A study of the reaction of 2,4-dinitrobenzenesulfenyl chloride with the cis- and trans-stilbenes

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Content A STUDY OF THE REACTION OF
2,4-DINITROBENZENESULFENIL CHLORIDE
WITH THE CIS- AND TRANS-STILBENES
A Thesis
Presented to the Faculty
of the Graduate School
University of Southern California
In Partial Fulfillment
of the Requirements for the Degree
Master of Science in Chemistry
by
Norman R. Slobodkin
August, 1959
UMI Number: EP41625
All rights reserved
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U N IVE R SITY O F S O U TH E R N C A L IF O R N IA
G R A D U A T E S C H O O L
U N IV E R S IT Y P A R K
L O S A N G E L E S 7 . C A L IF O R N IA
C '6/
This thesis, written by
Dean
Date AugU5t._19.60.
THESIS COMMITTEE
..
Chairman
...............H Q riaa2i-R *...S liib o .d kiii.... S
under the direction of hJ.S—Thesis Committee, JfZ |
and approved by a ll its members, has been pre- f
sented to and accepted by the Graduate School,
in partial fulfillm ent of requirements fo r the
degree of
Master of Science
To Jackie
ACKNOWLEDGEMENT
The author wishes to express his sincere appreciation to
Dr. Norman Kharasch for his understanding guidance of
this study, and to Dr. Sidney W. Benson and Dr. Ronald
P. Brown for helpful and stimulating discussions through
out the work.
The author is very grateful to the National Science
Foundation for fellowship support during the course of
this study.
TABLE OF CONTENTS
CHAPTER PAGE
I. INTRODUCTION........................... 1
II. THE KINETICS OF THE ADDITION OF 2,4-DI-
NITROBENZENESULFBNTL CHLORIDE TO CIS-
AND TRANS-STILBENB.......... 3
Discussion of Results ..... 3
General Discussion ........... 4
Experimental ...................... 17
Reagents and Solvents ........ 17
Preparation of 2,4-Dinitroben
zene sulf enyl Chloride Adduct to
trans-Stilhene ............... 18
Preparation of 2,4-Dinitroben
zene sulf enyl Chloride Adduct to
cis-Stilbene ....... 18
Dehydrohalogenation of 2,4-Di
nitrobenzene sulf enyl Chloride
Adduct to trans -Stilbene ..... 19
Dehydrohalogenation of 2,4-Di
nitrobenzenesulfenyl Chloride
Adduct to cis-Stilbene ...... 19
Kinetic Data ................. 20
A
VI
CHAPTER PAGE
III. THE EFFECT OF TEMPERATURE OH THE PRODUCT
OF THE REACTION OF 2,4-DINITROBENZENE-
SULFENYL CHLORIDE WITH TRANS-STILBENE ... 39
General Discussion ................. 39
Experimental ....................... 43
Reaction of 2,4-Dinitrobenzene-
sulfenyl Chloride with trans-
St ilhene in Refluxing Acetic
Acid ......................... 4-3
Reaction of er.ythro-2-Chloro-
(21,4 * -Dinitrophenylthio)-1,2-
Diphenylethane in Refluxing
Acetic Acid .................... 44-
Reaction of e rythro-2-Chioro-
(2*,4'-Dinitrophenylthio)-l,2-
Diphenylethane in Refluxing
Acetic Acid and Sodium Acetate. 44
Reaction of erythro-2-Chioro-
(2',4*-Dinitrophenylthio)-1,2-
Diphenylethane in Absolute
Acetone and Sodium Acetate .... 45
Reaction of 2,4-Dinitrobenzene-
sulfenyl Chloride with cis-
CHAPTER PAGE
Stilbene in Refluxing Aeetic
Acid ............ 45
Conversion of cis-Stilbene to
trans-Stilbene in Refluxing
Acetic Acid ....... 46
Reaction of threo-2-Chloro-
(2’ ,4* -Dinitrophenylthio)-
1.2-Diphenylethane in Refluxing
Acetic Acid .............. 46
Reaction of threo-2-Chloro-
(2‘,4'-Dinitrophenylthio)-
1.2-Diphenylethane in Refluxing
Aeetic Acid and Sodium Acetate. 47
Reaction of threo-2-Chloro
(2',4*-Dinitrophenylthio)-
1.2-Diphenylethane in Absolute
Acetone and Sodium Acetate .... 47
Reaction of 1,1-Diphenylethylene
with 2,4-Dinitrobenzenesulfenyl
Chloride ............... 48
Treatment of the 134° Vinyl
Sulfide with Raney Nickel ... 48
PAGE
Oxidation of the 134-° Vinyl
Sulfide ............ .......... 4-9
BIBLIOGRAPHY............................... 50
J
LIST OF TABLES
TABLE PAGE
1. Summary of Rate Runs, in Acetic Acid, for
the Reaction of 2,4-Dinitrohenzenesulfenyl
Chloride with trans-Stilbene.............. 10
2. Summary of Rate Runs, in Acetic Acid, for
the Reaction of 2,4-Dinitrohenzenesulfenyl
Chloride with cis-Stilbene................ 11
3. Summary of Rate Runs with Added Electro
lytes at 45°............. 12
4. Rate Constants for the Epoxidation of
Various Olefins.......................... 13
5. Rate Constants of Epoxidation of cis- and
trans-St ilbene......... 14
6. Rate Constants of Oxidation of cis- and
trans-Azobenzene .......... 15
7. Deviations from 1:1 Adduct Formation...... 42
CHAPTER I
INTRODUCTION
This study concerned itself with, the kinetics of
the addition of 2,4-dinitrobenzenesulfenyl chloride, I,
to cis- and trans-stilbene. This study was selected
since it offered an opportunity to investigate electro
nic character and steric effects on the rates of sulfeny-
lation.
The results of the work, including those of previous
kinetic studies involving electrophilic additions to cis-
and trans-stilbene are reported in the following chapters
Prior to this study, the only data on the kinetics of the
reaction of sulfenyl halides with cis- and trans-ole fins
was a qualitative study made by Havlik'L on the addition
of I to the cis- and trans-2-phenyl-2-butenes.
In the present work, it was established, Chapter II,
that the addition of I to cis- and trans-stilbene occurs
in a stereospecific manner. In addition, several other
points of interest were encountered. These included:
(a) observations that the reaction did not occur appre
ciably in purified nitrobenzene, ethylene bromide, or
carbon tetrachloride, (b) the reaction when carried out
in refluxing acetic acid gave a vinyl sulfide, 1,1-di-
phenyl -2-(2’ ,4' -dinit rophenylthio) -ethylene, as main
2
product, and (c) cis-stilbene was not converted to trans-
stirbene under the conditions of the kinetic study.
A second portion of the study, Ghapter III, con
cerned itself with the proof of structure of the vinyl
sulfide from the reaction in refluxing acetic acid. It
was found during this study, that dehydrohalogenation of
the adducts from the cis- and trans-stilbene gave the
same vinyl sulfide. This suggests (1) the cis-stilbene
adduct and trans-stilbene adduct differ only in configu
ration (i.e., they are diasteriomers) and (2) the elimi
nation is of the q g type and phenyl-phenyl repul
sion is considerable in the cis- situation.
CHAPTER II
THE KINETICS OP THE ADDITION OP
2,4~DINITROBENZENESULPENIL CHLORIDE
TO CIS- AND TRANS-STILBENE
Discussion of Results
This chapter reports the results of the kinetic
study of the addition of 2,4—dinitrobenzenesulfenyl
chloride, I, to cis- and trans-stilbene.
In dry acetic acid, I reacts with trans-stilbene
2
to form a previously reported adduct. The adduct of I
with trans-stilbene is er.ythro-2-chloro-C21.4*-dinitro-
phenylthio)-l,2-diphenylethane, assuming trans addition
of I to trans-stilbene.
In dry acetic acid, I reacts with cis-stilbene to
form threo-2-chloro-(2',4-'-dinitrophenylthio)-l,2-di-
phenylethane in over 90% yield.
- r ?
4
■H
The rate of addition of I to both cis- and trans-
stilbene is greatly increased by the presence of a trace
of anhydrous aluminum chloride.
Data for the runs of trans-stilbene are listed in
Table 1, and those for cis-stilbene are listed in Table 2.
Details for typical runs are given in the experimental
section. In determining the mean values of the constants,
points below 10-15% reaction were excluded.
The plot of log htrang vs. 1/T and log kcig vs. 1/T
gave excellent linear relationships; the slope of these
lines gave activation energies of 9*4 i 0.5 and 15.8 i 0.5
Kcal./mole, respectively. The reaction of I with trans-
stilbene showed a positive salt effect, as seen in Table 5«
General Discussion
Previous kinetic studies of epoxidation of the cis-
and trans-stilbenes (Tables 4,5,6) have indicated the cis-
\
5
x
olefin to be the more reactive. Robertson and Woodward,
have postulated that this difference in reactivity resul
ted from electronic differences in cis- and trans-stil
bene. trans-Stilbene, being planar, has some carbon-
carbon single bond character in the double bond, since
unsaturation electrons may become involved in resonance
with the two planar phenyl groups, thereby decreasing
electron density at the carbon-carbon double bond.
cls-Stilbene, suggested by molecular models to be
non-coplanar, has more double bond Character, since the
unsaturation electrons cannot become fully involved in
resonance with the phenyl groups since they cannot assume
a planar configuration.
Such differences in reactivity have also been shown
in the cis- and trans-azobenzene. Oxidation of cis-
azobenzene is more rapid than oxidation of the trans-
azobenzene, and the differences in rates were attributed
to the differences in electron density about the nitrogen
nitrogen double‘bond.
In contrast to the rates of epoxidation (Tables
4-,5,6), it is seen that from the present study of the
rates of sulfenylation, that the trans-stilbene.is more
reactive than the cis-olefin. This suggests that steric
factors are more important in the sulfenylation reaction
than in the epoxidation reaction studies by Woodward.
6
Cram^ has shown that the rates of ^ reactions from
1,2-diphenyl-1-propyl systems have marked differences.
The threo chloride, A, eliminated hydrogen chloride much
Since the diasteriomeric transition states (not
shown) differ with respect to eclipsing effects, Cram has
explained the differences in rates on the basis of the
eclipsing effects increasing the steric inhibition of
resonance of the phenyl groups. In the case of A, the
phenyl groups were not eclipsed, and became more planar
in the transition state complex. In the transition state
from the erythro isomer, B, the phenyl groups were e-^ .,
clipsed more than in the trans case and steric inhibition
of resonance was increased.
faster with potassium tert-butoxide than did the er.ythro
chloride, B.
7
In the intermediate of the sulfenylation of cis-stilbene,
assuming a cyclic sulfonium ion, the phenyl groups are
seriously eclipsing each other, and steric inhibition of
resonance with the phenyl groups results.
In the intermediate of the sulfenylation of trans-
stilbene, the phenyl groups are not eclipsed, may become
planar, and increased stability through resonance of the
resulting positive charge with the planar phenyl groups
results •
The size of the bulky 2,4—dinitrophenyl group at
tached to the sulfur in the transition state of sulfeny
8
lation as contrasted with a small hydrogen attached to
an oxygen in the transition state of epoxidation is sug
gested to account for differences in steric effects.
In the dehydrohalogenation of the threo and erythro-
2-chloro-(2',4'-dinit rophen.ylthio)-l,2-diphenylethane, ’
the, same vinyl sulfide resulted. This is explained by an
elimination reaction of the E-^ ^ - g type and lends evi
dence to support the argument that cis- phenyl repulsions
have serious implications.
9
_ _ ' i
*
Thus, eclipsing effects and steric inhibition, of
resonance of the phenyl groups is offered to explain the
larger rate constants for the addition of 2,4-dinitro-
benzenesulfenyl chloride (I) to trans-stilbene. In this
sulfenylation reaction, the steric factors appear to be
large enough to overbalance the electronic effect which
would predict the cis-olefin to react faster.
10
TABLE 1
SUMMARY OF RATE RUES, IN ACETIC ACID, FOR THE REACTION OP
2,4-DINITROBENZENESULFENYL CHLORIDE WITH Trans-STILBENE
mole/I. mole/I. k X 10p Mean Value
*
of of (mole/1 .)“' L of Temp.
Stilbene ArSCl sec .*”1 k X 105 C.°
.05152 .05251
1.84
1.85 ± .03
45.0 ±
.05755 .05251
1.86
.05148 .03706 3.08 3.07 i .03
55.0 ±
.06452 .03706 3.06
.05064 .03348 4.04 4.04 ± .06 63.0 ±
.02984 .03348 4.06
.03034 .03348 4.03
■ 6 ----------
11
TABLE 2
SUMMARY OF RATE RUNS, IN ACETIC ACID, FOR THE REACTION OF
2,4-DINITROBENZENESULFENYL CHLORIDE WITH Cis-ST ILBENE
mole/l. mole/I. k X 103 Mean Value
of of (mole/1. of Temp.
Stil'bene ArSCl sec. k X 103 C.°
.02491 .03564 1.08 1.11 ± .05 45.0 ± .1
.03326 .03564 1.08
.05391
.03564 1.16
.08583
.04182
2.07 2.07 ± .05
55.0 ± .1
.04268 .04182 2.10
.03593
.04182 2.04
.07439
.04752 3.90 3.95 ± .05
65.0 i .1
.05342 .04752 4.00
.03571
.04752 3.94
i
12
TABLE 3
SUMMARY OP RATE RUES WITH ADDED ELECTROLYTES AT 45°
Initial Concn. Electrolyte k X 103
trans-St ilbene ArSCl M, Concn. (mole/1,)“^sec
.05152 .05251
0
1.85 ± .03
.04256 .03136 .02 LiCl
1.85 i .03
.06188 103136 .05 LiCl 2.04 ± .05
.07108 .03136 .09 LiCl 2.34 ± .14
13
TABLE 4
I
BATE CONSTANTS FOR THE EPOXIDATION OF VARIOUS OLEFINS
Peracetic Acid
in Aeetic Acid
Temp. C.° k2
trans-Stilbene 25.8 6.7
cis-Stilbene
25.8 11.1
Styrene
25.8 11.2
1,1-Diphenylethylene 25.8 48.0
Perbenzoic Acid
in Aeetic Acid
Temp. C.° k2 X 105
trans-St ilbene 25-30 18
cis-Stilbene 15-16 9
Styrene 25-30 35
14
TABLE 5
RATE CONSTANTS OF EPOXIDATION OF Cis- AND Trans-STILBENE
Perbenzoic Acid
in Benzene
Temp. C.° k2 X
trans-Stilbene 20 2.69
25
4.2?
50 6.64
55 10.15
cis-Stilbene 20
5.75
25 8.85
50
15.55
55 19.65
15
TABLE 6
DILATE CONSTANTS OF OXIDATION OF Cis- AND Trans-AZOBENZENE5
Perbenzoic Acid
in Benzene
Temp • C.° k2 X
trans-Azobenzene
15
5.8
20 9.02
25 15.9
50 20.9
cis-Azobenzene
15
574
20
527
25 749
50
1085
EXPERIMENTAL
17
EXPERIMENTAL *
Dry Acetic Acid was obtained by refluxing 99*5%
acid (Baker and Adamson, Reagent Grade) with, acetic
anhydride (75 ®1* per liter of acid) for 15-20 hr., then
distilling through a 90 cm. column (packed with glass
helices) at a rate of 100 ml./day. The middle cut
(600-700 ml.) from one liter of distillate was used.
2,4—Dinitrobenzenesulfenyl Chloride was prepared by
the method of N. Kharasch and D. Lawson. Prior to each
kinetic run, it was twice recrystallized from carbon tet
rachloride and dried in a vacuum-desiccator, m.p. 97-93°.
trans-Stilbene was prepared by the method of R. L.
Shriner and A. Berger,^ m.p. 123-124-°.
cis-Stilbene was prepared by the method of Taylor
and Crawford,® b.p. 120-122°/6 mm.
Lithium Chloride was a C. P. reagent, dried at 110°
for 25 hours, and cooled in a desiccator.
♦All melting point determinations were taken on a Fischer-
Johns block, unless stated otherwise in the text.
Analyses were performed by Dr. Adalbert Elek of the Elek
Microanalytical Laboratories, Los Angeles, California,
Preparation of 2.4-Dinitrobenzenesulfenyl Chloride
Cl) Adduct to trans-Stilbene Cll-a) in Acetic Acid.—
trans-Stilbene (3*4 g.» 0.019 mole) was dissolved in 50
ml. of glacial acetic acid. To the clear solution was
added 4.0 g. (0.017 mole) of I and .1 g. of anhydrous a-
luminum chloride. The reaction was allowed to stand 2
days at 55°, during which time a large mass of yellow
crystals formed. The product was collected and repre
cipitated twice from chloroform solution with petroleum
ether (b.p. 50-60°) to yield an analytical sample, 5-7 g*
(81%), m.p. 174-175.5°.
Anal. Calcd. for C2qH^^C1N20^S: C, 57*90; H, 3*64.
Pound: C, 57*89; H, 3.74.
Preparation of 2.4-Dinitrobenzenesulfenyl Chloride
(I) Adduct to cis-Stilbene (Il-b) in Acetic Acid.—
cis-Stilbene (3.10 g., 0.0172 mole) was dissolved in 40
ml. of glacial acetic acid. To the clear solution was
added 3*5 g. (0.011 mole) of I and .1 g. of anhydrous a-
luminum chloride. The reaction mixture was allowed to
stand 3 days at 55°* during which time a large mass of
yellow crystals formed. The product was collected and
recrystallized from 95% ethanol to yield an analytical
sample, 3.7 g. (82%), m.p..153-154°.
Anal. Calcd. for CgQH^ClNgO^S: C, 57.90; H, 3.64.
Pound: C, 58.02; H, 3.75.
19
Sehydrohalogenation of 2 ,4-Dinitrobenzenesulfenyl
Chloride Adduct to trans-Stilbene.— erythro-2-Chloro-
(2*,4'-dinitrophenylthio)-l,2-diphenylethane (1.2 g.,
0.0029 mole) was dissolved in 25 ml. of benzene. To the
solution was added 2 ml. of triethylamine. The reaction
mixture was refluxed 24 hours on the steam-bath. The
reaction mixture was filtered. The benzene filtrate was
extracted with 10% hydrochloric acid and dried over an
hydrous sodium sulfate. The solvent was removed in vacuo.
The residue consisted of light-orange crystals. The pro
duct was recrystallized from 95% ethanol to give 1.0 g.
(90%), m.p. 210-212°.
Dehydrohalogenation of 2.4-Dinitrobenzenesulfenyl
Chloride Adduct to cis-Stilbene.— threo-2-Chloro-
(2',4'-dinitrophenylthio)-l,2-diphenylethane (1.7 g.,
0.0041 mole) was dissolved in 35 ml. of benzene. To the
solution was added 2.5 ml. of triethylamine. The reaction
mixture was refluxed 24 hours on the steam-bath. The
reaction mixture was extracted with 10% hydrochloric acid
and dried over anhydrous sodium sulfate. The solvent was
removed in vacuo. The residue consisted of light-orange
crystals. The product was recrystallized from 95%
ethanol to give 1.4 g. (90%), m.p. 209-212°. This was
shown to be identical to the dehydrohalogenation product
from the trans-stilbene adduct by observing no differences
in their infra-red spectra, and mixture-melting points.
20
Kinetic Data
The general procedure for runs in acetic acid is
given in reference 9. Successive blanks during the rate
runs showed no upward or downward values. In blanks, 10
ml. of solvent rather than reaction mixture was used.
The concentration of sulfenyl chloride was calcu
lated from the corrected volume of thiosulfate solution.
The initial concentration of stilbene was calculated from
the known weight of olefin introduced into the reaction
mixture and that of I was determined by titrating ali
quots of freshly prepared stock solution of I. The con
centration of olefin in the solution was calculated from
the measured concentration of sulfenyl chloride and the
difference in the initial concentrations of the two reac
tants. The specific reaction rate constants were calcu
lated from the familiar second-order expression:
j
21
Time
(Min.
0
243
626
1482
1951
3120
4610
RUN HO. 1-45
ml. of .0328 N ArSCl trans-olefin k X 10-
) RagSgO^ mole/1. mole/1
(mole/1.)
sec . ^
-1
16.01
13.65
11.62
8.83
7.47
5.80
4.40
.05251
.04470
.03820
.02897
.02450
.01904
.01442
.05152
.04371
.03721
.02798
.02351
.01805
.01343
2.17
1.86
1.75
1.88
1.82
1.86
average: 1.84 - .04
1
22
RUN NO. 2-45
Time ml. of .0328 N ArSCl trans-olefin
(Min.)
0
255
630
1485
1955
3120
4100
^a2^2°3
16.01
13.4-9
11.30
8.12
6.79
4.92
3.80
mole/1, mole/1.
.05251
.04291
.03701
.02663
.02223
.01630
.01246
.05755
.04795
.04205
.03167
.02727
.02134
.01750
k X KK
(mole/1 .)~^
sec
2.41
1.88
1.81
1.90
1.87
1.87
I
average: 1.86 - .02
. !
23
RUN NO. 3-45
Time ml. of .0328 N
(Min.) Na2S205
ArSOl trans-olefin
mole/1. mole/1.
k X 10'
(mole/1.)
sec
-1
0
220
670
1594-
1899
2820
11.30
8.87
7.15
4.11
3.31
2.31
.03706
.02909
.0234-3
.01348
.01086
.00738
.05148
.04351
.03787
.02790
.02528
.02200
3.86
3.10
3.05
3.14
3.02
average:3*08 - .04
24
Rim HO. 4-55°
Time ml. of .0328 H ArSCl traps-olefin k X 10^
(tin.) Ha2S20^ mole/1. mole/1. (mole/1,)
-1
i.r1
sec •
0 11.30 ♦03706 .06452
— —
223 8.52 .02787 .05533 3.56
452 6.82
.02237 .04983 3.10
1465 3.15 .01033 .03779 3.07
1898 2.86 .00774 .03520 3.0 7
2695
1.46 .00479 .03225
3.04
3142
1.15 .00377 .03123 3.05
average: 3.06 ± .02
25
RUN NO. 5-63
Time ml. of .0328 N ArSCl trans-olefin k X 10-
(Min.)
Na2S2°3
mole/1. mole/1. (mole/1.)
—1
see.
-1
0
275
456
640
804
1269
15.25
11.30
10.45
9.4-7
8.35
7.55
.0354-8
.02712
.02508
.02275
.02124
.01764
.03064
.02428
.02224
.01989
.01840
.01480
average :
4.67
4.05
4.10
4.00
4.02
4.04.± .03
I
26
RUN NO. 6-63°
Time ml. of .0328 N AxSCl trans-olefin k X 10^
(Min.) Na2S205 mole/1. mole/1. (mole/1.)"'1
sec.
0 13.95 .03348 .02984 ---
275 11.34 .02722 .02360 4.80
437 10.50 .02520 .02160 3*92
678 9.47 .02265 .01901 4.05
801 8.90 .02136 .01772* 4.12
1262 7.46 .01790 .01426 4.07
average: 4.06 i .05
27
RUN NO. 7-63°
Time ml. of .0328 N ArSCl trans-olefin k X 10^
(Min.)
0
278
475
666
759
1240
^ 282©^ mole/1, mole/1. (mole/1.) ^
sec
13.95
.03348 .03034 — —
11.35
.02724 .02410 4.52
10.47 .02513 .02199
3.90
9.40 .02256 .01942 4.07
8.94 .02153
.01844 4.10
7.41 .01778
.01464 4.04
average: 4.03
28
RUIT NO. 8-45
o a
Time ml. of .0328 IT ArSCl trans-olefin
(Min.) mole/1. mole/1.
k X 10'
(mole/1.)
sec. " " 1
-1
0 9.56 .03136 .04256 ---
21? 8.6? .02843 .03963 1.83
4-52 7.79 .02555 .03675 1.94
1453 5.37 .01761 .02881 1.92
1896 4.78 .01567 .02687 1.80
2910 3.70 .01213 .02333 1.78
3365 3.29 .01079 .02199 1.80
average:1.85 - .06
a. Lithium chloride added to make the solution .02 H
29
RUN NO. 9-45
o b
Time ml. of .0328 N
(Min.) Na2S20^
ArSCl trans-olefin
mole/1. mole/1.
k X 10^
(mole/1.)'
sec .“ ’1
0
214
479
1440
1897
2922
5562
9.56
7.89
6.81
3.61
2.96
1.95
1.75
.03156
.02591
.02239
.01185
.00969
.00683
.00567
.06188
.05543
.05186
.04137
.03921
.03585
.03519
2.06
1.94
2.15
2.08
1.97
1.86
average: 2.04
b. Lithium chloride added to make solution .03 N.
30
RUN NO. 10-45° °
Time ml. of .0528 N ArSCl trans-olefin k X 10^
(Min.) Na2S20^ mole/1. mole/1. (mole/1.)”^
sec.“1
0 9.56 .05136 .07108 ----
217 7.65 .02509 .06481 2.53
452 6.25 .02045 .06025 2.44
1453 3.13 .01027 .05109 2.27
1896 2.52 .00826 .04908 2.13
average: 2.34 - .14
e. Lithium chloride added to make solution .09 R.
31
EOT HO. 11-4-5°
Time ml. of .0240 H ArSCl cis-olefin k X 10^
(Min.) Ha2S205 mole/1, mole/1. (mole/1.)"1
sec. 1
0 14.85
.05564 .02491
269
14.20
.05408
.02555 1.15
593 14.09
.05381 .02508 1.10
805
13.32 .05197
.02124 1.07
2620 10.62 .02548 .01475
1.06
4600 9.25
.02220 .0114? 1.05
average:1.08 £ .05
32
RUN NO. 12-45°
Time ml. of .0240 N ArSCl cis-olefin k X 1(
(Min.) Na2S20^ mole/I• mole/I. (mole/I
sec.
0 14.85
.03564 .03326
-----
186 14.25
.03420 .03182
1.13
356
13.79 .03309 .03071 1.07
588 13.28 .03187
.02949
1.09
1270 11.80 .02832 .02594
1.07
2530 9.85
.02364 .02126 1.05
3770
8.34
.02001 .01763 1.07
average:1.08 i .02
33
RUN NO. 13-4-5°
Time ml. of .0240 N ArSCl eis-olefin k X 105
(Mir.) mole/1. mole/1. (mole/1.)""^
sec.”' * '
o
14.85
.03564
.05391
—---
172 13.90 .03326 .05163 1.20
2?6
13.45
.03228
.05055
1.14
561 12.47
.02993
.04820 1.12
1289 9.80 .02352 .04179
1.14
2300 7.50 .01800 .03627
1.14
3760 5.54- .01329 .03156 1.10
average:!.16 i .03
34
RUN NO.. 13-55°
Time ml. of .0328 N ArSCl c
(Min.)
0
150
4-31
1355
1890
2864
average: 2.07 - *05
Na2S2°3
mole/1 mole/I. (mole/1.)
sec
-1
12.75
.04182
.08583
— , —
11.50 .03772 .08173 1.37
8.45
.02771
.07172 2.02
4.00 .01312
.05713 2.05
2.87
.00941 .05342 2.04
1.40
.00459
.04860 2.16
35
RUN NO. 14-55
Dime ml. of .0328 N ArSCl cis-olefin k X 10'
(Min.) Na2S20^
0
130
554
1480
1885
2860
5301
mole/1. mole/1, (mole/1.)
-1
-1
12.75
11.80
10.47
6.98
6.37
5.00
4.75
.04182
.03870
.03444
.02289
.02089
.01640
.01558
sec
.04268
.03956
.03536
.02375
.02175
.01726
.01644
2.44
2.10
2.20
2.10
2.08
2.04
average: 2.10 - .03
36
RUN NO. 16-55
Time
(Min.)
ml. of .0328 N ArSCl cis-olefin k X 10'
mole/I. mole/I. (mole/I.)
sec
-1
0
149
437
1625
1902
2874
3085
12.75
12.30
10.50
7.56
7.20
6.00
3.72
.04182
.04037
.03444
.02479
.02361
.01968
.01876
.03595
.03450
.02857
.01892
.01774
.01381
.01289
1.1
2.30
2.08
2.01
2.01
2.06
average: 2.04 i .03
37
Dime
(Min.
V..
0
93
163
323
574
639
949
RUN NO. 17-65
ml. of .0328 N ArSCl
Na2S20^ mole/I.
cis-olefin
mole/1.
k X 10"'
(mole/I.)
sec
-1
14.50
13-30
12.75
11.50
10.07
9.67
8.42
.04752
.04352
.04175
.03772
.03300
.03170
.02760
.03571
.03171
.02994
.02591
,02119
.01989
.01579
average:
4.3
3.91
3.94
3.90
3.96
3.93
3.93 ± .02
Time
(Min.
0
61
109
180
239
308
RUN NO. 18-65
38
ml. of .0328 N ArSCl
Na2S20^ mole/I.
cis-olefin
mole/I.
k X HK
(mole/1.)
sec."1
-1
14.50
13.00
12.15
10.86
10.00
9.15
.04752
.04255
.03980
.03558
.03280
.02988
.07439
.06942
.06667
.06245
.05967
.05675
average :
4.2
3.90
3.88
3.91
3.90
3.90 ± .02
CHAPTER III
THE EFFECT OF TEMPERATURE ON THE
PRODUCT OF THE REACTION OF
2,4-DINITROBENZBNESULFENYL CHLORIDE
WITH TRANS-STILBENE
Previous workers^ (Table 7) have shown that a num
ber of olefins react with sulfenyl halides to give vinyl
sulfides or beta-acetoxysulfides instead of the expected
1:1 adducts. Orr^*^ has shown the effect of temperature
to be important in determining product composition. The
reaction of 2,4—dinitrobenzenesulfenyl chloride (I) with
p-methoxystyrene at 15° in acetic acid gave the 1:1 ad
duct ; while reaction at 4-0° gave the vinyl sulfide.
Since he found that the rate of dehydrohalogenation of
the 1:1 adduct, in this case, was less than the rate of
formation of vinyl sulfide from the reactants, he con
cluded that the adduct was not necessarily an interme
diate in the formation of the vinyl sulfide.
It has been found in this study, that the reaction
of trans-stilbene and I in refluxing acetic acid gave a
vinyl sulfide which is identical to the one obtained
12
from the reaction of I with 1,1-diphenylethy1ene.
Oxidation of the vinyl sulfide to benzophenone and re
duction of the vinyl sulfide with Raney nickel to give
______________________________ 33____________ _____ ___ ______________
40
1,1-diphenylethane showed the vinyl sulfide to he 1,1-
diphenyl-2-(2 *,4'-dinitrophenylthio)-ethylene. Addition
of ArS+ to 1,1-diphenylethylene could yield C, which by
loss of a proton would yield 3).
C V-
Addition of ArS* to trans-stilbene would yield the
cyclic sulfonium ion E; migration of phenyl and subse
quent loss of a proton would give the same vinyl sulfide
as from 1,1-diphenylathylene .
£
When the 1:1 adduct from trans-stilbene was refluxed
in acetic acid for four hours, the vinyl sulfide and a
beta-acetoxy compound resulted. In the acetolysis of
the adduct, participation by sulfur is postulated; the
resulting intermediate then rearranges or is subjected to
nucleophilic attack by acetate. When sodium acetate is
41
added, only the acetoxy compound is formed.
Treatment of the 1:1 adduct from trans-stilbene
under typical SH2 conditions yielded only starting ma
terials. The beta-acetoxysulfide formed under SN-^ con
ditions was postulated to be of the same configuration as
the 1:1 adduct formed from trans-stilbene and I#
The reaction of cis-stilbene and 2,4-dinitrobenzene-
sulfenyl chloride in refluxing acetic acid yielded the
same vinyl sulfide and the same acetate as were formed
from the trans-stilbene reaction with I under similar con
ditions . cis-Stilbene was converted to trans-stilbene
under the conditions of the reaction; it was postulated
that the cis-stilbene was converted to trans-stilbene
before any appreciable reaction between cis-stilbene and
2,4-dinitrobenzenesulfenyl chloride occured.
Acetolysis of the 1:1 adduct from cis-stilbene in
refluxing acetic acid appeared to proceed more slowly than
the acetolysis of the 1:1 adduct from trans-stilbene, but
the products were the vinyl sulfide and a beta-acetoxy-
sulfide different from the one from the acetolysis of the
1:1 adduct from trans-stilbene. Acetolysis of the 1:1
adduct from cis-stilbene with sodium acetate and acetic
acid yielded only the beta-acetoxysulfide as from the
acetolysis of the 1:1 adduct from cis-stilbene. Treatment
of the 1:1 adduct from cis-stilbene under typical SN2
conditions yielded only starting materials.
42
TABLE 7
DEVIATIONS FROM 1 :1 ADDUCT FORMATION
Derivative of Olefin
1,1-Diphenylethylene
4-~Methoxy styrene
Limonene
Vinyl acetate
1,4-Gxathiene
Camphene
Anethole
m.p
• j
'C.
135-136
198-200
195-196
158-159
148-149
121-122
160-161
Deviation
vinyl sulfide
vinyl sulfide
2:1 derivative
adduct less HC1
acetoxy deriv.
vinyl sulfide
acetoxy deriv.
43
EXPERIMENTAL
Reaction of 2.4-Dinitrobenzenesulfenyl Chloride Cl)
with trans-Stilbene in Refluxing Acetic Acid.— To a
refluxing solution of glacial acetic acid was added
trans-stilbene (2.31 g*, 0.0128 mole) and 3*74 g. of I.
The reaction mixture was refluxed 2 hours, during which
time the reaction mixture turned black in color. The
reaction mixture was aspirated to dryness. The residue
was dissolved in benzene and placed on a column of alu
mina (2.5 X 20 cm.) which was wet with petroleum ether
(b.p. 50-60°). The first fraction was eluted with a 50%
by volume mixture of benzene and petroleum ether. Metha
nol was gradually introduced to elute the second fraction.,
Fraction (1) gave 2.8 g., m.p. 133-133° (60%)
Fraction (2) gave 0.7 g., m.p. 122-125° (20%)
These separations indicate that two distinct pro
ducts are formed. Both products gave a negative Beil-
stein test, and both compounds had similar infra-red
spectra but (2) showed an absorption maxima in the 5*9 tL
region while (1) did not.
Elemental analysis of (1) showed that it was the
vinyl sulfide, 1,1-diphenyl-2-(2',4'-dinitrophenylthio)-
ethylene.
44
Anal. Galcd. for 02qH^^1?20^S : C, 63.47; H, 3-73.
Found: C, 63.70; H, 3.55.
Elemental analysis of (2) indicated that it was the
beta-acetoxysulf ide, er.ythro-2-acetox.y-(2r ,4*-dinitro-
phenylthio)-l,2-diphenylethane.
Anal. Calcd. for ^22^18^2®6®1 60.26; H, 4.14.
Found: G, 60.33; H, 4.01.
Reaction of er.ythro-2-Chloro-(2 * .4* -Dinitrophenyl-
thio)-1«2-Diphenylethane in Refluxing Acetic Acid.— To
a refluxing solution of glacial acetic acid was added
2.1 g. of the adduct from trans-stilbene. The reaction
mixture was refluxed 4 hours. The orange solution was
aspirated to dryness and dissolved in benzene. I&nplo-
ying a similar chromatographic procedure as described
above, it was found that the 1 :1 adduct from trans-
stilbene was converted into 70% of the vinyl sulfide and
erythro-beta-acetoxysulfide; 20% experimental loss.
Reaction of erythro-2-0hloro-(21.4* -Dinitrophen.yl-
thio)-1.2-Diphen.ylethane in Refluxing Acetic Acid and
Sodium Acetate.— To a refluxing solution of glacial
acetic acid was added 3*0 g. of anhydrous sodium acetate
and 1.3 g. of the 1:1 adduct from trans-stilbene. The
reaction mixture was refluxed 3 ' hours. The yellow
solution was filtered. The filtrate was aspirated to
dryness and dissolved in benzene. Employing a similar
chromatographic procedure as described above, it was
4-5
found that the 1:1 adduct from trans-stilbene was conver
ted into the erythro-beta-aeetoxysulfide only, m.p. 125-
125° (1.2 g., 87%).
Reaction of erythro-2-Chloro-(21.4-* -Dinitronhenyl-
thio)-1.2-Di~phen.ylethane in absolute Acetone and Sodium
AcetateTo a refluxing solution of dry acetone was ad
ded 15 g» of anhydrous sodium acetate and 1.2 g. of the
1:1 adduct from trans-stilbene• The reaction mixture was
refluxed 8 days. The slightly orange colored solution
was filtered. The filtrate was aspirated to dryness, and
dissolved in benzene. Employing a similar chromatographic
procedure as described above, it was found that only the
1:1 adduct from trans-stilbene could be recovered (1.1 g,
91%).
Reaction of 2.4—Dinitrobenzenesulfen.yl Chloride (I)
with cis-Stilbene in Refluxing Acetic Acid.— To a re
fluxing solution of glacial acetic acid was added cis-
stilbene (1.57 0.0087 mole) and 5.0 g. of I. The
reaction mixture was refluxed 5 hours, during which time
the solution turned black in color. The reaction mixture
was aspirated to dryness and dissolved in benzene* Chro
matography as previously described gave two fractions•
Fraction (1) gave 1.9 g«, m.p. 153-135°
Fraction (2) gave 0.5 g*» m.p. 125-126°
These products were shown to be identical with the
46
products obtained from the reaction of trans-stilbene and
2,4-dinitrobenzenesulfenyl chloride under similar reaction
conditions by infra-red spectra, and mixture-melting
points.
Conversion of cis-Stilbene to trans-Stilbene in
Refluxing Acetic Acid.— To a refluxing solution of
glacial acetic acid was added 1.0 g. of cis-stilbene.
The reaction mixture was refluxed 3 hours. The reaction
mixture was aspirated to dryness. The resulting white
solid melted at 123-124° (.9? g., 97%).
This was shown to be trans-stilbene by infra-red spectra
and mixture-melting points.
Reaction of threo-2-ghloro-(2I,4'-Dinitroohenvl-
thio ) -1.2-Dj-phen.y 1 e thane - in Refluxing Acetic Acid.— To a
refluxing solution of glacial acetic acid was added 1.5 g.
of the 1:1 adduct from cis-stilbene. The reaction mix
ture was refluxed 13 hours. The solution was aspirated
to dryness and dissolved in benzene. Chromatography as
previously described gave two fractions.
Fraction (1) gave .84 g., m.p. 133-135° (65%)
Fraction (2) gave ,22 g., m.p. 61-62° (15%)
These separations indicated that two products were
formed. Both products gave negative Beilstein tests, and
both compounds had similar infra-red spectra but (2)
showed an absorption maxima in the 5.9 ^ region while (1)
did not.
47
Elemental analysis of (2) indicated that it was the
beta-acetoxysulfide, threo-2-acetoxy-(2’,4'-dinitrophenyl-
thio)-1,2-diphenylethane♦
Anal. Calcd. for ♦ 0, 60,26; H, 4.14.
Pound: 0, 60.35; H, 4.01.
The infra-red spectra and melting point of (1) in
dicated it to be the vinyl sulfide, 1,l-diphenyl-2-
(2',4'-dinitrophenylthio)-ethylene.
Reaction of threo-2-Chloro-(2*.4'-Dinitrophenyl-
thio)-1,2-Diphenylethane in Refluxing Acetic Acid and
Sodium Acetate.— To a refluxing solution of glacial
acetic acid was added 4.0 g. of anhydrous sodium acetate
and 1.1 g. of the 1:1 adduct from cis-stilbene. The
reaction mixture was refluxed 5 hours. The yellow colored
reaction mixture was aspirated to dryness and dissolved
in benzene. Chromatography as described previously was
employed. It was found that the 1:1 adduct from cis-
stilbene was converted into the threo-beta-acetoxysul-
fide only, m.p. 61-62°, (1.0 g., 90%).
Reaction of threo-2-Chloro-(2' ,4* -iDinit rophenyl -
thio)-1,2-Diphenylethane in absolute Acetone and Sodium
Acetate,— To a refluxing solution of dry acetone was
added 13 g. of anhydrous sodium acetate and 1.0 g. of the
1:1 adduct from cis-stilbene. The reaction mixture was
refluxed 8 days. The lightly orange colored solution was
48
filtered. The filtrate was aspirated to dryness and dis
solved in benzene. Employing a similar chromatographic
procedure as described above, it was found that only the
1;1 adduct from cis-stilbene could be recovered (0.97 g.»
97%).
Reaction of 2,4-Binitrobenzenesulfenyl Chloride (I)
with 1,1-Diphenylethylene in Acetic Acid.— 1,1-Diphenyl-
ethylene (3.30 g., 0.0183 mole) was added to 40 ml. of
glacial acetic acid. To the clear solution was added
5.0 g. of I. The reaction mixture was heated one hour
on the steam-bath and refrigerated overnight. The orange
product was collected and recrystallized from 95% ethanol
to give 5*5 g« of product, m.p. 133-135° (80%).
Anal. Calcd. for C20H14N204S: C, 63.47; H, 3.73.
Found: C, 63.70; H, 3.55.
The vinyl sulfides from the reaction of I with cis-
and trans-stilbene in refluxing acetic acid and from the
reaction of I with 1,1-diphenylethylene were shown to be
identical by observing no detectable differences in their
infra-red spectra and no depression of the mixture-melting
point.
Treatment of the 134° Vinyl Sulfide with Raney
Nickel.— To a solution of 50 ml. of absolute ethanol
containing 15 g. of Raney nickel was added 4.0 g. (0.011)
mole of the 134° vinyl sulfide. The solution was re
fluxed 2 hours on the steam-bath. About 5 g. more of
49
catalyst was added., and reflux was continued an additional
hour. The mixture was filtered through diatomaceous earth
and the catalyst residue was washed with 2-15 por
tions of absolute ethanol. The washings were added to th€
filtrate, which was then concentrated in an air-stream to
dryness. The dark oil was distilled under reduced pres-
o
sure yielding a colorless oil, b.p. 110-112 /2 mm., m.p.
-8°. (1.0 g., 57%). This was shown to be 1,1-diphenyl-
etht aheiiby observing no differences in the infra-red spec
tra of it and authentic 1,1-diphenylethane.
Oxidation of the 134° Vinyl Sulfide.— To a solu
tion of 50 ml. of water containing 10 g. of potassium
dichromate was added 4.0 g. (0.011 mole) of the 134°
vinyl sulfide. Concentrated sulfuric acid (10 ml.) was
added to the mixture. The solution was allowed to stand
one hour. The reaction mixture was poured on ice and the
resulting white precipitate was collected. Reprecipita
tion from 95% ethanol with ice gave 1.6 g. of product,
m.p. 47-48° (84%).
This was shown to be benzophenone by observing no
differences in the infra-red spectra of it with authentic
benzophenone and observing no depression of the mixture-
melting point.
BIBLIOGRAPHY
1. A.J. Havlik, Ph.D. Dissertation, University of
Southern California (1954-)
2. ibid.
3. J.M. Robertson, M. Prasad, and I. Woodward, Proc.
Roy. Soc., A, 154-, 187
4. G.M. Badger, R.G. Buttery, and G.E. Lewis, J. Chem.
Soc., 2145 (1953)
5.. D.J. Cram, J. Am. GJhem. Soc., 80, 780 (1958)
6. D.D. Lawson and N. Kharasch, J. Org. Chem., 24, 857
(1959)
7. R.L. Shriner and A. Berger, Organic Synthesis, Coll.
Vol. Ill, John Wiley and Sons, Inc., New York, N.Y.,
1955, p. 4-86
8. T.W. Taylor and C.E. Crawford, J. Chem. Soc., 1130
(1934-)
9# N. Kharasch and M. Wald, Anal. Chem., 27, 996 (1955)
10. R.B. Langford and D.D. Lawson, J. Chem. Ed., 34-, 510
(1957)
11. W.L. Orr and N. Kharasch, J. Am. Chem. Soc., 78,
1201 ( 1956)
12. C.Mlii Buess and N. Kharasch, J. Am. Chem. Soc., 71,
2724 (194-9)
13«* B.M. Lynch and K.H. Pausaker, J. Chem. Soc., 1525
-------------(19-S 5-)--------------U niv e r s i t v~of - Southern C a l 1 rortXSl*

Asset Metadata

Creator Slobodkin, Norman R (author)

Core Title A study of the reaction of 2,4-dinitrobenzenesulfenyl chloride with the cis- and trans-stilbenes

Contributor Digitized by ProQuest (provenance)

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

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Advisor Kharasch, Norman (committee chair), Brown, Ronald J. (committee member), Copeland, C.S. (committee member)

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