The sanlfohaloform reaction.

The stepwise conversion of dialkyl

sulfides into alkanesulfonyl chlorides
J. STUARTGROSSERT F. LANGLER
A N D RICHARD
Clzernistr? Department, Dall~ousieU~~i,,ersiiy.
Halifnx, N.S., Canada B3H4J3
Received October 10, 1975l

J. STUART GROSSERT and RICHARD F. LAKGLER. Can. J. Chem. 55, 407 (1977).
A thorough examination of the aqueous oxidative chlorination of 1,3,5-trithiane is described.
The results are utilized to explore and delineate the scope of a general, stepwise, oxidative
cleavage reaction of dialkyl sulfides in which they are successively halogenated and oxidized to
a-polychloros~~lfoxides; subsequently, these cleave to form sulfinyl chlorides, which hydrolyze
and become further oxidized to yield alkanesulfonyl chlorides. The overall stepwise process is
named the 'Sulfohaloform reaction' and the structural requirements of the substrates at each
step are explored in detail. A practical, general synthesis of sulfonyl chlorides is presented.

J. STUART GROSSERT et RICHARD F. LANGLER. Can. J. Chem. 55, 407 (1977)

On a examine la chloruration oxydative du trithiane-1,3,5 eEectuCe en phase aqueuse. On
utilise les resultats obtenus pour explorer et delimiter I'etendue d'une reaction de clivage
oxydative generale qui s'opkre par etape et au cours de laquelle des sulfures de dialkyles sont
successivement halogenes, oxydes en sulfoxyde d'a-polychlores et par la suite clivCs de facon a
fournir des chlorures de sulfinyles qui par hydrolyse et oxydation subsequentes peuvent Ctre
transformis en chlorures d'alkanesulfonyles. On a appele ce processus global par etape 'reaction
sulfohaloforrnique' et on a determine en detail les conditions de structures du substrat qui sont
necessaires B chaque etape. On presente une synthkse gCnCrale et pratique des chlorures de
sulfonyle.
[Traduit par le journal]

Introduction conveniently. The nature of these other products

Some time ago, we outlined (I) the preliminary was revealed by carrying out a partial chlorina-
results from a study of the pathway by which tion af 1,from which it was ascertained that no 2
1,3,5-trithiane, 1, is converted upon treatment had been formed but rather a number of inter-
with molecular chlorine in aqueous media, into mediate products as detailed in Table 1. The
chloromethanesulfony1 chloride, CICH,~SO,~CI, results suggested the intermediacy of 1,3-
2. We now wish to report the results in detail. dichloro-2-thiapropane, 3, and this was con-
I n 1940, Lee and Dougherty (2) reexamined firmed by exhaustive chlorination of 3 in
the chlorination of 1,3,5-trithiane 1 in aqueous aqueous acetic acid from which 2 was isolated
medium, which had originally been reported in 7 0 z yield. Since Lee and Dougherty had
on by Kostsova (3) in 1935. Lee and Dougherty already shown that oxidative chlorination of
concluded that 1,4-dichloro-2,3-dithiabutanesulfides into sulfonyl chlorides did not proceed
might be a n intermediate and showed that n o via sulfones, it became apparent that a study
sulfone could be intervening. In a subsequent of the pathway of this conversion could be
study, Douglass et a/. (4) concluded that fruitful. In particular, the question as to whether
chloromethanesulfenyl chloride might be a C-S bond cleavage and S-CI bond formation
short-lived intermediate. occurred at the sulfenyl or sulfinyl oxidation
level was intriguing. Answers to these questions
Results and Discussion were obtained from a detailed examination of
The Aqueous Chloriization of /,3,5-Trithiane what emerged as a stepwise pathway by which
When we attempted to prepare 2 using the Lee the dichlorosulfide 3 is converted into the
a n d Dougherty procedure, it became obvious sulfonyl chloride 2 upon chlorination in aqueous
that 2 was grossly contaminated by other prod- medium. The study began with chlorination of
ucts and the mixture could not be separated the dicl~lorosulfide3 in glacial acetic acid with
varying water-sulfide ratios. This reaction
'Revision received September 20, 1976. provided the results shown in Scheme I .
 CAN. J. CHEM. VOL. 55. 1977

1. Products from partial chlorination of 1,3,5-trithiane (1 mol) in

TABLE
glacial acetic acid containing water (5 mol)

Number of moles Yield

Product* Yield (g) isolated (%)
-

CHzO 0.52 0.14 14

Co2 0.57 0.11 11
CICH~OAC (41, 42) 2.29 0.18 18
ClCH,.O.CH,Cl (43, 44) 1 .49 0.11 22
CICH2.S.CH2Cl3 (40) 8.00 0.53 53
C1CH2.SS.CH2CI i. 0.06 6
Unreacted (CH2S), 1 1.00 0.06 6
"NO CCI,, CHCl,, CH~CII,HC02H, CICH2.S02.CI, or ClCH2.S.CI was detected
TYleld determined on a separate run.

These experiments conclusively established Attempts to isolate the sulfinyl chloride 6

4, as the
1,3-dichloro-2-thiapropane-2-oxide, from acetic acid solution were unsuccessful.
next intermediate in the sequence. In a similar However, further chlorination led to a good
manner, chlorination of the dichlorosulfoxide conversion of 6 to the sulfonyl chloride 2 which
4 established the intermediacy of 1,1,3-trichloro- could be isolated without difficulty.
2-thiapropane-2-oxide (CI,CH.SO.CH,CI, 5) as CI,
the subsequent intermediate. CI,CH SO CHzCl HOAc r CICHL SO CI + CHCI,
When the trichlorosulfoxide 5 was chlorinated
in aqueous acetic acid, only chloromethane- 6 (75%)
sulfonyl chloride, 2, could be obtained. Although
Lee and Dougherty (2) had demonstrated that
some sulfones were inert to chlorine-water CICH, S02CI + 4cC1
oxidation, we prepared 1,1,3-trichloro-2-tl~ia-
propane-2,2-dioxide and subjected it to chlorina-
I n order to obviate the difficulties experienced
tion in aqueous acetic acid, from which it was
in isolating 6 from acetic acid, the trichloro-
recovered unchanged. Hence it was clear that
sulfoxide 5 was chlorinated in methylene chlo-
the intermediate sulfoxide(s) must have reacted
ride which permitted the isolation of 6 without
with chlorine and cleaved to furnish chloro-
complication.
methanesulfinyl chloride, 6 . Since sulfinyl chlo-
A summary of the pathway for the conversion
rides are readily hydrolyzed to sulfinic acids
of 1,3,5-trithiane, 1, appears in Scheme 2.
( 5 ) , it would have been futile to attempt the
The grounds for including 1,1,1,3-tetrachloro-2-
isolation of 6 from aqueous medium. When
thiapropane-2-oxide, 7, in Scheme 2 are pre-
the trichlorosulfoxide 5 was chlorinated in dry
sented later.
acetic acid, chloron~ethanesulfinylchloride, 6,
could be observed in the nmr of the crude reac- Mechanisms of Suljid~und Suljbxide Cl~louinu-
tion mixture. This was demonstrated by adding fions
authentic 6 to a sample of the crude and follow- Mechanisms for the various steps outlined in
ing the change in intensity of the chloromethyl Scheme 2 are available from previous work.
signal. The pathway by which 1,3-dichloro-2-thiapro-
 GROSSERT AND LANGLER

pane, 3, is converted to the corresponding ylene chloride are the most direct evidence
sulfoxide involves chlorosulfonium chloride salt available that the chlorination of sulfoxides
8 formation prior to nucleophilic attack by water proceeds through a n intermediate species having
o n the sulfur atom of the sulfoniurn salt. This a sulfur-chlorine bond.
reaction has ample precedent (6-10). The inter-
The Chloritie-itiduced C-S Cleat.nge Reactior~oj
~nediacyof a species with a sulfur-chlorine bond
is supported in a more direct fashion by later r-PoI~~c/iloros~~,foxi~/es
work in which chlorination of selected sulfides Although the reactions of sulfides and sulf-
has been shown to furnish sulfenyl chlorides oxides with chlorine to furnish cc-chloro com-
(1 1-18).
pounds via Pummerer rearrangements and/or
to hydrolyze to gi~tesulfoxides or sulfones had
beeil.observed previously, the c l e a ~ a g ereaction
of the c/.-polychlorosulfoxide 5 had not been
previously reported. We therefore examined it
in some detail, by comparison of products
fornied in three solvents of different polarities.
The mechanism for the Pummerer rearrange- Chlorination of 5 in rnethylene chloride
ment of chlorosulfoniurn chlorides has been fi~rnished chloro~iiethanesulfinyl chloride, 6
carefally examined by Wilson et 01. (13, 14). (72)",), chloroform (53%), and carbon tetra-
The mechan~smbasically involves a n E2 type chloride (11z).Direct cleavage of the oxo-
elimination of HCI from the intermediate chloro- chlorosulfoniurn chloride salt derived from 5
sulfonium chloride salt with attack by chloride gives 6 and chloroforni. However, the presence
ion on the resultant carbonium-sulfonium ion. of carbon tetrachloride as a product implicated
The chlorination of sulfoxides has receibed the intermediacy of the tetrachlorosulfoxide 7
a great deal of attention (19-30) since 1968 (see Scheme 3).'
and this now includes stereochemical studies Chlorination of the trichlorosulfoxide 5 in
(24, 27) also. These have led Montanari's group glacial acetic acid furnished chloromethane-
t o postulate that the intermediate oxochloro- suifinyl chloride (isolated as the sulfonyl
sulfonium chloride 9 undergoes simultaneous chloride) and chloroform. N o carbon tetra-
proton abstraction and chlorine atom migratio~l chloride was formed indicating that direct
-
to furnish the cc-chlorosulfoxide.
'An alterngive formulation in which trichloromethyl
Our own observations that cc-trichlorosulf- carbanion (:CCl,) Is displaced by attack of CI- at
oxides, such as 5, furnish sulfinyl chlorides sulfur in 7 is untenable in view of the product distribu-
a n d chlorocarbons upon chlorination in meth- tion when 10 or 11 are chlorinated (oide infva).
410 CAN. J. CHEM[. VOL. 55, 1977

mit the forn~ulationof a detailed pathway for

the chlorination of 5 in water (see Scheme 4).
The reactions which involve sulfinyl chloride
intermediates in aqueous medium are assumed
to proceed through the sulfinic acids. However,
in dry acetic acid, sulfinic acids cannot intervene.
Amongst the mechanistic possibilities is the
elimination of HCl from the intermediate oxodi-
chlorosulfonium chloride salt 9 to furnish a n
intermediate analogous to sulfene ( 31). Should
this have been the case, then chlorination of a
sulfinyl chloride in acetic acid-d, would have
furnished monodeuterated sulfonyl chloride. In
fact, chlorination of methanesulfinyl chloride in
acetic acid-d, furnished undeuterated methane-
sulfonyl chloride, thereby requiring acetolysis of
the intermediate oxodichlorosulfonium chloride
or, alternatively, the formation of a sulfinate-
acetate mixed anhydride before reaction with
molecular chlorine.
Hence, the complete pathway for the con-
version of 1,3-dichloro-2-thiapropane,3, into
chloromethanesulfonyl chloride, 2, has been
cleavage rather than Pummerer-type rearrange- established and the cleavage step shown to
ment is more favored in acetic acid than in the occur on 1,1,3-trichloro-2-thiapropane-2-oxide,
less polar methylene chloride. 5. It seemed appropriate at this point to examine
By contrast, the results in [ I ] showed that the structural requirements of the chlorosulf-
chlorination of 5 in water permitted solvolysis oxide substrates in general in terms of the
t o compete with cleavage by chloride ion. cleavage step. It will be shown In the ensuing
sections how both a-chlorosulfides and -sulf-
oxides, or just simply dialkylsulfides, may be
subjected to stepwise chlorination, oxidation,
and cleavage steps, leading ultimately to sul-
fonyl chlorides, by a process which we propose
is aptly named the 'sulfohaloform reaction'.
see footnote 3 Chlorination of Methyl Sulfoxides
In order to complement the work described
The isolation of carbon dioxide indicated that above on sl,u'-polychlorosulfoxides, I , l-dichlo-
much of the cleavage occurred by nucleophilic ro-2-thiapropane-2-oxide, 10, was chlorinated
attack of water on the most electrophilic carbon in methylene chloride and the results in [2] were
atom of the intermediate oxochlorosulfonium obtained.
chloride salt. The nucleophilic competition
observed when the chlorinations were carried
out in aqueous media is the basis for treating
the cleavage step as an ionic rather than free- C H , SO CI + CC14 + C H C I ,
radical reaction. (76%) (55%) (12%)
Chlorination of the tetrachlorosulfoxide 7
in water afforded chloromethanesulfonyl chlo-
Since carbon tetrachloride was formed it is
ride 2 (68%), carbon tetrachloride (2073, and
obvious that most of the cleavage reaction was
carbon dioxide (60z). Simple calculations per-
occurring on the more highly chlorinated sulf-
3Formic acid is readily oxidized to carbon dioxide oxide 11. Similar results were observed when
under the reaction conditions. either PO or 11 were chlorinated in glacial
 GROSSERT AND LANGLER

5 C1,
CICHz SO C1 + H C 0 2 H C K H , SO, C1 + C 0 2

F
(27%) (37%)

CICHz SO CI + CHCI, - CI,

CICH, SOz C1

\
(6%) (4%)
CI,C SO CHzCl
7 (50%)
CI
ClCH2 SO Cl + C 0 2 A
H,O CICHz S02Cl
(30%) (26%)

CI,
CICH, SO C1 s CCI, H20
A CICH, SO2 CI
(10%) ( 8%)

SLHEXIE 4

acetic acid: mits the formulation of a detailed pathway for

CH, .SO,.Cl CC1, AcCl the reaction of 10 with chlorine in water (see
CI,CH,SO.CH, -+ 75% 76% 67% Scheme 5). I t is now evident that, unlike the
haloform reaction which requires a-trichloro
substrates (ketones) for cleavage to occur in
aqueous medium, the sulfohaloform reaction
Hence, when cleavage occurs via nucleophilic can take place with a-dichloro substrates
attack by chloride ion, it is necessary for the (sulfoxides) in aqueous medium.
sulfoxide substrate to have at least three a-
chlorine atonis, regardless of the substitution Chlorination of a-Chlorosu@des to Form Sulfonyl
pattern. I t is interesting to note that the third Clilorides
chlorine atom 1s approximately equally effective Since the isolation of the intermediate sulf-
in promoting smooth chlorinolysis of the sulf- oxides in the sulfohaloform reaction was ex-
oxide (in methylene chloride or acetic acid) perimentally rather difficult we undertook a n
either when it is deployed to increase the examination of the chlorination of a-chloro-
electrophilicity of the carbon atom undergoing sulfides in aqueous medium in order to find
nucleophilic attack (e.g. 11) or when it is located evidence for the intermediacy of the a-chloro-
in a position which enhances the electronegativity sulfoxides. The chlorination of 1,3-dichloro-2-
of the leaving group (e.g. 5). thiapropane, 3, in water furnished the corre-
Chlorination of 10, 11, and 7 in water sponding sulfone (4z) and chloromethane-
furnished markedly different results, as follows : sulfonyl chloride 2 (70x1.
We have already established that chlorination
CI,IH,O CH3.SOz CI 2 CCL, CO, of 3 proceeds primarily through the corre-

-
ClzCH SO CH, .--+ 70% 40% 22% 68% sponding sulfoxide even in dilute aqueous
10 medium. Thus the observation of low yields of
CI,C SO CH, 50% 24% 20% 56% the corresponding sulfone in this type of
11
C1,C SO CHzCl
7
- 0% 68% 20% 60%
reaction can be taken to implicate the inter-
mediacy of the sulfoxide since the sulfone must,
of necessity, have been formed via the sulfoxide.
Application of this criterion to I-chloro-2-
The intermediacy of 11 in the chlorination of thiapropane, 12, was successful in implicating
10 and of 7 in the chlorination of 11 was the intermediacy of the corresponding sulfoxide
established by isolating 11 and 7 from the also, since the sulfone was isolated in 1% yield.
chlorination. A straightforward analysis per- These results along with those from 2-chloro-
 CAN. J. CHEM. VOL. 5 5 , 1977

C1, CI,
C12CH SO CH, HZO t CH, SO C1 HCO,H CH? SO2 C1 +CO:
(60%) (60%)
10

CH, S O C1 + CO, b CH, SO, C1

H,O
(9%) (9%)
CI;C SO CH3
11 (16%) C1
CH; SO C1 T CCI, ---L
H:O CH, SO, C1
(1%) i 1%)
I

ClCH2 SO C1 + CO, HCI,:O CCIH, SO, C1

(3%) (3%)
CI,C S O CH,Cl
CI,
7 (6%) CICH, S O Cl + CCI, H20 * CICH, SO, C1
i 1%) ( 1%)

3-thiapentane and 4-chloro-5-thianonane are sulfinyl group of the intermediate oxochloro-

tabulated in Table 2. The process is obviously sulfonium chloride.
a potentially useful sulfonyl chloride synthesis. Thus far we had observed that cr-polychlo-
The overall results from the chlorination of rinated sulfoxides could be converted to sulfonyl
chloromethyl phenyl sulfide in aqueous medium chlorides without the formation of any sulfones.
also showed the same behaviour, i.e. the Chlorination of a-dichloro and simple a -
formation of chloromethyl phenyl sulfone (2.5%) chlorosulfoxides gave rise to minor amounts of
(along with benzenesulfonyl chloride (68%)) sulfones. It appeared, however, that a potential
implicated the intermediacy of the chloro- barrier to extending this reaction to unchlori-
methyl sulfoxide. I n contrast to the previous nated sulfides and sulfoxides might be the forma-
cases, the chlorination of chloromethyl phenyl tion of substantial amounts of unchlorinated
sulfide took a long time to reach completion. sulfones. This problem was solved as follows.
Furthermore, analysis of the partially chlo-
Chlorination o f S~rlJides fo Form Sulfonyl
rinated reaction mixture indicated that large
Chlorides
amounts of trichlorometl~yl phenyl sulfoxide
We began this portion of the work by ex-
were present before any significant amount of
ploring reactions of some conveniently available
benzenesulfonyl chloride was formed. This result
sulfoxides in order both to maximize sulfone
indicated that the phenyl ring virtually nullifies
formation and to see if we could find reaction
the electron-withdrawing effect of one chlorine
conditions which would suppress it. Such
atom. Such a n observation can be readily
chlorinations of D M S O were illuminating,
rationalized via resonance forms in which the
giving the results in [3] and [4]. Similar results
phenyl ring shares its n electrons with the
H,O-HOAci 1 1)
TABLE2 Ylelds of sulfonyl chlorides prepared by [31 CH3 So CH3 *
shlorlnatlon of r-chlorosulfides In water CH, SO, C1 + C H 3 SO, CH, + C I C H z SO2 CH,
(48%) ( 15%) (3%)
Sulfide Sulfonyl chlor~de Yleld (%)

CICH2.S.CH2CI CICH2.SOz.Cl 70
CH3.S,CH2C1 CH3,SO,.CI 75 H,O +

[4] CH, S O CH, t Clz

Ph.S.CH2C1 Ph.S02.CI 67
CH3CH2.S.CHClCH3 CH3CH2.SOz.Cl 90 CH, SO2 C1 + CH, SO, CH,
n-C4H9.SCHCl,n.C3H7 iz-C,H,.S02.CI 94 (26%) (70%)
 GROSSERT AND LAWGLER 413

were obtained from the chlorination of di-n-

propyl sulfoxide in water. Hence, sulfone forma-
tion was indeed a major potential complication
to the useful formation of sulfonyl chlorides
from unchlorinated sulfides and sulfoxides.
This was not surprising since the results are sulfonium chloride salts are inert to acetolysis
consistent with those of Durst and Tin (32) and (35), the origin of this nionochlorosulfonyl
of Cinquini and co-workers (33), both of whom chloride, under either conditions, is undoubtedly
have observed sulfone formation via nucleo- through direct chlorinolysis of thiacyclopenta~le
philic attack on oxochlorosulfonium cations. to give 4-chlorobutane sulfenyl chloride. The
However, after experimentation, it was found driving force for this reaction is the release
that chlorination of su@des in dilute aqueous of ring strain and is parallel to the reactions of
acetic acid was s~~ccessfulin concerting the thiacyclobutane with chlorine in chloroform, or
su@des into sulfonyl chlorides, in high yield, with sulfuryl chloride in pentane (36), which
without the interference of sulfone formation furnish 3-chloropropanesulfenyl chloride. There-
(see Table 3). By contrast, chlorination of the fore the formation of 13 is not relevant to a
corresponding sulfoxides under the same con- consideration of the normal cleavage step in
ditions furnished significantly larger quantities the sulfohaloform reaction.
of sulfones, implying that the reactlon pathway However, Runge et a/. (34) did not report
from the sulfides does not proceed through the the formation of 4,4-dichlorobutanesulfonyl
corresponding sulfoxides but rather through the chloride, 14, upon chlorinating thiacyclopentane
corresponding a-chlorosulfides, and hence in glacial acetic acid. The sensitivity of Y-
through the E-chlorosulfoxides, etc. chloro-chlorosulfonium chloride salts to hydrol-
Since the conditions had been established, ysis, implicates the intermediacy of the a -
which permitted direct chlorination of sulfides chlorosulfoxide in the formation of 14. The
to sulfonyl chlorides by controlling the amount absence of larger amounts of the o-dichloro-
of water present in the solvent, one final sulfonyl chloride, as well as the failure of any o -
mechanistic problem remained. I n water, the trichlorobutanesulfonyl chloride to form, in-
cleavage step is primarily achieved with water dicate quite clearly that cleavage by chloride
functioning as the nucleophile. In dry acetic ions in dilute aqueous acetic acid is not a n
acid, chloride ion is the exclusive nucleophile. important or competitive process and therefore
I t was not obvious just how competitive chloride cleavage by the nucleophilic attack of water re-
ions would be zis-&cis water in dilute aqueous mains the major process in the cleavage step in
acetic acid, and in order to monitor this, we dilute aqueous acetic acid.
have chlorinated thiacyclopentane and isolated The major pathways in the generalized
the a-chlorinated butanesulfonyl chlorides, as sulfohaloform reaction have therefore been
in [ 5 ] . defined, a n d the overall reaction is outlined in
The formation of 13 was not unexpected, Scheme 6.
since chlorination of thiacyclopentane in glacial
acetic acid permits its isolation in 28.64, yield
as reported by Runge et al. (34). Since chloro-

TABLE3. Yields of sulfonyl chlorides prepared from

sulfides and sulfoxides by chlorination in dilute aqueous
acetic acid

Yield
Sulfides/sulfoxide Sulfonyl chloride (%)
CH3CH2,S.CHZCH3 CH3CHZ.SO2.Cl 97
CH3(CH2),,S.(CHZ)3CH3 CH3(CH2)3.S02.CI 86
PhCH2.S,CH2Ph PhCH2.SOz.Cl 74
CH~(CH~)~'SO.(CHZ)ZC CH3(CH2)2.S02.C1
H~ 76
SCHEME
6. The sulfohalofo~~m
reaction
414 CAN. J . CHEM. VOL. 5 5 , 1977

Experimental The aqueous phase was diluted to a volume of 150 ml

with 95% ethanol, from 100 ml of which authenticated
General 2,4-dinitrophenylhydrazone of formaldehyde (2.03 g)
Most experimental details have been described pre- was isolated (39). The results obtained after isolation and
viously (37). Mass spectral samples were directly in- identification of the major products are given in Table 1 .
troduced using an all-glass probe and the spectra run Full details of identification methods are provided
at 40 eV with a source temperature of 15OCC.Elemental elsewhere (37).
analyses were by Dr. F. Pascher (Bonn) or Galbraith
Laboratories (Knoxville, Tenn.). Gas-liquid chro- Preparation of l,3-Dichloro-2-ihiapropcme, 3
matographic analyses were carried out with a n N 2 1,3-Dichloro-2-thiapropane 3 was prepared from 1,3,5-
flow rate of 50 mllmin and the column temperature was trithiane as described by Truce ei 01. (40). The distilled
40 to 50 'C. Unless otherwise indicated, "washing a n material from this reaction contains a persistent im-
organic layer with NaOH" means that a 2 . 5 z w/v solu- purity which showed a n ir band at 1523 cm-'. The
tion of NaOH was used to wash the organic layer, contaminant was completely removed when the dichloro-
usually 100 ml aliquots, until the aqueous layer remained sulfide was chromatographed on silica gel with CCI,
basic. "Standard work-up" of hydrophobic solvents using sulfide-silica gel ratios as low as 1 : 3. In a typical
implies that they were dried (MgSO,), filtered, and then run 1,3,5-trithiane (300 g) furnished crude 1,3-dichloro-2-
rotary evaporated. thiapropane (170 g). After column chromatography and
redistillation, high purity dichlorosulfide 3 (121 g, 42.59,)
Chlorinations was obtained.
Chlorine flow rates were standardized by the use of a
calibrated rotameter. All chlorinations were maintained Chlorinaiion of 3 in H20/HOAc
at 25-30-C by an ice-water bath. Unless otherwise 1,3-Dichloro-2-thiapropane3 was dissolved in glacial
stated, rates and reaction times are given in the form acetic acid (50 ml) and distilled water added. Following
"232/50". This means a flow rate of 232 mllmin and a chlorination (232 ml/min), ice water (75 ml) was added
reaction time of 50 min. All times are given in minutes. and the resultant mixture extracted with CHCI, (4 x
100 ml). The combined CHC1, layers were washed first
Yields with NaOH then with distilled water. Standard work-up
It was often necessary to analyze reaction mixtures afforded products which were isolated by fractional
quantitatively before work-up in order to avoid obtaining distillation. 1,3-Dichloro-2-thiapropane-2-oxide, 4, had
yields which reflected losses during work-up. None of the mp 36.5-37.5 "C; tlc (37) RF 0.48 (ether), after recrystal-
sulfur-containing con~pounds were detectable on glc. lization from CCI,; ir (CHCI,) 1070 cm-' (vso); nrnr
All sulfur compounds were observable in the nrnr and (CDCI,) F 4.57 (q, J = 11.0 Hz); ms ions at m/e 146
integration of the nrnr spectrum furnished satisfactory (M t), 111 and 49. The dichlorosulfoxide 4 was identical
molar ratios. Carbon tetrachloride was detectable on with authentic material (45) by nmr, ir, mp, and mixture
glc and could be interrelated with the sulfur compounds mp. See Table 5 for details of products obtained.
by the addition of methylene chloride which appeared
both in the glc trace and the nmr spectrum. The molar Chlorination of l,3-Dichloro-2-thiapropane-2-oxide, 4
ratios, the total sample weight, and the following equa- 1,3-Dichloro-2-thiapropane-2-oxide 4 was chlorinated
tion permit the calculation of the weight of each com- as described in the previous experiment.
ponent in any mixture. The products were isolated by fractional distillation:
1,1,3-trichloro-2-thiapropane-2-oxide, 5, had bp 94 ^C/
0.25 torr; R, 0.55 on tlc (4: 1 CHC1,-ether); ir (CHCl,)
1080cm-' (vs,); nrnr (CDC1,) 6 4.70 (s, 2H) and 6.60
where x,= mole fraction of 'i'th component, a ; = (s, 1H); ms ions at m/e 180 ( M i ) 83, 49. Oxidation of 5
molecular weight of 'i'th component, K , =~ weight (in (40) furnished material identical to authentic trichloro-
grams) of the 'i'th component, T = total sample weight sulfone by ir, nmr, and bp. Details of the products ob-
(in grams). tained are found in Table 6.
COz Deierminations Preparation of Cl, CH,S.CN, Cl
Full details are provided elsewhere (37). Details are provided elsewhere (37). The product was
Chlorination of 1,3,5-Tvithiane identical to known material (40).
1,3,5-trithiane (17.11 g) was suspended in glacial Preparation of l,l,3-Trichlovo-2-thiaprogane-2-oside,5
acetic acid (38 ml) and distilled water (8 ml) was added. 1,1,3-Trichloro-2-thiapropane(24.56 g) was dissolved
The reaction became non-exothermic by the end of the in glacial acetic acid (100 ml), distilled water (4.4 ml)
chlorination (232140). The reaction mixture was diluted was added, and the mixture was chlorinated (232150).
with ice water (25 ml), the organic phase separated, and The reaction mixture was fractionated, furnishing 1,1,3-
the aqueous phase set aside. trichloro-2-thiapropane-2-oxide (19.6 g, 72.5%).
The organic ohase was diluted with CHC1,4 (150 ml).
dried (M&.o,): filtered, and the CHCI, distilied off. Chlorination of 5 in H20-HOAc
The residue was fractionated giving the results out- 1,1,3-Trichloro-2-thiapropane-2-oxide 5 (16.17 g) was
lined in Table 4. dissolved in glacial acetic acid (50 ml) and distilled water
(4.4 ml) was added. Following chlorination (232/39),
4An additional run was carried out using ether as the ice water (75 ml) was added and the organic phase was
solvent in order to check for the presence of chloro- separated. The aqueous phase was washed with CHCI,
carbons. (100ml) which was combined with the organic phase.
 GROSSERT AND LANGLER

TABLE
4. Fractionation of the products from the chlorination of 1,3,5-trithiane

Boiling point
Fraction ('Cjtorr) Components Weight (g)

2 20-40125 C1CH20Ac 0.71

CICHZ.O.CH2CI
3 40-68120 CICHZ.S.CHzC1 5.31
4 70-80120 CICHZ.S.CHZC1 3.87
ClCHZ.S.S.CH,Cl
Unidentified products
5 Cold trap in C1CH,.0.CH2CI 3.23
vacuum line CICHZOAC
CICH2.S.CHzCi
6 Solid deposited 1,3,5-trithiane 1. 0
in fractionating
column
*CAUTION: b~schloromethylether 1s a potent carcinogen (38).

TABLE5. Products of the chlorination of 3 in H,O/HOAc

Weight Chlorination Volume

(8) time (min) H 2 0 (ml) Products Yield (g)*

*Percentage yield in parentheses

Standard work-up gave a concentrate which was frac- fresh water for I h. Standard work-up of the CHCI,
tionated (glass-bead column, 67 torr), to give chloro- gave a residue which was fractionated at reduced pressure
methanesulfonyl chloride 2 (8.48 g, 64.0z) and a distilla- to yield chloromethanesulfony1 chloride 2 (3.90 g).
tion residue of unreacted 5 (1.80 g, 11.2%). B. Quantitative glc and nmr integration established
the yield of CHCI, to be equal to 759,. The ether solution
Chlorination of5 in HOAc was extracted with NaOH, washed with distilled water,
1,1,3-Trichloro-2-thiapropane-2-oxide 5 (15.85 g) was dried (MgSO,), and fractionated, to furnish pure CHCI,
chlorinated (232130) in glacial acetic acid (50 ml). An identical with authentic material by bp, glc, and nmr.
nmr spectrum of the reaction mixture showed a molar
ratio of 100:73 : 27, CHCI,;'CICH,~SO~CI~CICH2~S02~C1 Chlorination of 5 in CH2C12
respectively. The reaction was chlorinated further with 1,1,3-Trichloro-2-th1apropane-2-oxide 5 (15.34 g) wab
progress being monitored hourly. After 3.5 h the sulfinyl chlorinated (232130) in CH,C12 (50 ml). Methylene
chloride - suifonyl chloride ratio was 3 :7. chloride (10 ml) was dist~lledoff and the presence of
Ice water (75 ml) was added to the reaction mixture both CHCI, (53.2%) and CC1, (10.7%) was demon-
and the organic phase was removed. The aqueous phase strated (glc). The bulk of the chlorocarbons were distilled
was extracted with ether (l00m1) and the ether layer off and the residue rectified at reduced pressure affording
combined with the organic layer. The combined organic chloromethanesulfinyl chloride 6 (8.14 g, 71.7Y,), bp
portion was diluted with ether to 200 ml and then divided 163.5 T I 7 6 0 torr; ir (CHCI,) 1150 cm-' (vso); nrnr
into equal portions, A and B. (CDCI,) 6 4.83 (5); ms nz/e 62, 49. Hydrolysis in dis-
A. Portion A was dried (MgSO,) and concentrated. tilled water, followed by chlorination in CH,C12,
The bulk of the acetic acid was distilled off at 75 torr. furnished chloromethanesulfonyl chloride 2 as expected.
Thc residue was dissolved in CHCI, (50 ml) and con-
tinuously extracted with water for 1 h. The aqueous Chlorination of 5 in H20
phase was discarded and the extraction resumed with 1,1,3-Trichloro-2-thiapropane-2-oxide 5 (1 1.32 g) was
 CAN. J. CHEM. VOL. 5 5 . 1977

4
TABLE6. Products of the chlorination of 1,3-dichloro-2-thiapropane-2-oxide,

Weight Chlorination Volume

(g) time (min) H 2 0 (ml) Products Yield (g)*

*Percentage yield in parentheses

chlorinated (2321'105) in distilled water (50 ml). The Preparation of I,]-Dichloro-2-thiapropane-2-oxide, IOs
organic phase was pipetted off and dried (CaCI,). Gas- DMSO (16.21 g) was chlorinated (232143) in glacial
liquid chronlatography established the presence of CHCI, acetic acid (50 ml) and distilled water (6.6 ml). The reac-
(6.3%) and CC1, (10%). The organic phase was distilled tion was repeated on a second portion of DMSO (1 6.01 g).
at reduced pressure furnishing chloromethanesulfonyl The combined reaction mixtures were diluted with water
chloride 2 (6.05 g, 64.5%). (150 ml) and extracted (CHCI,, 6 x 100 ml). The CHCI,
In a separate experiment on 5 (1.155 g), the CO2 was was washed with NaOH then with distilled water (100 ml),
isolated as BaC03 (0.802 g, 66.6%). Chlorination time dried (MgSO,), and evaporated. The residue was distilled
was 50 min (1 16 mljmin). at reduced pressure to yield 1,l-dichloro-2-thiapropane-2-
oxide l o 5 (17.53 g, 28.8%). Recrystallization (CCI,)
Preparation qf 1-Chloro-2-thiopropane, 12 of the distilled material afforded pure 10 as bundles of
Details of this preparation are given elsewhere (36, 37). crystals (mp 32-33 'C); R, 0.49 (ether); ir (CHCI,)
Preparatiorz of CI, C.S.CH2CI 1080cm-I (vSO);nmr (CDCI,) 6 3.75 (3H, s) and 6.42
I-Chloro-2-thiapropane 12 (100 g) was chlorinated (IH, s); ms rnje 146 ( M t ) , 83 and 63. Oxidation of 10
(4481330) in CCI, (250 ml). The reaction mlxture was (40) yielded material identical to authentic dichloro-
rectified furnishing 1,1,3-tetrachloro-2-thiapropane (181.9 - sulfone by nmr, ir, and mixture mp.
g, 87.4%); bp 188 C/760 torr; nmr 6 5.00 (s) (CDCI,). Chlorination of 10 in CH2C12
Preparation of 1,1,1,3-Tetrachloro-2-thiapropane-2-oxide, l,l-Dichloro-2-thiapropane-2-oxide10 (1 6.22 g) was
7 chlorinated (232125) in CH2CI (50 ml). A fraction was
Distilled water (12 ml) was added to 1,1,1,3-tetra- distilled at atmospheric pressure (44-75 "C). The residue
chloro-2-thiapropane (31.19 g) in acetic acid (100 ml). was rectified at reduced pressure with a -75 "C cold
After chlorination (232/50), the reaction mixture was trap in the vacuum line. The fraction from the atmo-
fractionated to give 7 (16.8 g, 50%), bp 78 "C10.5 torr; spheric distillation plus the trap material contained CHCI,
R, 0.65 (CHCI,) which could be crystallized from 95% (1.5 g, 11.8%) and CCI, (8.8 g, 51.8%). The vacuum distil-
ethanol at O c C but melted upon returning to ambient lation furnished methanesulfinyl chloride (8.24 g, 76.3%);
temperature; ir (CHCl,) 1135 cm-' (vso); nmr (CDCI,) bp 136.5"C/760 torr; ir (CHCI,) 1140cm-' (vso);
6 4.57 (q, J = 1l.OHz); ms rnle 117, 82, 62, and 49. nmr (CDCI,) 6 3.37 (s); ms rille 98 (M?), 82, 63, and 48.
Anal. calcd. for C,H,CI,SO: C 11.13, H 0.93, 0 7.41; Hydrolysis in distilled water, followed by chlorination
found: C 11.35, H 0.98. 0 7.38. Oxidation of 7 (40) in CH,C12 furnished methanesulfonyl chloride.
yielded material identical to authentic tetrachlorosulfon~ Chlorination of I0 in HOAc
by nmr, ir, and mixture mp. I ,1-Dichloro-2-thiapropane-2-oxide 10 (1 5.81 g) was
Chlorination of 7 in H,O chlorinated (232130) in glacial acetic acid (50 ml). Acetyl
1,1,1,3-Tetrachloro-2-thiapropane-2-oxide 7 (1 6.56 g)
was chlorinated (448/240) in distilled water (50ml). 5CAUTION: this sulfoxide (Cl,CH.SO.CH,) is very
The organic phase was pipetted off and dried (CaCI,). unstable at room temperature and if stored in a tightly
Gas-liquid chromatography showed that CC1, (20%) stoppered container may generate sufficient gas pressure
had been formed. The residue was distilled furnishing to explode the container within 4 h. Proper storage for
chloron~ethanesulfonylchloride 2 (7.80 g, 67.5%). periods of 2 weeks (maximum) requires that the sample
In a separate experiment (C1, : 232150) on 7 (1.030 g) be stored in the dark using an explosion-proof container,
C 0 2 was isolated as BaC0, (0.500 g, 60%). at or below - 32 'C.
 GROSSERT ALND LANGLER 417

chloride was established as being present in a 1 :I ratio under "Chlorination of 10 in HOAc" afforded CCI,
with CCI, by nmr and glc. The reaction mixture was (9.95 g, 69.9%) and methanesulfonyl chloride (9.20 g,
added to CH2Clz (100 ml) and ice water (100 ml). The 86.1%).
organic phase was separated, dried (MgSO,), filtered,
and the CHzC12 distilled off. A fraction (bp 44-75 "C) Chlorination of 11 in Hz0
was collected at atmospheric pressure and the residue ( a ) Partial Chlorination
was distilled at 50 torr with a cold trap in the vacuum l,l,l-Trichloro-2-thiapropane-2-oxide 11 (5.01 g) was
line. The atmospheric pressure fraction plus the trap chlorinated (232130) in distilled water (25 ml). The
material contained CCI, (1 1.10 g, 66.6%). The vacuum organic phase was pipetted off and added to CHCI,
distillation afforded methanesulfonyl chloride (9.2 g, (100 ml), which was washed with NaOH (50 ml aliquots)
7573. and then with water. After standard work-up, the residue
was a mixture of unreacted 11 (0.75 g) and 1,1,1,3-
Chlorination of 10 in H20 tetrachloro-2-thiapropane-2-oxide 7 (1.06 g, 18.5%). The
( a ) Partial Chlorination sulfoxide mixture was chromatographed on a column
1,l-Dichloro-2-thiapropane-2-oxide10 (4.30 g) was of silica gel (180 g). Elution with CHCI, (1 100 ml)
chlorinated (232128) in distilled water (25 ml). The furnished 7 and an additional litre of CHCI, furnished
reaction mixture was extracted with CHCI, (100 ml) 11. The tetrachlorosulfoxide 7 was distilled and shown
which was washed with NaOH (50 ml aliquots), then to be identical with authentic material by bp, nmr, ir,
with distilled water (50 ml), followed by a standard and tlc.
work-up. The residue was the trichlorosulfoxide 11 ( b ) Exhaustice Chlorination
(0.54 g, 10.3%), as established by nmr, ir, and tlc. 1,1,1-Trichloro-2-thiapropane-2-oxide 11 (16.04 g) was
( b ) E.uhaustive Chlorination chlorinated (4481185) in distilled water (50ml). The
1,l-Dichloro-2-thiapropane-2-oxide10 (16.18 g) was organic phase was pipetted off and dried over CaCI,.
chlorinated (232185) in distilled water (50 ml). The or- Gas-liquid chromatography established that CCI, had
ganic phase was pipetted off and dried over CaCI,. formed in 20% yield. The aqueous phase was extracted
Gas-liquid chromatography established the presence of with CHCI, (2 x 100 ml) which was combined with the
CCI, (2.4%), a sample of which was obtained by distilla- original organic phase. Standard work-up gave a residue
tion at atmospheric pressure and was shown to be which was fractionated at reduced pressure to furnish
identical with authentic material by glc, ms, and bp. a mixture of methanesulfonyl chloride (5.08 g, 50%) and
Distillation of the residue at reduced pressure yielded chloromethanesulfony1 chloride (3.16 g, 23.8%). Further
methanesulfonyl chloride (8.84 g, 70.0%). distillation at atmospheric pressure gave four fractions,
In a separate experiment on 10, (1.130 g; CI,: 232/50), each of which was still a mixture. Fraction 1 (bp 161-
CO, was isolated as BaCO, (1.067 g, 67.5%). 163 "C) contained ca. 15% chloromethanesulfonyl chlo-
ride and 85% methanesulfonyl chloride.
Preparation of l,l,I-Trichloro-2-thiapropane A portion of fraction 1 (212 mg) was added dropwise
1-Chloro-2-thiapropane (16.01 g) was chlorinated to a cooled (5 'C) solution of vanillin (21 1 mg) in pyridine
(232135) in CH,CI, (50 ml). The reaction mixture was (0,5ml). The ice water bath was removed and the solution
distilled, furnishing 1,1,1-trichloro-2-thiapropane(16.88 was stirred at room temperature for 1 h. The reaction
g, 61%); bp 148-149 'C; nmr (CDCI,), singlet at 6 2.75. mixture was diluted with CHCI, (50ml) which was
extracted with 2.5% NaOH (50 ml), 2.5% HCI (50 ml),
Preparation of l,l,l-Trichloro-2-tJiiapropane-2-oxid (11) and distilled water (50 ml). Standard work-up gave a
1,1,1-Trichloro-2-thiapropane (1 6.36 g) was chlorinated pale yellow oil (287 mg) which was dissolved in 95%
(232127) in glacial acetic acid (50 ml) and distilled water ethanol (3 ml) and stored in the refrigerator overnight.
(6.6 n ~ l ) Water
. (75 ml) was added and the solution was Colorless crystals were filtered off and dried affording
extracted with CHCI, (4 x 100 ml), which was washed vanillin methanesulfonate (186 mg). After recrystalliza-
with NaOH, followed by distilled water. After standard tion, the sulfonate ester was shown to be identical to
work-up, the residue was distilled furnishing 11 (1 1.00 g, authentic material by tlc, ir, and mixture mp.
61.7%) bp 86-88 "C/1.6 torr; crystals (from methanol) The concentrated mother liquor from the first crystal-
had mp 63-65 "C; R, 0.62 (4: 1 chloroform-ether); lization was chromatographed on a preparative-layer
ir (CHCI,) 1100cm-' (vs,); nmr (CDCI,) 6 2.92 (s); plate (ether-CHCl,, 1 : 19). Methanol extraction of the
ms mle 180 ( M t ) , 117, 82, 63, and 47. Anal. calcd. for upper band ( R F 0.55, detected by 250nm uv light)
C2H3CI3SO:C 13.24, H 1.67, O 8.82, S 17.67; found: furnished a colorless oil (30.2 mg), which was identical
C 13.26, H 1.56, 0 8.74, S 17.27. Oxidation of 11 (40), to vanillin chloromethanesulfonate by tlc, nmr, and ir.
yielded material identical to authentic trichlorosulfone In a separate experiment on 11 (1.030g) carbon
by nmr, ir, and mixture mp. dioxide was isolated as BaC0, (0.928 g, 55.5%). Chlorina-
tion time was 45 min.
Chlorirlation of 11 in HOAc
l,l,l-Trichloro-2-thiapropane-2-oxide 11 (16.83 g) was Chlorination of 3 in H20
chlorinated (232130) in glacial acetic acid (50 ml). 1,3-Dichloro-2-thiapropane 3 (16.41 g) was chlorinated
Acetyl chloride was established as being present in a 1 : 1 (4481200) in distilled water (50ml). Ice water (75 ml)
ratio with CCI, by glc on the crude mixture. A small was added and the reaction mixture extracted with
amount of acetyl chloride was distilled off and identified CHCI, (2 x 100 ml). The residue from standard work-up
by ir, nmr, and glc. Work-up identical to that described of the CHCI, was distilled at reduced pressure yielding
418 CAN. J. CHEM.

chloromethanesulfonyl chloride (13.07 g, 70.4%). The 242 (Mt), 125, 117, 109, 77, and 51. Anal. calcd. for
distillation residue was covered with sufficient 10% NaOH C,H,CI,OS: C 34.52, H 2.07, C1 43.7; found: C 34.79,
to establish a p H z 7. The solution was acidified (con- H 2.28, C1 42.9. Oxidation of the sulfoxide (40) gave
centrated HCI) and poured into CHCI, (200 ml). Stan- sulfone identical to that obtained by oxidation of the
dard work-up gave 1,3-dichloro-2,2-dioxide(790 mg, sulfide by tlc, nmr, ir, and mixture mp.
3.8%); after recrystallization (95% ethanol), this was
shown to be identical with authentic dichlorosulfone by Chlorination of CH3CH2.S.CHC1CH3in H z 0
nmr, ir, mp, and mixture mp. 2-Chloro-3-thiapentanc (16.77 g) was chlorinated
(448/104) in distilled water (50 ml). The reaction mixture
Chlorination of 12 in H20 was partitioned between ice water (75 ml) and CH2C12
I-Chloro-2-thiapropane 12 (15.76 g) was chlorinated (10 ml). The aqueous phase was extracted with CH2CI,
(448198) in distilled water (50 ml) similarly to the chlori- (100 ml). Standard work-up of the combined CH2C12
nation of 3. Products were methanesulfonyl chloride layers gave a residue which was rectified at reduced
(14.10 g, 75.4%) and 1-chloro-2-thiapropane-2,2-dioxide pressure giving ethanesulfonyl chloride (15.54 g, 89.6%)
(193 mg, 1.2%). Details are provided elsewhere (37). bp 90-92 "C/55 torr.
Cl~loririarionof Ph.S,CH2Cl in H20 Chlorination of n-C4H,,S.CHCl.CH2CH2CH3in H20
Chloromethyl phenyl sulfide (16.01 g) was chlorinated 4-Chloro-5-thianonane (15.95 g) was chlorinated (448,
(4481130) in distilled water (50 ml). By the end of this 100) in distilled water (50 ml). The reaction mixture
time all of the organic material had crystallized from was extracted with CHCI, (2 x 100 ml) which was dried
solution and all reaction had ceased. The reaction mixture (MgS04), and evaporated. The residue was fractionated
was extracted with CHC1, (2 x 100ml), followed by at reduced pressure furnishing 1-butanesulfonyl chloride
standard work-up. Analytical tlc (CHC1, eluant) showed (13.0 g, 94.3%).
a spot at RF 0.49 (assumed to be C12CH.S0.Ph), a
spot at RF 0.70 (identical to CI,C.SO,Ph), and a spot at of DMSO in I : I H20-HOAc
Ci~lorit~ation
R, 0.81 (identical to Ph.S02.CI). The bulk of the material DMSO (15.91 g) was chlorinated (4481110) in glacial
was Cl3C.SO.Ph and an ir of the crude showed the acetic acid (25 ml) and distilled water (25 ml). Products
expected band at 1100 cm-I (vso). The crude product were methanesulfonyl chloride (11.30 g, 48%), dimethyl
was dissolved in acetic acid - H 2 0 , 1 : 1, (50 ml) and sulfone (2.78 g, 14.7%), and 1-chloro-2-thiapropane-2,2-
chlorination (4481130) was repeated. Repetition of the dioxide (0.75 g, 2.9%). Details are provided elsewhere
work-up outlined above furnished crude product which (37).
showed about a 1 : 1 mixture of CI,C.SO,Ph to Ph.SO2.C1 Chlorination of DMSO in H z 0
on tlc and the complete absence of the product previously DMSO (16.11 g) was chlorinated (448197) in distilled
observed at R, 0.49. This new crude product was further water. Total dimethyl sulfone isolated was 13.64 g
chlorinated (4481130) in glacial acetic acid (15 ml) and (70.3%) and total methanesulfonyl chloride isolated was
distilled water (25 ml). The reaction mixture was ex- 6.23 g (26.2%). Details are provided elsewhere (37).
tracted with CHCI, (4 x 100ml) which was dried
(MgSO,) and rotary evaporated. Analytical tlc (37) Clzlorination of (n-C3H7)2S0in H20
showed the absence of CI,C.SO.Ph. The residue was Di-n-propyl sulfoxide (15.79 g) was chlorinated (448/
fractionated at reduced pressure providing benzene- 105) in distilled water (50 ml). Ice water (75 ml) was
sulfonyl chloride (12.04 g, 67.3%), identical to authentic added and the mixture was extracted with CHCI, (2 x
material by tlc, nmr, ir, and bp. The distillation residue 100 ml). Standard work-up gave a residue which was
contained Ph.S02.CH2.C1 (500 mg, 2.5%). Two pre- fractionated at reduced pressure to yield l-propane-
parative-layer plates were spotted with residue (100 mgl sulfonyl chloride (6.71 g, 39.8%); bp 104-106 "C/65 torr,
plate) and eluted with CHCI,. Methanol extraction of the and di-n-propyl sulfone (5.65 g, 31.3%); bp 88 "Ci0.1
bands at RF 0.70 furnished chloromethyl phenyl sulfone torr.
identical with authentic material by nmr, ir, and tlc.
Preparation of Sulfonyl Chlorides from the Coriesporiding
Preparation of P/L.SO.CC~, Symmetric Sulfide or Sulfoxide
Trichloromethyl phenyl sulfide (16.20 g) was chlori- The substrate was dissolved in glacial acetic acid
nated (232127) in glacial acetic acid (50 ml) and distilled (50 ml) and the appropriate quantity of distilled water
water (6.6 ml). The reaction was rerun on more Ph.SO.C- was added. Chlorine (448 m1,'min) was bubbled through
CI3 (15.96 g). The combined reaction mixtures were the solution. Chlorination was interrupted as necessary
diluted with water (100ml) and extracted with CHCI, to maintain the reaction at room temperature. Ice water
(4 x 100ml) which was washed with 5% NaOH and (75 ml) was added to the reaction mixture which was
then with distilled water. Standard work-up gave a then extracted with CHCI, (4 x 100ml). The CHCI,
residue which contained unreacted sulfide (10.44 g) and layers were washed with 2.5% ww,v NaOH (3 x 100 1111)
Ph.SO.CCI3 (20.19 g, 58.9%). and subjected to standard work-up.
Some crude material (26.33 g) was chromatographed Diethyl sulfide (16.01 g, 7.5 ml H,O, 108 min chlo-
on silica gel (1560 g). Elution with CC1, (6 1) furnished rination) gave a residue which was fractionated at
trichloromethyl phenyl sulfide (8.86 g). Further elution reduced pressure to yield ethanesulfonyl chloride (22.12 g,
with diethyl ether (5.2 1) yielded trichloroniethyl phenyl 96.6%).
sulfoxide (17.35 g). Recrystallization (95x ethanol) to Di-n-propyl sulfoxide (16.00 g, 6.6 ml K 2 0 , 90 min
give colorless needles; mp 77-78 ' C ; RF 0.61 (CHCl,); chlorination) gave a residue which was fractionated at
ir (CHCI,) 1100cn1-' (vso); nmr 6 7.75 (m); ms mie reduced pressure to yield di-n-propyl sulfone (1.50 g,
 GROSSERT AND LANGLER 419

8.4%) and 1-propanesulfon~lchloride (12.94 g, 75.6%). postgraduate fellowship to one of us (R.F.L.)

Di-n-butyl sulfide (16.00 g, 6.6 ml H 2 0 , 126 min is gratefully acknowledged.
chlorination) gave a residue which was rectified at re-
duced pressure t o furnish 1-butanesulfanyl chloride
(14.74 g, 86.2%). 1. J . S. GROSSERT and R. F. LANGLER. J. Cheni. Soc.
Dibenzyl sulfide (16.01 g, 6.6 ml H 2 0 , 75 min chlo- Chem. Commun. 49 (1973).
rination) gave a residue which was crystallized from 2. S. W. LEE and G . DOUGHERTY. J . Org. Chem. 5. 81
benzene - low-boiling petroleum ether to yield phenyl- (1940).
methanesulfonyl chloride (8.82 g). The mother liquor 3. A, G . K o s r s o v ~ Acta
. Univ. Voroneg. 8. 92 (1935);
furnished another 1.71 g to give a total yield of 73.3%. Chem. Abstr. 32.6618 (1938).
4. 1. B. DOLGLASS, V. G. SIMPSON, and A. K . SAWYER.
Chlovir2ation of Thiacyclopentane in HOAc-Hz0 J . Org. Chem. 14, 272 (1949).
Thiacyclopentane (15.97 g) waschlorinated(4481106) in 5, F, WUDL,D, A , LIGHTYER, and D. J , C R A M , J , Am,
glacial acetic acid (50 ml) and distilled water (7.5 ml). Ice
89. 4099 (1967),
water (75 ml) was added and the mixture was extracted
6, W, E, LAWSON and T , P, DAWSON, J , Am, Chem,
with CHCI, (4 x 100 ml). The CHCI, was washed with
Sot, 49, 3119(1927),
2.5%w/v N a O H ( 3 x 100 nll)anddistilledwater(100ml), 7, K , and W, VoGT, J~~~~~ ~ i ~ b them. i ~ ~
dried (MgSO,), and rotary evaporated. The residue was 381, 337 (1911).
fractionated at reduced pressure t o yield a mixture of 8, T , ZINCKE and W, FROHNEBERG, pr,n t s c h , them,
sulfonyl chlorides. The mixture contained C1(CH,),S02- Ges. 43. 837 (1910).
C1 13 (3.10 g, 8.9%) and CI,CH(CH2)3SOzC114 (1.83 g, 9, T , Z I ~ C K Eand W . RUPPERSBERG. Ber. ntsch. Chem.
4.573. A sample (2.01 g) of the distillate was chroma- Geb. 48, 120 (1915).
tographed on a silica gel column (200 g). Elution with 10, T , zlNcKE and W, FROHNEBERG, B ~~ ~t ,~Chem, ~ h ,
CHCI, (650 ml) furnished a clean mixture of 13 and 14 Ges. 42,2721 (1909).
( 2 : 1). A second column run on 1.99 g of distillate 11, H, KWART L, J , M ~J , A ~~ Chem,
, ~ sot, 80, ~ ~ .
furnished additional 2: 1 mixture. The total chroma- 884 (1958).
tographed mixture from chromatography weighed 1.78 g. 12, W, G , p H l ~ ~and 1 ~Ks . W. R ~ r r sJ.. Org. Chem. 36.
Strong bands at 1350 and 1162 cm-' were virtually 3145 (1971).
the only bands present in the ir of the 2: 1 mixture. 13. G. E. W r ~ s oJR. ~ ,and M. G . HUANG.J . Org. Chem.
A portion of the chromatographed mixture (1.01 g) 35, 3002(1970),
was added drop-wise to a "Id solution of phenol 14, G. E . WILSON, J R . and R. ALBERT.J . Org. Chem. 38.
(419 mg) in pyridine (3 ml) and the reaction mixture 2160(1973),
was stirred at room temperature for 1 h. Chloroform 15, H , KWARTa n d R . K . MILLER.J . Am. Chem. Soc. 78.
(100 ml) was added and the solution washed with 2.5% 5008 (1956).
N a 0 H (50 ml), 2.5% HCl (50 ml), and distilled water 16, H, KWARTand R. W. BODY.J. Org. Chem. 30. 1188
(50 ml). The CHC1, was dried (MgS04), and rotary (1965).
evaporated to yield a crude phenate mixture (938 mg), 17, H , KW,\RT. R , W , B ~ alld ~D, M~, H , o F ~ ~ ~ ~ ,
crystallization of which (95% ethanol) afforded three Chem. Commun. 765 (1967).
crops. Crops 1 and 2 (150 mg) were mixtures of ~ h e n a t e s . 18, H . KWARTand P. S. STRILKO. Chem. Commun. 767
Crop 3 (130 mg) was pure C12CH(CH2)3S020Ph. The (1967).
mother liquor from the third crystallization afforded 19, R , N , L~~~~~~and D, C, K , cHANG, ~ ~ t ~ ~ h ~
residual phenate mixture (560 mg). Lett. 5415 (1968).
The (560mg) was chromatographed On five 20, G. T ~ U C H I H A Sand H I S. IRIUCHIJIMA. Bull. Chem.
preparative tlc plates with benzene elution (2 x ). Each Sot, Jpn, 43. 2271 (1970),
plate had five bands visible under uv light, i.e., RF 0.97, M , CINQUINI, S, coLONNA. and F, M ~J , ~ ~
0.91, 0.83, 0.77, 0.68. Chem. Soc. D, 607 (1969).
he band at R, 0.77 gave C1(CH2),S02OPh (251 mg) 22, S, I R ~ ~ C H ~and J ~ G.
MA TSUCHIHASHI. Tetrahedron
as a colorless oil. Lett. 5259 (1969).
The band at R~ 0.83 gave C12CH(CH2)3S020Ph 23, M . CINQUINI and S. COLOKNA. J . Chem. Soc. Perkin
(138mg) as fine needles from 95% ethanol, mp 60- Trans. 1, 1883 (1972).
61.5 'c; (CHCI,) 1375 and 1140 cm-' ( ~ ~ 0 2nmr ); 2.25
24. M, C I N Q U I N S. I , COLONNA, R. FORNASIER, and F.
(4H, t), 3.34 (2H, t), 5.83 ( l H , t), and 7.34 (5H, s); MONTANARI. J . Chem. Soc. Perkin Trans. 1. 1886
ms m/e 125,94,65 and 53. Anal. calcd. for C , , H , 2C1203S:
(1972).
42.427 4.27, C1 25.04, O 16.95, 11.32; found: 25, M. CINQUINI, S. COLONNA, and D. IAROSSI. Boll. Sci.
C 42.80, H 3.94, CI 24.84, 0 17.04, S 11.19. Fac. Chim. Ind. Bologna, 27, 197 (1969).
The remaining three bands gave minor quantities and 26, M, CINQUINI. S, COLoNNA,and D, L A N D I N I , J ,
were discarded. Chem. Soc. Perkin Trans. 2,296 (1972).
27. P. CALZAVARA, M. CINQUINI. S. COLONNA, R. FOR-
NASIER, and F. MONTANARI. J. Am. Chem. Soc. 95.
Acknowledgements 7431 (1973).
28. J . K L E ~ N and H. STOLLAR. J . Am. Chem. Soc. 95,
We thank Dalhousie University and the 7437 (1973).
National Research Council of Canada for 29. 6, TSUCHIHASHI and K . OGURA.~ ~ 1Chenl. 1 . sot.
financial support. The award of an NRCC Jpn. 44. 1726 (1971).
420 CAN. J. CNEM. VOL. 5 5 , 1977

30. K.-C, T I N and T . DURST.Tetrahedron Lett. 4643 Chromatogr. 97, 83 (1974); R. F. LANGLER. Ph.D.
(1970). Thesis, Dalhousie University. 1975.
31. J . F . K I N G .ACC.Chem. Res. 8 , 10 (1973, and refer- 38. Org. React. 19.422 (1972).
ences therein. 39. R. L. SHRINER. R . C. FUSON,and D. Y . CURTIN.The
32. T . DURSTand K.-C. T I N . Can. J. Chem. 49, 2374 systematic identification of organic compounds. 5th
(1971). ed. Wiley. New York. 1964. p . 126.
33. R . ANNUNZIATA, M. CINQUINI, and S . COLONNA. J. 40. W . E. TRUCE.G . H . BIRUM, and E. T. MCBEE.J . Am.
Chem. Soc. Perkin Trans. 1,2057 (1972). Chem. Soc. 74,3594 (1952).
34. F. RUNGE,E. PROFFET,and R . DRUZ.J . Prakt. C h e n ~ . 41. H. E. FRENCH and R. ADAMS.J. Am. Chem. Soc. 43.
2,279 (1955). 651 (1921).
35. J . S. GROSSERT, W. R . HARDSTAFF, and R. F. LANG- 42. P. M. G . BAVIN.Can. J. Chem. 42.704 (1964).
LER.J . Chem. Soc. Chem. Commun. 50 (1973). 43. F. S. H . HEAD.J . Chem. Soc. 2972 (1963).
36. F. G. BORDWELL and B. M. PITT.J . Am. Chem. Soc. 44. S. R . Buc. U . S . Patent No. 2704299 (1955): Chem.
77,572 (1955). Abstr. 50. 1891c (1956).
37. G . K. CHIP and J. S. GROSSERT. Can. J . Chem. 50. 45. F. 6 . MANNand W. J . POPE.J . Chem. Soc. Trans.
1233 (1972); J. S . GROSSERT and R. F. LAKGLER. J. 123, 1172 (1923).
 Sulfides as precursors for sulfonyl chloride synthesis
RICHARDFRANCIS
LANGLER,'
ZOPITOALESSIOMARIKI.AND EDWARD
SOLIMERS
PALD DING
Cher?li.~frx
Drprri.ttrzo~r,Dalholrsie Ut~i~.er..sir~,
Hnl$o.~, .V.S., Car~n~lcr
B3H4.33
Received April 16. 1979
RICHARDFRANCIS LANGLER, ZOPITOALESSIO MARIKI,and EDWARDSOMMERS SPALDING.
Can. J. Chem. 57,3193 (1979).
Sulfides are advanced as sulfonyl chloride precursors. SN2cleavage of the intermediate sul-
fonium ions is discussed in conjunction with both the sulfohaloform pathway and our pre-
vious hypothesis that asymmetric chlorosulfoniuni chloride salts undergo Purnmerer re-
arrangements which exhibit regioselectivity that can be anticipated on the basis of substituent
electronegativity difference (AX,). Thioglycolic acid is developed as a new sulfur transfer
agent for sulfonyl chloride synthesis.

RICHARDFRANCISLANGLER, ZOPITOALESSIOMARINIet EDWARDSOMMERS SPALDING.

Can. J. Chem, 57.3193 (1979).
On propose les sulfures colnme prCcu~.seursdes chlorures de sulfonyles. On discute du clivage
des ions sulfoniums intermediaires selon un mCcanisnie S,2 conjointement avec le cheminenient
du sulfohaloforme et de notre hypothkse anterieure. Cette derniere stipule que les chlorhydrates
de chlorosulfonium asymetriques subissent des transpositions de Pummerer qui niontrent une
rCgiosClectivitC et qui peuvent &ire prCvus & partir de la difference d'ClectronCgativite des
substituants (AX,). On a rnis en evidence I'acide thioglycolique comme un nouvel agent de
transfert de soufre dans la synthkse du chlorure de sulfonyle.
[Traduit par le journal]
Imtroduetion The conversion of sulfides into sulfonyl chlorides
Our previous studies of the chlorinolysis of sulfur requires a cleavage step in the chlorinolysis reaction.
compounds (1-8) have been directed toward the These reactions proceed, in general, by chlorosul-
development of new synthetic methods for the pre- fonium cation intermediacy so that cleavage2 may
paration of sulfonyl chlorides (2, 4, 5). Sulfonyl Occur in either Or S ~ fashion
2 as shown in
chlorides can furnish a variety of functionalities Scheme 1. We have previously reported the applica-
(9-17) and may be prepared with well established tion of benzylic sulfides to the synthesis of sulfonyl
methods (2, 9, 18, 19). A widely employed approach chlorides (5). We believe that the cleavage step in
involves the aqueous chlorinolysis of sulfur-con- these an mechanism.
tainirlg substrates viz. sulfenyl chlorides (20, 211, Extensions of the approach which utilizes sulfides
mercaptans, disulfides, thiolesters, B~~~~ salts (221, in which one substituent attached to sulfur will form
isothioureas (23), thiocyanates (24), sulfinyl chlorides a carbocation during chlorinolysis are readily en-
(25), thiolsulfonates (26), and sulfinic acids (2, 27). visioned. In particular, in cases where the desired
We have beell developing the aqueous chlorinolysis sulfonyl chloride requires a carbon substituent which
of sulfides as an approach to the preparatioll of would itself form a stable carbocation, one would
sulfonyl chlorides (4, 5, 7). choose a sulfide in which the group to be lost would
excellent review of methods for the pre- give rise to a carbocation of superior stability to that
paration of sulfides has recently become available e x ~ e c t e d f o r t h egroup to be retained. unfortunately,
(28). The most general approach t o sulfide synthesis extensions of this approach have very little utility
involves llucleophijic substitutioll by mercaptide since sulfonyl chlorides in which the carbon sub-
anions on carbon bearing a suitable leaving group, stituent can form a particularly stable carbocation
This reaction has been extended to include simple are themselves unstable%nd cannot be prepared (12,
aromatic substrates with a leaving group attached 15, 30); e.g., aqueous chlorinolysis of 1-naphthyl-
directly to a phenyl ring (29). A simple general methyl mercaptan affords I-chloromethyl naphtha-
scheme for sulfonyl chloride synthesis is shown in lene and not the expected sulfonyl chloride (15).
eq. [I 1. -
The detailed pathway by which alkyl sulfides are
g Cl,/H,O %vidence that these reactions are ionic and not free radical
[ I ] R'SH + X-R" +R'SR" -R"S02CI has been presented previously (4).
HOAc 3We have suggested that the mode of decomposition is a
'Enquiries should be directed to Dr. R . F . Langler, unimolecular ionic process (15) whereas Kice has suggested a
Chemistry Department, Mount Allison University, Sackville, radical mechanism (12) or a cyclic transition state formed by
N.B., Canada EOA 3C0. attack of chlorine on the ci carbon as it leaves from sulfur.
0008-40421791243193-07$0 1 .OO/O
91979 National Research Council of CanadaIConseil national de recherches du Canada
 C A N J . CHEbI. VOL 57. 1979

/ X = 0 or lone pair
\

HOAc

transformed into sulfonyl chlorides without the analysis of asymmetric sulfide chlorinations requires
intermediacy of carbocations in the cleavage step that one be able to predict which of the first formed
(the sulfohaloform reaction) has been reported a-chlorosulfides will predominate. The substituent
recently (4). (See Scheme 2.) which incorporates the first chlorine atom is the one
which will be ultimately cleaved. We have previously
(la) reported that asymmetric sulfide chlorinations
in aprotic media introduce chlorine more readily

R , SO. CC12R' - +
R , SO. CHCIR'
on the a-carbon bearing the nlore electronegative
substituent. If this postulate holds in protic media,
the major sulfonyl chloride formed will be the one
which retains the sulfide substituent having the a-
carbon atom with the less electronegative group(s).
R.SO.C1 R.S02.C1 Mercaptans could then be assessed as sulfur transfer
\
R,SO.OH
,-' agents for sulfonyl chloride synthesis by choosing R'
(in eq. [I]) so that Xp(Rt) > XP(R1').
2. The sulfohaloform reaction
SCHEME

The cleavage step in the sulfohaloform reaction TABLE1 . Group electronegativities*

appears to proceed by an S,2 mechanism (4).
Several recognized complications may arise which Pauling
electronegativity
interfere with the cleavage step: (i) steric crowding Group (X,) a b
may preclude the existence of the desired p r ~ d u c t , ~
(ii) steric crowding in the intermediate a-polychloro- H-
oxochlorosulfonium chloride can shift preferred CH3-
CH3CH2-
nucleophilic attack by H,O (4) to chloride ions with CICHZ-
a consequent reduction in overall reaction rate and PhCH,-
some concomitant shift in the electrophilic site at- CH30C(O)CH2-
tacked (la), and (iii) carbocation formation prior to K02C-
formation of the requisite a-polychlorosulfoxide CI-I3(CH2)2
CH3tCH213-
intermediate can give rise to a sulfonyl chloride in CH3iCHz)4-
which the carbon a to the sulfonyl group bears CHS(CHZ)S-
chlorine atoms (6). CH~SOZ(CHZ)~-
Application of the sulfohaloform pathway to the PhS0z(CH2)2-
*Group electronegati~itieswithout a and b values are taken from Huheey's
data (32, 33). Group electronegativities uhere a and b Palues are supplied
4Reference 31 gives a possible example. were calculated using Huheey's method.
 LANGLER E T AL

TABLE
2. Exhaustive chlorinations of asymmetric sulfides in aqueous acetic acid

Sulfonyl chlorides
Sulfide substrates Ax,
(RICH~SCHZRZ) Major (2yield) Minor (2yield) ( X R , - XR,)

'Exhaustive chlorinations of last 3 cases mere reported pre viously (4)

Results and Discussion which hydrolyze to furnish the corresponding sul-

In order to test these proposals, a simple series of foxides rather than Pummerer rearranging to the
sulfides was subjected to exhaustive chlorination in corresponding a-chlorosulfides. Therefore the sulfide
aqueous acetic acid. The appropriate substituent acid l a must react as shown in Scheme 3. Details
electronegativities are shown in Table 1. Results of for the mechanisms have been given previously
the chlorinations with appropriate AX, values are (la, 3, 4).
presented in Table 2. These results are consistent with The pathway elaborated for the transformation of
the outcomes expected on the basis of AX, and the sulfide acid l a into a sulfonyl chloride mixture
sulfohaloform reaction arguments as presented presents a problem. Namely, there is no Pulnmerer
above. rearrangement of a chlorosulfoniuin chloride salt
Inspection of the substituent electronegativities anywhere in the pathway. Since the first step very
tabulated by Huheey (32, 33) led to the conclusion likely produces a sulfoxide, all Pummerer rearrange-
that thioglycolic acid would be an excellent sulfur ments are occurring from oxochlorosulfonium
transfer agent for sulfonyl chloride synthesis as chloride salts. In order that substituent electro-
depicted in eq. [I]. We have prepared a series of negativity be a useful basis for evaluating mercaptans
sulfides from a variety of halides and thioglycolic as sulfur transfer agents vis-8-vis sulfonyl chloride
acid as shown in eq. [ 2 ] . synthesis, sulfoxide chlorinations must also exhibit
CH30H
regioselectivity which correlates with substituent
(21 R-X + HSCH2C02H RSCH2COzH electronegativity difference (AX,). Table 3 presents
CH,ONa the asymmetric sulfoxide chlorinations which are
1 presently known. The data in Table 3 suggest that
The first problem is that of delineating the path- AX, may very well continue as a useful basis for
way by which the sulfide acids 1 are transformed CIz/H,O
into sulfonyl chlorides upon exhaustive chlorination CH, . S . C H 2 C 0 2 H CH3. SO. CHzCO2H
HOAc
in aqueous acetic acid. The pathway study was la
carried out on the sulfide acid l a (R = CH,). I
C
Chlorinolysis of l a in aqueous acetic acid for a CH3. SO. CC12COzH 4------ C H ? . S O . CHCICOzH
short time furnished 1,1,1-trichloro-2-thiapropane-
2-oxide (2) in 75% yield. Since we have previously
established (4) that 1,I-dichloro-2-thiapropane-2-
oxide reacts5 under these conditions to furnish
methanesulfonyl chloride in 60% yield without
CH,. SO. CCI, + CO,
2
-
CICH, . SO. CCI,
1

proceeding through the trichlorosulfoxide, it follows

that the dichlorodimethyl sulfoxide is not the prin-
CH, . S O . C1+ CCI, + C 0 2 CICH,. S O . C1+ CCI, + C 0 2
cipal intermediate giving rise to 2. Furthermore, we
have shown (la, 4) that sulfides with strongly
electron-withdrawing groups on a carbon a to the
sulfur atom furnish chlorosulfonium chloride salts
5The dichlorosulfoxide is converted to the trichlorosulfoxide
in 16% yield under these conditions (4).
 TABLE
3. Regioiso~nericchlorosulfoxides from sulfoxide chlorinations

Sulfoxide substrate Chlorosulfoxide products AX,

(R,CH,SOCH,R,) (% yield) (XR, - XR,) Reference

*There has been a report that benzyi methyl sulfoxide chlorinates with l ~ t t l eo r no reg~oselecti\,ity\\hen iodobenzene dichloride is em.
ployed as the chlorinating agent (35).

4. Yields* of sulfonyl chlorides obtained via sulfide acids 1

TABLE

Substrate Product Overall yield (2)

CH3CH2Br CH,CH,SO,CI 70
CH3(CH2)2Br CH3(CH2),S0,C1 65
CH3(CH,)3CI CH3(CH2),S0,CI 60
CH3(CH2I45r CH3(CH,),SO2CI 80
CH3(CH2I5Br CH3(CH2)5S02CI 78
CH3S0,(CH2)3CI CH3S02(CH2)3S02CI(3n) 50
PhS02(CH2)3CI PhS02(CH2)3S02CI(30) 60
*Yields are reported for si~lfonylchlorides after p iirification by distillation or recrystallization

assessing mercaptans as sulfur transfer agents chlorides have substituents attached t o sulfur via
whether chlorinolyses of the sulfide intermediates primary carbon atoms. Consequently we have
follow the sulfohaloform pathway o r the closely examined a secondary system in order to compare

-
related pathway shown in Scheme 3. the two methods. The results are shown in eqs. [3]
We have chlorinated a series of sulfide acids B and [4].
which furnished the expected sulfonyl chlorides in Clz/H20
good yields as shown in Table 4. The sulfonyl [3] (CH3)2CHSCH2C02H (CH3),CHOAc
chlorides 3a and 3b were prepared as examples of 10 HOAc 46%
more interesting substrates which can be accessed + (CH,),CHSO,CI + CI,CHS02C1
with this new method. The complete route for the 54% 46%
preparation of their precursors 7a and 7 b appears in CIZ/H20
Scheme 4. [4] (CH3)2CHSCH2Ph (CH3)2CHS02CI
All of the substrates examined for the development HOAc
of both the present method and our previously + PhCH2C1
published method (5) for the synthesis of sulfonyl The results shown in eq. 131 indicate that chlorino-
pyridine lyses of the sulfide acids 1 are subject to complication
RSH + CHZ=CHCOZCH, ------+ RSCH,CH2C02CH3
by S,1 dissociation prior to formation of the a-
4 0 R = CH,-
40 R = Ph- polychlorosulfoxide intermediates necessary to ob-
tain S,2 cleavage. However, as shown in eq. [4],
benzylic sulfides are not susceptiblc to such a com-

-
plication since S,1 cleavage of the benzyl group
SOCI,
occurs very early in the reaction pathway (5). The
RSCH2CH,CH,CI RSCH,CH,CH,OH pathway for the chlorinolysis of I b appears in
CHCI,
6u R = CH2- 5a R = CH,- Scheme 5.
6b R = Ph- 5b R = Ph- We have now successfully developed two sulfur
transfer agents for sulfonyl chloride synthesis i.e.

ICr0,IHOAc

R . SO2.CH,CH,CH2CI
phenylmethanethiol (5) and thioglycolic acid. While
yields are generally higher and reaction times
shorter for chlorinolvses of benzylic sulfides. there
is a drawback in thei; apglication;o the synthesis of
7<1R = CHs-
7 b R = Ph- smaller sulfonyl chlorides. When benzylic sulfides
are exhaustively chlorinated in aqueous media the
sulfonyl chloride product is contaminated with ap- E.ulznustice Chlorinntions 111 Aqueo~lsMediunz
proximately one equivalent of benzyl chloride and The sulfide substrate was dissolved in glacial acetic acid
(25 mL) and water (3 i11L). Chlorine (ca. 200 mL/min) was
a small amount of benzyl acetate (5). When the bubbled into the reaction mixture for 2.5 h with iceiwater
desired sulfonyl chloride has a volatility comparable cooling as necessary to maintain the temperature of the reac-
to that of benzyl chloride, purification is tedious and tion lnixture between 20 and 30 C. Water (50 mL) was added
time consuming. In contrast, the chlorinolysis of and the resultant mixture washed with methylene chloride
(100mL). The organic layer was washed with 2.5% wiv
sulfide acids 1 produces the desired sulfonyl chlorides NaOH (two 50 mL aliquots), dried (MgSO,), filtered, and the
carbon dioxide and carbon tetrachloride and the solvent evaporated. The residue was distilled or recrystallized
sulfonyl chlorides are therefore isolated in good before yield was determined.
purity directly from the reaction mixtures. Thus Pi,epamtion of PIzCH2CH2SCH3
thioglycolic acid is a superior sulfur transfer agent Sodium metal (0.851 g) was dissolved in absolute ethanol
for the preparation of small sulfonyl chlorides where (100 mL). Methanethiol (5 mL) was slowly distilled into the
the carbon bearing the chlorosulfonyl group in the cooled ethoxide solution. 2-Phenyl-1-chloroethane (5.021 g)
product will not be a suitable carbocationic centre. in ethanol (10 mL) was added dropwise over 15 min and the
rcaction mixturc stirred at ambient temperature for 48 h.
Phenylmethanethiol is a superior transfer agent for Water (100 mL) was added and the resultant mixture washed
the preparation of crystalline or non-volatile sul- with chloroform (three 100 mL aliquots). The combined
fonyl chlorides or systems in which the carbon organic layers were dried and concentrated. The crude con-
bearing the chlorosulfonyl group can bear positive centrate was rectified at reduced pressure affording the sulfide
(4.572 g, bp 96-C/5 Torr), nmr (CDCI,) 6 : 7.70 (5H, s), 3.00
charge with some facility. (4H, m), and 2.10 (3H, s); ms n / e : 152 ( M f , 28Y,), 91 (5373,
In conclusion, we have developed thioglycolic and 61 (100%).
acid as a new sulfur transfer reagent for sulfonyl 0
chloride synthesis. Sulfonyl chloride synthesis re-
quires substrate analysis in terms of (i) stability of Preprri rrr~onof CH,SCH2CH2C-0CH3 4a
carbocations which could be formed by S,1 dis- Sodium metal (4 210 g) was dissolved 111 methanol (200 mL)
and the solution cooled Methaneth~ol(10 mL) was d ~ s t ~ l l e d
sociation of intermediate chlorosulfollium and oxo- Into the reactlon m~xture and methyl acrylate (15 691 g)
chlorosulfonium cations, (ii) AX, for asymmetric added The reactlon ln~xturewab refluxed 1 h Water (250 mL)
sulfides for which neither carbon attached to sulfur was added and the lesultant m ~ r t u r ewashed w ~ t hchloroform
is a potential carbocationic centre, and (iii) steric (four 200 niL aliquots). The combined organic layers were
dried and concentrated. The residue was distilled at reduced
factors which may complicate the cleavage of a-
pressure yielding the sulfide ester (8.586 g, bp 106-108'Cl
polychloro-oxochlorosulfonium chloride intermedi- 100Torr), ir (CHCI,): 1740cm-'; nmr (CDCI,) 6 : 3.76
ates. ( 3 H , s), 2.73 (4H, m), and 2.13 (3H, s); ms m / e : 134 ( M f ,
64%), 74 (98%), and 61 (100%).
Experimental
Chlorination of Asymmetric Szilfides
General A series of asymmetric sulfides were subjected to aqueous
The ir spectra were recorded on a Perkin-Elmer 237B chlorinolysis as described under "Exhaustive Chlorinations".
spectrophotometer. The nmr spectra were obtained on a The relative yields were determined by integration of the
Varian T-60 instrument using TMS as the internal standard. nmr spectru~nof the crude product. Results are shown in
The mass spectra were recorded on a Dupont-CEC model Table 2.
21-104 mass spectrometer. The samples were directly in-
troduced using an all glass probe and the spectra run at 30 eV Preparation of CH3SCH2CH2C H 2 0 H 5a
with a source temperature of 150'C. Melting points were Lithium aluminum hydride (1.701 g) was covered with
determined on a Fisher-Johns melting point apparatus and are T H F (15 mL) and the mixture refluxed for 0.5 h. The mixture
uncorrected. was cooled to room temperature and a solution of CH3S-
(CH2),C0,CH3 (6.000 g) in T H F (10 mL) added dropwise The crude acid was covered with methanol (5 mL) and
over 10 min. The reaction mixture was refluxed for 0.5 h. concentrated HC1 (6 mL). The reaction mixture was stirred at
Upon conipletion of the reflux ethyl acetate (2.5 mL) was ambient temperature for 5 min. Chlorofornl (250 mL) was
added dropwise; 10% HCI (30 mL) was added dropwise, the added and the mixture dried (MgSO,), filtered, and con-
layers separated, and the organic layer dried and con- centrated. The residue was rectified at red~lcedpressure af-
centrated. The residue was fractionated at reduced pressure fording the sulfide acid methyl ester (1.820 g, bp 106-108'C/
furnishing the sulfide alcohol (4.238 g, bp 136-C/100 Torr), 100 Torr); ir (CHCI,): 1730 c m - I ; nrnr (CDCI,) 6: 3.73
ir (CHCl,): 3620 and 3450cm-I; nmr (CDCI,) 6 : 3.76 (3H, s), 3.23 (2H, s), 2.66 (2H, q), and 1.26 (3H, t); ms nzle:
(2H, t), 2.60 (2H, t), 2.33 (IH, s), 2.13 (3H, s), and 1.90 134 ( M t , 38.0%), 75 (loo"%,),and 74 (60%). Anal. calcd. for
(2H, m); ms twe: 106 (M*, 100%), 88 (67%), and 73 (40%). C,H,,O,S: C 44.75, H 7.51; found: C 44.25, H 7.73.
CH3SCH2C02Hl a had ir (CHCI,): 3000 and 1720 cm-';
Preparation of PIIS(CH,)~CI6 b and CH3S(CH2)3CI6a nrnr (CDCI,) 6: 11.53 (IH, s), 3.23 (2H, s), and 2.26 (3H, s):
CH,S(CH,),OH or PhS(CH,),OH (15) (10 g) was dis- ms m/e: 106 ( M t , 44%) and 61 (100%).
solved in chloroform (40 niL) and the solution brought to CH3CH2SCH2C02Hhad ir (CHCI,): 3000 and 1720 cm-' ;
gentle reflux. Thionyl chloride (1 equiv.) in chloroform (20 mL) nmr (CDCI,) 6 : 11.50 ( l H , s), 3.26 (2H, s), 2.70 (2H, q), and
was added dropwise to the reaction mixture over 10 min. 1.26 (3H, t).
Upon completion of the addition the reaction mixture was CH3(CH2),SCH2C02H had ir (CHCI,): 2990 and 1720
refluxed. cm- ' ; nrnr (CDC1,) 6 : 11.09 (IH, s), 3.26 (2H, s), 2.66 (2H, t),
After 4.5 h reflux the solvent was renloved and the residue 1.73 (2H, m), and 1.00 (3H, t); ms m/e: 134 ( M f , 50%), 75
distilled affording PhS(CH,),CI (4.876 g, bp 13OCC/2.2Torr), (loo%), and 47 (86%).
nmr (CDCI,) 6: 7.20 (5H, s), 3.60 (2H, t), 3.03 (2H, t), and CH3(CHZ),SCH2CO2H had Ir (CHCI,): 3000 and
2.00 (2H, m); ms m:e: 188 (19%), 186 (Mf , 5773, 123 (loo%), 1720 c m - 5 nmr (CDCI,) 6: 11.10 (IH, s), 3.50 (2H, s), 2.70
and 110 (82%). (ZH, t), 1.60 (4H, m), and 1.OO (3H, t) ; ms nl/e : 148 (M t , 5 I%),
After 24 h reflux the solvent was removed and the residue 89 (78%), 61 (51%), and 47 (100%).
rectified yielding CH3S(CH2),C1 (8.309 g, bp 114-1 16'Ct CH3(CH,),SCH2C02H had ir (CHCI,): 3000 and
100 Torr), nmr (CDCI,) 6: 3.70 (2H, t), 2.70 (2H, t), 2.13 1720 c m - I ; nmr (CDCI,) 6: 11.23 ( l H , s), 3.23 (2H, s), 2.66
(5H, m); ms t71/e: 126 (4.473, 124 ( M t , 13.3%), 88 (42%), and (2H, t), 1.40 (6H, m), and 0.90 (3H, t); nis mje: 162 ( M t ,
61 (100%). 3773, 103 (8021, and 69 (100%).
Preprrration ~ ~ P / I S O ~ ( C H7b
~ )and
~ CCH3SO,(CH2),C1
I 7a CH3(CH2),SCH2C0,H had ir (CHCI,): 3000 and
Chronliunl trioxide (2.5 equiv.) was covered with glacial 1720 cm-I ; nmr (CDCI,) 6 : 11.37 (IH, s), 3.23 (2H, s), 2.66
acetic acid (140 mL) and a solution of the appropriate chloro- (2H, t), 1.40 (8H, m), and 0.90 (3H, t); ms t11,'e: 176 ( M t , 3421,
sulfide (5.00 g) in glacial acetic acid (10 mL) added. The 117 (loo%), and 83 (64%).
reaction mixture was cigorouslj~stirred and the temperature CH3S02(CH2)3SCH,C02H had Ir (CHCI,): 3000 and
1720 cni- : nrnr (CDCIA 6: 11.30 l l H . s). 3.30 (2H. s). 2.96
maintained at 90-100-C for 0.5 h. Water (150 mL) was added
and the resultant mixture washed with methylene chloride m);
(7H, ni), and 2 . 1 6 ' ( 2 ~ , ms m/e: 195(27%), 121 (27%), and
(four 100 mL aliquots). The combined organic layers were 73 (IOOZ).
washed with 5% NaOH (100 n1L aliquots) until the aqueous PhS02(CH2),SCH2C02H had ir (CHCI,): 3000 and
layer remained basic. The organic layer was dried, concen- 1720 cm-' ; nrnr (CDCI,) 6 : 11.45 (IH, s), 7.90 (5H, m), 3.26
trated, and the residue distilled. (4H, m), 2.83 (2H, t), and 2.13 (2H, m); ms m/e: 256 (50%), 143
CH3SO2(CH2),C1 (3.816 g, bp 168-170 Ci4 Torr) had ir (82%), and 77 (100%).
(CHCI,): 1325 and 1145 cm-'; nrnr (CDCI,) 6: 3.80 (2H, t), (CH3),CHSCH2CO2H Ib had ir (CHCI,): 3000 and
3.26 (2H, t), 3.00 (3H, s), and 2.20 (2H, m); ms m,'e: 158 1720 cm-' ; nrnr (CDCI,) 6: 11.25 ( l H , s), 3.33 (3H, m), and
(3.1%), 156 ( M t , 9.373, 94 (60%), and 41 (100%). 1.30 (6H, d); nis m/e: 134 ( M ? , 55%), 92 (42%), and 75
PhSO2(CHZ),C1 (3.139 g, bp 180-182"C/1.9 Torr) had ir (100%).
(CHC1,): 1325 and 1150 cm-' ; 11111r (CDCI,) 6 : 7.80 (5H, m), Chlorinolysis of l a
3.60 (2H, t), 3.30 (2H, t), and 2.20 (2H, m); ms rille: 220 Crude sulfide acid l a (0.93 g) was chlorinated for 10 min
(2.7%), 218 ( M + , 8.1%), 77 (loo%), and 41 (57%). employing the procedure outlined under "Exhaustive Chlori-
Preyai.ution of Sulfide Acids 1 nations". Trichloromethyl methyl sulfoxide (1.212g) was
The preparations of the sulfide acids were all carried out in obtained. After purification by column chromatography
the same manner as illustrated for the preparation of the employing silica gel and chloroform elution, the product was
methyl system l a . The crude samples were checked to confirm shown to be identical to authentic material by nmr, ir, and
that the expected product had formed. Sodium metal (0.407 g) tlc.
was dissolved in methanol (25 mL) and thioglycolic acid
(0.807 g) added. A solution of methyl iodide (1.216 g) in Chlorincrtiort of Sulfide Acids
methanol (1OmL) was added dropwise and the reaction The desired alkyl sulfide acid (5 g) was chlorinated as
mixture stirred at ambient temperature for 24 h. The solvent described under "Exhaustive Chlorinations" and the alkane
was evaporated and the residue tlzor.o~rghlydried. Water sulfonyl chloride products distilled. In each case the product
(5 mL) was added, followed by concentrated HC1 (1 mL). had the known ir, nmr, and bp. Overall yields for conversion
Chloroforn~(250 mL) was added, the solution dried (Mg- of the alkyl halides into the corresponding sulfonyl chlorides
SO,), filtered, and concentrated affording crude sulfide acid. are given in Table 4.
CH3S0,(CH2),S02C1 30 was recrystallized from chloro-
Preparation of CH3CH2SCH2C 0 2CN, form and had mp 62-65,C; ir (CDCI,): 1380, 1310, 1170,
Crude sulfide acid was prepared from ethyl bromide and 1145 c m - l ; nrnr (CDCI,) 6 : 3.96 (2H, t), 3.26 (2H, t),
(4.264 g), thioglycolic acid (3.614 g), and sodium metal 2.96 (3H, s), and 2.56 (2H, t); ms tnle: 143 (6.821, 141 (20.4%),
(1.866 g) in methanol (60 mL) as described for the sulfide 79 (13.3%), and 41 (100%). Anal. calcd. for C,H,C10,S2:
acids 1. C 21.76, El 4.11; found: C 21.35, H 4.18.
 LANGLER ET A L . 3199

PhS02(CH2)3S02C1 36 was recrystallized from chloro- 9. J . MARCH.Advanced organic chemistry. McGraw-Hill.

form and shown t o be identical t o previously prepared material New York. NY. 1968. pp. 373,374.
(15) by ir, nmr, mp, a n d mixture mp. 10. J . F. KIYG.Acc. Chem. Res. 8, 10 (1975).
11. W. E. T R U C and ~ A . M. MURPHY.Chem. Rev. 48. 69
Cl~lo~.itzarion of (CH,) ,CHSCH2CO2H I b (1951).
T h e sulfide acid (4.71 g) was subjected t o the procedure 12. J . L. K I Ct . in The chen~istr>of organic sulfur compounds.
outlined under "Exhaustive Chlorinations". The crude Editril b? N . Kharasch and C. Y . hleycrs. Pergamon. NY.
product contained 2-acetoxypropane (1.499 g), 2-propane- 1966. pp. 120. 121.
sulfonyl chloride (2.284 g), and dichloromethanesulfonyl 13. M. ASSCHER and D. VOFSI.J . Chem. Soc. 4962(1964).
chloride (2.509 g) as determined by a method described pre- 14. F. G . BORD\\'LLLand H . M. A U D E R S E NJ . Am. Chem.
viously (4). The identity of the constituents in the mixture Soc. 75,6019 (1953).
was confirmed by the addition of authentic samples of each 15. H . 0. Fo\o. W . R . HARDSTAFF. D. G . K A Y .R. F. L A \ G -
conlpound which resulted in the change of the intensities L E R . R. H . MORSE.. and D. N . SANLIOVAL. Can. J . Chern.
of the appropriate signals in the n m r spectrum of the mixture. 57. 1206 (1979).
Chlorinariorr of (CN,) ,CHSCHzPlz 16. 6. OLAH.Friedel-Crafts and related reactions. Vol. 3. Part
T h e benzylic sulfide (5.84 g) was subjected t o the procedure 2. Interscience, NY. 1964. p. 1319.
outlined under "Exhaustive Chlorinations". The crude 17. H . BURTO\ and W . A. D A V YJ. . Chem. Soc. 528 (1948).
product contained 2-propanesulfonyl chloride (4.281 g). The 18. E . E. GILBERT.Sulfonation and related reactions. Inter-
identity of the sulfonyl chloride a n d benzyl chloride were con- science, NY. 1965. pp. 84 and 126.
firmed by the addition of authentic samples to the crude which 19. L . A. P A Q U E T T ~ R. B. HOUSLR.J . Am. Cheni. Soc. 91.
and
resulted in the change in intensities of the appropriate signals 3870 (1969).
in t h e nmr spectrum of the mixture. N o isopropyl acetate was 20. H. B R ~ N I Z I \ G E RH. . KODDEBCSCH K . K L I L G .and G .
present in the crude. SUNG.Ber. 85.455 (1952).
21. 1 . B. DOUGLASS.V. SIMPSO\.and A. S A W Y E RJ.. Org.
Chem. 14.272 (1949).
22. I. B. D o u c r s s and T. B. J D H % S O N J .. Am. Chem. Soc. 60.
The authors are indebted to Mr. T. P. Ahern for 1486 (1938).
23. T . B. JOHYSON and J . M .SPRAGUL. J . Am. Chem. Soc. 58,
some technical assistance and to Dr. J. H. Kim for 1348(1936).
running the mass spectra. We are grateful to Dal- 24. T . B. JOHNSO% and I . B. D ~ U Gs sI s . J . Am. Chem. Soc. 61.
housie University for financial support in the form 2548 (1939).
of a grant from the Research Development Fund. 25. I. B. D o u c ~ l i s s B.
. S. FARAH.and E . G . THOXIAS. J . Org.
Chem. 26. 1996 (1961).
26. I. B. D o u c ~ ~ s s a nC.d E. OSBORYE. J . Am. Chem. Soc. 75.
1. ( 0 ) T. P. AHERIL. D. G . K A ) . and R . F. LANGLER. Can. J. 4582 (1953).
Chem. 56,2422(1978): ( b )D. G . K A Y .R. F. L ~ I \ G L ~and R . 27. R . O T T O Ann.. Chern. 145,323 (1868).
J . E. TREYHOLM. Can. J. Chem. 57.2185 (1979). 28. W . T A G A K IIt? . Organic chemistry of sulfur. Eilitc.d S.
2. R . F. LAUGLER. Z. A. M A R I N Iand
. J . A. P I ~ C O C Can.
K . J. Oae. Plenum Press. New York. NY. 1977. p. 231.
Chem. 56.903 (1978). 29. J. R . C ~ M P B E LJL. Org.. Chem. 29. 1830(1964).
3. J . S . GROSSERT.W . R . H A R D S ~ I A Fand . 51. S. KHARASCH.E . N . MAY.and F. R. MAYO.J . Org.
F , R. F. L A ~ G L ~ K30.
Can. J . Chem. 55,421 (1977). Chem. 3. 189 (1940).
4. J . S. GROSSERT and R. F. L A N G L E RCan.. J. Chenl. 55,407 31. J . Bu.1LE.R and R. M. K ~ L L O G G J . . Org. Chem. 12. 973
(1977). (1977).
5. R. F . LAYGLER. Can. J . Chem. 54.498(1976). 32. J. E. H U H ~ J. E P
~ h. y s Chem. 69.3284(1965).
6. W . R. HARDSTAFF, R. F. L A \ G L L R J, . L E A H Yand
, M. J . 33. J . E. HUHEEY.J . Phys. Chem. 70.2086(1966).
NE\VI\IAN. Can. J. Chem. 53.2664(1975). 34. ( ( I ) K . C . T I Nand T. D U R ~ TTetrahedron
. Lett. 4643 (1970):
7 . 5. S. GROSSERT,W . R. HARDSIAFF.and R . F. L A N G L E R . (h) T. DURST.K. C . T I N . and M . 5 . V . MARCIL..Can. J .
Chem. Commun. 50 (1973). Chem. 51. 1704 (1973).
8 . J . S . GROSSERT and R. F . L A N G L E RChem.
. Commun. 49 35. M. C I ~ Q U Iand ~ I S . COLO>YA.J . Chem. Soc. Perkin
(1973). Trans. I, 1883 (1972).
Intermediate stages of the sulfohaloform reaction. Preparation sf a-halosulfoxides
and sulifinyl chlorides. Oxygen-transferreactions
J. STUARTGROSSERT,
WILLIAMR . HARDSTAFF,A ~ RICHARD
D F. L A ~ G L E R
Chernrrtr~Deprirrmer~r,Drilhorrsre U ~ I ersro,
IL Hallfak, A S , Car~citftrB3H4J3
Recelved October 10, 1975'

J. STUARTGROSSERT, WILLIAMR . HARDSTAFF, and RICHARDF. LANGLER. Can. J. Chem. 55,

421 (1977).
Details are provided of synthetic routes from dialkyl sulfides to both a-halosulfoxides and
sulfinyl chlorides. In the case of the former, oxidation of cr-halosulfides to the sulfoxide stage is
achieved by chlorine in acetic acid containing controlled amounts of water. Sulfinyl chlorides
are prepared by chlorination of a-polyhalosulfoxides in methylene chloride. During investiga-
tions into the details of the sulfohaloforn~reaction, a number of novel redox reactions involving
oxygen transfer between sulfur species have been observed and these are presented. They include
a reduction of a sulfoxide with thionyl chloride.

J. STUARTGROSSERT, WILLIAMR. HARDSTAFF et RICHARDF. LANGLER. Can. J. Chern. 55,

421 (1977).
On fournit des details permettant de synthetiser a la fois les a-halosulfoxydes et les chlorures
de sulfinyles a partir des sulfures de dialkyles. Dans le premier cas, I'oxydation des sulfures
a-haloginis en sulfoxyde est effectuee par du chlore dans de l'acide acetique contenant des
quantites contr61Ces d'eau. On prepare les chlorures de sulfinyles par chloruration de sulfoxydes
a-polyhalogenes dans le chlorure de methylene. Au cours des etudes effectukes afin d'elucider
les dktails de la reaction sulfohaloformique, on a observe un certain nombre de nouvelles
reactions d'oxydo reduction impliquant un transfert d'oxygtne entre des especes contenant du
soufre; on presente ces nouvelles reactions. Elles colnprennent une reduction d'un sulfoxyde par
le chlorure de thionyle.
[Traduit par le journal]

Synthesis of a-Polyehlorosulfoxides
Sulfoxides are usually synthesized by the con-
trolled oxidation of sulfides (1,2). Such a reaction
always has the potential of giving higher oxida-
tion products, for example, sulfones, and there is
ample literature documentation of reactions low nucleophilicity of such sulfides introduces a
designed to avoid such complications (2, 3). rate retardation, in comparison to that of un-
Initial investigations of the use of halogens in chlorinated sulfides, which makes the reaction
aqueous media to oxidize sulfides deinonstrated easy to control. The complication involved in
that molecular bromine afforded much smoother chlorinating more nucleophilic sulfides and
and more readily controlled reactions than did sulfoxides is that the product is often nearly as
molecular chlorine (ref. 1, p. 216). Since the work reactive as the starting material. For example,
of Fries and Vogt in 1911 (4), no further attempts chlorination of DMSO in aqueous acetic acid, a t
appear t o have been made to use chlorine for the room temperature, leads to the formation of i -
oxidation of sulfides to sulfoxides. chloro-2-thiapropane-2-oxide, 1, which is seri-
The excessive reactivity of chlorine becomes an ously contaminated with 1,l-dichloro-2-thia-
advantage, however, when the oxidation of propane-2-oxide. 2. The desired control for the
heavily chlorinated sulfides is attempted since the oxidation of sulfides with chlorine in aqueous
R,RZR3C.S0.CH2R4 media does not obtain until the starting sulfide
1 R1 = C1; R 2 = R 3 = R4 = H
has a t least two a-chlorine atoms. Thus con-
trolled chlorination of 1,3-dichloro-2-thiapro-
2 R, = R Z = C 1 ; R 3 = R 4 = H pane furnished the corresponding sulfoxide 3
without difficulty ( 5 ) .
'Revision received September 20, 1976. In a typical experiment, the polychlorosulfide
 C 4 N . J. CHEM. VOL. 55. 1977

TABLE1. Preparation of a-polychlorosulfoxides from a-polychlorosulfides by

chlorination (232 ml/min) in glacial HOAc containing 3 equiv. of water

Yield Chlorination
Starting sulfide Sulfoxide product (%I time (min)

(cri. 16 gm) was dissolved in acetic acid (50 ml) method center around finding a suitable solvent
a n d 3 equiv. of water were added. Chlorine was in which to carry out the solvolysis. For ex-
bubbled into the solution and the temperature ample, when acetic acid is employed as the sol-
maintained at 25 t o 30 "C. The results obtained vent, excess chlorine initiates a slow but smooth
on the systems utilized in this study are given in transformation of the sulfinyl chloride into the
Table 1. corresponding sulfonyl chloride. However, this
Many reagents available for the conversion of problem seems to have been overcome by
sulfides to sulfoxides give rise to some sulfone as employing acetic anhydride for the solvent.
well (2, 6). Although the preparation of a-poly- Using a different synthetic method, some aro-
chlorosulfoxides utilizing chlorine and aqueous matic sulfinyl chlorides have been prepared by
acetic acid is not complicated by sulfone forma- reaction between the sulfinic acid and thionyl
tion, it is normally complicated by sulfonyl chloride (10).
chloride formation. However, sulfonyl chloride Our studies on the cleavage of a-polychloro-
formation occurs as a minor side reaction and the sulfoxides with chlorine (5) led to the selection of
sulfonyl chloride can be readily removed by methylene chloride as the solvent in order t o
washing the sulfoxide with aqueous base. By prevent solvolysis reactions. The results of the
contrast, sulfones are often difficult to remove initial examination of this reaction indicated that
from the corresponding sulfoxide, particularly a-trichlorosulfoxides would undergo facile clea-
when purification is attempted by recrystalliza- vage when treated with chlorine in methylene
tion (6). chloride, whereas a-dichlorosulfoxides would not
A useful modification of this synthetic method undergo cleavage in useful yields.
involves the conversioil of a sulfide to the corre- A summary of the sulfoxide substrates exa-
sponding a-chlorosulfoxide in one step. Since mined is presented in Table 2.
chlorosulfonium chloride salts are inert t o It is noteworthy that the yield of sulfinyl
acetolysis (7), the starting sulfide can be chlori- chloride from chlorination of phenyl trichloro-
nated in glacial acetic a c ~ d to furnish the methyl sulfoxide was poor and that the com-
homologous a-chlorosulfide. After the addition pound could not be separated intact from the
of water further chlorination affords the corre- reaction mixture. This observed poor yield and
sponding sulfoxide. I n this way, 1,3-dichloro-2- the long chlorination time are precisely what
thiapropane has been converted routinely into would have been expected from a n alkyl u,a-
1,1,3-trichloro-2-thiapropane-2-oxide, 4, in 50% dichloroalkyl sulfoxide. It appears, therefore,
yield. that the phenyl ring acts to suppress the electron-
withdrawing effect of approximately one chlorine
Synthesis of Sulfinyl Chlorides atom, which may be rationalized by postulating
The development of synthetic methods for the the delocalization in the intermediate oxochloro-
preparation of sulfinyl chlorides has received sulfonium chloride of positive charge o n sulfur
relatively little attention. Most sulfinyl chlorides around the aromatic ring.
have been made by variations of the same reac- In its generalized form, this method of alkane-
tion developed by Douglass, namely the con- sulfinyl chloride preparation requires that tri-
trolled solvolysis of alkyldichlorosulfonium chloromethyl alkyl sulfoxides be available. Since
chloride salts (8,9). The chief difficulties with this the chlorination of alkyl methyl sulfides normally
 GROSSERT ET AL

TABLE
2. Preparation of alkanesulfinyl chlorides from a-polychlorosulfoxides
by chlorination (232 ml/min) in CH2Cl2

Sulfinyl chloride Yield Chlorination

Starting sulfoxide product (%I time (min)
C1CHz,SO.CHCl24 C1CH2.S0,Cl 72 30
CICH2.SO.CC13 5 ClCH2.SO.Cl 80 50
CH3.S0.CHC12 2 CH3.S0.CI 76 25
CH?.SO.CCl, 6 CH3.S0,CI 77 25

goes preferentially into the alkyl group ( l l ) , it shown in [I] were obtained. The previous report
might appear that this method is not generaliz-
able on account of the lack of availability of the
intermediate trichloromethyl sulfides. However,
this is not so, since both chloromethyl and + C13C.S~CH2Cl(26%) + CHCI, (26%)
dichloromethyl aikyl sulfides are available 8
through established methods. Bohme (12, 13) has ( 5 ) established that the chloromethanesulfony1
developed the preparation of chloromethyl alkyl chloride, 9, is produced from the corresponding
sulfides from alkyl thiols, paraformaldehyde, and sulfinyl chloride which in turn is produced from
HCI. More recently a method for the preparation the trichlorosulfoxide, 4. It is also clear that the
of dichloromethyl alkyl sulfides from the thiol- sulfinyl chloride acquires an oxygen atom from a
formates and phosphorus pentachloride has been sulfoxide which is converted to the corre-
published by Holsboer and van der Veek (14). sponding cx-chlorosulfide. The simplest assump-
These authors have also reported the preparation tion, since the isolated sulfide is in fact the tetra-
of a number of trichloromethyl alkyl sulfides chlorosulfide 8, is that oxygen is transferred
from the dichloromethyl alkyl sulfides. from the trichlorosulfoxide 4. Chlorination of the
It should be noted that the preferred method trichlorosulfoxide 4 in glacial HOAc furnishes no
for the preparation of metha~lesulfinylchloride tetrachlorosulfide 8 as we have shown previously
utilizes 1,l -dichloro-2-thiapropane-2-oxide, 2, as (5). It therefore follows that the oxygen transfer
starting material. Although the chlorination of must have occurred from the dichlorosulfoxide 3.
1,1,l-trichloro-2-thiapropane-2-oxide, 6 , has been This reasoning was supported by chlorination of
examined and proceeds quite satisfactorily, 6 is a -1 : 1 mixture in glacial acetic acid of chloro-
considerably less convenient to prepare than is 2. nlethanesulfinyl chloride and the dichlorosulf-
oxide 3 which did indeed furnish the expected
Oxygen-transfer Reactions mixture of chloromethanesulfony1 chloride 9 and
Most of the reactions which we encountered tetrachlorosulfide 8 in a 1 : 1 ratio. The pathway
during our studies on the sulfohalofor~nreaction for the chiorination of the dichlorosulfide 3 in
(5, 7 ) involved sulfur behaving as a nucleophile glacial acetic acid is depicted in Scheme 1.
towards eiectrophilic chlorine. However, we also It is interesting to compare the reactions of 3
observed a number of reaction pathways in which (cf reaction 1 ) and 2 (reaction 2) (5) with
sulfoxides acted as nucleophiles at oxygen. This
type of reaction by sulfoxides is of course well
documented (15, 16), but the reactions described
below are novel and warrant a brief discussion.
Although chlorination of i,3-dichIor0-2-tllia-
-
chlorine in glacial acetic acid. No oxygen-
C12
[2] 2 HOAc CH,,SOZ.CI (72%) t CC1, (72%)

propane-2-oxide, 3, in dilute aqueous acetic acid transfer products were observed in 121. The
was a relati.iely straightforward reaction yielding differences between 2 and 3 may be explained by
primarily 4 (5), the use of glacial acetic acid as a number of factors. These include the fact that 2
solvent permitted the obser1-ation of a chlori- undergoes rapid further chlorination to the less-
nated sulfoxide behaving as an oxygen nucleo- nucleophilic trichlorosulfoxide 6 and the fact
phile in a more complex reaction. The products that in [I], the oxygen transfer arises from the
 CAN. J. CHEM. VOL. 55, 1977

CI,
C1CH,.S0.CH2CI --A ClzCH.S0.CH2CI
HOAc
3 4

i
more nucleophilic sulfoxide 3 attacking the more CI~CH.SO.CH, CI,C. SO.CH,CI
electrophilic oxodichlorosulfonium salt 10. This
compares with [2] in which for a comparable
process t o occur, the predominant sulfoxide
would be 6 and the comparable electrophilic
species to 10 would be I1 (cf. Schemes 1 and 2).
/
C1, CH,CI, Clz

That an oxygen-transfer reaction could occur CI3C'SO'CH3 C~CH:.SO.Ci + CCI,

6
in the case of dichlorosulfoxide, 2, was found by
a careful examination of its chlorination in I
0 :a:-
II
methylene chloride solvent. The reaction is CH .I1+

depicted in [3]. J
II
1 11
cI2 C H 3 . S 0 . C 1 + CCI, CI2CH.S.CH3
I31 2 7 CH,.SO.CI (75%) + C H , , S 0 2 C I (1%) 2
CH,C12 ,

The chloromethanesulfinyl chloride must origi-

nate from the tetrachlorosulfoxide 5 since
methanesulfinyl chloride did not give rise to any :cj:-
chloromethanesulfinyl chloride when chlorinated C1
in methylene chloride. The selective oxidation of CI,CH I +CH, + SO, CI '-\
+ C12CH,S ,CHI +
rnethanesulfinyl chloride to the sulfonyl chloride r"
in the presence of chloromethanesulfinyl chloride :cI:-
can be rationalized on the grounds that the con-
centration of methanesulfinyl chloride is much
greater during the reaction and that the methane-
C I , ~s. ,-H, --
Cl, CI,C.S.CH~CI
8
sulfinyl chloride reacts at a faster rate with S C H E ~ I E2
 GROSSE

chlorine to form the oxodichlorosulfoniun~ dented reduction of a sulfoxide by thionyl

chloride salt 11. A reasonable reaction pathway chloride (ref. 10, p. 341) can be rationalized as
is outlined in Scheme 2. depicted in Scheme 3.
It might have been expected that methane-
sulfinyl chloride would best be prepared by Experimental
simple chlorination of DMSO, especially in light General
of the literature report that sulfoxides may be Details have been provided previously (5).
cleanly chlorinated in methylene chloride (17). Preparation of Cl, CH.S0.CH2Cl, 4
However, in our hands, DMSO produced a 1,3-Dichloro-2-thiapropane(1 6.00 g) in glacial acetic
plethora of products with chlorine in either acid (50 ml) was chlorinated (232 ml/min) for 20 min.
methylene chloride or glacial acetic acid. T h ~ sis Water (6.6 ml) was added and C1, (232 ml!rnin) was
undoubtedly due to oxygen-transfer reactions. bubbled through the reaction mixture for a n additional
35 min. Water (75 nil) was added and the solution was
We did find that these processes could be sup- extracted with chloroform (4 x 100 ml). The cornbinecl
pressed to give a useful reaction by use of a chloroform layers were washed with 2.5% NaOH until
controlled amount of water in the acetic acid (5). the p H of the aqueous layer remained basic, and then
We have also observed a novel oxygen transfer given a standard work-up. The residue was fractionated at
reduced pressure to furnish 4 (11.08 g, 50%).
reaction which did not involve molecular
chlorine. 111 1955, Bordwell and Pitt (18) Chlorination of C13C,S0,CH2Cl,5
examined the reaction of sulfoxides with thionyl 5 (15.25 g) was dissolved in methylene chloride (50 ml)
and chlorine (232 ml/nlin) was bubbled through the reac-
chloride. Upon subjecting thiacyclopentane- 1- tion mixture for 50 min. The solvent was distilled off at
oxide to the appropriate conditions, they re- atmospheric pressure and the residue was rectified at
ported the formation of "a dark colored material reduced pressure affordingchloromethanesulfinyl chloride
with a wide boding range". A reinvestigation of 9 (7.62 g, 80.3%) bp 94 ' C 80 torr.
this reaction furnished the unexpected result that Chlorination of Cl,C.SO.C, H,, 7
the major isolable product was thiacyclopentane 7 (9.64 g) was dissolved in methylene chloride (50 nll)
(25% yield). As initially isolated, it was contami- and chlorine (232 mlln~in)was bubbled through the reac-
nated with a small amount of material that may tion mixture for 90 min. The methylene chloride was
rotary evaporated to yield an orangish rcsiduc (10.02 g).
have been the expected 2-chlorothiacyclopentane Methanol (50 ml) was added to the residue and the solu-
(nmr). Redistillation gave thiacyclopentane of tion stirred at ambient temperature for 60 min. The
satisfactory purity. This apparently unprece- methanol was rotary evaporated affording a residue con-
taining Ph,SO,OMe (1.90 g, 3973, unreacted Ph.SO.CC1,
(2.25 g, 23Y,), as well as at least two other con~pounds.
S o m e of this residue was chromatographed on two
preparative-layer plates (150 mglplate) which were eluted
with carbon tetrachloride. The lowest band (RF 0.12
detected by uv light) was removed, and chloroform
extraction gave a partially crystalline residue (142.7 mg)
which was about equal parts CI,C.SO.Phand Ph.SO.OMe.
This residue was rechromatographed (plc, chloroform
eluant), the lower band (R, 0.62) from which furnished
methyl benzenesulfinate (66 mg), which was identical with
authentic material by tlc, nmr, and ir, and the upper band
(R, 0.83) from which furnished Ph,S0,CC13 7 (67 mg),
identical with the starting material by tlc, nmr, and ir.
Chlorination of CICH,.SO. CH, CI, 3
3 (15.01 g) (5) was dissolved in glacial acetic acid (50nll)
and chlorinated (232 ml/min) for 30 min. The nmr of the
crude showed that C1,C.SCH2C18 and C1CH2.S02CI9
were presellt in a 1 : 1 ratio. Ice water (75 nil) was added
and the solution extracted with chloroform (2 x 100 ml).
The chloroform layer was extracted with 2.5% NaOH
(100 ml aliquots) until the p H of the aqueous layer re-
mained basic. Standard work-up gave a residue which was
fractionated at reduced pressure affording CI3C,S.CH,CI
8 (5.47 g, 26.4%) and Cl,CH~SO~CH,CI 4 (3.72 g, 19.6%).
Both compounds were identical with authentic sanlples by
nmr, ir, and bp.
426 C A N . J . C H E M . VOL. 5 5 . 1977

The reaction was repeated. After addition o f water and methylene chloride (40 m l ) and was added drop-wise over
chloroform extraction, a portion o f the chlorofor~nsolu- a period o f 1 % h to a gently refluxing solution o f thionyl
tion (50 m l ) was continuously extracted with water2 for chloride (34.89 g) in methylene chloride (40 ml). U p o n
24 h . The chloroform was dried (MgSO,), filtered, and completion o f the addition the reaction mixture was
concentrated and a portion o f the residue (500 mg) was fractionated and the material (7.32 g) which had bp 90-
added drop-wise t o a chilled solution o f vanillin (218 mg) 120 ' C was collected. Redistillation furnished clean thia-
in dry pyridine ( I ml). After the reaction mixture was cyclopentane (bp 116-120 ' C , 3.65 g) which was identical
stirred at ambient temperature for 1 h , work-up in the with authentic material by bp, nmr, and ir.
usual way gave a residue which was chromatographed on
five preparative-layer plates usingether-chloroform, 5 :95. Acknowledgements
Extraction o f the band visible under uv light furnished
vanillin chloromesylate (152 mg) which was identical with
We thank Mr. J. Leahy for technical assistance
authentic material by tlc, ir, and nmr. and the National Research Council of Canada
for financial support, as well as for the award of a
Clzlorirtafionof CI,CH.SO.CH,, 2
2 (16.81 g) in rnethylene chloride was chlorinated (232
Postgraduate Fellowship to one of us (R.F.L.).
ml/min) for 25 min. The methylene chloride was distilled 1 . A . SCHOBERL and A . W A G N E RIn. Methoden der or-
o f f at atmospheric pressure and the residue was frac- ganischen Chemie (Houben-Weyl).V o l . 9. Edited by
tionated at 34 torr. Methanesulfinyl chloride (bp 52- E . Miiller. G . Thieme. Stuttgart. 1955. p. 21 1 .
54 'C:34 torr) was removed and a residue (1.00 g) was 2. H. H . S Z M A N TI12. Organic sulfur compounds. Vol. 1 .
obtained. Nuclear magnetic resonance spectra indicated Editeclby N . Kharasch. Pergamon. N . Y . 1961.p. 154.
the presence o f Cl,C~S~CH,CI 8 (264 mg, 1.273, 3 . G . C . BARRETT. In Organic compounds o f sulphur.
CICH2.S0.C1(437 mg, 2.9%), CH3.S02.C1(163 mg, 1 . 2 x ) , selenium, and tellurium. Chem. Soc. Spec. Publ.
and CH,.SO.Cl (139 mg, 1.273. The crude residue was London. 1,71 (1970);2.35 (1973).
treated with vanillin (1.002 g) in pyridine (2.5 m i ) as out- 4. K . F R I E Sand W . V O G T Justus
. Liebig's Ann. Chem.
lined previously, the product o f which was evacuated 381. 337 (1911).
(0.45 torr) and immersed in an oil bath (which had been 5. J . S . G R ~ S S E R and
T R. F . LANGLER. Can. J . Chem.
preheated t o 100 ' C ) , for 2 min. Condensation o f the This issue.
distillate in a cold trap (- 50 ' C ) furnished 8 (153 mg) 6 . F. G . B ~ R D W E Land L P . J . BOUTON. J . .4m. Chem.
identical t o authentic material by nmr, ir, and bp. The Soc. 79.717 (1957).
residue from the bulb-to-bulb distillation weighed 498 mg. 7 . J . S . G R O S S E KWT .. R . H A R D S T A Fand
F , R . F. LANG-
A portion o f the residue (200 mg) was chroinatographed L E R . J . Chem. Soc. Chem. Commun. 50(1973).
on two preparative tlc plates (silica gel HF-254) which 8. M. L . K E Eand I . B. D O G G L . ~ SOrg. S . Prep. Proc. 2,
were developed with 573 ether in chloroform. Vanillin 235 (1970).
mesylate (32.3 mg, R F 0.50) was isolated and shown t o be 9. C . G . V E K I E RH.. H. H S I E Hand , H . J . BARAGERIII. J.
identical t o authentic material by ir, nmr, and tlc. Org. Chem. 38. 17 (1973).
The chlorination was rerun and a portion o f the distilla- 10. J . S. P I Z E Y .Synthetic reagents. V o l . 1 . Ellis Hor-
tion residue (250 mg) was chlorinated (232 mljmin) in woodIJ. Wiley. Chichestel-. 1974. p. 336.
distilled water (1.7 ml) for 5 min. The reaction mixture 11. D. L. T U L E E Yand T . B. S T E P I I E KJ .SOrg.
. Chem. 34.
was diluted to 10 ml with distilled water and extracted 31 (1969).
with chloroform (3 x 10 ml). Standard work-LIPgave a 12. H. BOHML.Bei-. Dtsch. Chem. Ges. 69, 1610 (1936).
residue which was treated with vanillin (200n1g) in 13. H. B O H M EH. . FISHER andR.
, F R A N KJ.U S ~ L I SLiebig's
pyridine (1.0 ml) as described previously. Vanillin Ann. Chem. 563.54 (1949).
chloromesylate (48.2 mg. R F 0.55) was isolated by pre- 14. D. H. HOLSBOER and A . P . M. vi\r D E R V E E KRecl. .
parative-layer chromatography, as outlined above and was Trav. Chim. Pays Bas. 91,349 (1972).
shown to be identical t o authentic material by nmr, ir, and 15. T . DLRST.Adv. Org. Chem. 6.285 (1969).
tlc. 16: W . S . MACGREGOR. Q. Rep. Sulfur Chem. 3. 149
cmd SOC/,
Renrtion of Tl~iacyclopenfa~~e-I-o.~ide (1968).
Thiacyclopentane-I-oxide (28.85 g) was dissolved in 17. K . C . T I N and T . DUKST.Tetrahedron Lett. 4643
(1970).
' T h e water was distilled from 5% NaOH t o prevent 18. F . G . B ~ R D W E and L L B. P . PITT.J . Am. Chem. Soc.
recycling o f the acetic acid. 77,572 (1955).
 Mechanisms in the chlorinolysis of sulfinyl chlorides
TERENCEPATRICK
AHERN,MICHAEL FRANCIS HALEY,RICHARD FRANCIS LANGLER,'AND JUNEELLENTRENHOLM
Department of Chemistry, Mount Allison University, Sackville, N.B., Carlacla EOA 3C0
Received February l I , 1983'

TERENCE PATRICK AHERN,MICHAEL FRANCIS HALEY,RICHARD FRANCIS LANGLER, and JUNEELLENTRENHOLM. Can. J.
Chem. 62, 610 (1984).
The successful synthesis and chlorinolysis of a-mercaptodimethyl sulfone have provided additional support for our con-
tention that Pummerer rearrangements may occur during the chlorinolyses of a-sulfonyl sulfinyl chlorides. Further exploration
of chlorinolyses of a-sulfonyl systems has uncovered the first observations of CS bond cleavage during the chlorinolyses of
(i) a sulfinyl chloride and (ii) a sulfinate ester.

TERENCE PATRICK AHERN,MICHAEL FRANCIS HALEY,RICHARD FRANCIS LANGLER et JUNEELLENTRENHOLM. Can. J.

Chem. 62, 610 (1984).
Le fait que des a-mercaptodimCthylsulfones aient pu Stre chlorolysCes fournit une preuve additionnelle a notre suggestion
que des transpositions de Pummerer peuvent se produire lors de la chlorolyse de chlorures d'a-sulfonylsulfinyles. Une Ctude
plus poussCe de chlorolyses de systkmes a-sulfonyles a permis de mettre en Cvidence les premikres observations de rupture
de liaisons C-S au cours de chlorolyses (i) d'un chlorure de sulfinyle et (ii) d'un ester sulfinate.
[Traduit par le journal]

Introduction Attempts to deacetylate the sulfone-thiolacetate with

Some time ago ( I ) , we reported the results of a study on the H 2 0 / - O H , LiA1H4, or NaBH4 furnished complex mixtures a n d
were abandoned. The successful conversion of the sulfide-

-
chlorinolysis of the sulfone-sulfide 1 as shown in eq. [I].
thiolacetate into the corresponding sulfone-thiolacetate sug-
CIZ/HxO gests that acetyl groups m a y have use in protecting mercaptans
[I] PhCH2SCH2SOzCH3 CH3S02CC12SOzCI
HOAc when peroxidic oxidation of substrates is intended to alter other
+ PhCHzCl functional groups.
1 2 The successful synthesis of 3 d was accomplished as shown
Our proposal for the pathway of this reaction involved the in Eq. [3].
intermediacy of the sulfenyl chloride 3 a and the sulfinyl chlo- Pyridine
ride 3b. [3] CHzSOzCHzSSPh + PhSH -CH3SO2CH2SH
CH'Cll
+ (PhS)?
CH,.SOz.CH?.S.CI CH3.SOz.CHC1. SO. CI
3a 3b
The mercaptosulfone 3d appears to b e the first known
CH3.SOz.CHZ.S.S.Ph CH3.SOz.CHZ.S H a-mercaptosulfone. As expected on the basis of the properties
I 3c 3d of the corresponding a-mercaptosulfide 3 e (4), the oily mer-
captosulfone 3 d decomposed at room temperature depositing
crystalline material which was insoluble in all common organic
solvents (tl12= 6 days). W e presume that t h e crystalline mate-
Subsequently, we have undertaken the synthesis of a variety of rial was polymeric thioformaldehyde.
potential intermediates and intermediate precursors which re- Aqueous chlorinolysis of freshly prepared 3d produced the
sulted in the successful preparation of 3 c (2). Chlorinolysis of sulfone-sulfonyl chloride 2 in a reaction which must involve the
3c, as w e have pointed out (2), is very likely to produce 3a and sulfone-sulfenyl chloride 3a as shown in e q . [4].
does furnish the sulfone-sulfonyl chloride 2 as we had hoped.
We wished to pursue this problem further in the hope that w e
could establish the intervention of an unprecedented process in
[4] CH?SO2CH2SH -
CIz/H?O
HOAc
[CH3SOzCH?.SCI]
the chlorinolysis of sulfinyl chlorides, viz. facile Pummerer
rearrangement of a dichlorooxosulfonium cation (3a).

Results and discussion

Our initial efforts were focused on the preparation of the While the results shown in eq. [4] prove o u r contention that 3a
I
mercaptosulfone 3d. One of the earlier attempts is shown in would be transformed into 2 under the reaction conditions
employed for the reaction shown in eq. [I], thus confirming 3a
e q PI.

[2] CHzSCH2CI + AcSH -

Pyridine
CHzSCH2SAc
a s a possible intermediate for that reaction, further examination
of the pathway followed b y 3 a in this reaction would require
the and chlori~olysis("in an anhydrous medibm"
(2)) of other potential intermediates (e.g. t h e sulfone-sulfinyl
chloride 3b).
'Author to whom correspondence should be directed at: Department Earlv
- svnthetic
, efforts aimed at 3 c were unsuccessful until
of Chemistry and Chemical Engineering, Florida Institute of w e adopted an approach which accomplished skeletal mod-
Technology, 150 West University Boulevard, Melbourne, Florida ification using a chlorinolysis step followed b y a dechlorination
32901, U.S.A. step carried out on the appropriate ester. Consequently, w e
'Revision received September 23, 1983. began our efforts to produce the possible sulfone-sulfinyl chlo-
 AHERN ET AL. 61 1
..
..<,>\O
R-S,
R
I

larly prone to undergo CS bond rupture pursuant to oxo-

chlorosulfonium cation formation. Nucleophilic attack on the
oxochlorosulfonium cation at the a-carbon bearing chlorine is
usually the exclusive process. It is clear, however, that severe
steric hindrance at the a-carbon bearing chlorine can shift some
nucleophilic attack to the a'-carbon (9). A reasonably close
ride intermediates for the reaction in eq. [ I ] by preparing the sulfoxide relative of 4 has been shown to furnish 1 , l ,I-tri-
sulfone-sulfinate ester 5 as shown in eq. [5]. chloro-2-thiapropane-2,2-dioxide in good yield (9) (see
Scheme 3, pathway b).
In view of the results available from sulfoxide chlorinolyses,
the rupture of a CS bond during the chlorinolysis of 4, while

-CHZOH
CH,S02CCIZ. SO. OCH3
5
unprecedented, is not surprising. However, the results from the
chlorinolysis of the sulfone-sulfinate ester 5 are remarkable
indeed. Not only is the methyl group attached t o oxygen (the
usual electrophilic site in an 0-alkylated dioxochlorosulfonium
In addition to the spectroscopic evidence obtained for the struc- cation) much less crowded, but it bears a superior leaving
ture of 4, we have subjected it to hydrolysis which was accom- group, viz. 2 a s opposed to the C 1 . S 0 . 0 C H 3 attached to the
panied by desulfinylation as shown in eq. [6]. alternative electrophilic carbon. There can be n o question that
[6] CH3SO2CCl2.SO.CI + Hz0 + CHSOzCHClz the trichlorosulfone is an authentic chlorinolysis product since
4 6 (i) both hydrolysis and alcoholysis of the sulfinate ester 5
furnish the dichlorosulfone 6, (ii) hydrolysis o f the sulfonyl
This behaviour parallels that observed for the hydrolysis of 2 chloride 2 furnishes 6, and (iii) one- to two-hour chlorinolvsis
(1) and is entirely consistent with the intermediacy of a sulfin~c of simple sulfones like 6 affoids unchanged starting material
acid which has anion stabilizing groups on C ( l ) (5). (10).
While the chlorinolysis of sulfenate esters (vide eq. [5]) is W e were unaware of any examination of possible reactions
precedented (6, 7), previous groups were unable to isolate the between sulfinyl chlorides a n d molecular chlorine and were
expected sulfinyl chlorides. O u r conversion of 3f to 4 appears thus unable to judge whether the C S bond cleavage observed
to be the first report of the successful isolation of a sulfinyl during the chlorinolysis of the sulfinyl chloride 4 was a typical
chloride from a sulfenate ester chlorinolysis. Chlorinolysis of or unusual result. Consequently, we have prepared a series of
a sulfenate ester produces an 0-alkylated oxochlorosulfonium simple sulfinyl chlorides 7a --,7c and subjected them to chlo-
cation. Douglass and Poole (8) have produced 0-alkylated rinolysis in aprotic media.
oxochlorosulfonium cations by the alcoholysis of dichlorosul-
fonium cations. T h e two approaches for generating 0-alkylated
oxochlorosulfonium cations are depicted in Scheme 1 (X = : ).
0-Alkylated dioxochlorosulfonium cations may be produced
in similar manner (see Scheme 1; X = 0 ) . T h e usual fate of
0-alkylated dioxochlorosulfonium cations involves nucleo- T h e chlorinolysis of chloromethanesulfiny1 chloride3 70 in
philic attack at carbon with resultant C O bond cleavage (3b). methylene chloride produced unchanged sulfinyl chloride

- Clz
[7] PhCH2CHz. SO .OCH3 CH2C12 PhCHzCHzSOzCl + [CH3C1]
quantitatively. A second run conducted in carbon tetrachloride
showed no methylene chloride present in the product.
Chlorinolysis of methanesulfinyl chloride' 7b produced un-
Expecting to obtain the sulfonyl chloride 2, we have chlo- changed sulfinyl chloride along with a 13.5% yield of meth-
rinated the sulfinate ester 5 in order to obtain some simple anesulfonyl chloride, presumably arising from hydrolysis of
chemical support for the structure of 5 . The unexpected obser- the oxodichlorosulfonium cations by moisture present in the
vation of C S bond cleavage in the chlorinolysis of 5 prompted methylene chloride employed as solvent.
us to chlorinate the sulfinyl chloride 4 which furnished a similar
result, as shown in Scheme 2. Both chloromethansulfinyl chloride 7a and methanesulfinyl chlo-
C S bond cleavage is a well-known process in the chlo- ride 7 b were produced free of the corresponding sulfonyl chlorides
rinolysis of sulfoxides (3). a-Polychlorosulfoxides are particu- using our previously published method (1 I).
 CAN. J. CHEM. VOL. 62. 1984

The phenethyl sulfinyl chloride 7c employed in our study

was prepared by chlorinolysis of phenethyl thiolacetate fol-
lowing the procedure of Kee and Douglass ( 12). Hydrolysis of
a sample of 7c prepared in this way showed it to contain ca.
20% phenethyl sulfonyl chloride. Chlorinolysis of phenethyl
I sulfinyl chloride 7c did not furnish any phenethyl chloride. The
product was, in fact, ca. 50% 7c and ca. 50% phenethyl
sulfonyl chloride.
These results indicate that the CS bond cleavage observed
during the chlorinolysis of 4 is not a routine feature of sulfinyl
chloride chlorinolyses.
Since our initial report of CS bond cleavage during the
chlorinolyses of a-polychlorosulfoxides (13), we have been
concerned about the probability that a nucleophile would be
SCHEME 4
capable of attacking such severely hindered electrophilic car-
bon atoms. Our subsequent report (9) (see Scheme 2, Y = Ph)
in which the substantially more crowded electrophilic carbon
atoms in the sulfonium salts derived from a-sulfonyl-a-poly-
chlorosulfoxides appeared to suffer nucleophilic attack, albeit
more slowly, heightened our concern. In fact, on a number of The absence of dichlorosulfone in the product mixture (eq.
occasions, referees of our papers have suggested an alternative [8]) cannot be rationalized by assuming that it was quan-
mechanism for CS bond cleavage in these reactions (see titatively converted to trichlorosulfone under the reaction con-
Scheme 4). This mechanism would circumvent steric prob- ditions.
lems, although we have had serious reservations about the The results depicted in eq. [8] are of some interest. That
likelihood that the requisite ion pair formed in the cleavage step reaction is the first example of an a-polychlorosulfoxide chlo-
I
of Scheme 4 would actually form. In order to test this proposal rinolysis in which attack at the a'-carbon is the major pathway.
I we have carried out the following reaction. The absence of benzenesulfinyl or benzenesulfonyl chlorides in
I

I
[8] CH3S02 CC12.SO.Ph + CI2 I HCI -
CH2CI2
CH3SO2CCI,
the product mixture implicates the dichlorosulfone-sulfinyI
chloride as the intermediate leading to the trichlorosulfone.
Despite our dissatisfaction with the Scheme 4 mechanism, the
results from the chlorinolysis of the sulfinate ester 5, in our
view, require a more complex mechanism than the simple
The absence of the dichlorosulfone, which would arise from picture presented in Scheme 2. The revised mechanism would
proton capture by the carbanion pictured in Scheme 4, suggests apply to the cleavage steps in the chlorinolyses of all the
that this mechanism is an unlikely one. Because the reaction a-sulfonyl systems we have studied (vide Schemes 2 and 3). At
pictured in eq. [8] is very slow (chlorination time 8 h), we have this stage, the most reasonable modification of the cleavage
camed out a chlorination on 1,l-dichloro-2-thiapropane-2,2- step mechanism would likely involve a complexing interaction
dioxide. between the incoming chloride ion and the a-sulfonyl group.
 V ET AL. 613

Since we have recently initiated a program of theoretical chloride 2 (0.186 g) which was identical with authentic material ( I ) by
calculations designed to clarify mechanistic details for the var- ir, nmr, and tic.
ious steps of the Sulfohaloform reaction (see ref. 14, for exam- Hydrolysis of 2
ple), we shall defer a more detailed proposal for cleavage step The dichlorosulfone-sulfonyl chloride (0.186 g) obtained from the
transition states for a-sulfonyl substituted systems until sup- chlorinolysis of 3d (described above) was dissolved in water (I0 mL)
porting calculations can be carried out. and the reaction mixture refluxed for I h. Chloroform (200 mL) was
In conclusion, we have prepared and chlorinated a- added, and the mixture dried with MgS04 and filtered. The chloro-
mercaptodimethyl sulfone which has established that the sul- form was evaporated, affording clean dichloromethyl methyl sulfone
fenyl chloride 3a is transformed into 2 upon aqueous chlo- (0.072 g) which was identical to authentic material by ir, nmr, and
rinolysis, as w e had proposed earlier (1). The role of Pummerer mp (1).
rearrangements in the transformations involved in the con- Preparation of CH3SOZCC12.SO. C14
version 3a + 2 remains to be established. The chlorinolyses of The dichlorosulfone-sulfenateester 3f (2) (1.045 g) was dissolved
both the sulfinyl chloride 4 and the sulfinate ester 5 have in methylene chloride (25 mL) and Clz (ca. 200 mL/min) bubbled into
revealed unprecedented CS bond cleavage for these functional the reaction mixture for 0.5 h. The solvent was evaporated and the
crude residue recrystallized from CCI,, affording pale yellow crystals
groups, indicating a need to revise the simple mechanism ad-
of sulfone-sulfinyl chloride (0.637 g, mp 38-40°C). The sulfinyl
vanced previously for CS bond rupture during chlorinolysis of chloride 4 had ir (CHCI,): 1350, 1 166, and 1 175 c m - ' ; A,,,,, (hex-
a-sulfonyl sulfoxides (9). anes):' 226 (E 3 488), 274 (E 377); nrnr (CDCI,) 6: 3.36 (s); ms mle:
79 (35.5%) and 63 (100%). Anal. calcd. for CzH3CI,03SZ:C 9.78, H
Experimental 1.23; found: C 9.31, H 1.37.
General Preparation of CH.3S02CC12.S0 OCH.<5
Details have been provided previously (10). The sulfone-sulfinyl chloride 4 (I .003 g) was dissolved in methanol
Preparation of CH3SCH2SAc (25 mL) and the reaction mixture stirred at ambient temperature for
A solution of thioacetic S-acid (0.739 g) in dry pyridine (25 mL) 0.5 h. The solvent was evaporated, the residue dissolved in chloro-
was cooled and chloromethyl methyl sulfide (1.002 g) in carbon tet- form (5 mL), and the resultant mixture filtered. The chloroform was
rachloride (2 mL) was added dropwise over 3 min. The reaction evaporated and the residue crystallized from methanol, affording clean
mixture was stirred at ambient temperature for 1 h. Methylene chlo- 5 (0.820 g, mp 56-58°C). The product had ir (CHC13): 1345, 1200,
ride (100 mL) was added and the resultant solution washed with 5% and 1 150 cm- I; nrnr (CDCI,) 6: 3.33 (3H, s) and 4.10 (3H, s); ms
HC1 (100-mL aliquots) until the aqueous pH remained acidic. The m/e: 79 (100%) and 63 (27.8%). Anal. calcd. for C3H6CI2O4S2:C
organic layer was dried and concentrated and the residue distilled at 14.94, H 2.51; found: C 14.86, H 2.59.
reduced pressure, affording the sulfide-thiolacetate (0.544 g, bp Hydrolysis of CH3SOZCClr.S0 C 1 4 -
78-80"C/2.4 Torr); ir (CHCI,): 1695 cm-'; nrnr (CDCI,) 6: 4.13 The sulfinyl chloride 4 (0.985 g) was added to distilled water
(2H, s), 2.46 (3H, s), and 2.26 (3H, s); ms mle: 136 (M?, 35. I%), (10 mL) and the reaction mixture refluxed gently for 0.5 h. The reac-
61 (63.7%), and 43 (100%). tion mixture was homogeneous by the time reflux began. The reaction
Preparation of CH3S02CH2SAc mixture was cooled to room temperature and poured into chloroform
m-Chloroperoxybenzoic acid (85%, 3.145 g) was added to a cooled (300 mL). The chloroform was dried (MgS04) and concentrated,
solution of the sulfide-thiolacetate (1.002 g) in chloroform (30 mL). affording the dichlorosulfone 6 (0.535 g). After recrystallization, the
The reaction was allowed to reach ambient temperature while stirring dichlorosulfone 6 was shown to be identical with authentic material by
overnight. Methylene chloride (170 mL) was added and the resultant ir, nmr, mp, and mixture mp.
solution washed with 1% NaOH (two 50-mL aliquots). The organic -
Chlorinolysis of CH3S02CClz SO OCH.3 5
layer was dried and concentrated, affording clean sulfone-thiolacetate The sulfinate ester 5 (0.991 g) was dissolved in methylene chloride
(1.20 g); ir (CHCI,): 1720, 1320, and I 1 10 cm-'; nrnr (CDCI,) 6: (25 mL) and CIZ(ca. 200 mL/min) was bubbled into the solution for
4.50 (2H, s), 3.03 (3H, s), and 2.56 (3H, s); ms tnle: 168 (M?, 1 h. The solvent was evaporated and the residue recrystallized from
0.9%), 89 (13.6%), and 43 (100%). 95% ethanol, affording 1,l.l -trichloro-2-thiapropane-2,2-dioxide
Preparation of CH.qSOrCH2SH 3d (0.464 g) which was identical with authentic material by nmr, ir, mp,
The sulfone-disulfide 3c (0.200 g) (2) was dissolved in a solution and mixture mp.
containing methylene chloride (10 mL), pyridine (0.1 mL), and ben- Chlorinolysis of CH3S02CC12.SO. C14
zenethiol (0.200 g). The reaction mixture was stirred at ambient tem- The sulfinyl chloride 4 (1.000 g) was dissolved in methylene chlo-
perature for 2 h and the solvent evaporated. The residue was chro- ride (25 mL) and CI2 (ca. 200 mL/min) was bubbled into the reaction
matographed on silica gel (10 g) employing chloroform elution (5-mL mixture for 2 h. The solvent was evaporated. The residue was re-
fractions). Fractions 4 and 5 contained diphenyl disulfide and crystallized from 95% ethanol, affording 1,1,1-trichloro-2-thiapro-
unreacted benzenethiol. Fractions 7-13 contained oily a-mercapto- pane-2,2-dioxide (0.202 g) which was identical with authentic mate-
dimethyl sulfone 3d4 (0.078 g) which had ir (CHCI,): 2590, 1320, rial by ir, nmr, and ms. The mother liquor from the recrystallization
and 1125 cm-'; nrnr (CDCI,) 6: 3.83 (2H, d), 3.33 (3H, s), and 2.30 contained 1,l-dichloro-2-thiapropane-2,2-dioxide(0.210 g) and re-
( l H , t); ms m/e: 126 ( M I , 23.6%), 93 (24.7%), 81 (loo%), and 65 sidual trichlorosulfone (0.197 g).
(62.5%). Thus the sulfinyl chloride had been converted to the trichloro-
sulfone (50% yield) by the 2-hour chlorinolysis.
Aqueous chlorinolysis of 3d
Mercaptosulfone 3d (0.100 g) was dissolved in glacial acetic acid Preparation of PhCH2CHzSAc
(25 mL) and water (5 mL). C1, (ca. 200 mL/min) was bubbled into The mesylate of 2-phenyl ethanol (9.2278 g) and thioacetic S-acid
the reaction mixture for 0.5 h. Methylene chloride (I00 mL) and water (3.517 g) were added to dry pyridine (100 mL) and the reaction
(50 mL) were added and the layers separated. The organic layer was mixture stirred at ambient temperature for 7 days.' Chloroform (200
washed with 2.5% w/v sodium hydroxide solution (two 50-mL ali-
quot~),dried, and concentrated. The residue was the sulfone-sulfonyl 5Compare with CH,-SOsC1, A,, (hexane): 196 (E6 320) and 289
(E600) (15).
4Thi~ compound was too unstable for analysis, but its spectra pro- 6~ run terminated after 3 days at room temperature afforded a
vide unambiguous evidence for the structure. mixture of thiolester (75%) and unchanged mesylate (25%).
 614 CAN. J . CHEM. VOL. 62. 1984

mL) was added and the resultant mixture washed with 5% HCI dichlorosulfone-sulfoxide (0. I91 g) and 1.1-dichloro-Zthiapropane-
(100-mL aliquots) until the aqueous pH remained acidic. The organic 2,2-dioxide (0.038 g)."he identity of the dichlorosulfone was con-
layer was dried (MgS04) and concentrated. The residue was rectified firmed by addition of authentic material to the mixture, which in-
at reduced pressure, affording clean thiolester (5.096 g, bp creased the relative intensity of the appropriate signals in the nrnr
80-84"C/0.3 Torr). The product had ir (CHCI,): 1695 cm-'; nmr spectrum of the mixture.
(CDCI,) 6: 7.26 (5H. s), 3.00 (4H, m), and 2.30 (3H, s); ms nl/e: 180 Run 2
(M?, 3.8%), 104 (78.2%), 91 (36.9%). and 43 (100%). Anal. calcd. The dichlorosulfone-sulfoxide (0.5190 g) was dissolved in methy-
for Cl"HlzOS: C 66.62, H 6.70; found: C 66.83, H 6.74. lene chloride (50 mL). CIZ (ca. 300 mL/min) and HCI (ca. 100
Preparation of PhCHzCHL. SO CI 7c mL/min) were bubbled into the reaction mixture for 8 h. The reaction
C12 (ca. 200 mL/min) was bubbled into a solution of 2-phenethyl mixture was evaporated to ca. 20 mL. Gas chromatography carried out
thiolacetate (5.00 g) in acetic anhydride (2.83 g) for 0.5 h. The reac- on the solution indicated the presence of chlorobenzene (peak intensity
tion temperature was maintained just above the freezing point with an increased upon addition of authentic material). The solution was con-
acetone/Dry Ice bath as necessary. By the end of the reaction, the centrated. Nuclear magnetic resonance indicated a 1 : 1 mixture of
mixture had taken on a persistent orange color. The reaction mixture chlorobenzene (relative intensity of chlorobenzene signal increased
was concentrated in vacuo and the residue rectified, affording impure upon addition of authentic material) and I , ] , 1-trichloro-2-thiapro-
sulfinyl chloride (1.24 g, bp 128-130"C/0.5 Torr). The sulfinyl pane-2,2-dioxide. Reflux of the crude in water (10 mL) for 1 h did not
chloride7 had ir (CCI,): 1155 cm-'; nmr (CDCI,) 6: 7.30 (5H, s) and furnish any dichlorosulfone, indicating that the chlorinolysis had gone
3.45 (4H, m). to completion. Product was isolated by pouring the aqueous mixture
The purity of the sulfinyl chloride sample was established as fol- into methylene chloride (500 mL), drying (MgSO,), and concentrating
lows. A sample of the sulfinyl chloride (1.0 g) was added to a solution the organic phase. The residue was recrystallized from methanol,
of glacial acetic acid (25 mL) and water (5 mL) and the reaction affording 1,1,1-trichloro-2-thiapropane-2Jdioxide (0.17 14 g).
mixture stirred at ambient temperature for 0.5 h. Water (35 mL) was Chlorino1)~sisof CH.3SOzCHCIZ
added and the resultant mixture washed with chloroform (three 50-mL The dichlorosulfone (0.4799 g) was dissolved in methylene chlo-
aliquots). The combined organic extracts were washed with 2.5% ride (50 mL). C12 (ca. 300 mL/min) was bubbled into the reaction
NaOH (50-mL aliquots) until the aqueous pH remained basic. The mixture for 8 h and the solvent evaporated. The crystalline crude was
organic layer was dried (MgSO,) and concentrated. The residue was a mixture of 1 ,I-dichloro-2-thiapropane-2,2-dioxide(86%) and
2-phenethyl sulfonyl chloride (0.187 g) which was identical with au- 1,1,1-trichloro-2-thiapropane-2,2-dioxide (14%). Identity of the tri-
thentic material by ir and nmr. Thus the original sulfinyl chloride chlorosulfone was confirmed by the addition o f authentic material
sample was ca. 81% (by weight) sulfinyl chloride and 19% sulfonyl which increased the relative intensity of the appropriate signal in the
chloride.' nmr of the mixture.
Preparation of CH3 SO CI 7b and CICHz.SO. CI 7a
The sulfinyl chlorides 70 and 7b were prepared using our published Acknowledgements
procedures (I I). The sulfinyl chlorides prepared in this way were not The authors are indebted to Dr. J. H. Kim for running t h e
contaminated with the corresponding sulfonyl chlorides. mass spectra. W e are grateful to Dalhousie University a n d
Chlorinol)~sesof 7a, 7b, 7c Mount Allison University for financial support in the form o f
The appropriate sulfinyl chloride (I .O g) was dissolved in methy- grants from their respective Research Development Funds.
lene chl&ide-(25 mL) and CIz (ca. 200 m o m i n ) was bubbled into the
reaction mixture for 2 h. The solvent was evaporated. 1. W. R . HARDSTAFF, R. F. LANGLER, J . LEAHY,and M. J . NEW-
Chloromethane sulfinyl chloride 7a was recovered unchanged from MAN.Can. J . Chem. 53, 2664 (1975).
the chlorinolysis. 2. T. P. AHERN,R. F. LANGLER, and R. L. MCNEIL.Can. J . Chem.
Crude product from the chlorinolysis of 7c was subjected to hydrol- 58, 1996 (1980).
ysis in aqueous acetic acid as described under "Preparation of 3. (a) W. R. HARDSTAFF and R. F. LANGLER. In Sulfur in organic
and inorganic chemistry. Vol. 4. Edited by A. Senning. M.
PhCHzCHz.SO. C17c". Phenethyl sulfinyl chloride 7c was converted
Dekker, Inc., New York. 1982. p. 229; (b) p. 230.
into a mixture containing 7c (0.450 g) and phenethyl sulfonyl chloride
(0.536 e ) . 4. M. R. ALTAMURA, T. HASSELSTROM, and L. LONG, JR. J . Org.
~ e t h a n e s u l f i n ~chloride
l 7b was converted into a mixture of Chem. 28, 2438 (1963).
methanesulfinyl chloride (0.688 g) and methanesulfonyl chloride 5. C. M. STIRLING.Int. J . Sulfur Chem. Part B , 6, 277 (1971).
(0.158 g). 6. H. KWART,E. N. GIVENS,and C. J . COLLINS.J . Am. Chem.
SOC.91, 5532 (1969).
Chlorir~olysisof CHSO2CCIz .SO Ph 7. J. G. TRAYNHAM and A. W. FOSTER.J. Am. Chem. Soc. 93,
Run 1 6216 (1971).
The dichlorosulfone-sulfoxide (0.5582 g) was dissolved in methyl- 8. I. B. DOUGLASS and D. R. POOLE.J . Org. Chern. 22,536 (1957).
ene chloride (50 mL). Clz (ca. 200 mL/min) and HCI (ca. 200 9. D. G. KAY,R. F. LANGLER, and J . E. TRENHOLM. Can. J. Chem.
mL/min) were simultaneously bubbled into the reaction mixture for 57, 2185 (1979).
8 h. The solvent was evaporated. The crude contained no 10. J . S. GROSSERT and R. F. LANGLER. Can. J . Chem. 55, 407
1,l-dichloro-2-thiapropane-2,2-dioxide as indicated by nmr. The (1977).
I
~ crude product was chromatographed on silica gel (45 g) employing
carbon tetrachloride elution (thirty-one 50-mL fractions). Fractions
11. J . S. GROSSERT,W. R. HARDSTAFF,
Chem. 55, 421 (1977).
and R. F. LANGLER. Can. I.

13-20 were combined and concentrated, afford~ngI, I, l -trichloro- 12. M. L. KEE and I. B. DOUGLASS. Org. Prep. Proced. 2, 235
2-thiapropane-2,2-dioxide (0.0835 g) which was identical with au- (1 970).
thentic material by ir, nrnr, and mp. Further elution with chloroform 13. J . S. GROSSERTand R. F. LANGLER. Chem. Commun. 49 (1973).
(six 50-mL fractions) furnished a mixture of unchanged 14. J. L. GINSBURG and R. F. LANGLER. Can. J. Chem. 61, 589
- (1983).
7The ir indicated contaminating sulfonyl chloride was present. 15. R. F. LANGLER. Ph.D. Thesis, Dalhousie University. 1975.
Moderate intensity bands were present at 1385 and 1170 cm-'. 16. R. F. LANGLER. Can. J. Chem. 54, 498 (1976).
"here is little or no hydrolysis of sulfonyl chlorides under the
conditions employed. Such conditions permit the isolation of sulfonyl 9The origin of the dichlorosulfone was very likely from hydrolysis
chlorides in high yields (16). of sulfinyl chloride 4 present in the crude.
 The consequences of steric effects in the cleavage step of the sulfohaloform reaction

Dep(rrtmerrt ~$Cllctnistr?~, Utrioef-sity,HtrlV(i.v, N . S . , Crrtrotltt B3H 453

Doll~o~r.sie
Received Febluary 16, 1979

DENISGEORGEKAY, RICHARD FRANCISLANGLER, and JUNEELLENTRENHOLM. Can. J.

Chem. 57.2185 (1979).
The pathway for the aqueous chlorinolysis of a series of p-sulfonyl-sulfides is elucidated and
the SN2cleavage step examined. Steric effects in the cleavage of the a-polychloro-oxochloro-
sulfonium chloride intermediates are held to be responsible for the suppression of the estab-
lished nucleophilic competition between water molecules and chloride ions with the result that
all cleavage products arise from nucleophilic attack by chloride ions. This report details the
second known example of successful SN2displacement on a carbon atom ci to a sulfonyl group.

DENISGEORGE KAY,RICHARD FRANCIS LANGLER et JUNEELLENTRENHOLM. Can. .IChem.

.
57,2185 (1979).
On a etudit les chemins reactionnels impliques lors de la scission d'une serie de p-sulfonyl-
sulfures sous I'influence du chlore et on a examine l'etape de clivage SN2. On croit que des
effets steriques dans le clivage d'interrnkdiaires chlorure d'a-polychloro-0x0-chlorosulfoniurn
sont responsables de la suppression de la competition nucleophile bien etablie entre les mole-
cules d'eau et les ions chlorures qui donne lieu au fait que tous les produits de clivages provien-
nent d'une attaque nucleophile par les ions chlorures. Dans ce travail, on donne les dttails du
deuxieme exemple d'une substitution SN2reussie sur un atome de carbone en a d'un groupe
sulfonyle.
[Traduit par le journal]

Introduction TABLE1. * Relative percentages of oxo-

chlorosulfonium chloride cleavage by
As a part of our program to study the chlorination competing nucleophiles
of sulfur compounds (1-lo), we have recently
published details which support a generalized path- Nucleophile (%)
way for the conversion of dialkyl sulfides into Sulfoxide
sulfonyl chlorides (5). The generalized pathway was precursors Hz0 CI -
called the sulfohaloform reaction (vide Scheme 1).

R. S . CH,R'
(R = CH2R1)
- CIJH20
HOAc
R. S. CHCIR'

I
'Data calculated from previously published
results ( 5 ) .

furnish another a-polychlorosulfoxide. These com-

peting processes are presented for trichloronlethyl
methyl sulfoxide in Scheine 2.
low charts were detailed (5) defining the balance
SCHEME
1. The sulfohaloform reaction between the competing processes when the di- and
trichlorodimethyl sulfoxides were converted into
The intermediate cc-polychloro-oxochlorosulfo- methane and chloromethane sulfonyl chlorides.
nium chloride salts were shown (5) to undergo three Table 1 presents the relative percentages of the
competing processes, viz. (i) cleavage by nucleophilic cleavage products from the oxochlorosulfonium
attack of water molecules on the chlorine-bearing chloride salts2 (derived from the sulfoxides listed)
carbon cc to the sulfoniuln sulfur atom, (ii) cleavage induced by nucleophilic attack of water molecules
by nucleophilic attack on the same carbon atom by and chloride ions.
chloride ions, and (iii) Pummerer rearrangement to
'Structure A, Scheme 2 depicts the structure of an oxo-
'To whom all correspondence should be addressed. chlorosulfonium chloride salt.

0008-40421791162 185-06$01 .OO/O

0 1 9 7 9 National Research Council of CanadaIConseil national de recherches du Canada
 C A N . J . CHEM. VOL. 57, 1979

t
C 0 2 + HCI
SCHEME
2

From the data in Table 1, we have tentatively Later, the surprising report of Robson et al. (20)
inferred that increasing incorporation of bulky documented, without comment, the successful dis-
chlorine atoms in the oxochlorosulfonium chloride placeinent of the chlorine atom of chloroinethyl
intermediates hinders nucleophilic attack by water methyl sulfone by mercaptide anions. This reaction
molecules substantially more than nucleophilic attack was subsequently exploited for synthetic purposes
by chloride ions. I11 order t o test this point experi- (8, 21) and formed the basis for a more extensive
mentally, we have undertaken the preparation of investigation of nucleophilic displacen~entsinvolving
systems which would (i) provide even more crowded chlorinated sulfones and mercaptide anions (3).
a-polychloro-oxochlorosulfonium chloride interme- Furthermore, a n examination of space-filling models
diates and (ii) structurally preclude complicating convinced us that a mesyl group is very similar in
Pummerer rearrangements. We have chosen t o meet volume t o a tertiary butyl group and that the analogy
these objectives with substrates of the type shown of the mesylmethyl group with the neopentyl group,
below: first suggested and discarded by Bordwell (15), is a
0 very good one. It appeared, a t least tentatively, that
the assumption of nucleophilic repulsion by sulfonyl
oxygen atoms might be unnecessary t o account for
For some time, it was believed that leaving groups the known chemistry. In this connection, it is inter-
attached to a sulfonyl-bearing carbon atom could esting t o note that di-tert-butyl-methanesulfinyl
not be displaced (11-19). The lack of reactivity for chloride could not be converted t o the corresponding
these systems was ascribed to "the repulsion of the sulfonyl chloride, even under forcing conditions (22).
nucleophilic species by the negative field of the Such a n observation might well be a consequence of
sulfonyl oxygen atoms" (17). An examination of the crowding necessary t o introduce a bulky chloro-
models led t o the conclusion that a mesyl group3 sulfonyl group into an already crowded molecule.
would have "only a small steric effect, unless it is
assumed that the partial negative charge o n the Results and Discussion
oxygen atoms would greatly extend their effective Our previous study (5) established two modes of
radius" (1 5). behaviour for chlorosulfonium chloride salts gener-
ated in aqueous media, i.e., ( i ) dialkyl chlorosul-
3Mesyl is an abbreviation of methylsulfonyl. fonium chloride salts are very resistant t o hydrolysis
 K A Y ET A L .

TABLE
2. Chlorinolysis of 0.1 g CH3S02CH2SPh(la)

Volume
of CIz/HzO' CH3S02CH2SPh CH3S02CH2SOPh CH3SO2CHC1SOPh CH3SO2CCI2SOPh
(mL) (7,) (%I (%I (%I

* H 2 0 was saturated with CI2 at ambient temperature.

and react essentially exclusively by Pummerer re-
arrangement ( I b ) and ( i i ) a-chlorodialkyl chloro-
sulfonium chloride salts undergo quantitative hydro-
+
R. SOI,CHZCI HSR' - EtONa
EtOH
R . SO2,CHZSR1
lrr-6n

lysis with essentially no Pummerer rearrangement as

shown in Scheine 1 .
A priori, either reaction could be advanced as the
first step in the pathway for the aqueous chlorinolyses
of the sulfone-sulfides la-6a, since ( i ) the sulfonyl
methyl groups are substantially more electron with-
drawing than a chloromethyl group4 and therefore
should enhance the electrophilicity of the sulfonium
sulfur atom, thus facilitating hydrolysis of the
chlorosulfonium chloride salts derived from la-6a,
and (ii) the sulfonyl methyl groups greatly enhance
the acidity of the protons adjacent to the sulfonium 2 R = CH,, R' = pClPh
R. S02CCIf SO. R'
sulfur atom and consequently might be expected to lb-6b 3 R = CH,, R' = pCH,Ph
enhance the rate of the elimination step by which 4 R = Ph,R'= Ph
the sulfenium ion (Pummerer intermediate ( I b ) ) 5 R = Ph, R' = pClPh
6 R = Ph, R' = pCH,Ph
forms.
The results of a series of controlled chlorinolyses
of l a are presented in Table 2. These results establish HCl, hydrolyze, decarboxylate, and react with mole-
that the first formed chlorosulfonium chloride salt cular chlorine to furnish the appropriate sulfonyl
undergoes hydrolysis preferentially and that further chloride, e.g., this sequence in the case of l b would
products arise through the intermediacy of the result in the formation of methanesulfonyl chloride.
unchlorinated sulfone-sulfoxide. Larger amounts of In no case was there any detectable sulfone-derived
chlorine furnished the corresponding a,a-dichloro- sulfonyl chloride present in the product mixture.
sulfoxide l b . Scheme 3 presents the synthesis and Consequently the only nucleophiles to attack at the
pathway for the reactions which provided the central carbon atom in the oxochlorosulfonium
dichlorosulfone-sulfoxides lb-66. The structure of l b chlorides derived from lb-66 were chloride ions.
was confirmed by converting a sample into the Scheme 4 presents a rationale for the formation of
corresponding dichlorodisulfone ( I d ) . The disulfone the observed products.
Id was shown to be identical to a sample prepared
TABLE3. Yields* of sulfones and sulfonyl chlorides from
by oxidation of the dichlorosulfone-sulfide l c . exhaustive aqueous chlorinolyses of lb-66
Exhaustive chlorinolysis of the dichlorosulfone-
sulfoxides lb-66 furnished an equimolar mixture of Products
the appropriate trichloromethyl sulfone and sulfonyl
chloride shown in Table 3. Nucleophilic attack by RSOZCI R'SOZCCI3
water molecules at the carbon atom of the dichloro- Substrate (% yield) (% yield)
methylene group in the intermediate oxochloro- lb R = Ph (80) R' = CH3 (78)
sulfonium chloride would result in the formation of 26 R = pC1-Ph (80) R' = CH3 (80)
an intermediate hydroxydichloromethy1 sulfone. 36 R = pCH3Ph (75) R' = CH3 (83)
Such a compound would be expected to eliminate 46 R = Ph (86) R' = Ph (90)
56 R = pClPh (72) R' = Ph (78)
4Pauling electronegativities: X , (CICHZ) = 2.47, X, 66 R = pCH3Ph (83) R'=Ph (81)
(CH3SO2CHZ)= 2.85, and X, (PhSOzCHZ)= 2.75 (lb, 23). *For mechanism see Scheme 4.
2188 CAN. J . CHEM. VOL. 5 7 . 1979

R SO: CCIZ SO. R'

CIZIH,O
The successful displacement of the sulfinyl chloride
lh-611 group by chloride ions represents the second known
case of an S,2 displacement a to a sulfonyl group.
CI Both nucleophiles, viz. chloride ions and mercaptide
ions, which have been effective in accomplishing
these displacements involve third-row nucleophiles.
An intriguing possibility is that of a complexing inter-
action between these nucleophiles and the adjacent
sulfonyl sulfur atom. We have recently proposed
such an interaction in order to rationalize a novel
thiolester hydrolysis (la).
R ' SO. CI + R. SO, CCI, The chlorinolyses of the sulfone-sulfoxides 16-3b
resulted in the formation of a minor product (ca. 5%)
which gave rise to a singlet in the nmr of the crude
at 6 3.50. Thin layer chromatography, visualized
with NaI-acetone (7), showed the presence of a
compound at R,0.50. These properties are in accord
We have previously observed (5) a difference in with the presence of CH3S02CC12S02C1(7) which
the overall rate of reaction for the aqueous chlo- we have characterized previously (8). Furthermore,
rinolysis of chloromethyl phenyl sulfide (product: column chromatography furnished dichloromethyl
benzenesulfonyl chloride; relative rate: 1) and the methyl sulfone which was absent in the crude
aqueous chlorinolysis of chloromethyl methyl sulfide reaction mixture.
(product: methanesulfonyl chloride, relative rate: Dichloromethyl methyl sulfone is the known
6.5). The slower reaction for the phenyl sulfide was hydrolysis product obtained from CH3S02CC12-
attributed to an electron-donating effect from the S02Cl (3, 8). Chromatography has been shown to
phenyl group which would reduce the electrophilicity furnish substantial hydrolysis of a close structural
of the sulfonium sulfur atom in the oxochlorosul- relative of 7 (7).
fonium chloride intermediate. However, a com- It appears that the severe crowding in the oxo-
parison of the overall rate of the chlorinolysis of the chlorosulfonium chloride salts derived from lb-3b
mesyl dichlorosulfoxide l b , and the rate of chlo- has succeeded in diverting some nucleophilic attack
rinolysis of phenyl trichloromethyl sulfoxide (5) to the phenyl ring. Attack at the less crowded centre
indicates that l b reacts some 22.3 times slower. This would presumably be carried out by water molecules.
difference cannot be attributed to an electronic effect A rationale for this process is presented in Scheme 5.
originating with the phenyl group. One might then The preceding account details the first evidence that
examine the possible role ofthe mesyl group in terms nucleophilic attack can be diverted from the chlorine-
of the effect of sulfonyl oxygen atoms on approaching bearing carbon atom in the cleavage of a-polychloro-
nucleophiles, as outlined earlier. Clearly, if the oxochlorosulfonium chlorides.
sulfonyl oxygen atoms offer a 'negative field' they A consequence of the results reported in this paper
would repel incoming chloride ions much more than is that methylsulfonyl groups have potential applica-
incoming water molecules. Since cleavage by nucleo- tion in the design of molecules intended for the study
philic attack at the central carbon atom occurs of steric effects on chemical reactions. A feature
exclusively by the agency of chloride ions we con- worth noting is the great facility with which they
clude that the effect of the mesyl group is not a may be introduced into substrates, a feature which
special electronic effect but rather a more familiar they do not share with the ubiquitous tertiary butyl
steric effect. group. A potentially useful property of these groups
In order to determine the relative sizes of chloride is their destablization of nearby carbocationic
ions and water molecules, we have made accurate centres (24) which would permit studies of SN2
scaled drawings of each species. The somewhat cleavages without facilitating SN1 processes.
remarkable conclusion was that there is essentially In conclusion, a study of sulfonyl substituted
no difference in the cross-sectional area of a chloride a-polychlorosulfoxide chlorinations has shown that
ion and a water molecule. The most likely reason for the corresponding oxochlorosulfonium chlorides
the superior nucleophilicity of chloride ions lies with undergo cleavage in which steric factors favor
the greater polarizability of these nucleophiles. An nucleophilic attack by chloride ions and disfavor
interesting alternative or additional consideration nucleophilic attack by water molecules. The results
arises from an overview of SN2 displacements of obtained are inconsistent with the view that the
leaving groups a to sulfonyl groups. adjacent sulfonyl groups offer a 'negative field'
 KAY ET AL. 2189

PhSO,CH,SPh 40 (1 1.OO g, mp 56-58°C); ir (CHCI,): 1320

C H , S O , CCI,- S O ~ X and 1140 cm- ' ; nmr (CDCI,) 6: 7.66 (lOH, m) and 4.40 (2H,
16 X = H s); ms tn/e: 264 ( M f , 7.3%), 123 (loo%), and 45 (30%).
26 X = C1 p-C1PhSCH2S02Ph 5a (1 1.88 g, mp 67-69°C); ir (CHCI,) :
311 X = CH, 1320 and 1145 cm-'; nrnr (CDCI,) 6: 7.57 (9H, m) and 4.30
(2H, s); ms m/e: 300 (2.273, 298 ( M t , 6.673, 159 (33.373,
157 (loo%), and 45 (40%).
p-CH3PhSCH2S02Ph60 (1 I .10 g, mp 8345°C); ir (CHCI,):
1320 and 1145 cm-'; nrnr (CDCI,) 6 : 7.40 (9H, m), 4.30
(2H, s), and 2.26 (3H, s); rns m/e: 141 (58%), 91 (33%), and
77 (100%).
Prepmation of CH3S02CCI,SPh (Ic)
The sulfone-sulfide l a (1.000 g) was dissolved in carbon
tetrachloride (20 mL) and C12 (ca. 200 mL/min) was bubbled
into the solution for 20 min. The solvent was evaporated and
the residue recrystallized from 95% ethanol affording l c
(1.176 g, rnp 53-54°C); ir (CHCI,): 1320 and 1145 cm-I ; nmr
C H , SOz CCIy SO. CI + HO
[ ex] (CDCI,) 6: 7.66 (5H, m) and 3.50 (3H, s); ms tn/e: 195 (14%),
193 (69%), 191 (loo%), 109 (34x1, and 77 (44%).
Preparation of CH3S02CC12S02P/1(Id)
The dichlorosulfone-sulfide l c (0.5002 g) was oxidized with
chromium trioxide in glacial acetic acid in standard fashion
(3). The crude dichlorodisulfone was recrystallized from 95%
ethanol (0.276 g, mp 102-105°C); ir: 1355 and 1152cm-';
nmr (CDCI,) 6: 7.90 (5H, m) and 3.53 (3H, s); ms m/e: 141
(7373, 125 (41%), and 77 (100%).
which repels nucleophiles. Finally, the substantial Preparation of Dichlorosulfone-s~rlfoxirles(Ib-6b)
crowding achieved in the transition state has shifted The desired sulfone-sulfide (10-60) (5.00 g) was added to a
solution of glacial acetic acid (25 mL) and water (5 mL). C1,
a small amount of the nucleophilic attack t o the less (ca. 200 mL/min) was bubbled into the reaction mixture for
crowded carbon attached t o the sulfonium sulfur 0.5 h. During the chlorination the product precipitates from
atom. solution. Upon completion of the chlorination water (50 mL)
and methylene chloride (100 mL) were added. The layers were
Experimental separated and the organic layer washed with 2.5% w/v NaOH
(2 x 50 mL aliquots), dried (MgSO,), filtered, and the solvent
Getzero1
evaporated. The residue was recrystallized from 95% ethanol
Their spectra were recorded on a Perkin Elmer 237B grating
affording the following compounds.
spectrophotometer. The nmr spectra were obtained on a
CH3S02CC12~S0.Ph16 (5.284 g, mp 149-151°C); ir
Varian T-60 instrument using TMS as the internal standard.
(CHCI,): 1345, 1150, and lO8Ocm-'; nmr (CDCI,) 6: 7.77
The mass spectra were recorded on a Dupont-CEC model
(5H, m) and 3.46 (3H, s); ms tn/e: 290 (0.1%), 288 (0.6%),
21-104 mass spectrometer. The samples were directly intro-
286 ( M t , I%), 125 (loo%), 109 (3973, and 77 (43%). Anal.
duced using an all glass probe and the spectra run at 30 eV
calcd. for C8H8CI20,S2: C 33.45, H 2.80; found: C 33.07,
with a source temperature of 150°C. Melting points were
H 2.91.
determined on a Fisher-Johns melting point apparatus and
p-ClPhS(0)CC12S02CH3 26 (5.353 g, mp 8486°C); ir
are uncorrected.
(CHCI,): 1340, 1145, and 1080 cm-' ; nmr (CDCI,) 6: 7.73
Preparation of Suljbne-sulfides la-6a (4H, pseudo-quartet) and 3.50 (3H, s); ms nrle: 229 (2.2%),
Sodium metal (1 equiv.) was dissolved in absolute ethanol 227 (5.773, 225 (5.7%), 161 (33.373, and 159 (100%). Atiul.
(100 mL) and the appropriate mercaptan (1 equiv.) added. calcd. for CRH7ClaOaSz:
. . - C29.87. H 2.19; found: C29.95,
Chloromethyl phenyl sulfone (25) or chloromethyl methyl H 2.15.
sulfone (26) (10 g) was added and the reaction mixture refluxed p-CH,PhS(O)CCI,SO,CH, 36 (5.150 g, mp 145-147°C); ir
for 24 h. Water (100 mL) was added and the resultant mixture (CHCI,): 1345, 1150, and 1085 cm- ' ; nrnr (CDC13) 6: 7.73
was washed with chloroform (3 x 100 mL aliquots). The (4H, pseudo-quartet), 3.50 (3H, s), and 2.53 (3H, s); ms m/e:
organic layers were combined, dried (MgS04), filtered, con- 139 (loo%), 91 (27.5%), and 45 (12.5%). Anal. calcd. for
centrated, and the residue recrystallized from 95% ethanol. CeH10CIZ03S2: C 35.88, H 3.34; found: C 35.83, H 3.14.
CH3S02CH2SPh l a (9.413 g, mp 4749°C); ir (CHCI,): PhSO2CCI2,SO.Ph4b(4.894 g, mp 134136°C); ir (CHCI,):
1320 and 1145 cm-'; nrnr (CDCI,) 6: 7.36 (5H, m), 4.23 (2H, 1350, 1150, and 1 0 9 0 ~ m - ~nmr
; (CDCI,) 6: 7.80 (m); ms
s), and 2.93 (3H, s); ms tn/e: 202 ( M f , 4.7%), 123 (86%), and tnje: 141 (36%), 125 (64%), 109 (48.6%), and 77 (100%). Anal.
45 (100%). calcd. for C13HIOC1203S2: C44.70, H 2.88; found: C44.82,
p-C1PhSCH2SO2CH3 20 (15.88 g, rnp 105-106°C); ir H 2.57.
(CHCI,): 1320 and 1145cm-'; nmr (CDCI,) 6: 7.43 (4H, p-CiPhS(O)CCI2SO2Ph 5b (3.8708, mp 115-117°C); ir
pseudo-quartet), 4.17 (2H, s), and 2.97 (3H, s); ms tnle: 238 (CHCI,): 1350, 1150, and 1095 cm-'; nrnr (CDCI,) 6: 7.83
(1.8%), 236 (M+, 5.773159 (33.379157 (100%),and 45 (80%). (m); ms t~i/e:161 (33.373 159 (loo%), 141 (43.6%), and 77
p-CH3PhSCH2S02CH3 30 (14.67 g, mp 63.5-65°C); ir (65.9%). Anal. calcd. for Cl3H9CI3O3S2:C40.69, H 2.36;
(CHCI,): 1320 and 1140 cm-'; nmr (CDCI,) 6: 7.37 (4H, found: C 40.47, H 2.42.
pseudo-quartet), 4.20 (2H, s), 2.90 (3H, s), and 2.33 (3H, s); p-CH3PhS(0)CC1,S02Ph 6b (4.563 g, mp 140-141°C); ir
ms mle: 216 ( M t , 10.3%), 137 (loo%), and 45 (41.5%). (CHCI,): 1350, 1150, and 1095 cm-'; nmr (CDCI,) 6: 7.70
2 190 CAN. J. CHEM. VOL. 57, 1979

(9H, m) and 2.46 (3H, s); ms m/e: 139 (loo%), 91 (16.6%), and p-chlorobenzenesulfonyl chloride (0.262 g) which was identical
77 (26.8%). Anal. calcd. for Cl4Hl2ClZO3S2: C 46.28, H 3.32; to authentic material by ir, nmr, ms, and tlc. Fractions 40-60
found: C 46.01 and H 3.49. were combined and concentrated furnishing trichloromethyl
methyl sulfone (0.245 g) which was identical to authentic
Preparation of PII~SO~CH,SO,CH~ le material (27). Fraction 95 contained dichloromethyl methyl
The sulfone-sulfide l a (1.002 g) was dissolved in a solution sulfone (0.015 g) which was identical to authentic material by
of 30% H 2 0 z (0.568 g) in dioxane (25 mL). The reaction ir, nmr, and mp (27).
mixture was refluxed for 0.75 h. The solvent was evaporated
and the residue recrystallized from 95% ethanol, (0.815 g, mp Acknowledgements
88-90°C); ir (CHCI3): 1320, 1140, and 1045 cm-'; nmr
(CDC13)S:7.60(5H,s),4.20(1H,d,J= 3Hz),4.13 ( l H , d , The authors are indebted t o Dr. J. H. Kim for
J = 3 Hz) (26), and 3.23 (3H, s); ms tnle: 218 ( M i , 10.9%), running the mass spectra. We are grateful to Dal-
125 (loo%), 109 (23.1%), and 77 (32.9%). At~rrl.calcd. for housie University for financial support in the form
C8H1003S3:C 44.01, H 4.61 ; found: C 43.89, H 4.21.
of a grant from the Research Development Fund.
Cot~rrolledAqrreolrs Cl~lorit~ol~~sis
of l a
A series of chlorinolyses of l o were conducted and the 1. ((I)H. 0 . FONG.W. R. HARDSTAFF, D. G. KAY.R. F.
results are tabulated in Table 2. Details below are provided for L,INGLER,R . H. MORSL.and D. N . S A N D O V ACan. L . J.
the run from which products were isolated. Chem. 57. 1206 (1979); ( h ) T. P. AHERN.D. G. KAY.and
The sulfone-sulfide l a (0.100 g) was dissolved in glacial R. F. L A N G L L Can.
R . J. Chem. 56.2422 (1978).
acetic acid (75 mL) and distilled water (9 mL). Water (9 mL) 2. R. F. L A N G L E 2R., A. M A R I N and I . J. A. PINCOCK. Can. J.
which had been saturated with CIZ at ambient temperature Chem. 56.903 (1978).
was added and the reaction mixture stirred at room tempera- 3. R. F. L A N G L EiindR J. A. PINCOCK. Can. J. Chem. 55,2316
ture for 0.5 h. Water (150 mL) was added and the reaction (1977).
mixture washed with chloroform (300 mL). The organic layer 4. J. S . GROSSERT. W . R. HARDSTAFF, and R. F. LANGLER.
was washed with 2.5% w/v NaOH (3 x 100 mL aliquots), Can. J . Chem. 55,421 (1977).
dried, and concentrated. The residue showed four spots on 5. J. S. GROSSEK.~ iind R. F. L A N G L E Can. R . J. Chem. 55, 407
analytical tlc (chloroform development). The nmr of the crude (1977).
indicated the presence of l a (21%), the corresponding sulfone 6. R. F. L A N G L E Can.
R . J. Chem. 54,498 (1976).
0 7. J. R. J A R D I Niind
E R. F. L A N G L E J. R .Chromatogr. 116,211
/ (1976).
sulfoxide (le) (31%), CH3S02CHC1SPh (2173, and l b (26%). 8. W. R. HARDSTAFF, R. F . L A N G L E R J. , L E A H Yand
, M. J.
The mixture was run on preparative tlc, developed with NEWCIAN. Can. J. Chem. 53,2664 (1975).
CHCI3-Et20 (1 :I). The band at R, 0.27 was scraped and 9. J . S. GROSSERT, W. R. HAKDS.~AFF, and R. F. LANGLER.
washed with CHCI, (60 mL) affording l e which was identical Chem. Commun. 50(1973).
with authentic material by nmr, ir, and tlc. The band at R, 0.57 10. J. S. GROSSERT i~ndR. F. L A N G L E K Chem.
. Commun. 49
was handled in the same way and furnished a mixture of l a (1973).
and another compound. The identity of l a was confirmed by 1I. F. RASCHIG ilnd W. PRZHL. Justus Liebigs Ann. Chem. 448,
tlc and addition of authentic material which caused the 307 (1926).
expected change in the appropriate signals in the nmr of the 12. T . THOMSON i ~ n dT . S. STEVENS. J . Chem. Soc. 69 ( 1932).
mixture. Subtraction of the signals due to l o from the nmr of 13. W. M. ~ I E G L E Rand R. C O N N O RJ.. Am. Chem. SOC.62.
the mixture left the spectrum 6 : 7.50 (5H, m), 5.17 (IH, s), and 2596 (1940).
3.23 (3H, s). On this basis the second compound in the mixture 14. T . B. JOHNSON and I. B. DOUGLASS. J. Am. Chem. Soc. 63,
was assigned the monochlorosulfone-sulfoxide structure 1571 (1941).
shown above. The band at R, 0.81 was processed as described 15. F. G. B O R D W E LG. L D.
~ ~COOPER.
~ J. Am. Chem. Soc. 73,
above, and afforded l b which was identical with authentic 5184(1951).
material by nmr, ir, and tlc. 16. F. G. BORDWELL and W. T . B R A N N E J. N .Am. Chem. Soc.
86,4645 ( 1964).
Oxidation of l b 17. L. A. PAQUETTE. J. Am. Chem. Soc. 86.4085 (1964).
The dichlorosulfone-sulfoxide l b (0.500 g) was oxidized to 18. F. G. BORDWELL and B. JARVIS.J. O g . Chem. 33, 1182
the dichlorodisulfone I d in the same way described for the (1968).
oxidation of lc. After recrystallization, the disulfone (0.350 g) 19. M. C I N Q U I ND.I , L A N D I NandI , A . MAIA.Chem. Commun.
was shown to be identical to authentic disulfone by ir, nmr, 734 (1972).
mp, and mixture mp. 20. P. ROBSON, P. SPEAKMAN, iind D. STEWART. J.Chem. Soc.
Exl~austiveClllorit~ationof lb-6b C, 2180(1968).
Exhaustive chlorinations of the dichlorosulfone-sulfoxides 21. W. G. PHILLIPS and K. W. RATTS.J. Org. Chem. 36. 3145
lb-6b were carried out as illustrated by the details provided (1971).
below for the reaction on 2b. Results for these systems appear 22. J. BUTLERand R. M. KELLOGG. J. Org. - Chem. 42, 973
in Table 3. (1977).
The sulfone-sulfoxide 2b (0.500 g) was dissolved in glacial 23. J. E. H U H E E YJ.. Phys. Chem. 69. 3284 (1962): 70. 2086
acetic acid (75 mL) and water (18 mL) added. CI, (ca. 200 ( 1966).
mL/min) was bubbled into the reaction mixture for 8 h. Water 24. T. DURSTand F. DE REINACH-HIRTZBACH. Tetrahedron
(150 mL) was added and the resultant mixture washed with Lett. 3677 (1976).
methylene chloride (3 x 100 mL aliquots). The combined 25. P. P. DAVIS,J. S. GROSSERT, R. F. LANGLER, and W. S.
organic layers were washed with 2.5% w/v NaOH (3 x 100 mL MANTLE. Org. Mass Spectrom. 12.659 (1977).
aliquots). The organic layer was dried and concentrated. 26. W. R. HARDSTAFF and R. F. L A N G L E R 01.g.
. Mass Spec-
The residue was chromatographed on silica gel (50 g) em- trom. 10,215 (1975).
ploying carbon tetrachloride elution (50 mL aliquots). 27. W. E. T R U C EG. , H. B I R U Mand , E. T. MCBEE.J. Am.
Fractions 6 9 were combined and concentrated affording Chem. Soc. 74,3594 (1952).
 The sulfohaloform reaction revisited and revised
JAMESCLAYTONBAUM,WILLIAMRAYNEHARDSTAFF,RICHARDFRANCISLANGLER,'
A N D ANTHONY
MAKKINJE
Departtnent qf Chemistnj, Florida Institute of Technologj, Melbourtle, FL 32901, U . S . A .
Received November 20, 1983
JAMESCLAYTON BAUM,WILLIAM RAYNEHARDSTAFF, RICHARDFRANCIS LANGLER, and ANTHONY MAKKINJE. Can. J.
Chem. 62, 1687 (1984).
A study of the aqueous chlorinolyses of a series of benzylic dithioacetals along with related a-chlorobenzylic sulfides is
reported. These results require a modification of our previously proposed sulfohaloform reaction, so that thionium ion
intermediates which have at least one alkyl group on sp2 carbon follow a different pathway.

JAMESCLAYTON
BAUM,WILLIAM RICHARDFRANCIS
RAYNEHARDSTAFF, LANGLER
et ANTHONY
MAKKINJE.
Can. J. Chem.
62, 1687 (1984).
On rapporte une Ctude sur la chloronolyse, en milieu aqueux, d'une serie de dithioacktals benzyliques et des sulfures
a-chlorobenzyliques apparentCs. Pour expliquer ces rCsultats, il faut modifier le micanisme de reaction sulfohaloformique que
nous avons proposi antkrieurement de facon B ce que les ions thionium intermediaires qui portent au moins un groupe alkyle
sur le carbone sp2 suivent une voie diffkrente.
[Traduit par le journal]
Introduction C1
Some time ago, we published an examination of the pathway
followed by dialkyl sulfides upon chlorinolysis in aqueous ace-
tic acid ( I ) . The study involved a detailed examination of
sulfides and led to a proposed general pathway which we called
the sulfohaloform reaction. W e have subsequently carried out +
studies on the regiochemistry of the first step in aprotic media RSCH2Cl t R.S=CH2 + HCI + Cl-
(2, 3) as well as an examination of steric effects in the cleavage
step (4) in aqueous acetic acid.
The first step in the sulfohaloform pathway is believed to
proceed as shown in Scheme 1. The proposed intermediacy of
a-chloro-chlorosulfonium cations (derived from a-chloro- aqueous chlorinolyses. Such species, if hydrolyzed, would
sulfides) in the sulfohaloform reaction rested on the following give rise to a-hydroxy sulfides which could dissociate to fur-
evidence: the chlorinolysis of the corresponding chlorine-free nish phenylmethanethiol which would be transformed into
sulfoxides furnished different products from those obtained by phenylmethanesulfonyl chloride in aqueous acetic acid satur-
chlorinolysis of the chlorine-free sulfides, thus ruling out sulf- ated with C12. On the other hand, if they undergo exclusive
oxides as the first formed intermediates. The disturbing feature nucleophilic attack by chloride ions, the intermediate
of the original proposal is the apparent inability of the thionium a-chlorosulfide would be transformed into the corresponding
ion2 intermediates, formed in the second step, to undergo hy- a-chlorosulfonyl chloride and benzyl chloride (8).
drolysis. Simple alkyl benzylic sulfides are ruled out as precursors
W e have subsequently developed benzylic sulfides as pre- since (i) they appear to undergo dissociation into sulfenyl chlo-
cursors for sulfonyl chlorides (8). While we did not establish rides and benzyl cations after chlorosulfonium cation formation
whether aqueous chlorinolysis of benzylic sulfides proceeds by (8), and (ii) any thionium ion intermediates would form by
SN1dissociation of the intermediate chlorosulfonium cations or abstraction of a benzylic proton rather than abstraction of a
by the intermediacy of the corresponding sulfoxides with uni- proton from the alkylated a-carbon (2, 3).
molecular dissociation of the corresponding oxochlorosulfon- T o circumvent these problems we have decided to employ
ium cations, we did demonstrate that these reactions proceed some dithioacetals, B, as precursors. Such substrates are
without Pummerer rearrangement (see Scheme 1 ). W e decided
to generate benzylic thioniums ions, A, in order to determine
whether they have any tendency to hydrolyze during exhaustive
I
+ /R1 R2
PhCH2S=C B
R
'2
known to cleave pursuant to chlorosulfonium cation formation
A
(9). The corresponding S-hydroxysulfonium sulfides are also
known to dissociate in a parallel process (10). The expected
' Author to whom correspondence should be addressed. mechanism for thionium ion formation is shown in Scheme 2.
'Durst et a / . have called R .SO CHR an oxosulfenium ion 15).
. . We
have called RSCHR a sulfenium ion (6) while Trost et a / . call it a Results and discussion
thionium ion (7). A referee of this paper has pointed out that the term
sulfenium ion has also been applied to RS'. To avoid confusion we T o begin our study of the simplest system, we have prepared
shall refer to the first two species as oxothionium and thionium ions and chlorinated benzyl chloromethyl sulfide, which gave re-
respectively. sults consistent with our previous report (8):
 C A N . I. C H E M . VOL. 62, 1984

Volume of Volume of Volume of

Clz/H20" Cl2/HOAcT HOAC (PhCH2S)I (PhCH2S)>CHCH1 PhCHrSOrCl PhCH2CI PhCH,OAc
(mL) (mL) (mL) (%I (%I (%I
10 - 50 8.8 69.2 - - -

10 25 25 10.1 17.8 30.9 18.0 20.6

10 50 - - - 52.0 24.5 26.5
" H 2 0 was saturated with CI, at ambient temperature.
t HOAc was saturated with C12 at ambient temperature

HOAc
[I] PhCH2SH + CH20 HC1 + PhCH2SCH2C1 [4] PhCH2SCHCICH, + C12/H20 PhCH2SOrCI

C12IH2O
--------+
HOAc
PhCH2C1 + ClCH2S02Cl These results suggest the intermediacy of the thionium ion
(38%) (54%) derived from 6 via unimolecular dissociation followed by hy-
drolysis prior to reaction with Clz. Since we were concerned
that significant hydrolysis may have occurred before the intro-
duction of CI,, and because we wished to learn more about the
course of the conversion of 6 + 4, we have undertaken a series
of partial chlorinolyses of 6 in which chlorine was introduced
before the sulfide. The results of this series of partial chlor-
We have, subsequently, subjected bis(thiobenzy1)methane to inolyses are presented in Table 1, and show that a-alkyl-a-
exhaustive aqueous chlorinolysis which furnished the results chlorosulfides dissociate to form chlorine-free thionium ions
shown in eq. [2] (in aqueous acetic acid) faster than they react with limited
amounts of Clz to furnish chlorosulfonium cations, clearly rul-
ing out a-chloro-chlorosulfonium cations as principal inter-
mediates in the chlorinolysis of dialkyl sulfides.
While it remains unclear whether a-chlorosulfides intervene
in these reactions, it is clear that hydrolysis of the chlorine-free
thionium ion is the principal pathway by which the reactions
proceed.
To complete our study of these systems we have chlorinated
the dithioketal 7 as depicted in eq. [5].
The results shown in eq. [2] are in complete accord with our
previous results on methyl sulfides as well as with our ex- C12/H20
pectation that dithioacetals will dissociate to furnish thionium [5] (PhCH2S)2C(CH,)r 2- PhCH2SOzCl
HOAc
ions and sulfenyl chlorides following chlorosulfonium cation
formation (vide Scheme 2). We note that these results (i) sup-
port our past proposal (1) that unsubstituted thionium ions react The change in behaviour of unalkylated thionium ions vs.
with chloride ions in preference to water molecules, (ii) offer alkylated thionium ions vis-B-vis hydrolysis could have been
further support to Wilson's proposal (I 1) that thionium ions are anticipated on the grounds that alkyl groups are more electron
intermediates in the chlorinolyses of simple sulfides, and (iii) releasing than hydrogen atoms. In order to see whether selected
offer additional support to our contention (2) that thionium ions thionium ions have gas phase stabilities which parallel their
are unable to isomerize to the more stable regioisomeric thio- ease of formation in solution, or whether solvent effects must
nium ions under normal conditions (2, 6). be invoked to rationalize the apparently greater facility of al-
We then chlorinated 1,I-bis(thiobenzy1)ethane 5 (eq. [3]) kylated thionium ion formation, we have undertaken a modest
and a-chloroethyl benzyl sulfide 6 (eq. [4]). MNDO study of the appropriate species A,'

'We intend the present MNDO study to supplement the one we

have recently published (6).
 BAUM ET A L

TABLE2. MNDO heats of formation and substituent effects on energetics of thionium ion formation

Sulfides AHc (kcal/mol) Thionium ions A H f (kcal/mol) AAHf AAHr

TABLE3. MNDO results on selected thionium ions substituted thionium ion for chloride ions over water mole-
cules, is compatible with our MNDO results. Scheme 3
AHr a Bond a Electron presents our conclusions about the pathway followed by dialkyl
Thionium ion (kcal/mol) order CS population S sulfides upon exhaustive aqueous chlorinolysis.
The original version of the sulfohaloform reaction (1) was
based on an extrapolation of detailed study of aqueous chlo-
rinolyses of a-polychloromethyl sulfides and sulfoxides. The
first intermediate for this reaction is shown in eq. [8] (X = Cl).

MNDO calculations - method and results

Computations on a selected series of thionium ions and their
corresponding sulfides were done using the MNDO (Modified
Neglect of Differential Overlap) semi-empirical method de- Since that time, similar behaviour has been observed for sul-
scribed previously (6). Geometries were fully optimized except fides bearing an a-sulfonyl group (4) or two a-fluorine atoms
that the phenyl rings were constrained to be planar, with equal (12). Parallel behaviour has also been suggested for sulfides
C-C bond lengths, C-H bond lengths, and 120" HCC and bearing an a-carboxyl group (13). The intermediacy of the
CCC bond angles. corresponding sulfoxide in the aqueous chlorinolysis of a sul-
The calculated heats of formation for the compounds studied fide is clearly the result of hydrolysis of the first formed chlo-
are listed in Table 2. The AHf's are consistent with our earlier rosulfonium cation (depicted in Scheme 1). The hydrolysis is
results (6) except that the sulfide geometry is slightly more evidently faster than the competing elimination reaction which
stable (0.2 kcal) with the Ph-C bond trans, instead of cis, to would otherwise produce a thionium ion.
The 5 - c ~bond ~ in benzyl methyl sulfide. This added sta- We conclude that aqueous chlorinolysis of sulfides is not as
bility for the phenyl-substituted sulfides increases with alkyl simple as originally proposed. The following facts have
substitution. The important point is that the stability of the emerged: (i) highly electronegative substituents attached to an
phenyl-substituted thionium ion increases with alkylation of the a-carbon in the sulfide substrate accelerate hydrolysis of the
sp2carbon, as indicated by the decreasing AHf's. first formed chlorosulfonium chloride salt leading to formation
The CS .rr bond orders and .rr electron populations at S are of a sulfoxide, (ii) sulfides without strongly electronegative
tabulated for the thionium ions in Table 3. As the thionium ion a-groups form thionium ions which react preferentially with
stability increases, the .rr bond order decreases and the .rr elec- the chloride counter ions leading to formation of an
tron population at S increases. These trends agree with our a-chlorosulfide, and (iii) the presence of inductive stabilizers
previous calculations (6) and indicate that the electron- (i.e., alkyl groups) on sp2carbon results in the intermediacy of
releasing alkyl substituent is acting through the thionium ion .rr thionium ions which hydrolyze. Scheme 4 presents this more
system to stabilize the system. complex array of pathways as The Revised Sulfohaloform
Reaction.
Mechanistic and pathway conclusions
The calculated AH, values for the appropriate sulfides and Experimental
the corresponding thionium ions (see Table 2) permit one to Aqueous chlorinolysis of I
obtain AAH, values for the reaction shown in eq. [6] relative to Crude benzyl chloromethyl sulfide (6.935 g) (14) was dissolved in
the reaction in eq. [7]. glacial acetic acid (25 mL) and water (3 mL). Clz (ca. 200 mL/min)
was bubbled into the reaction mixture for 2 h. The reaction mixture
was maintained between 20 and 30°C with an ice/water bath as nec-
[6] ZYCHSCHZPH + ZYC = kH2Ph + fi essary. Methylene chloride (100 mL) and water (50 mL) were added
and the layers separated. The organic layer was washed with 2.5%
w/v sodium hydroxide (two 50-mL aliquots). The organic layer was
dried (MgS04) and concentrated, affording a crude mixture which
Calculated AAH, results, reflecting the impact on thionium ion contained phenylmethanesulfonyl chloride (0.728 g) , chloro-
I
energetics of progressively incoprorating methyl groups on sp2 methanesulfonyl chloride (3.182 g), benzyl chloride (1.930 g), and
benzyl acetate (0.970 g). The bulk of the phenylmethanesulfonyl
carbon, are presented in Table 2. These results indicate that chloride crystallized from the crude and was filtered off. It was shown
solvent effects, while potentially important, do not need to be to be identical to authentic material by ir, nmr, and tlc.
invoked to make calculated gas phase stabilities compatible The filtered concentrated crude was chromatographed on silica gel
with our solution phase results. The higher presumed inherent (400 g) employing carbon tetrachloride elution (100-mL fractions).
reactivity of A (R' = R' = H) over the other thionium ions, Fractions 12- 18 were concentrated and combined, affording benzyl
previously advanced to rationalize the preference for the un- chloride which was identical to authentic material by nmr, ir, and tlc.
 CAN. J. CHEM. VOL. 62. 1984

-
C121H20 I
RCH~~CH~R' HOAc RCH2SCH2R'
Y
+ :CI:
( R , R = alkyl)

Fractions 37-40 were concentrated and combined, affording clean (50 mL). HCI (ca. 200 mL/min) was bubbled into the reaction mixture
chloromethanesulfony1 chloride which was identical with authentic for 1 h. The solvent was evaporated and the residue rectified at re-
material by ir and nmr. duced pressure, affording PhCH2SCHCICH3 (3.847 g. bp 92-93OC/
Aqueous chlorinolvsis of 3 0.9 Torr) which had nrnr (CDCI,) 6: 1.86 (3H. d). 3.90 (2H, s), 4.96
( I H , q), and 7.33 (5H, s); msmle: 188 (5.8%), 186(M:, 17.6%). 151
Bis(thiobenzy1)methane 3 (5.007 g) was suspended in glacial acetic
acid (25 mL) and water (5 mL). The reaction mixture was chlorinated (25%), and 91 (!00%).
and worked up as described above. Phcnylmethanesulfonyl chloride Exhaustive aqueous chlorinolysis of 6
(1.394 g) crystallized from the crude and was shown to be identical The chlorosulfide (5.0160 g) was added to glacial acetic acid (25
with authentic material by mp, ir, and nmr. mL) and water (5 mL). The reaction mixture was chlorinated and
The filtered concentrated crude mixture was rectified at reduced worked up as described above. An nrnr of the crude showed no
pressure, affording a mixture (bp 120- 130°C/ 100 Torr) ( 1 Tom = observable a-chloroethanesulfonyl chloride present. 'The residue was
133.3 Pa) which contained chloromethanesulfonyl chloride (1.532 g), crystallized from carbon tetrachloride, affording phenylmethanesul-
benzyl acetate (0.289 g), and benzyl chloride (1.729 g). The identity fonyl chloride (3.747 g) which was identical with authentic material
of the components was established by the addition of authentic com- by ir, nmr, mp, and mixture mp.
pounds which, in each case, increased the intensity of the expected
signals in the nmr spectrum of the mixture. Controlled aqueorrs chlorinolysis of 6
A series of chlorinolyses of 6 were conducted. The results are
Aqueous chlorinol~ysisof 5 presented in Table 1. Details below are provided for the second run.
I , I-Bis(thiobenzy1)ethane 5 (5.002 g) was added to glacial acetic Water (10 mL) was saturated with Clz at ambient temperature.
acid (25 mL) and water (5 mL). The reaction mixture was chlorinated Glacial acetic acid (25 mL) was saturated with C12 at room tem-
and worked up as described above. The residue (5.050 g) was shown perature. The chlorosulfide 6 (1.0084 g) was added to the CI2/H20,
to be identical to authentic phenylmethanesulfonyl chloride by nmr, HOAc/CI2, and glacial acetic acid (25 mL) and the reaction mixture
tlc, and mp. stirred at ambient temperature for 0.5 h. Water (50 mL) was added and
Preparation of PhCHZSCH=CH2 the resultant mixture bashed with chloroform (three 75-mL aliquots).
Sodium metal (0.8025 g) was dissolved in refluxing 2-propanol (30 The combined organic layers were washed with 2.5% w/v sodium
mL). A solution of PhCHzSCHzCHzCl(6.038 g) (15) in 2-propanol hydroxide (four 50-mL aliquots). The organic layer was dried and
(30 mL) was added and the reaction mixture refluxed for 1 h. Water concentrated, affording a residue which contained benzyl acetate
(60 mL) was added and the resultant mixture washed with chloroform (0.164 g), phenylmethanesulfonyl chloride (0.3 1 16 g), benzyl
(four 60-mL portions). The combined organic layers were dried and chloride (0.1205 g), dibenzyl disulfide (0.066 g). and 1.1-bis(thio-
concentrated. The residue was rectified at reduced pressure, affording benzy1)ethane (0.129 g).
clean benzyl vinyl sulfide (3.166 g, bp 52-56"C/0.4 Torr) which had The crude residue was chromatographed on silica gel (100 g) em-
ir (CHCI,): 1585 cm-'; nrnr (CDCI3) 6: 3.86 (2H, s), 5.20 ( I H, d, J,,, ploying carbon tetrachloride elution (100-mL fractions). Fraction 4
2 15 HZ), 5.26 ( I H , d , J I 1 HZ), 6.36 (1H. 4, J A x = 15 HZ, JBX contained benzyl chloride and dibenzyl disulfide. The presence of
= 11 Hz); Cmr (CDCI,) 6: 35.71, 1 1 1.01, 126.73, 128.10, 128.34,
benzyl chloride was confirmed by the addition of authentic material
131.66, 136.75; ms tn/e: 150 (M:, 28.6%) and 91 (100%). and observing the change in intensity of the appropriate signals in the
nrnr spectrum of the mixture. Fraction 5 afforded clean dibenzyl
Preparation of 6 disulfide which was identical to authentic material by ir, nmr, and tlc.
Benzyl vinyl sulfide (5.006 g) was dissolved in carbon tetrachloride Fractions 6- 10 were combined and concentrated, affording
 BAUM ET AL.

SCHEME4. The reviscd sulfohaloforrn reaction

I, I-bis(thiobenzyl)cthane which was identical with authentic material 3. J. R. HANCOCK,W. R. HARDSTAFF, P. A. JOHNS,R. F. LAN-
by ir, nmr, and tlc. Fractions 13- 18 were combined and concentrated, GLER, and W. S. MANTLE.Can. J . Chern. 61, 1472 (1983).
affording phenylrnethanesulfonyl chloride which was identical to au- 4. D. G. KAY,R. F. LANGLER, and J . E. TRENHOLM. Can J. Chern.
thentic material by ir, nmr, and tlc. Fraction 31 was combined with a 57, 2185 (1979).
final elution with diethyl ether (400 rnL). Upon concentration of this 5. T. DURST,K. C. T I N ,and M. J . V. MARCIL.Can J. Chem. 51,
eluent, benzyl acetate was obtaincd which was identical with authentic 1704 ( 1973).
material by ir, nmr, and tlc. 6. J. L. GINSBURGand R . F. LANGLER.Can J . Chern. 61, 589
(1983).
Aqueous chlorinolysis of 7 7. 9. M. TROST, M. VAULTIER,and M. L. SANTIAGO.J . Am.
2,2-Bis(thiobenzy1)propane (1.0190 g) was added to glacial acetic Chern. Soc. 102, 7029 ( 1 980).
acid (50 rnL) and water (10 mL). The reaction mixture was chlorinated 8. R. F. LANGLER. Can J . Chern. 54, 498 (1976).
and worked up as described above, furnishing clean crystalline 9. H. BOHMEand H. GRAN.Justus Licbigs Ann. Chern. 577, 68
phenylrnethancsulfonyl chloride (1.1948 g). (1952).
10. R. KUHNand F. A. NEUGEBAUER. Ber. Dtsch. Chern. Ges. 94,
Acknowledgments 2629 (1961).
T h e authors are indebted to Dr. J. H. K i m w h o ran the mass l I . G. E. WILSON,JR. and M. G. HUANG.J. Org. Chern. 35, 3002
spectra and Dr. D. L. Hooper w h o ran the I3C n m r spectrum. (1970).
W e are grateful to Mount Allison University for financial sup- 12. G. G. 1. Moore. J. Org. Chem. 44, 1708 (1979).
port in the early stages o f the work and t o the Florida Institute 13. R. F. LANGLER,Z. A. MARINI,and E. S. SPALDING. Can. J.
Chem. 57, 3193 (1979).
of Technology for financial support in the latter stages o f the
14. L. A. PAQUEITE, L. S. WI~TENBROOK, and K. SCHREIBER. J.
work and for the use o f F.I.T. computing facilities. Org. Chern. 33, 1080 (1968).
15. H. 0 . FONG,W. R. HARDSTAFF, D. G. KAY,R . F. LANGLER, R.
1. J . S. GROSSERTand R. F. LANGLER.Can. J . Chern. 55, 407 H. MORSE, and D. N. SANDOVAL. Can. J . Chem. 57, 1206
I ( 1977). (1979).
I
2. T . P. AHERN,D. G. KAY,and R. F. LANGLER.
Can. J . Chern. 56,
2422 (1978).