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SYNWE’E‘EC SEEKERS £3 “FEE
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EQCHEGAN STATE UREVEREET’Y
Jeffrey N. Smith
197E

1111111111111 11 1111 1111111

300994 3691

 

ABSTRACT

SYNTHETIC STUDIES IN THE PREPARATION OF A VARIETY
OF SUBSTITUTED ACETYLENES

BY

Jeffrey N. Smith

The synthesis of a variety of substituted acetylenes
was encountered in an attempt to prepare a series of

charge transfer or w-complexes.

The copper acetylides of two different electron-

donating molecules (compounds é'and Z)

EC-H and H3CO @ CEC-H

.
H3
4 Z.

 

were prepared. The attempted coupling reactions were
performed with three different electronawithdrawing
molecules: iodo-4-nitrobenzene, iodo-2,4-dinitrobenzene

and picryl chloride.

Jeff rey N . Smith

The various substituted acetylenes were evaluated
and shown to exhibit charge transfer bands in the
visible spectrum. Some interesting conclusions can be

drawn, concerning the properties of these U-complexes.

SYNTHETIC STUDIES IN THE PREPARATION OF A VARIETY
OF SUBSTITUTED ACETYLENES

BY

Jeffrey N. Smith

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
of the degree of

MASTER OF SCIENCE

Department of Chemistry

1971

To my wife, Betty, and to

the memory of my father

ii

ACKNOWLEDGMEN TS

The author wishes to express his sincere gratitude to
Dr. Eugene LeGoff for his guidance and assistance through-
out the course of this investigation.

Special appreciation is extended to my fellow graduate
students, especially Mr. Thomas R. Kowar, who contributed
significantly to make this degree possible and to make the

last two years an enjoyable experience.

iii

TABLE OF CONTENTS

INTRODUCTION . . . . . . . . . . . . . . . . . . . .

RESULTS

.DISCUSSION . . . . . . . . . . . . . . . . . . . . .

EXPERIMENTAL . . . . . . . . . . . . . . . . . . . .

1.

General Procedures . . . . . . . . . . . .

A. Spectra . . . . . . . . . . . . . . . .
B. Microanalysis . . . . . . . . . . . . .
C o Melting POintS o o o o o o o o o o o o

Hydroxymeth l-triphenyl—phosphonium
Chloride (1' . . . . . . . . . . . . . . .

Chloromethyl—triphenyl-phosphonium
Chloride (g) . . . . . . . . . . . . . . .

9-(B-Chlorovinyl)anthracene (2) . . . .
9-Anthrylacetylene (g) . . ... . . . . . .
Copper Acetylide of 9~Anthrylacety1ene (2)
1-(4-Nitrophenyl) 9-anthrylacetylene (2). .

Page

18
24
24
24

24
25

25

1-(2,4-Dinitrophenyl) 9-anthrylacetylene (£2130
2-Anthryl-6-nitro-3§findol-3-one-N-oxide (11)32

1-(fi-Chlorovinyl)~3,4-dimethoxy-benzene (g)
3,4—Dimethoxy-phenylacetylene (Z) . . . ...

COpper Acetylide of 3,4-Dimethoxy-phenyl-
acetylene (g) . . . . . . . . . . . . . .

1-(4-Nitrophenyl) 3,4-dimethoxy-pheny1-
acetylene (10) . . . . . . . . . . . . . .

iv

32
34

35

36

TABLE OF CONTENTS (Cont.)
Page
14. 1-(2,4-Dinitrophenyl)-3,4-dimethoxy-phenyl—
acetylene (12) . . . . . . . . . . . . . 37

15. 2-(3,4—Dimethoxyphenyl) 6-nitro-3gfindol-
3-one-N-oxide (12) . . . . . . . . . . . 39

BIBLIOGRAPHY . . . . . .'. . . . . . . . . . . . . 40

APPENDIX . . . . . . . . . . . . . . . . . . . . . 42

Table

II.

III-

Scheme

II.

LIST OF TABLES AND SCHEMES

TABLES

Page

.Collected data on the various coupled

acetylenes and isatogens . . . . . . . . . . 19

Collected ultra-violet Spectral data on the
various electron donor and acceptor components 20

Collected ultra-violet spectral data on some
compounds used to study substituent effects

on a few of the electron donor and acceptor
molecules . . . . . . . . . . . . . . . . . . 22

SCHEMES

.Reaction sequence for the preparation of the

copper acetylide of 3,4-dimethoxy-phenyl-
acetylene (g) . . . . . . . . . . . . . . . 7

Proposed mechanism for the photochemical

rearrangement of ortho-nitro-acetylenes to
their corresponding isatogens . . . . . . . . 13

vi

LIST OF FIGURES

Figure Page

1A. Nmr spectrum of 9-(B-chlorovinyl)
anthracene (3) . . . . . . . . . . . . . . . 42

IB. Nmr spectrum of 9-(B-chlorovinyl)
anthracene (3); recrystallized from methanol 43

2. Infrared spectrum of 9—(B-chlorovinyl)
anthracene (3) . . . . . . . . . . . . . . . 44

3. Nmr spectrum of 9-anthrylacetylene (4) . . . 45
4. Infrared spectrum of 9—anthrylacetylene (4) . 46

5. nfiiared-spectrum of 1— —(4-nitrophenyl)-9-
anthrylacetylene (9) . . . . . . . . . . . . 47

6. Ultra-violet and visible spectra of 1-(4-
nitrophenyl)-9-anthrylacetylene (9) . . . . 48

7. Infrared spectrum of 1-(2,4-dinitrophenyl)
9-anthrylacetylene (12) . . . . . . . . . . . 49

8. Ultra-violet and visible spectra of 1-(2, 4—
dinitrophenyl) 9-anthrylacetylene (12) . . . 5O

9. Infrared spectrum of 2-anthryl- -6-nitro-3H—
indol-3-one-N-oxide (11) . . . . . . . . . . 51

10. Ultra-violet and visible spectra of 2-anthryl-
6-nitro—3§findol-3-one-N-oxide (ll) . . . . . 52

11. Nmr spectrum of 1-(B-chlorovinyl) '-3,4-dimethoxy-
benzene (6) . . . . . . . . . . . . . . . . . 53

12. .Infrared Spectrum of 1- (fi-chlorovinyl) 3, 4-
dimethoxy-benzene (6) . . . . . . . . . . 54

13. Nmr spectrum of 3,4-dimethoxy-phenyl-
acetylene (Z) . . . . . . . . . . . . . . . . 55

vii

LIST OF FIGURES (Cont.)
Figure Page

14. Infrared spectrum of 3,4-dimethoxy—phenyl-
acetylene (Z) . . . . . . . . . . . . . . . 56

15. Nmr spectrum of 1-(4-nitrophenyl)-3,4-dimethoxy-
phenylacetylene (12) . . . . . . . . . . . . 57

16. Infrared spectrum of 1-(4-nitrophenyl)~3,4-
dimethoxy-phenylacetylene (12) . . . . . . . 53

17. Ultra-violet and visible speCtra of 1- 4—nitro—
phenyl) 3,4-dimethoxy-phenylacetylene 12) . 59

18. Nmr spectrum of 1-(2,4-dinitrophenyl) 3,4-
dimethoxy-phenylacetylene (13) . . . . . . . 50

19. Infrared spectrum of 1-(2,4-dinitrophenyl)
3,4-dimethoxy-phenylacetylene (12) . . . . . 51

20. Ultra-violet and visible spectra of 1—(2,4-
dinitrophenyl) 3,4-dimethoxy—phenylacetylene
lg) . . . . . . . . . . . . . . . . . . . . 62

21. Infrared spectrum of 2-(3,4-dimethoxyphenyl)
6-nitro-3gfindol—3-one-N-oxide (12) . . . . . 53

22. UHIa-violet and visible spectra of 2-(3,4-di-

methoxyphenyl) 6-nitro-3gfindol-3-one-N-
oxide(1'4').................64

viii

INTRODUCTION

The objective of this thesis is the synthesis of a
variety of substituted acetylenes in an attempt to prepare
a series of charge transfer complexes. A great deal of
interest has been generated over the years by the molecular
complexes formed by mixing certain aromatic hydrocarbons
with a large variety of aromatic nitro-compoundsllz.

The main spectral feature accompanying complex formation
is the broad, intense absorption band in the ultra-
violet or visible spectral region, due to the electronic
transition from the ground state to the excited state. As
the strength of the charge transfer complex is increased
the energy gap for excitation is decreased and a higher
wave length of absorption is observed, since the two are
related inversely. The color of the complex will also
become more intense as the energy gap is reduced.

This exploratory work was initiated to study the
pr0perties of charge transfer complexes and to relate
these results to the future development of a linear, organic
superconductor. »A large volume of work has been generated
on the preparations of organic semi-conductors3, but, to
date, only theoretical predictions exist for organic super-

conductors.4

2

Two criteria are necessary for an organic molecule to
exhibit conducting properties. The first being a high de-
gree of electron delocalization within the molecule. The
higher the electron mobility within the system, the smaller
the energy gap is between the ground state and the excited
state. The second requirement is the flow of electrons
from one molecule to the next. Some low energy process is
needed for this electron promotion.

The model which was, therefore, chosen for this study
consisted of an acetylene substituted with an aromatic,
electron donor on one end and a nitro-aromatic, electron

acceptor on the other end.
D-AR-CEC-AR—A

D - electron donor
AR - aromatic molecule
A

— electron acceptor

The flow of electrons from one molecule to the next should
be facilitated by this type of structure. The donor end
of one molecule could line up with the acceptor end of

another molecule to form the charge transfer complex.

D-AR-CEC-AR-A
1

D-AR-CEC-AR-A

The synthetic work entailed the preparation of the
terminal acetylenes of the electron donor end and sub-
sequent coupling of the acetylides with the electron

acceptor end.

3
The electron donating molecules used were 9-anthryl-

acetylene (2) and 3,4-dimethoxy-phenylacetylene (Z).

@ CEC -H and H3 C0 CEC -H

E. Z.

The copper acetylides of these molecules were prepared and
then reacted with three different electron accepting
halides: iodo-4—nitrobenzene, iodo-2,4-dinitrobenzene and
picryl chloride.

-From the observation of the visible spectral data,
the preparation of some charge transfer complexes has
succeeded. Some interesting conclusions can be drawn,
concerning the properties of these complexes.

The results of this work are encouraging. The future
preparation of an organic superconductor of this type is
supported, however, further exploratory work is needed

before a working model can be developed.

RESULTS

The preparation of the starting material, chloro-
methyl-triphenyl-phosphonium chloride (2), was easily
accomplished by variations to the literature preparations

described by Wittig5 and Kobrich.6

¢3P + paraformaldehyde + HCl E§§%£> ¢;;1CH30HC1

1

~

ED CH2C12> G9 69

¢3@-CH20HC1 + soc 12 A ¢3P-CH2C1C1

1 2

~ ~

Simple treatment of triphenyl phosphine and paraformalde-
hyde with gaseous hydrogen chloride in ether at room tem-
perature leads to hydroxymethyl-triphenyl-phosphonium
chloride (L) in a 55% yield. This can be converted to
compound (2) by treatment with thionyl chloride in methylene
chloride under reflux in a 98% yield.

If the ylid of compound g'is generated in the
presence of 9-anthraldehyde by sodium methoxide, the normal
Wittig type reaction will occur at the carbonyl to yield

9-(6-chlorovinyl)anthracene (3) in a 40% conversion.

. o .
II 6) G) CH3OH
C-H + ¢3P-CH2C1C1 + NaOCH3 A > O H=CHC1
2’
51

Both the cis and trans isomers of compound 3 were observed

 

in this reaction. This can be shown through the nmr spec-
trum. Two proton bands, consisting of two AB quartets, are

located at 6 6.40 (doublet, J = 14 Hz) and 6 6.80

trans
(doublet, Jcis = 8 Hz), the two lower doublets of each AB
system are superimposed on the nine proton multiplet

between 6 7.20-8.40 (aromatic)(Figure 1A). The gig iso—
meric product can be partially separated from the trans
isomer by recrystallizing the mixture from methanol. An

nmr spectrum of this material (Figure 13) shows a decrease
of the intensity of the doublet at 6 6.40, indicating
partial fractional crystallization of the gig product.

Very careful thin layer chromatography with aluminum
oxide and carbon tetrachloride produces a definite separa—
tion of the isomers. Further work on their ultimate separa-
tion, however, was not carried out, since conversion of

compound g'to the corresponding terminal acetylene is not

affected by the mixture of isomeric products.

   

H o
=CHc1 + E-BuLi etheL, 2 :

 

6
Dehydrogalogenation can be accomplished with nfbutyl
lithium as the base in an ether solution. Hydrolysis with
water completes the reaction in a 95% yield.
Through a procedure similar to that developed by
Castro7 9-anthrylacetylene (4) is converted to the cor-
responding copper acetylide (5) with cupric sulfate and

hydroxylamine-hydrochloride in a 52% yield.

0 _ CuSO4~5H20 O _
SC'H NHZOH-HCl ’ Cfc’cu
0 i Q 2

Similar work was carried out with another donor type

 

molecule. The reaction sequence (Scheme I) with 1-sub-
stituted-3,4-dimethoxy—benzene was analogous to that of
9-substituted-anthracene, except for minor differences.

Now that the copper acetylides have been prepared the
various coupling reactions can now be attempted. The pro-
cedures used were similar to those reported by Castro7 in
his synthetic acetylene investigations.

The reaction of iodo-4-nitrobenzene with compound 5'
in dimethyl formamide at 120° was accomplished in 40 hours

in a 73% yield.

   

O
n g? C)
H3CO + ¢3 ‘CHzClCl + NaOCH3

 

0 .CH3OH
H3 A 57%
1.£7BuLi/ether
25°
H3C0 EC-H‘ <2.H20 _,1. H3CO
87%
H3 H3
Z.
CUSO4'5H20
NHgOH'HCl
70%
4
H3CO EC-Cu
H3
§.

Scheme I.

H=CHC1

1m

8
The same reaction procedure was attempted with compound
g, but surprisingly, there was no reaction, even after
three days of stirring at 120°. The insoluble copper ace-
tylide was then removed from the reaction media by filtra-
tion and purified. The same conversion was attempted again
with a three fold excess of iodo-4-nitrobenzene, but still

no reaction was apparent.

CEC-Cu + I©N02 9%?» No Reaction

0 three-fold
3 excess
é.

H3CO

   

.A possible explanation of the lower reactivity of
the copper acetylide of 3,4-dimethoxy-phenylacetylene (g)
over that of the copper acetylide of 9-anthrylacetylene
(5), would be the added amount of electron donation from
the unshared electron pairs on the para methoxy oxygen.
Delocalization of the electrons through the phenyl ring
and the triple bond would be expected to strengthen the

C-Cu bond significantly and thus retard the reaction.

{X r} @ -9
H3C-Q CEC-Cu < > CHa-g. c=C*Cu

O 0
H3 H3

 

The vacant d-orbitals on the copper could accommodate the
extra electrons to strengthen the C-Cu bond through back-

bonding.

9

Instead of isolating the copper acetylide again from
the reaction mixture, another electron accepting type mole—
cule was added directly to the suspension. Iodo-2,4—di-
nitrobenzene was chosen because the added nitro group in
the ortho position will withdraw electron density from
the reaction center and, therefore, facilitate the reac-
tion. An immediate reaction occurred with this addition,
observable by the production of a dark red solution and
the disappearance of the copper acetylide. Quite sur—
prisingly, the mononitro coupled product (12) was re-

covered instead of the dinitro coupled product in a 65%

yield.
0
H3CO CEC‘CU + I‘@'N02 + I N02
H3 three-fold
8 excess A DMF

~

H3CO :—: @Noz

H3 10

A preliminary explanation of this phenomena comes
from the possibility of a U-complex forming between compound

g'and the electrondwithdrawing, iodo-2,4-dinitrobenzene.

 

If electrons are removed by this v-complex, the amount of
electron donation from the unshared electron pairs on the
para oxygen would be decreased; the C—Cu bond strength
would subsequently be weakened. This would lead to a more
favored reaction.

The formation of the product could be governed by
either the steric hindrance of the ortho nitro group Or
by the statistical factor of a three fold excess of the
iodo-4-nitrobenzene.

An experiment was designed to test this theory. The
reaction was repeated substituting meta-dinitrobenzene for
iodo-2,4-dinitrobenzene. If the w-complex is a real
species, the reaction should proceed to the expected pro-

duct.

No
H3CO =C-Cu + I‘@—NOZ + ©N02WJ>R93C1210D

2H Two-fold
3 8 excess

Since no reaction occurs under the conditions previously

used, the w-complex theory was disproven.

b——-‘

11

Since the mechanism does not proceed through a 7-
complex, some other unknown complex must be forming with
the acetylide to weaken the C-Cu bond.

To determine if free iodide will complex with the
copper acetylide to weaken the C-Cu bond, the same reac-
tion was run with potassium iodide as a catalyst. .It was
found that the reaction did go and in a good yield (75%),
but a catalytic amount was not enough; a full equivalent

was needed for the reaction to go to completion.

CH309:=C-Cu + I‘@-N02 + KI MA“? >

Apparently the iodide is complexing with the copper

 

to weaken the C-Cu bond and help locate the negative

charge on the carbon atom.

H3Co @ EQ-Cu > HSC' @ CECGCUI
, . x9 .
I

g 0
H3 H3

 

This localization of the charge would increase the nucleo-

philicity of the carbon atom of the acetylene to promote

the reaction.

12

This explanation, however, does not explain why the
iodo-2,4-dinitrobenzene will also catalyze the reaction.
In that system no free iodide should be present. Apparent-
ly, it must be complexing with the copper in some unknown
fashion to facilitate the reaction. Further work to
determine the actual mechanisms of these catalysts was not
investigated.

The next objective is to prepare the respective di-
nitro coupled products. Iodo-2,4-dinitrobenzene was then
reacted with compound 5 under the normal conditions in di-
methyl formamide at 1200 and allowed to stir for three
hours. Disappearance of the copper acetylide was observed
with the production of a dark red solution. Analysis of

the reaction product produced another surprise.

@ .

@ EC-CU+I .NOZP-X-L @
N02

@ 2

Instead of the expected dinitro coupled product, the cor-

V
@0@

W
w

responding rearranged, green isatogen was isolated in a
54% yield.
After searching the literature, it was discovered
that ortho-nitro-acetylene compounds rearrange in the pres-
ence of sunlight and a variety of solvents (mainly chloro-

form and pyridine) to their respective isatogens.3'9v1°

13
‘1
CEC-Ph 1,-
-—> l\Pc-Ph
N02 /
1
o

The mechanism for this rearrangement has not been

investigated, but can be postulated to be as shown in

 

Scheme II.
Scheme II. 0
H
Ph C
\
g-Ph'-> C-Ph
N4?

In order to avoid this complication, the identical
reaction was run in the dark with potassium iodide as a
catalyst. The isatogen formation was halted and a yield

of 78% was observed for the production of compound 12

Q dark

If this dark red compound (12) is then put in a solution
of pyridine and chloroform and allowed to stir in the

presence of a florescent light bulb for one day, a 50%

conversion is obtained to the isatogen (“1).

14

C
_ , CHCla-Pyr.‘ \\
Q C=C N02 florggcent ’ ye @
light NO N
@ 2 2 ’ Q
22. 0

A characteristic difference is observed in the infrared

 

spectrum. An acetylene stretch (CEC) occurring at 2200
cm"1 for compound 12.15 observed (Figure 7), while the
spectrum of compound ll’has no acetylene stretch, but
instead, a carbonyl absorption (C=O) at 1700 cm".1 (Fig-
ure 9).

This same type of photochemical rearrangement is ob-
served in the reaction of compound 8 with iodo-2,4-dinitro-
benzene, however, not as much isatogen is formed. If the
reaction is performed under normal conditions with
potassium iodide as the catalyst, both the acetylene (£3)

and the isatogen (14) are isolated.

H3O c.=_c-Cu + I No2 + KI 239%.
02
H3
1 1
H3CO ’/ + H3CO 2c 02
%N No
1 ‘ 2 °’
H 3
3 14 ° .152.

15
If the same reaction is run in the dark only the
orange acetylene (13) is recovered in a 69% yield. Simi-
larly, the conversion of the acetylene (£3) to the violet
isatogen (14), can be accomplished by allowing compound £3
to stir in the presence of a florescent light bulb for two

days. The product can be isolated in a 50% yield.

 

N02 5 C33 CHCla-Pyr.
Florescent
N02 OCH3 light 1
a

Z
.9
Q§h//-*O
o
0:
run
“In
a

Conversion of the acetylenes to the isatogens is also
observed in the solid state, so extreme precaution is
necessary to keep the acetylene protected from light.

Now that the preparations had been worked out for the
mono and dinitro coupled products, the trinitro products
were desired. Initial experiments were performed with
compound 8'and picryl chloride in dimethyl formamide at
120°. The reaction was complete in one hour but the ex-

pected coupled product was not obtained.

16

 

 

N02
EC-Cu c1 N02 D253 H3CO @ .=.c—H
No '
2 H3
§. .1

The terminal acetylene was the product isolated. Appar-
ently, the copper acetylide is being hydrolyzed during the
reaction. This could be caused by either picric acid in
the picryl chloride or from water in the dimethyl formamide.
Another trial of the reaction was attempted with special
precautions made to recrystallize the picryl chloride
(ethanol) and to dry the dimethyl formamide (molecular
sieves, type 4A). In addition potassium carbonate was
added to the reaction mixture to remove any residual source
of protons and potassium iodide was added to catalyze the
reaction. The same results as the preceding experiment
.were observed, however. It was also discovered through
further experimentation that trace amounts of oxygen in

the system will cause dimerization to the diacetylene (15)}1

E) G)
H3CO @ '="C Cu .23... H3CO ace Cu®

H3 8 31-13

@
H3CO 2c £2C@GH3 < H3CO‘@-(EC - Cu

3 0CH3 g
‘ H3 H3

15

 

17
Therefore, mixtures of compounds Z and IE will be obtained,
if care is not taken to remove all oxygen from the re-
action vessel.
The same type of results were obtained in the reac-

tion of compound Q'with picryl chloride.

. No2

— - .DMF
@ ._C Cu + C1 @ N02 + K2C03 + KI A Trace
‘::J 02
N02 {‘::)} {<::>’

Q

16

W

The terminal acetylene (4) can be isolated, if all oxygen
is removed from the system.

The possible reason for this strange behavior could
be due to the steric hindrance to formation of the coupled
product. The two ortho nitro groups are probably blocking
the entry of the copper acetylide. The nucleophilic
acetylide then abstracts a proton, possibly from the sol-

vent, to complete the reaction.

DISCUSSION

Now that the various model compounds have been pre—
pared, they must be evaluated to determine if charge
transfer or w-complexes have been formed.

The formation of a charge transfer complex can easily
be determined through the ultra—violet and visible spec-
tra. If a long wave length of absorption exists for the
various substituted acetylenes and isatogens, which is
not present in either the electron donor or acceptor
molecules, a charge transfer complex is indicated. This
absorption is due to the electronic transition from the
ground state of the complex to the excited state}:2

The highest wave length of absorption for the various
substituted acetylenes and isatogens are presented in
Table I. The respective absorptions for the individual
donor and acceptor molecules are listed in Table II. By
comparing the various visible spectral data, it can be
clearly shown that charge transfer or U-complexes are
being formed by these molecules. .None of the selected
donor or acceptor components approach the higher wavelengths
of the charge transfer bands present in these systems.

Some substitutions have been made in Table II for the
spectral data of some unavailable compounds. For instance,

18

19

Table I. Collected data on the various coupled acety-
lenes and isatogens.

 

 

 

_ Charge
Structure Color Solvent Transfer
Band (mu)
@ Ec—-.—N02 Orange Ethanol 430
Q 9
N
9 °2
2...

@ C/>: @ Green CH3C12 562
0

N02 1;:
11 o
95%
H3CO Q EC—-.-—N02 Yellow Ethanol 356
0
H3 £9.
H3COHECN02 orange CH2C12 403
2 °2
H3 15?.
'0
g
\ .
C .CH3 VlOlEt CH2C12 523
459
N02 OCH3

 

 

20

Table II. Collected ultra-violet spectral data on the
various electron donor and acceptor components.12

 

 

Highest Wave Length
Structure Solvent of Absorptions,mu

 

@ EC‘H -C6H12 391
HSCO Q 95% Ethanol 274

NOg‘—<:::>—CEC-H 95% Ethanol 286
N02 fiHzCH3 95% Ethanol 241
02

ED): >c© ccl4 43813

(kao

 

 

21
the ultra—violet spectra of 2,4—dinitro-phenylacetylene
and 3,4-dimethpxy-phenylacetylene have not been recorded
in the literature. Substitution of these with 1—ethyl-
2,4-dinitrobenzene and 3,4—dimethoxy-benzene, respectively,
have been shown to be representative by the data in Table
III. A series of 9-substituted and unsubstituted anthra-
cenes (Table III) exhibit similar ultra-violet spectral
absorptions.

The model system for the isatogens (2-phenylisatogen)
is not strictly correct, either; the best model would have
another nitro group in the 6-position. This has been
shown not to be a serious problem by a study of nitro-
benzenes (Table III). The substitution of a nitro group
in the meta position of nitrobenzene does not significantly
change the absorption.

The color of the various complexes has been shown (see
the Appendix) to arise from long tailing of the broad ab-
sorptions into the respective color regions and not from
sharp absorptions. This can be attributed to the loose
nature of binding in the ground state of the complex}:2

Three general conclusions can be drawn, if Table I
is examined carefully.

1.) As the amount of electron withdrawing power is
increased (nitro groups) within the molecule, the wave—
length of the charge transfer band is increased. This
tends to indicate the v-complex is strengthened as the

amount of electron accepting ability is increased. The

 

 

22

Table III. Collected ultra-violet spectral data on some
compounds used to study substituent effects on
a few of the electron donor and acceptor
molecules.

 

 

Highest Wave Length
Structure Solvent of Absorptions, mu

 

@ EC‘H C6H12 391
Q 2.

’11:; 95% Ethanol 375.5
Q 95% Ethanol 274
@402 95% Ethanol 259
£§>~No2 95% Ethanol 235

z
0
u

 

23
energy gap between the ground state and the excited state
is, therefore, decreased.

2. In all cases the 9-substituted-anthracenes absorb
at higher wavelengths than the corresponding 1-substituted-
3,4-dimethoxy-benzenes. Although the 1-substituted-3,4-
dimethoxy-benzenes should be more electron donating, be-
cause of the unshared pairs of electrons on the methoxy
oxygens, the 9-substituted anthracenes must overcome this

effect through their extended conjugated systems.

 

3. Although the acetylene moiety has been destroyed
in the isatogens, charge transfer complexes are still pre—
sent. The formation of isatogens has increased the wave-
length of absorption significantly in both cases. This
is probably due to the presence of additional conjugation
and the formation of a new chromophore. Charge transfer
complexes in these systems seem extremely good.

It has, therefore, been shown that charge transfer
complexes will form with these systems. Hopefully, this
new knowledge will be useful for the furture preparation of

organic superconductors of this type.

 

EXPERIMENTAL

1. General Procedures

A. Spectra

Nuclear magnetic resonance spectra were determined on

 

a Varian T-60 high resolution spectrometer with tetra-
methylsilane as a standard.

Infrared spectra were obtained on a Perkin-Elmer 237B
Grating Infrared Spectrophotometer. Sodium chloride cells
were used for all determinations.

Mass spectra were obtained using a Hitachi Perkin-
Elmer Model RMU-6 low resolution instrument.

Ultraviolet and visible spectra were measured using
1 cm quartz cells on a Unicam Model SP-800 spectrophoto-

meter.
B. Microanalysis

Microanalytical data were obtained from Spang Micro-
analytical Laboratory, Ann Arbor, Michigan and Water

Quality Research Laboratory, Michigan State University.

24

25

C. -Me1ting Points

 

Melting points were determined on a Thomas Hoover
capillary melting point apparatus. All temperatures are

uncorrected and recorded in degrees Centigrade.
2. Hydroxymethyl-triphenylephosphonium chloride (1)5:3

Triphenyl phosphine (26.2 g., 100 mmoles) was dis-

 

solved in 125 ml of anhydrous ether. Subsequent addition

\
:‘A
21 '
E
q
E‘.
1r
v

of 3.3 g (110 mmoles) of paraformaldehyde (trioxane) to the

.E

< ‘fi_
'1 “- ‘y l. _

solution formed a suspension. Gaseous hydrogen chloride
was passed slowly through the stirred mixture for a period
of 3 hours at room temperature. The product precipitated
as a white solid which was removed by filtration and washed
with several portions of ether. Further purification in-
volved reprecipitating the hydroxymethyl-triphenyl-phos-
phonium chloride (1) from methylene chloride with ether.
This produced 18 g (55 mmoles) of pure, white product in a
55% yield: m.p. 192-194o [lit. m.p. 194-19805‘6]. This
white, powdery material is hydroscopic and should be dried
in an oven for 10 hours at 90° under a vacuum (27 in Hg)

for best results before further use.

3. Chloromethy1-triphenyl-phosphonium Chloride (2)5:6

 

Thionyl chloride (11.3 g, 95 mmoles) was slowly drip-
ped into a solution of 15.55 g (47.5 mmoles) of hydroxy-
methyl-triphenyl—phosphonium chloride (1) in 100 m1 of

methylene chloride. The reaction mixture was then refluxed

26
for 45 minutes, after which, the solvent was removed in
the hood with a water aspirator. (Normal solvent removal
with the rotary evaporator and a vacuum pump on the bench
is not recommended because of the toxic effects of thionyl
chloride.) The remaining residue was precipitated from a
methylene chloride solution with ether. The white, powdery
product (16.1 g, 46.5 mmoles) was isolated in a 98% yield:
m.p. 256° [lit. m.p. 260-26105'6]. The product is hydro-
scopic and should be dried in an oven for 10 hours at 90°
under a vacuum (27 in Hg) for best results before further

use .

4. 9-(fifghlorovinyl)anthracene (3) [The procedure used was

similar to that described by Wittig5.]

Under a nitrogen atmosphere 3.47 g (10 mmoles) of
chloromethyl—triphenyl-phosphonium chloride (2) was dis-
solved in 75 m1 of dry methanol. Sodium methoxide (0.54 g,
10 mmoles) was then added to the solution. After the mix—
ture was refluxed for fifteen minutes, 2.06 g (10 mmoles)
of 9-anthraldehyde in 10 ml of methylene chloride was added
dropwise. The reaction mixture was then refluxed for one
hour and subsequently neutralized with 0.5 g of ammonium
chloride. After the reaction mixture was cooled the sol-
vent was removed and the residue taken up in ether and
water. The ether portion was extracted with water, dried
(M9804) and the solvent stripped off under vacuum with a

rotary evaporator. The residue which resulted was

 

27
chromatographed on dry column alumina (50 g, 27 mm column)
with carbon tetrachloride. The first yellow band off the
column contained the desired product. When the solvent had
been stripped away, a yellow oil was obtained, which crys-

tallized upon standing for half an hour. The 9-(5-chloro-

 

vinyl)anthracene (3) was then recrystallized from methanol

m.p. 79—810: nmr spectrum (CC145, 2§_band consisting of two

to yield 0.96 g (4 mmoles) of nice, yellow crystals (40%): I
d
E

AB quartets at 6 6.40 (J = 14 Hz) and 6 6.80 (J

trans cis

8 Hz), the lower two doublets of each AB system are super-

 

imposed on a 9g multiplet between 5 7.2-8.4 (aromatic),
Figure 1; infrared spectrum (C82) gmfl, 1612 (c=c), 725 (C-
Cl) and 707 (9-substituted anthracene), Figure 2: mass

spectrum (70 eV) £13, 238(P) and 203(P-Cl).

Anal; Calcd. for C16H11Cl: C, 80.50; H, 4.61.
Found: C, 80.23; H, 4.45.
This reaction has also been performed with gfbutyl
lithium as the base in an ether or tetrahydrofuran solution

at room temperature, but the yields were much lower.

5. 9-Anthry1acetylene (2) [The procedure used was similar

 

to that described by Kobrich6 and Staab15.]14

To 100 ml of anhydrous ether [previously dried through
an aluminum oxide (basic) column] 1.45 g (6.1 mmoles) of
9—(B-chlorovinyl)anthracene (3) was dissolved under a
nitrogen atmosphere. nfButyl lithium (8 ml, 1.5! solution

in hexane, 12 mmoles) was added dropwise to the solution

28

over half an hour. Formation of a white precipitate

(LiCl) was noticed after approximately half of the £7
butyl lithium had been added. The reaction mixture was
allowed to stir one hour at room temperature and was then
hydrolyzed with 30 ml of water. The ether portion was
then extracted with water and dried (CaClz). The ether
was removed and the yellow oil which remained was chromato-
graphed on dry column alumina (20 g, 17 mm column) with
carbon tetrachloride. The first yellow band off the col-
umn contained the desired product. When the solvent was
stripped away, a yellow oil was isolated, which crystal-
lized when allowed to stand for half an hour. This was
then recrystallized from petroleum ether (30-600) to

yield 1.17 g (5.8 mmoles) of nice, yellow crystals (95%»
m.p. 71-73o [lit m.p. 73-75014]: nmr spectrum (C014), 6
3.80 (singlet, 1H) and a 9g multiplet between 6 7.25-

8.75 (aromatic), Figure 3; infrared spectrum (CC14) Eflflv
3275 (CEC-H) and 2080 (CEC), Figure 4. Care must be taken
with this compound because it tends to self-polymerize
under ambient conditions. Storage at 00 is recommended

for best results.

6. Copper Acetylide of 9-Anthrylacetylene (§)[The pro—

cedure used was similar to that described by Castro.7]

Under a nitrogen atmosphere 1.92 g (7.7 mmoles) of
hydrated cupric sulfate was dissolved in 25 ml of 28%

ammonium hydroxide, after which, 100 m1 of water was added.

29
Hydroxylamine~hydrochloride (1.07 g, 15 mmoles) was then
added as a Solid and the dark blue solution became lighter.
9—Anthrylacetylene (2) (1.55 g, 7.7 mmoles) was then added
to the stirred, reaction mixture in 25 ml of tetrahydro—
furan, dropwise. The formation of an orange solid was ob-
served immediately. After the acetylene had all been
added, the suspension was stirred for an additional fifteen
minutes at room temperature and filtered. The product was
washed several times with water, methanol and ether, suc-
cessively. The bright, orange copper acetylide (1.06 g,
4.4 mmoles) was isolated in a 52% yield. Due to the insol-
ubility of the product in all solvents, no physical tests
were performed. Unreacted 9-anthrylacetylene (4) can be

recovered from the washings for further use.

7. 1—(4éNitrophenyl) 9-anthrylacetylene (g) [The procedure

used was similar to that described by Castro.7]

To 40 ml of dry (dried over molecular sieves, type 4A)
and oxygen-free dimethyl formamide, 0.3 g (1.13 mmoles) of
the copper acetylide of 9-anthrylacetylene (5) was suspended.
Iodo-4-nitrobenzene (0.9 g, 3.6 mmoles) in 5'ml of dimethyl
formamide was added dropwise to the reaction mixture under
a nitrogen atmosphere. The contents were then heated at
1200 for 40 hours. Slowly the copper acetylide disappeared
and the solution became dark red. The solution was then

cooled and poured into an evaporating dish and allowed to

 

 

30
remain on the steam bath in the hood until the solvent had
been removed (half an hour). Minimum exposure to dimethyl
formamide is desirable. The product was extracted from the
remaining residue with chloroform and the insoluble material
filtered away. Stripping off the solvent left a yellow
solid, which was chromatographed on silicic acid (50 g,
27 mm column) with carbon tetrachloride. A red band moving
slowly down the column contained the desired coupled pro-
duct. After the carbon tetrachloride was removed, the
solid material was crystallized from methanol to give 0.265
g (0.825 mmole) of orange needles in a 73% yield: m.p.
212-2130: compound g'was too insoluble for an nmr spectrum;
infrared spectrum (CHC13) Emil, 2175 (CEC) and 1520, 1335
(N03), Figure 5: mass spectrum (70 9V).EZEJ 323(P) and 277
(P'NOa); Kmax (95% ethanol) mg, 252 (€ 85,300), 296 (6
11,900), 312 (6 10,100), 414 (6 18,650) and 430 (6 18,550).

Figure 6.

Anal. Calcd. for C32H13N02: C, 81.73: H, 4.02

Found: C, 81.52: H, 4.11.

8. 1-(2,4-Dinitrophenyl) 9-Anthrylacetylene (12) [The

procedure used was similar to that described by Castro7]

Under a nitrogen atmosphere and in the dark 0.1 g
(0.378 mmole) of the copper acetylide of 9-anthrylacetylene
(5) was suspended in 35 ml of dry and deoxygenated dimethyl
formamide. To this reaction mixture was added a solution

of 0.11 g (0.378 mmole) of 1-iodo-2,4-dinitrobenzene and

31
0.063 g (0.378 mmole) of potassium iodide in 10 ml of di-
methyl formamide. The contents were then heated at 1200
for one hour. The disappearance of the copper acetylide
and the formation of a darkly colored, red solution was
observed. The solvent was driven off and the product ex-
tracted from the remaining solid material with chloroform.
After the insoluble material was filtered away, the solu-
tion was concentrated and cooled to 0°. The product
crystallized as red cubes. Further recrystallizations
were needed for a pure product. A 78% yield was obtained
in which 0.11 g (0.3 mmole) of product was obtained: m.p.
279-2800: compound lz'was too insoluble for an nmr spec-

trum: infrared spectrum (CHC13)‘gmf1

, 2175 (02c) and 1540,
1350 (N02), Figure 7; mass spectrum (70 eV) mge, 368(P),

322(P-N02) and 276(P-2N02); (CH2C12) EH, 255.5 (e

7“max
104,500), 330 G 5,260), 375 (6 6,590), 387 (6 6,780) and
476 (6 5,410), Figure 8. As discussed in the RESULTS,
ortho-nitro-acetylenes rearrange in the presence of light
to their corresponding isatogens. Since the preparation
of an analytically, pure sample of compound 12,15 diffi-
cult to obtain, because of this sensitivity, the elemental
analysis was not attempted. The corresponding isatogen
(11), however, is stable to light and can easily be puri-
fied. Since the elemental analysis for compound ll'has

been performed and shown to be correct, the structure of

compound lg'is subsequently supported.

'31:;4 _

32

9. 2-Anthryl-6-nitro-3Hrindol-3-one-N-oxide (ll)

 

To 3 ml of chloroform and 5 ml of pyridine 0.1 g (0.3
mmole) of 1-(2,4-dinitrophenyl) 9-anthrylacetylene (12)
was dissolved. The red solution was stirred in the hood
at room temperature for one day under a florescent light
bulb. The reaction media slowly changed color to a reddish-
green. The residue remaining, after stripping off the
solvent, was chromatographed on silicic acid (8 g, 14 mm
column) with chloroform. The green isatogen eluted from
the column slowly, but was very pure. After the chloro-
form was removed, a dark green solid (0.05 g, 0.15 mmole)
was recovered, indicating approximately a 50% conversion
from the acetylene: m.p. 225—2260: compound ll'was too
insoluble for an nmr spectrum: infrared spectrum (CHC13)
ggfl, 1710 (c=c), and 1525, 1340 (N02), but no Cac stretch,
-Figure 9; mass spectrum (70 eV) gig, 366(P), 322(P-N02)
and 294(322-c0); lmax (CH2C12) may 254.3 (6 84,400), 332
(5 4,550), 348 (6 5,250), 370 (6 6,650), 385 (6 6,600)

and 562 (e 491), Figure 10.
Anal. Calcd. for C22H12N204: C, 71.74; H, 3.26.

Found: C, 71.72: H, 3.44.

10. 1:(B-Chlorovinyl)-3,4-dimethoxy-benzene (Q) [The pro-

cedure used was similar to that described by Wittig5]

Under a nitrogen atmosphere 3.47 g (10 mmoles) of

chloromethyl—triphenyl-phosphonium chloride (2) was dissolved

 

33
in 75 ml of dry methanol. Sodium methoxide (0.549, 10
mmoles) was then added to the solution. After refluxing
for 15 minutes, 1.66 g (10 mmoles) of 3,4-dimethoxy-benz-
aldehyde in 10 ml of methanol was added dropwise. The
reaction mixture was then refluxed for one hour and subse-
quently neutralized with 0.5 g of ammonium chloride. After
the reaction mixture was cooled, the solvent was removed
and the residue taken up in ether and water. The ether
portion was extracted with water, dried (CaClg) and the
solvent stripped off under vacuum with a rotary evaporator.
The yellow oil which remained was distilled with a
fractionating column to give a clear oil, however, further
purification was needed. The product was then chromato-
graphed on silicic acid (50 g, 27 mm column) with methylene
chloride. The first band off the column contained the
1-(fi-chkmpvinyl) 3,4-dimethoxy-benzene (6) in good purity.
Removal of the solvent yielded 1.42 g (5.65 mmoles) of
the product (56.5%) as a clear oil: b.p. 910 (0.1 mm):
nmr spectrum (CDC13), 0 3.85 (singlet, 6g) and a 5g
multiplet between 6 6.10-7.50 (aromatic and vinyl), Figure
11; infrared spectrum (C82) SE71: 1600 (c=c), 1260 (C-O-C),
930 (c=c—c1) and 730 (C-Cl), Figure 12; mass spectrum

(70 eV) mZe, 198(P) and 183(P-CH3).

Anal. Calcd. for C10H11C102: C, 60.45: H, 5.54.

 

Found: C, 60.18; H, 5.51.

 

 

34
11. a3,4—Dimethoxy-phenylacetylene (Z) [The procedure
used was similar to that described by Kébrich6 and

Staab13116,17

To 100 m1 of anhydrous ether [previously dried through
an aluminum oxide (basic) column] 3.3 g (16.2 mmoles) of
1-(B-chlorovinyl) 3,4-dimethoxy-benzene (6) was dissolved
under a nitrogen atmosphere. ngutyl lithium (22.2 ml,
1.5M solution in hexane, 33.3 mmoles) was added dropwise
to the solution over half an hour. Formation of a white
precipitate (LiCl) was noticed after approximately half of
the gfbutyl lithium had been added. The reaction mixture
was allowed to stir one hour at room temperature and was
then hydrolyzed with 30 ml of water. The ether portion
was then extracted with water and dried (MgSO4). After
removing the ether, the yellow oil which remained was
chromatographed on silicic acid (50 g, 27 mm column) with
methylene chloride. The first yellow band off the column
contained the desired product. When the solvent was
stripped away, a yellow oil was isolated, which crystal-
lized upon standing for half an hour. This was then re—
crystallized from petroleum ether (30-600) to yield 2.28 g
(14 mmoles) of nice, yellow crystals (91%): m.p. 72-73o

[lit. m.p. 73 -74°16 17

]: mr spectrum (CDC13), 0 3.00
(singlet, 1H), 0 3. 85 (s singlet, 6H), 0 6.80 (AB doublet,
15, J = 9 Hz), 6 7. 00 (AC doublet, 1 H, J = 2 Hz) and o
7.15 (ABC doublet of doublet, 1g, J = 2 and 9 Hz), Figure

13: infrared spectrum (CHC13) ggfl, 3300 (C2C5H): 2100 (C'C)

 

35

and 1260 (C-O-C), Figure 14.

12. Copper Acetylide of 3,4-Dimethyoxyephenylacetylene (8)
[The procedure used was similar to that described by

Castro7.]

Under a nitrogen atmosphere 4.8 g (19.2 mmoles) of
hydrated cupric sulfate was dissolved in 25 ml of 28%
ammonium hydroxide, after which, 100 ml of water was added.
Hydroxylamine-hydrochloride (2.65 g, 38.2 mmoles) was then
added as a solid and the dark blue solution became lighter.
3,4-Dimethoxy—phenylacetylene (2) (3.1 g, 19.2 mmoles) was
then added to the stirred reaction mixture in 25 ml of ‘
ethanol. The formation of a yellow solid was observed im-
mediately. After the acetylene had all been added, the
suspension was stirred for an additional 15 minutes at
room temperature and filtered. The product was washed
several times with water, methanol and ether, successively.
The bright yellow copper acetylide (3.69 g, 16.4 mmoles)
was isolated in an 86% yield. No physical tests were per-
formed on this product because of its insolubility in all
solvents. .Unreacted 3,4-dimethoxy-phenylacetylene (6)

can be recovered from the washings for further use.

 

'fy'flxw . r'.. o 7

36
13. 1-(4-Nitrophenyl) 3,4-dimethoxyjphenylacetylene (12)
[The procedure used was similar to that described by

Castro7].

To 40 ml of dry (dried over molecular sieves, type 4A)

and oxygen free dimethyl formamide 0.1 g (0.45 mmoles) of

 

the copper acetylide of 3,4-dimethoxy—phenylacetylene (8)
was added. Iodo-4-nitrobenzene (0.11 g, 0.45 mmole) and :a
0.075 g (0.45 mmole) of potassium iodide were dissolved in

10 ml of dimethyl formamide and added to the suspension - f

 

under a nitrogen atmosphere. The reaction mixture was

then heated to 1200 for one hour. The color of the solu-
tion became dark red as the copper acetylide reacted. The
solution was then cooled and poured into an evaporating
dish and allowed to remain on the steam bath in the hood
until the solvent had been removed. The product was ex-
tracted from the remaining residue with chloroform and the
insoluble material filtered away. Stripping off the solvent
left a yellow solid, which was chromatographed on silicic
acid (20 g, 17 mm column) with chloroform. The second yel-
low band off the column contained the desired coupled pro-
duct. After the chloroform was removed, the solid material
was crystallized from ethanol to give 0.95 g (0.33 mmole)
of yellow crystals (75%): m.p. 125.5—130.5°: nmr spectrum
(CDC13), 0 3.95 (singlet, 6H), 0 6.90 (AB doublet, 1H, J =
9 Hz), <5 7.10 (AC doublet, lg, J = 2 Hz), 6 7.25 (ABC

doublet of doublet, 1g, J = 2 and 9 Hz) and an A'B' quartet

37
at 0 7.70, 8.25 (doublets, 4H, J = 9 Hz), Figure 15;

’1, 2200 (c=c), 1500, 1340

infrared spectrum (CHC13) gm.
(N02) and 1275 (C—O-C), Figure 16: mass spectrum (70 eV)
Egg, 283(P), 268(P-CH3), 253(P-2CH3) and 237(P-N02);

lmax (95% ethanol) ms» 261 (6 14,400) and 356 (6 16,800),

Figure 17.

Anal. Calcd. for C16H13NO4: C, 67.84; H, 4.59: N, 4.95.

Found: C, 67.02; H, 4.54; N, 4.87.

14. 1-(2,4-Dinitrophenyl)-3,4-dimethoxy-phenylacetylene (12)
[The procedure used was similar to that described by

Castro7].

Under a nitrogen atmosphere and in the dark 0.1 g
(0.45 mmole) of the copper acetylide of 3,4-dimethoxy-
phenylacetylene (8) was suspended in 35 ml of dry and deoxy-
genated dimethyl formamide. To this reaction mixture was
added a solution of 0.13 g (0.45 mmole) of iodo-2,4-dinitro-
benzene and 0.074 g (0.45 mmole) of potassium iodide in
10 ml of dimethyl formamide. The contents were heated at
1200 for one hour. The disappearance of the copper acety-
lide and the formation of a darkly colored red solution was
observed. The solvent was driven off and the product ex-
tracted with chloroform from the remaining solid material.
After the insoluble material was filtered away, the solvent
was stripped off and a silicic acid column (20 g, 17 mm
column) was run with the residue, eluting with methylene

chloride. The third yellow band off the column contained

 

38
the desired, coupled product. After the methylene chloride
was removed the solid material was crystallized from
methanol to give nice, orange crystals (0.101 g, 0.31 mmole)
in a 69% yield: m.p. 137.5-138.5°: nmr spectrum (CDC13),
0 3.95 (singlet, 6g), 0 6.94 (AB doublet, 1H, J = 9 Hz),
0 7.14 (AC doublet, 1H, J = 2 Hz), 0 7.34 (ABC doublet of
doublet, 1H, J = 2 and 9 Hz), 0 7.94 (A'B' doublet, 1H)
J = 9 Hz), 6 8.49 (A'B'C' doublet of doublet, 1H, J = 2
and 9 Hz) and 0 9.00 (A'C' doublet, 1g, J - 2 Hz), Figure
18: infrared spectrum (CHC13) 91-1: 2200 (c=c), 1525, 1350
(N03) and 1260 (C-O-C), Figure 19; mass spectrum (70 eV)
m, 328(P), 282(P-N02) and 236(P-2N03); Amax (CH3C12) ‘12:
259.5 (6 20,000), 280.5 (6 16,400), 321 (6 8,910) and 403
(6 18,100), Figure 20. As discussed in the RESULTS, ortho-
nitro-acetylenes rearrange in the presence of light to
their correSponding isatogens. Since the preparation of
an analytically, pure sample of compound lg'is difficult
to obtain, because of this sensitivity, the elemental analy-
sis was not attempted. The corresponding isatogen (12),
however, is stable to light and can easily be purified.
Since the elemental analysis for compound 14.has been per-
formed and shown to be correct, the structure of compound

‘33 is subsequently supported.

 

39

15. 2-(3,4-Dimethoxy-phenyl) 6-nitro-3Hfindol-3—one~N-

 

oxide (14)

To 3 ml of chloroform and 5 ml of pyridine 0.1 g (0.3
mmole) of 1-(2,4-dinitrophenyl) 3,4-dimethoxy-phenylacety-
lene (13) was dissolved. The orange solution was stirred
in the hood for two days at room temperature under a flor-
escent light bulb. The reaction media slowly changed color
to red. The residue remaining, after the solvent was re-
moved, was chromatographed on silicic acid (8 g, 14 mm
column) with methylene chloride. The violet isatogen
eluted from the column slowly, but was very pure. After
the chloroform was removed, a dark purple solid (0.05 g,
0.15 mmole) was recovered, indicating approximately a 50%
conversion from the acetylene: m.p. 226-227.5°: infrared

spectrum (CHCl3) EYE-1

, 1700 (c=0), 1525, 1335 (N02) and
1260 (C-O-C), but no CEC stretch, Figure 21; mass spectrum
(70 eV) mge, 328(P), 382(P-N09) and 254(382-C0): xmax
(CH2C12) as, 282 (6 17,150), 322 (6 10,050), 366 (6 10,930)

and 523 (6 1,885), Figure 22.

Anal. Calcd. for C16H12N203: C, 58.54; H, 3.66.

 

Found: C, 58.70; H, 3.82.

 

11.

12.

13.

14.

BIBLIOGRAPHY

Foster, R., ”Organic Charge-Transfer Complexes," ed.
by A. T. Blomquist,.New York, Academic Press, Inc.,
1969.

Rao, C. N. R., "Ultra-Violet and Visible Spectroscopy,"
New York: Plenum Publishing Corporation, 1967.

Okamoto, Y. and W. Brennen, "Organic Semi-conductors,"
New York: Reinhold Publishing Corp., 1964.

“Proceedings of the International Conference on Or-
ganic Superconductors," Ed. by W. A. Little, New York:
Interscience Publishers, 1970.

Wittig, G. and M. Schlosser, Chem. Ber., 923 1373 (1961).
Kabrich, G., et al., Chem. Ber., 22“ 689 (1966).
Castro, C..E., et al., Jour. Org. Chem., 31“ 4071 (1966).

Ruggli, P., E. Caspar and B. Hegedfis, Helv. Chim.
Acta., 29', 1250 (1937).

Smith, L., Chem. Rev., 22“ 244 (1938).

Campbell, K., et al., Jour. Amer. Chem. Soc., 22“ 2400
(1953).

Viehe, H. G., "Chemistry of Acetylenes," Chapter 9,
New York: Marcel Dekker, Inc., 1969.

"Organic Electronic Spectral Data," New York: Inter-
science Publishers, Inc.

Richman, R. J. and A. Hassner, Jour. Org. Chem., 33,
2548 (1968).

Michel, R. H., Jour. of Poly Sci., 5, 925 (1967).

40

 

15.

16.

17.

41

Staab, H. A., et al., Tetrahedron Let., 1465 (1968).

Fulton, J. D., and R. Robinson, Jour. of Chem. Soc.,
1463 (1933).

Sch6pf, C., et al., _iebigs Ann..Chem,, 544, 61 (1940).

 

 

W'fi- I ’ O '~n \ 'f“
-’ . _
q

APPENDIX

 

 

42

 

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.3; ocoooufism Smeaaosoesounvum so sandman .22 .fi mucosa

 

 

.: x.
, HocC

Homofln.

 

 

 

 

 

43

.Hocmzuma Bonn

 

 

 

 

 

 

 

omNHHHmummuomu xfimv mamomunucm AH>GH>OHOHSUIvam mo Eduuommm HEZ .mH musmflm

0 0.. 0.0 0.0 0.0 . - . g 0.0 . 0.0 0.5 0..
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