550 (706),
543 (758), 553 (s, 692), 333 (575), 323 (infl.), 310 (1950),
274 (s, 619), 226 (20100) nm.
UV and Visible (ethanol): 537 (502), 314 (1780),
270 (505), 228 (20100).
2,5-Diphenyl-l,3,4-thiadiazole (84)
A mixture of 103 g (1.00 moles) of benzonitrile, 206 g
(4.20 moles) of hydrazine hydrate, 300 ml of absolute ethanol,
and 20 g (0.62 moles) of flowers of sulfur was refluxed 1.5
hours to yield a yellow-orange precipitate (mostly dihydrodi-
phenyltetrazine). The yellow-orange precipitate was filtered
off and oxidized with excess anhydrous iron trichloride in
acetone to yield mostly 3,6-diphenyl-1,2,4,5-tetrazine (1)
which was recrystallized from benzene-methanol.
The purple mother liquor from the oxidation was treated
with cyclopropene until no tetrazine remained. The resulting
yellow diphenyldiazanorcaradiene 6 and colorless thiadiazole
84 were separated by Soxhlet extraction with hexane. The

192
thiadiazole 84 is slightly soluble in hot hexane whereas the
diazanorcaradiene 6 is completely insoluble. The thiadiazole
was brought to final purity by chromatography over basic
alumina. About 3 g (2.5%) of beautiful, colorless plates of
84, mp 141.3-142.5° (lit.,40 mp 141-142°), were obtained.
Mass Spectrum: 240 (6%), 239 (16%), 238 (92%), 136 (10%),
135 (100%), 121 (26%), 103 (13%), 77 (48%).
Analysis for Ci4HiqN2S:
element calculated found
C 70.56% 70.82%
H 4.23% 4.27%
NMR (CDC13):
tl. 80-2.20 multiplet 4H
2.36-2.68 multiplet 6H
3,6-Dicyclopropylpyridazine (80)
A sample of 397 mg (2.44 mmoles, glpc purified) of 79
was refluxed for 50 minutes in freshly distilled norbornadiene
to yield a colorless solution from which the excess norbor¬
nadiene was removed by distillation. The resulting heavy
oil was chromatographed over silica gel to give 399 mg
(2.43 mmoles, 99.6%) of a tan solid which was further purified
by passing through a 2' x 3/8" 5% FFAP on DMCS-treated Chrom-P
column held at 130°. The colorless crystals obtained from
the glpc melted at 66.0-66.5°.
Mass Spectrum: 160 (11%), 159 (100%).

193
Analysis for CioHi2N2:
element calculated found
c
74.96%
74.84%
H
7.55%
7.72%
NMR (CDC13):
x2.92
sh. singlet
2H
7.81-8.23
multiplet
2H
8.78-9.10
multiplet
8H
Infrared (KBr) :
3100, 1600,
1550, 1450, 1440, 1060,
985, 880, 820, 785 cm 1.
UV (cyclohexane): 342 (299), 276 (1330), 225 (14800) nm.
UV (ethanol): 317 (s,-248), 278 (1550), 226 (13400) nm.
3,6-Pi -iso-propyl-1,2,4,5 -tetrazine (8 8)
Sulfuric acid dried hydrogen chloride gas was bubbled
into a mixture of 173.8 g (2.52 moles) of iso-butyronitrile
and 116 ml of absolute ethanol at 0° until an increase in
weight of 90 g (7.47 moles) was observed.
Crystallization of the imidate ester could not be
induced so a yield of 324 g (2.14 moles, 85%) of iso-
butyronitrile ethyl imidate ester hydrochloride was assumed
and the imidate ester was converted into 1,2-dihydro-3,6-di -
iso-propyl-1,2,4,5-tetrazine by addition of 69.8 g (2.18 moles)
of anhydrous hydrazine in 150 ml of absolute ethanol at -60°
over 1 hour under nitrogen, with stirring. Further stirring
for 0.5 hours at -60° and 17 hours at room temperature
completed the reaction.
Without isolation, the dihydrotetrazine was oxidized by

194
adding the reaction mixture containing the dihydrotetrazine
to 4 liters of ice water containing 209.7 g (3.04 moles) of
sodium nitrite, 152 g of glacial acetic acid, and 450 ml of
methylene chloride. After separation and drying, the purple
methylene chloride solution was concentrated by distillation
through a packed column. Removal of as much remaining starting
nitrile as possible was effected by vacuum pumping. As in
the case of 79,codistillation of tetrazine was a problem.
Crude yield: 47.7 g (90% pure via glpc, 0.287 moles, 22.8%)
of a deep purple oil. Final purification for spectral
purposes was effected by passing through a 2' x 1/4" FFAP
on DMCS-treated' firebrick column at 60°C. Tetrazine 88 was
never obtained in a crystalline state.
Mass Spectrum: 168 (1.5%), 167 (2.5%), 166 (21%),
70 (91%), 69 (34%), 68 (56%), 54 (46%), 43 (100%), 42 (93%),
41 (13%).
NMR (CC14) :
t6.40
septuplet
2H
O
II
Hz
8.48
doublet
12H
O
II
Hz
Infrared (film):
2940, 1450,
1390, 1360,
1345,
1320
1270, 1230 , 1150 , 1070, 1060 , 890 , 875 cm 1 .â– 
UV and Visible (cyclohexane): 576 (s, 392), 552 (537),
280 (inf1.), 271 (3020) nm.
UV and Visible (ethanol): 544 (460) , 273 (2920) nm.
3,6-di-iso-propyl pvridazine (89)
A mixture of 29.7 g (assumed 90% pure, 0.161 moles) of

195
88 and 47 g (0.51 moles) of norbornadiene was refluxed for
7.5 hours at the end of which time all color due to the
tetrazine had disappeared. After removal of excess norborna¬
diene and dicyclopentadiene,the resulting crystalline slush
was chromatographed over basic alumina and then recrystallized
from hexane at dry ice temperatures to yield two crops of
crystals, mp 75.0-76.5°, and weighing a total of 10.6 g
(0.0645 moles or 39.8%). The second crop was slightly tan.
Material recrystallized several times from diethyl ether
melted at 77.5-79.0°. Vacuum sublimation and glpc separation
on a 5% FFAP column at 120°C only served to lower the melting
point.
Mass Spectrum: 165 (3%), 164 (17%), 163 (25%), 151
(12%), 150 (100%), 146 (84%), 144 (11%), 121 (10%), 41 (11%).
Analysis for CiqHi6N2‘
element
calculated
found
C
73.12%
73.08%
H
9.82%
9.95%
N
17.06%
16.83%
NMR (CC14):
x2.65
sharp singlet
2H
6.75
septuplet
2H
J= 7.0
Hz
8.65
doublet
12H
J= 7.0
Hz
Infrared (KBr):
3100, 3000, 1580, 1450,
1420,
1370 ,
1160, 1140, 1060
, 1055, 1040,
1020, 865
, 805
cm 1.
UV (cyclohexane) :
344 (290),
262 (1720)
, 257
(1670)
UV (ethanol): 320 (227), 257
(1650) nm.

196
Pyrolysis of 68
With the glpc injector at 260° and a 5’ 6% XF-1150 column
at 90°C (the column temperature at which £-tolunitrile and
benzonitrile were well separated) , 2 pi of 68 in benzene
(saturated) were injected into the Hy-Fi instrument. Both
£-tolunitrile and benzonitrile peaks were observed. Tailing
was a problem as was expected. The peaks were identified
solely on the basis of retention times. No attempt was made
to determine the relative amount of each nitrile.
Reaction of diazanorcaradiene 6 with DDQ
A solution of 899 mg (3.96 mmoles, benzene dust-free
filtered and freshly recrystallized from chloroform) of DDQ
in 80 ml of dry benzene (orange solution) and a solution of
975 mg (3.96 mmoles, chloroform dust-free filtered and freshly
recrystallized from chloroform-ligroin) of 6 in 90 ml of dry
benzene (bright yellow solution) was mixed to form a very deep
red solution which was refluxed 30 minutes and allowed to sit
overnight at room temperature. After sitting overnight, 797
mg of almost jet black crystals of unknown (94) crystallized.
After filtering off the dark crystals, the reaction was
returned to reflux for 2 more hours and allowed to cool.
Upon cooling, another 474 mg of brown,but crystalline material
precipitated.
Mass Spectrum: 246 , 245 , 230 ,' 228 , with peaks at as
high a mass as 486.

197
Analysis for
C2 5H14CI2N2O2:
element
calculated
found
C
63.441
64.96
H
2.98%
3.41
N
11.84%
11.22
Cl
14.98%
13.22
NMR (trifluoroacetic acid):
t1.6-2.8 br. multiplet
2.70 singlet
Infrared (KBr): 2960, 2190, 1620, 1590, 1550, 1540,
1440, 1400, 1380, 1270, 1200, 890, 780, 765, 695 cm"1.
Attempted Reaction of 3,6-diphenyl-4-methylpyridazine3
(95) and DDQ
A solution of 50 mg (0.203 mmoles) of 95 and 45.1 mg
(0.203 mmoles) of DDQ in 50 ml of benzene was refluxed for
75 minutes with no perceptible change. No change or pre¬
cipitate was found on allowing the mixture to stand overnight.
Attempted Reaction of 6 and Trityl Fluoroborate
A solution of 100 mg (0.406 mmoles) of 6 in 100 ml of
acetonitrile was mixed with 134 mg (0.406 mmoles) of fresh
trityl fluoroborate. There was no noticeable change.
Heating produced nothing but what is assumed to be tar.
Attempted Reaction of DiphenyIcyclopropenone77 with 9
A mixture of 206 mg (1.00 mmole) of diphenylcyclo-

198
propenone77 and 198 mg (1.00 mmole) of 9 in 25 ml -of methylene
chloride was allowed to stir at room temperature for 48 days.
The resulting yellow mixture yielded white solid on addition
of low boiling petroleum ether. After chromatography over
deactivated alumina, the white solid appeared to be an impure
sample of diphenylcyclopropenone.
Attempted Bromination of 5,4,5,6,7-Pentaphenyl-4H-1,2 -
diazepine (3)2
A solid sample of 237 mg (0.500 mmoles) of'3 was
suspended in 250 ml of carbon tetrachloride and a small
amount of bromine was added. After stirring for 2 days, the
suspension dissolved and then depositéd yellow crystals of
97 which, on workup, gave an NMR spectrum very similar to that
of the starting material 3. The material 97 was tentatively
identified as the N-bromo bromide salt of 3. No attempt at
obtaining an elemental analysis or mass spectrum was made
due to the instability of the material.
NMR (CDC13):
t2. 15-2.4
multiplet
2H
2.46-3.25
multiplet
23H
3.95
br. singlet
1H
Diphenylcyclopropenone Ethylene Ketal (106)78
A solution of 3.1 g (15 mmoles) of diphenylcyclopro¬
penone77 in 3.8 ml of dry methylene chloride was added to a
solution of 3.0 g (16 mmoles) of triethyloxonium fluorobroate
in 5 ml of dry methylene chloride. The combined solutions,

199
which sometimes crystallized, were added to 750 mg (33 mmoles)
of sodium dissolved in 19 ml of dry ethylene glycol at 10-20°.
The workup was that described in the literature78 except
that the major portion of the ketal was found in the
cyclohexane mother liquor rather than the first crop of
crystals. The ketal had properties which agreed with those
in the literature.78
Attempted Cycloaddition of 9 with 106
Under anhydrous conditions 250 mg (1.00 mmoles) of
106 and 188 mg (0.950 mmoles) of 9 were stirred in 25 ml of
methylene chloride for 2 days and then, due to the sluggish¬
ness of the reaction, refluxed in chloroform for 3 days to
yield an orange oil which turned dark green in the vacuum
desiccator. Chromatography of the green oil over deactivated
alumina gave unidentified blue, yellow, and dark green bands.
Attempted Preparation of Dimethyl 4,6-Diphenyl-3,7-dicarboxy-
l,2-diazepin-5-one
A mixture of 141 mg (0.919 mmoles) of potassium dihydrogen
phosphate as a saturated aqueous solution, 250 mg (0.691
mmoles) of 22, 79.5 mg (0.689 mmoles) of selenium dioxide,
and 5 ml of dioxane was combined at which time the color of
the diazanorcaradiene 22 was discharged. The still faintly
yellow suspension was maintained at 90-93°C for 21 hours,
filtered, washed with water, extracted with methylene chloride,
and concentrated to yield a yellow oil which gave no identifi¬
able peaks in the NMR. Chromatography over deactivated
alumina also gave no identifiable product.

200
Reaction of 26 with Trityl Perchlorate
A solution of 343 mg (1.00 mmole) of trityl perchlorate
in 15 ml of dry methylene chloride was mixed with 322 mg (1.00
mmole) of 26 in 10 ml of dry methylene chloride under anhyd¬
rous conditions and stirred for 14 hours at which time a pre¬
cipitate had been formed. The precipitate was filtered and
washed with a small amount of methylene chloride to yield 129
mg (0.305 mmoles or 30.5%) of bright yellow microneedles,
mp 213.7-213.9° (dec.). The compound was identified as 3,5,7-
tripheny1-4H-1,2-diazepine hydroperchlorate (98).
Analysis for C23Ht9CIN2O4:
element calculated found
C
H
NMR (TFA):
Tl. 80-2.75
5.70
Infrared (KBr)
770, 760, 695 cm'1.
65.32%
4.52%
multiplet
br. singlet
65.18%
4.62%
17H
2H
3100, 1600, 1490, 1120, 1100, 1090,
Reaction of 26 with Trityl Fluoroborate
Under anhydrous conditions, a saturated solution of
693 mg (2.10 mmoles) of trityl fluoroborate in dry methylene
chloride was stirred with 645 mg (2.00 mmoles) of 26 in 20 ml
of dry methylene chloride for 18 hours. Filtration yielded
293 mg (0.715 mmoles or 35.7%) of yellow crystals melting at
196-199° with decomposition. Chromatography of the dark

201
mother liquor yielded no triphenylmethane. The NMR sample
of the compound in trifluoroacetic acid did not decompose
or change even on standing for 22 days. The compound was
identified as 3,5,7-triphenyl-4H-diazepine hydrofluoroborate
(99).
Low temperature NMR work was done on this compound.
Mass Spectrum: 324 (41), 323 (321), 322 (95%), 220
(36%), 219 (100%), 218 (19%), 115 (15%), 103 (15%), 77 (12%),
49 (18%), 45 (20%).
NMR (trifluoroacetic acid):
tl. 80-2.75 multiplet 17H
5.70 br. singlet 2H
Infrared (KBr): 3100, 1600, 1490, 1125, 1100-1040,
1000, 970, 775, 695, 685 cm'1.
Treatment of 99 with Sodium Borohydride
A small undetermined amount of the salt 99 was added to
a solution of excess sodium borohydride in acetonitrile
producing immediate gas evolution and decolorization. Solvent
evaporation, washing with water, and extraction with chloro¬
form yielded a pale green solid which melted at 193.0-193.8°
(dec.) after recrystallization from ethanol.
The mixed melting point with an authentic sample of
3,5,7-triphenyl-4H-1,2-diazepine (26) 17 was 193.8-194.0° (dec.)
The infrared spectrum of this material was identical to that
for authentic 26.

202
3,5,7-Triphenyl-4H-l,2-diazepine Hydroperchlorate (98)
To an ice-cold solution of 0.18 ml (2.0 mmoles) of 70%
perchloric acid in 20 ml of acetic anhydride was added, with
stirring, a suspension of 644 mg (2.00 mmoles) of 26 in acetic
anhydride. The orange solution, which was produced, was
stirred for 1 hour and then poured into 300 ml of anhydrous
diethyl ether. The crystalline solid was filtered and washed
to a light yellow-orange with methylene chloride-diethyl
ether. After drying the crystals gave mp 212.0-213.0°
(dec.). The NMR spectrum of this compound was identical to
that for the compound obtained on mixing trityl perchlorate
and 3,5,7 - triphenyl-4H-1,2-diazepine (26). No attempt was
made at obtaining a yield for this reaction.
Attempted Preparation of Bis(dimethyl 1,6-diphenyl-5,4-diaza-
blcyclo[4,1.0]hepta-2,4-dien-7-yl-2,5-dicarboxylate) Ether
To a stirred solution of 458 mg (1.10 mmoles) of
bis(1,2-diphenylcyclopropen-3-yl) ether (109)75 in 50 ml of
methylene chloride was added 479 mg (2.20 mmoles) of solid
9 producing immediate nitrogen evolution for about the first
50% of the reaction at which time the reaction appeared to
terminate. The reaction mixture which was still red was
flash evaporated to yield 184 mg unreacted tetrazine. Dark
yellow crystals of what at first was thought to be diazanor-
caradiene were brought out of the benzene solution with light
petroleum ether. Since the NMR showed a peak for what was
assumed to be unreacted starting ether, the reaction was

203
continued with another 184 mg of tetrazine 9 in 50 ml of
methylene chloride. Even after 4 more days of stirring
there was no further change in the reaction mixture.
Attempted Preparation of 1,2-Diphenylcyclopropen-3-yl 1,6-
Diphenyl-3,4-diazabicyclo[4.1.0]hepta-2,4-dien-7-yl-2,5-
dicarbomethoxy Ether (105)
A solution of 198 mg (1.00 mmole) of 9 in 20 ml of methyl¬
ene chloride was added with magnetic stirring to 438 mg (1.10
mmoles) of 10375 in 50 ml of 5:1 methylene chloride-diethyl
ether resulting in slow but definite gas evolution and
decolonization. After stirring overnight, the bright yellow
solution was filtered, flash evaporated, dissolved in carbon
tetrachloride and filtered again to remove 27 mg (0.068 mmoles)
of what is assumed to be excess 103, mp 163-165°. The yellow
carbon tetrachloride solution yielded a total of 373 mg
(0.657 mmoles or 65.7%) of bright yellow crystals, mp
167.8-170.5°. Two recrystallizations from chloroform-1ight
petroleum ether raised the melting point to 173.7-174.1°.
The compound is tentatively identified as 4,5-dipheny-
3,6-dicarbomethoxy-1 -(1,2 -diphenyIcyclopropen -3-yl)-l,4-
dihydropyridazine-4-aldehyde (104) .
Mass Spectrum: 570 (1.5%), 569 (3.5%), 568 (10%),
540 (11%), 539 (25%), 482 (13%), 481 (34%), 465 (0%),
362 (0%), 350 (14%), 349 (55%), 206 (0%), 192 (21%), 191
(100%), 86 (50%), 84 (30%), 43 (18%), 42 (12%).

204
Analysis for C36H28N2O5:
element calculated
found
C
H
N
NMR (CDC13):
76.041
75.84
4.96%
5.01
4.93%
4.89
Tl .08
sh. singlet
1H
1.93-3.23
multiplet
2 OH
5.32
sh. singlet
1H
6.42
sh. singlet
3H
6.52
sh. singlet
3H
Infrared (KBr):
2950, 2840,
2730, 1730, 1700, 1540
1440, 1435, 1340, 1230, 1200, 1140, 780, 770, 760, 705,
692 cm 1.
UV and Visible (chloroform): 590 (approx. 180), 377
(4880), 312 (inf1.), 303 (26000), 298 (24600) nm.
Attempted Preparation of 3,5,7-Tripheny1 -1,2-diazacyclohepta-
trienylium Cation
A solution of 645 mg (2.00 mmoles, dust-free, freshly
recrystallized from ethanol) of 26 in about 75 ml of dry,
dust-free benzene (pale green solution) was placed in a
nitrogen-filled, oven-dried flask fitted with an addition
funnel charged with 454 mg (2.00 mmoles, benzene dust-free
filtered, freshly recrystallized from chloroform) of DDQ in
about 35 ml of dust-free benzene (orange solution). As
the DDQ solution was added to the diazepine solution, a deep
red solution resulted. After about an hour of stirring, the

205
deep red solution slowly deposited needles of colorless
material which yellowed slightly on isolation. A total of
972 mg (1.77 mmoles or 88.51) of material (102) was isolated.
The first crop melted at 178.0-178.5° with extensive
decomposition.
Mass Spectrum:
548 (trace)
, 546 (trace), 532 (3%),
430 (51), 323 (24%),
322 (85%),
321 (20%),
308 (23%), 307
(79%), 306 (31%), 294
(13%), 232
(16%), 230
(79%), 229 (15%
228 (97%), 220 (46%),
219 (100%)
, 218 (30%)
, 217 (17%), 215
(13%), 204 (13%), 202
(47%) , 200
(67%), 191
(19%), 189 (13%
137 (18%), 117 (13%),
116 (15%),
115 (31%),
110 (24%), 109
(13%), 103 (23%) , 102
(15%), 101
(17%), 91
(16%), 89 (12%),
87 (34%), 77 (42%), 76 (16%) , 51
(19%) .
Analysis for C3i
Hi8C12N402:
element
calculated
found
C
67.77%
67.92%
67.91%
H
3.30%
3.39%
3.36%
N
10.20%
10.16%
10.17%
Cl
12.91%
12.79%
12.86%
NMR (TFA):
T1.6 -2.7 mult ip let
Infrared (KBr):
2960, 2200
, 1600, 1470, 1440, 1410,
1350, 1010, 1005, 930
, 775, 760,
690 cm 1.
UV (acetonitrile): 295 (s, 18000), 528 (31900),
221 (38100), 201 (53200) nm.

206
Reduction of Complex 94
A slurry of 160 mg (4.2 mmoles) of sodium borohydride in
a small amount of acetonitrile was added to a deep red
partial solution of 200 mg (0.422 mmoles) of 94 in 35 ml of
acetonitrile producing immediate gas evolution and gradual
color change to orange-yellow. The voluminous precipitate,
which also resulted, was filtered and washed with chloroform.
The chloroform-acetonitrile solution was extracted with water,
dried, and concentrated. Addition of low boiling petroleum
ether to the concentrated solution produced colorless crystals
covered with yellow resin. Filtration and washing with a
small amount of diethyl ether yielded 27.8 mg (0.112 mmoles
or 26.5%) of almost colorless, very fine needles, mp 165.3-
165.5. A recrystallization from chloroform-ligroin removed
most of the color and raised the melting point to 166.0-166.5°.
The NMR and infrared spectra of this compound were exactly
identical to those for a sample of 2,5-diphenyl-3,4-diaza-
bicyclo[4.1.0]hepta-2,4-diene (6) which had been subjected
to sodium borohydride reduction.
Reduction 6
A sample of 500 mg (2.03 mmoles) of 6 was dissolved in
60 ml of acetonitrile by warming to produce a bright yellow
solution. To this bright yellow solution was added with
magnetic stirring 380 mg (10 mmoles) of sodium borohydride
and 0.50 ml of water. No reaction occurred.
Addition of another 400 mg (106 mmoles) of sodium

207
borohydride and 1 ml of water produced immediate gas
evolution and gradual decolorization. After 1.5 hours of
stirring the reaction mixture was colorless and contained
a voluminous, cottony precipitate. The acetonitrile was
removed, the precipitate filtered, washed with water, and
dried to a constant weight of 492 mg (1.98 mmoles or 97.61)
of cottony, almost colorless microneedles, mp 161.5-163°.
A recrystallization from chloroform-diethyl ether gave
as a first crop 397 mg (1.60 mmoles) of snow-white micro¬
needles, mp 166.7-168.0°. On standing, solutions of the
reduction product 96 turn a greenish-yellow presumably due to
air oxidation back to the diazanorcaradiene 6. Compound 96
is tentatively identified as 2,5-diphenyl-3,4-diazabicyclo-
[4.1.0]hept-2-ene. No attempt has been made at assigning the
stereochemistry of this compound.
Mass Spectrum: 250 (2.7%), 249 (22%), 248 (100%), 171
(26%), 157 (15%), 144 (20%), 143 (13%), 117 (19%), 115 (19%),
104 (11%), 91 (16%), 77 (14%).
Analysis for Ci7Hi6N2:
element calculated found
C 82.22% 82.29%
H 6.50% 6.60%
N
11. 28
11.29%

208
NMR (CDC13):
t2.1-2.43 muItiplet
2.43-2.92 multiplet
8H
2H
4.59
v. br. singlet
1H
5.92
br. singlet
1H
7.75-8.15 multiplet
3H
8.8-9.1 multiplet
1H
Infrared (Or); 3170, 2920, 2760, 1590, 1480, 1390, 1140,
1020, 1005, 852, 762, 752, 700, 688 cm"1.
Attempted Oxidation of 104
To a yellow solution of 50 mg (0.088 mmoles) of 104
in about 3 ml of glacial acetic acid was added 3 drops of
water and 10.7 mg (0.352 mmoles) of potassium dichromate.
The orange solution thus produced was heated on the steam
bath producing an immediate dark green color. After heating
2 hours, addition of water, extraction with chloroform,
neutralization with sodium bicarbonate, and addition of
ligroin only resinous material was produced. Dissolving the
resinous yellow oil in diethyl ether and cooling only
precipitated resin again.
2,5-Diphenyl-3,4-diazabicyclo[4.1.0]hepta-2,4-diene (6)2
Diazanorcaradiene 6 was prepared by the method of Battiste
and Barton.2 The NMR spectral data.were recorded as given
below.

209
*
NMR (CDC13):
xl.6-2.0
multiplet
4H
2.25-2.65
multip let
6H
7.05-7.45
multiplet
2H
7.65-8.05
multiplet
1H
9.5-9.85
multiplet
1H
NMR (TFA/CDCla):
Tl. 75-2.0
multiplet
4H
2.0-2.6
multiplet
6H
6.4-7.15
multiplet
3H
8.95-9.25
multiplet
1H
Diphenylpyridazine
(93) 1
The known 3,6-diphenylpyridazine (93) was synthesized in
only 601 yield by stirring 4.68 g (20.0 mmoles) of 1 in about
15 ml of freshly distilled norbornadiene for 2.5 hours at
room temperature. Crystallization of the desired pyridazine
was induced by the addition of 150 ml of hexane to the
reaction mixture.
NMR (CDC13):
xl .72-2.02
multiplet
4H
2.10
singlet
2H
2.32-2.67
multiplet
6H
UV (ethanol):
279 (29300).

"Who are you? What have you sacrificed?"
Jesus Christ Superstar, 1970

REFERENCES
1. J. Sauer and G. Heinrichs, Tet. Letters, 4979, 1966.
2. M. A. Battiste and T. J. Barton, ibid., 1227, 1967.
3. G. Maier, Chem. Ber., 98, 2438 (1965).
4. R. G.Amiet and R. B. Johns, Aust. J. Chem., 21,
1279(1968). —
5. G. Heinrichs ejt al. , Tet. Letters, 1617, 1970.
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BIOGRAPHICAL SKETCH
Robert Merrifield White was born July 24, 1945, at
Terre Haute, Indiana. In June, 1963, he was graduated from
Huntsville High School, Huntsville, Alabama. In June, 1967,
he received the degree of Bachelor of Arts with a major in
Chemistry from Vanderbilt University. Upon receiving the
Bachelor of Arts degree, he was also commissioned as a
second lieutenant in the United States Army Signal Corps.
In 1967 he enrolled in the Graduate School of the University
of Florida. During his pursuit of the degree of Doctor of
Philosophy he has held both teaching and research assistant-
ships. From September, 1967, until the present time he has
pursued his work toward the degree of Doctor of Philosophy.
Robert Merrifield White is married to the former Ann
Marie Bischof, and is the father of one child. Mr. White
is a member of Eta Sigma Phi, National Honorary Classical
Fraternity; Scabbard and Blade, Alpha Chi Sigma, chemists'
fraternity, and The American Chemical Society.
215

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.
Merle A. Battiste, Chairman
Professor of Chemistry
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
Associate Professor of
Chemistry
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
d n
John A. Zoltewicz ^
Associate Professor of Chemistry
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.

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.
Egbert Krispyn
Professor of Germanic and Slavic
Languages and Literatures
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.
March, 1972
Dean, Graduate School

"And I think I shall sleep well tonight
Let the world turn without me tonight."
Jesus Christ Superstar, 1970

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