Improved selective synthesis of (Z)- and (E)-1,2-bis(phenylsulfonyl)-chloroethylene

Article abstract of DOI:10.1081/SCC-100000175

The preparation of the title compounds (Z)- and (E)-1, which are synthetic substitutes for the unstable bis(phenylsulfonyl) acetylene and key reagents for the asymmetric preparation of polycyclic ketones, has been revisited and improved. Starting from inexpensive materials such as trichloroethylene, thiophenol, and hydrogen peroxide, (Z)- and (E)-1 are selectively obtained in multigram quantity in 52% overall yields.

Full text of DOI:10.1081/SCC-100000175

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IMPROVED SELECTIVE SYNTHESIS OF (Z)- AND (E)-1,2-
BIS(PHENYLSULFONYL)-CHLOROETHYLENE
Sergio Cossu a , Ottorino De Lucchi a , Paola Peluso a & Raffaella Volpicelli a
a Dipartimento di Chimica , Università Ca' Foscari di Venezia , Dorsoduro 2137, Venezia,
I-30123, Italy
Published online: 09 Nov 2006.
To cite this article: Sergio Cossu , Ottorino De Lucchi , Paola Peluso & Raffaella Volpicelli (2001) IMPROVED SELECTIVE
SYNTHESIS OF (Z)- AND (E)-1,2-BIS(PHENYLSULFONYL)-CHLOROETHYLENE, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 31:1, 27-32, DOI: 10.1081/SCC-100000175
To link to this article: http://dx.doi.org/10.1081/SCC-100000175
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SYNTHETIC COMMUNICATIONS, 31(1), 27–32 (2001)
IMPROVED SELECTIVE SYNTHESIS OF
(Z)- AND (E)-1,2-BIS(PHENYLSULFONYL)-
CHLOROETHYLENE
Sergio Cossu,∗ Ottorino De Lucchi, Paola Peluso,
and Raffaella Volpicelli
Dipartimento di Chimica, Universita` Ca’ Foscari di
Venezia, Dorsoduro 2137, I-30123 Venezia, Italy
ABSTRACT
The preparation of the title compounds (Z)- and (E)-1, which
are synthetic substitutes for the unstable bis(phenylsulfonyl)
acetylene and key reagents for the asymmetric preparation of poly-
cyclic ketones, has been revisited and improved. Starting from inex-
pensive materials such as trichloroethylene, thiophenol, and hydro-
gen peroxide, (Z)- and (E)-1 are selectively obtained in multigram
quantity in 52% overall yields.
(Z)- and (E)-Bis(phenylsulfonyl)chloroethylenes (1) are powerful dieno-
philes (1) and synthetic equivalents of the unstable bis(phenylsulfonyl)acetylene
in Diels-Alder cycloadditions (2). The dehydrochlorinated cycloadducts of 1 are
useful precursors of a variety of symmetric polycyclic hydrocarbons and of their
alkyl and aryl substituted derivatives (1,2). Furthermore, the same compounds
are used in the asymmetric synthesis of enantiopure polycyclic ketones, that
in turn are key intermediates in the synthesis of a number of natural and
∗ To whom correspondence should be addressed. E-mail: cossu@unive.it
27
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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COSSU ET AL.
Scheme 1.
biologically active compounds (antibiotics, AZT derivatives, anticancer drugs)
(3,4).
Due to their usefulness and the need for large quantities, we here report a
large-scale preparation of these reagents that replaces the former first synthesis
reported several years ago by Modena and Montanari (5,6). Indeed, the original
methodology needed to be adjusted for preparation of larger quantities of material
and especially optimized to overcome the problem of the facile isomerization of
the (E)- to the (Z)-isomers in the final steps of the synthesis.
Because it is not possible to introduce in a single step the two sulfur residues,
the preparation of (Z)- and (E)-1,2-bis(phenylsulfonyl)chloroethylene (1) requires
a well-defined reaction sequence that entails a double thiophenol addition (as the
sodium salt) and two oxidation steps as depicted in Scheme 1. Careful control of
the reaction conditions is fundamental to obtain the final products with good regio
and stereoselectivity and in high yields. Particularly crucial are the oxidation steps
from 2 to 3 and from 4 to (E)-1 and the transformation of 3 into 4.
The reaction of thiophenol with trichloroethylene leads to the thioether 2
in 63–71% yield after distillation. This compound is oxidized to 3 with hydrogen
peroxide in acetic acid in the presence of sulfuric acid (see Experimental section).
Under the described reaction conditions, pure product 3 is obtained as a crystalline
solid in 86–91% yield merely by adding water to the crude reaction mixture. The
transformation of 3 into 4 is strongly influenced by the solvent, the concentration,
the nature of the base, and the temperature. Using different reaction conditions
and a different solvent (ethanol as an example), the formation of a mixture of
acetalic and thiacetalic derivatives formed through competitive reaction pathways,
as depicted in Scheme 2, takes place (7).
In view of this fact, the reaction is performed by adding a methanolic solution
of less than the equivalent amount of sodium thiophenate to a methanolic solution

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(Z)- AND (E)-1,2-BIS(PHENYLSULFONYL)CHLOROETHYLENE
29
Scheme 2.
of 3, then cooling at 0◦C for 12–14 hrs. Under these conditions, compound 4
separates by crystallization during the reaction. It should be noted that, if the
reaction is carried out at room temperature, cis-trans isomerization of 3 takes place.
The subsequent oxidation of 4 to (E)-1 is performed as previously described for the
oxidation of 2. Also, in this case, the optimized reaction conditions allows for the
recovery of the oxidized compound (E)-1 simply on cooling the reaction mixture.
The exposure of a dichloromethane solution of (E)-1, containing a few crystals of
iodine, to a 250-Watt halogen lamp for 48 hr allows for the clean preparation of
the corresponding (Z)-1 isomer.
EXPERIMENTAL
Melting points are uncorrected and were determined with a Bu¨chi 535 ap-
paratus. 1H NMR spectra were recorded on a Varian Unity 400 spectrometer op-
erating at 400 MHz, using tatramethylsilane as an internal standard. 13C NMR
spectra were recorded with a Brucker AC200 spectrometer operating at 50 MHz.
IR spectra were performed on a Perkin Elmer 2400 spectrophotometer.
(E)-1,2-Dichlorophenylthioethylene (2)
Sodium metal (23 g, l g atom) is added in portions to 700 mL of absolute
ethanol (CAUTION! exothermic reaction with evolution of hydrogen) contained
into a 2-L, three-necked, round-bottomed flask equipped with mechanical stirrer,
reflux condenser, and dropping funnel. After 3–4 h, or when the hydrogen evolution
subsides, thiophenol (89.6 mL, 96.14 g, 0.873 mol, d = 1.073) is added dropwise
during 1 h. The resulting solution is stirred at room temperature for an additional
hour, treated with 1,1,2-trichloroethylene (89.9 mL, 131.39 g, 1 mol, d = 1.46),
and stirred at reflux temperature for 12 h by means of a preheated oil bath. During
this time, sodium chloride separates as a white powder. The resulting clear orange

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COSSU ET AL.
reaction mixture is cooled to room temperature and most of the ethanol is removed
by rotoevaporation under reduced pressure. The resulting concentrated solution is
treated with water (200 mL) and extracted with diethyl ether (3 × 70 mL). The
combined ethereal solutions are washed with water (3 × 100 mL) and with brine
(100 mL) and dried (Na2SO4). Evaporation of the solvent leads to an orange
oil (CAUTION! vesicant compound), which is purified by distillation at 86◦C,
0.5 mm Hg (lit.:5 bp 136–8◦C, 16 mm Hg) to give 130 g (63% yield) of a pale
yellow oil.
1H NMR (400 MHz, CDCl3), δ, ppm: 6.65 (1H, s), 6.77–7.20 (5H, m, Ar).
13C NMR (50 MHz, CDCl3, 1C atom omitted), δ, ppm: 120.4, 128.6, 129.2, 130.5,
132.4. IR (neat), νmax, cm−1: 3057, 1581, 1559, 1476, 1439, 1215, 1090, 1024,
913, 823, 742, 640. Anal. Calcd for C8H6Cl2S: C, 46.85; H, 2.95. Found: C, 46.64;
H, 3.07.
(E)-1,2-Dichlorophenylsulfonylethylene (3)
A 1-L, three-necked, round-bottomed flask equipped with magnetic stirrer,
reflux condenser, and dropping funnel is charged with crude (E)-1,2-dichlorophe-
nylthioethylene (98.0 g, 0.48 mol), glacial acetic acid (200 mL), 36% hydrogen
peroxide (10 mL), and sulfuric acid (4 mL). While being stirred vigorously, the
reaction mixture is heated to 80◦C. After an induction period that can last from
seconds to minutes, the reaction takes place with a strong exothermicity that causes
the solution to reflux. More hydrogen peroxide (170 mL) is added in portions (3–
5 mL each) during 3 h and the mixture is kept stirring at 100◦C for 2 h and
for an additional 12 h at 80◦C in a pre-heated oil bath. The reaction mixture is
cooled to room temperature and colorless crystals are separated. Water is added
(ca. 300 mL), and the solid is filtered through a sintered glass funnel and washed
with water and brine until neutrality (98 g, 86.5% yield). The solid is recrystallized
from petroleum ether: mp 71–72◦C (lit. (5): mp 70–72◦C).
1H NMR (400 MHz, CDCl3), δ, ppm: 6.43 (1H, s), 6.95–7.75 (5H, m,
Ar). 13C NMR (50 MHz, CDCl3), δ, ppm: 120.2, 128.3, 129.1, 129.8, 131.7,
134.5, 138.2, 143.4. IR (KBr), νmax, cm−1: 3047, 1575, 1475, 1446, 1329, 1221,
1157, 1085, 997, 913, 756, 660, 645, 579. Anal. Calcd for C8H6Cl2O2S: C, 40.53;
H, 2.55. Found: C, 40.74; H, 2.81.
(E)-1-Chloro-1-phenylsulfonyl-2-phenylthioethylene (4)
A sodium thiophenate solution, freshly prepared from sodium (9.27 g,
0.4 g atom) in methanol (400 mL) and thiophenol (44.60 g, 41.57 mL, 0.40 mol)
as described for 2, is added dropwise during 12 h, to a stirred and ice-cooled

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(Z)- AND (E)-1,2-BIS(PHENYLSULFONYL)CHLOROETHYLENE
31
suspension of (E)-1,2-dichlorophenylsulfonylethylene 3 (96.7 g, 0.41 mol) in dry
methanol (200 mL) under argon. The resulting mixture is stirred at 0◦C for 12 h
and the precipitated solid is filtered through a sintered glass funnel [92 g, 80%
yield, mp 97–98◦C (methanol) (lit.:5 mp 96–98◦C from ligroin)] The volume of
the methanolic solution is reduced to ca. 100 mL by rotoevaporation at reduced
pressure and 0◦C and another amount of precipitate (21 g, 18% yield) is collected
as above.
1H NMR (400 MHz, CDCl3), δ, ppm: 6.76 (1H, s), 6.80–7.75 (10H, series of
m, Ar). 13C NMR (50 MHz, CDCl3), δ, ppm: 120.5, 128.3, 128.71, 129.1, 129.2,
129.7, 131.8, 134.4, 134.4, 138.2, 143.0 IR (KBr), νmax, cm−1: 3057, 3012, 1583,
1532, 1479, 1446, 1439, 1325, 1308, 1151, 939, 844, 818, 727, 684, 646, 572.
Anal. Calcd for C14H11ClO2S2: C, 54.10; H, 3.57. Found: C, 53.92; H, 3.70.
(E)-1,2-Bis(phenylsulfonyl)chloroethylene (1)
A 1-L, three-necked, round-bottomed flask equipped with magnetic stirrer,
reflux condenser, and dropping funnel is charged with the crude (E)-1-chloro-
1-phenylsulfonyl-2-phenylthioethylene (91.9 g, 0.268 mol), glacial acetic acid
(400 mL), 36% hydrogen peroxide (10 mL), and sulfuric acid (10 mL). While
being stirred vigorously, the reaction mixture is heated to 80◦C. After an induction
period that can last from seconds to minutes, the reaction takes place with a strong
exothermicity that causes the solution to reflux. More hydrogen peroxide (140 mL)
is cautiously added in portions (3–5 mL each) during 3 h and the mixture is kept
stirring in an oil bath at 100◦C for 2 h and at 80◦C for additional 12 h. The reaction
mixture is cooled to room temperature and the colorless crystals are separated.
Water is added to the mother liquors (ca. 300 mL) and the precipitated solid
is filtered and washed with water. The combined product is recrystallized from
absolute ethanol: 89 g, 96.7% yield, mp 136–7◦C (lit. (6): mp 136–7◦C).
1H NMR (400 MHz, CDCl3), δ, ppm: 7.20 (1H, s), 7.55–7.81, 8.01–8.17
(10H, series of m, Ar). 13C NMR (50 MHz, CDCl3), δ, ppm: 128.4, 129.3, 129.4,
129.8, 134.4, 135.3, 136.2, 139.7, 140.4, 144.6. IR (KBr), νmax, cm−1: 3097, 3072,
1580, 1568, 1550, 1472, 1444, 1392, 1352, 1329, 1312, 1257, 1173, 1164, 1130,
1082, 911, 807, 781, 759, 729, 716, 868, 635, 580. Anal. Calcd for C14H11ClO4S2:
C, 49.05; H, 3.23. Found: C, 49.32; H, 3.40.
(Z)-1,2-Bis(phenylsulfonyl)chloroethylene (1)
A saturated solution of (E)-1,2-bis(phenylsulfonyl)chloroethylene (20 g,
0.058 mol), dichloromethane (40 mL) containing iodine (ca. 50 mg or up to a
dark-colored solution) is exposed to a 250-Watt halogen lamp at room temperature.

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COSSU ET AL.
After 48 h of exposure, the solvent is distilled off at reduced pressure and the
solid is recrystallized from ethanol: 20.0 g (quantitative yield) mp 132–3◦C
(lit. (6): mp 132–3◦C).
1H NMR (400 MHz, CDCl3), δ, ppm: 7.50–7.81, 7.83–7.92 (11H, series of
m, 10Ar and 1 vinyl.). 13C NMR (50 MHz, CDCl3, 1C atom omitted), δ, ppm:
128.3, 129.5, 129.6 (2C), 134.0, 135.0, 135.3, 138.7, 139.6. IR (KBr), νmax, cm−1
:
3095, 3070, 1470, 1358, 1329, 1256, 1184, 1164, 1130, 803, 760, 730, 869, 634,
582. Anal. Calcd for C14H11ClO4S2: C, 49.05; H, 3.23. Found: C, 49.25; H, 3.36.
ACKNOWLEDGMENT
Thanks are due to Mr. A. Canu of the University of Sassari for the microan-
alytical determinations. Work co-funded by MURST (Rome) within the national
project “Stereoselezione in Sintesi Organica. Metodologie e Applicazioni.”
REFERENCES
1. Azzena, U.; Cossu, S.; De Lucchi, O.; Melloni, G. Tetrahedron Lett. 1989, 30,
1845.
2. Cossu, S.; De Lucchi, O. Gazz. Chim. It. 1990, 120, 569.
3. Cossu, S.; De Lucchi, O.; Pasetto, P. Angew. Chem. Int. Ed. Engl. 1997, 36,
1504.
4. Cossu, S.; De Lucchi, O.; Peluso, P.; Volpicelli, R. Tetrahedron Lett. 1999, 40,
8705.
5. Modena, G.; Montanari, F. Gazz. Chim. It. 1956, 86, 432.
6. Montanari, F.; Negrini, A. Gazz. Chim. It. 1957, 87, 1069.
7. Cossu, S.; De Lucchi, O.; Fabris, F.; Ballini, R.; Bosica, G. Synthesis 1996,
1481.
Received in the U.K. January 18, 2000

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