Synthesis of novel trithiocarbonate-S-oxides

Article abstract of DOI:10.1080/714040954

The oxidation of the trithiocarbonates 3 with m-chloroperoxybenzoic acid (m-CPBA) in chloroform at room temperature provides an efficient stereoselective synthesis of the (E) sulfine 4_a and (Z) sulfine 4_b. The expected (E) and (Z) co

Full text of DOI:10.1080/714040954

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Synthesis of Novel Trithiocarbonate-S-Oxides
I. El-Sayed a , K. M. H. Hilmy a , S. M. El-Kousy a , A. Fischer b & H. S. Slem a
a Menoufia University, Shebin El-Kom, Egypt
b Royal Institute of Technology, Stockholm, Sweden
Published online: 18 Jun 2010.
To cite this article: I. El-Sayed , K. M. H. Hilmy , S. M. El-Kousy , A. Fischer & H. S. Slem (2003) Synthesis of Novel
Trithiocarbonate-S-Oxides, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:11, 2403-2413, DOI:
10.1080/714040954
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Phosphorus, Sulfur, and Silicon, 178:2403–2413, 2003
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500390235352
SYNTHESIS OF NOVEL
TRITHIOCARBONATE-S-OXIDES
I. El-Sayed,a K. M. H. Hilmy,a S. M. El-Kousy,a A. Fischer,b
and H. S. Slema
Menoufia University, Shebin El-Kom, Egypta and Royal
Institute of Technology, Stockholm, Swedenb
(Received March 21, 2003; accepted May 26, 2003)
The oxidation of the trithiocarbonates 3 with m-chloroperoxybenzoic
acid (m-CPBA) in chloroform at room temperature provides an effi-
cient stereoselective synthesis of the (E) sulfine 4a and (Z) sulfine 4b.
The expected (E) and (Z) configurations of 4a,b were confirmed by x-ray
structure determination. The Sulfines 4 were further structurally eluci-
dated by their cycloaddition reactions with 2,3-dimethyl-1,3-butadiene
in chloroform at room temperature to give the corresponding dihydroth-
iopyran S-oxides 5a,b in a quantitative yield.
Keywords: Chlorodithioformates; dihydrothiopyran-S-oxide; oxida-
tion; sulfines; trithiocarbonate
>
Sulfines 1 are important heterocumulenes with a C S O moiety. Ex-
tensive studies of these thiocarbonyl oxides were carried out by the
group of B. Zwanenburg1−4 in the 1970s. In spite of recent studies by
other groups,5−25 sulfine chemistry, in particularly the synthetic appli-
cations of sulfine, has yet to be fully exploited.
Sulfines are synthesized via several synthetic pathways. The most
two versatile routes to these sulfur-centered heterocumulenes are the
oxidation of thiocarbonyl-containing compounds with peracids, and the
alkylidenation of sulfur dioxide by means of α-silyl carbanions.3,4
The purpose of the work presented in this article is to extend the
chemistry of chlorodithioformates 2. Another intriguing point to be ad-
>
dressed is the question of the relative reactivities of the C S double
bonds of the starting 2 and the corresponding sulfine 4. The present
work also quantifies the steric demands of the R1S and R2S groups
Partial financial support from DANIDA at the Danish Ministry of Foreign Affairs is
highly appreciated.
Address correspondence to K. M. H. Hilmy, Chemistry Department, Faculty of Science,
Menoufia University, Shebin El-Kom, Egypt. E-mail: khaledhilmy@hotmail.com
2403

2404
I. El-Sayed et al.
of 3 and their competition for the E- and Z-positions in the resulted
sulfines 4, and examines the selective oxidation of trithiocarbonates, a
compound which contains three oxidizable sulfur atoms.
RESULTS AND DISCUSSIONS
The starting unsymmetrical diaryltrithiocarbonates 3 were prepared
by the reaction of arylchlorodithioformates 2 with p-chlorothiophenol
in the presence of NaOH according to (1) in 90% yields.
(1)
The 13C NMR signal of the C S group of 3 resonates at 224 ppm for
>
3a and at 216.53 ppm for 3b lower field shift compared with the starting
chlorodithioformates 1 which resonate at 198.10 for 1a and 189.50 ppm
for 1b respectively.
The oxidation of trithiocarbonates 3 with m-chloroperbenzoic acid (m-
CPBA) at 0◦C in chloroform for 1 h affords the corresponding sulfines
4 in quantitative yields with a high chemoselectivity according to (2).
The crude material of the yellow sulfines 4 was analyzed by NMR which
showed that the oxidation of the thiocarbonyl group was stereo selective
and mainly a single isomer was formed. No evidence for the oxidation of
the other sulfur atoms of 3 was detected when the crude material was
(2)

Trithiocarbonate-S-Oxides
2405
FIGURE 1 The molecular structure of sulfine 4a with 50% probability ellip-
soids. Crystal system: orthorhombic, space group: P n a 21, unit cell dimensions
3
˚
˚
(A): a = 26.1600, b = 6.9700, c = 15.3300, Cell volume: 2795.2 (A ), RAll = 0.068.
˚
Selected geometric parameters (A): S2 O35 = 1.45, S2 C7 = 1.632, S4 C7 =
1.734, S4 C8 = 1.735, S6 C7 = 1.720, S6 C14 = 1.776; C8 S4 C7 = 104.99,
C7 S2 O35 = 110.93, S2 C7 S6 = 113.04, C7 S6 C14 = 103.71, S4 C7 S6
= 128.16, S2 C7 S4 = 117.76.
carefully inspected by the NMR. It should be noted that the E-sulfine
isomer is predominantly obtained in case of sulfine 4a according to x-ray
structure determination (Figure 1) which reveals that oxygen delivery
occurs opposite to the more bulky aryl group, where as in case of sulfine
4b the oxygen atom located cis to the bulky pentachlorophenyl group.
Namely it prefers Z-geometry according to x-ray structure determina-
tion (Figure 3).
>
The quaternary ( C S O) carbon of the sulfines 4 exhibited an up
field shift of 187.00 ppm for 4a and 181.00 ppm for 4b, respectively, in
13
>
C NMR, up field from the corresponding ( C S) group of the starting
thiocarbonyl compounds 3 (224.00 ppm for 3a and 216.53 ppm for 3b)
respectively. This shift was found to be within the range reported for
other sulfines (176–196 ppm).
Moreover, the strong IR absorption at 1110 and 1088 cm−1 for 4a, and
at 1115 and 1095 cm−1 for 4b can be attributed to the ( C S O) group
>
for the corresponding sulfines 4a and 4b respectively. It should be noted
that the sulfines 4 can be kept without alteration for months at ambi-
ent temperature in contrast to other reported sulfines.1 Also 4 can be
purified by column chromatography on silica gel or by crystallization.
The stability of Z-sulfine 4b is not configurationally stable in CDCl3

2406
I. El-Sayed et al.
solution at 80◦C. Because of isomerization to (E) and (Z) mixtures af-
ter 8 hours in (1:1) ratio according to (3), while sulfine 4a remains
stable (unchanged). Thus (E) and (Z) isomers of 4b have relatively
close thermodynamic stabilities. The isomerization mechanism is not
yet clear and is not observed with sulfines derived from thioketones26
or thionoesters.27
(3)
This observation revealed that the kinetic isomer is not the one which
>
has the oxygen atom on the less hindered side of the C S double bond,
(i.e. The kinetic oxidation has taken place on the more hindered position
of the thiocarbonyl sulfur). While the thermodynamically stable isomer
is the one which has the oxygen on the opposite side of the bulky group.
>
The non-linearity of the C S O system of 4a was established by
∗
>
a single crystal x-ray structure determination (Figure 1). The C S
and S O bonds were found to be 1.632 and 1.45 A, respectively, while
˚
◦
>
the C S O angle was found to be 110.93 . The sulfine exhibits a
nonplanar arrangement with the oxygen atom located trans to the
p-chlorophenyl group. The dihedral angle between the planes of the
sulfine group and the p-chlorophenylthio group is 103.71◦, demonstrat-
ing a nonplanar arrangement around the C(7) S(6) bond. The sulfine
moiety π-plane and the p-chlorophenylthio group are arranged per-
pendicular to each other, where the bulky parachlorophenylthio group
hinders the sulfine moiety to adopt a position in the same plane as the
p-chlorophenyl ring.
\
>
Also, the non-linearity of the C S O system of 4a was estab-
lished by a single crystal x-ray structure∗ determination (Figure 2). The
˚
>
C S and S O bonds were found to be 1.618 and 1.483 A, respectively,
◦
>
while the C S O angle was found to be 111.59 . The sulfine exhibits
a nonplanar arrangement with the oxygen atom located trans to the
p-chlorophenyl group. The dihedral angle between the planes of the
sulfine group and the p-chlorophenyl group is 102.99◦, demonstrat-
ing a nonplanar arrangement around the C(34) S(5) bond. The sulfine
∗The crystallographic data has been deposited at the Cambridge Crystallographic
Data Center, U.K.

Trithiocarbonate-S-Oxides
2407
FIGURE 2 The molecular structure of sulfine 4a with 50% probability ellip-
soids. Crystal system: orthorhombic, space group: P n a 21, unit cell dimensions
˚
˚
(A): a = 26.1600, b = 6.9700, c = 15.3300, Cell volume: 2795.2 (A), RAll = 0.068.
˚
Selected geometric parameters (A): S3 O36 = 1.483, S3 C34 = 1.618, S5 C34
= 1.704, S5 C28 = 1.784, S1 C34 = 1.719, S1 C25 = 1.775; C34 S3 O36 =
111.59, S1 C34 S3 = 113.25, C25 S1 C34 = 102.99, S1 C34 S5 = 118.29,
C28 S5 C34 = 104.17, S5 C34 S3 = 128.71.
moiety π-plane and the p-chlorophenylthio group are arranged
perpendicular to each other, where the bulky chlorophenyl group
hinders the sulfine moiety to adopt a position in the same plane as
the p-chlorophenyl ring. This may explain that the oxygen atom was
>
introduced to the more hindered side of the C S double bond, namely
that of pentachlorophenylthio group. This might be a new example
of π-stacking, taking place between the pentachlorophenyl nuclei of
the trithiocarbonate and the electrophilic (m-CPBA) as shown in the
structure below.

2408
I. El-Sayed et al.
FIGURE 3 The molecular structure of sulfine 4b with 50% probability ellip-
soids. Crystal system: monoclinic, space group: P 1 21/n 1, unit cell dimensions
(A): a = 10.614, b = 12.995, c = 13.381, = 112.14◦, Cell volume: 1709.54, R
˚
ꢀ
All
˚
= 0.086. Selected geometric parameters (A): S1 C13 = 1.738, S1 C1 = 1.761,
S3 C13 = 1.752, S3 C7 = 1.777, S2 O1 = 1.467, S2 C13 = 1.642, C13 S1 C1
= 99.72, C13 S3 C7 = 103.34, O1 S2 C13 = 113.88, S2 C13 S1 = 119.57,
S2 C13 S3 = 112.32, S1 C13 S3 = 127.14.
>
The nonlinearity of the C S O system of 4b was established by a
>
single crystal x-ray structure determination (Figure 3). The C S and
˚
S O bonds were found to be 1.642 and 1.4◦67 A, respectively, while
>
the C S O angle was found to be 113.88 . The sulfine exhibits a
non-planar arrangement with the oxygen atom located cis to the pen-
tachlorophenyl group. The dihedral angle between the planes of the
sulfine group and the pentachlorophenyl group is 99.72◦, demonstrat-
ing a nonplanar arrangement around the C(13) S(1) bond. The sulfine
moiety π-plane and the pentachlorophenylthio group are arranged per-
pendicular to each other, where the bulky group hinders the sulfine
moiety to adopt a position in the same plane as the p-chlorophenyl ring.
The sulfines 4 were further structurally elucidated by their cycload-
dition reactions with 2,3-dimethyl-1,3-butadiene in chloroform at room

Trithiocarbonate-S-Oxides
2409
temperature. The corresponding Diels-Alder adducts 5 were formed in
nearly quantitative yield according to (4) with the formation of two
isomers as concluded from the NMR spectra of the crude product.
(4)
A 13C NMR signal of the thiocarbonyl carbon of 4 shifted to a higher
field and became tertiary in the corresponding adducts 5 and splits
into two signals owing to the nonplanarity of the sulfoxide moiety in
dihydrothiopyran-S-oxides 5. An attempt to isolate both isomers has
been failed due to spontaneous decomposition on silica gel.
EXPERIMENTAL
All 1H and 13C NMR experiments (solvent CDCl3) were carried out with
1
a Varian Unity 400 MHz spectrometer (400 MHz for H, 100 MHz for
13C) in Uppsala University, Sweden. Chemical shifts were expressed
as δ in parts per million (ppm) relative to the respective solvent. Mass
spectroscopy was measured on a Kratos 50 tc spectrometer, and melt-
ing points were recorded on a Bu¨chi melting point apparatus and
are uncorrected. TLC was done on Merck Kiesel gel F254 precoated
plates (Merck), column chromatography was carried out using silica
gel (0.040–0.063 mm) from Merck, and the microanalysis performed in
the microanalysis lab at (Cairo University). Single crystals suitable for
x-ray studies from sulfines 4a,b were obtained by slow crystallization
from hexane. Aryl chlorodithioformates28 and aryl trithiocarbonates29
were prepared according to literature procedures.
p-Chlorophenyl(phenyl)trithiocarbonate 3a
The p-chlorothiophenol (306 mg, 2.10 mmol) in benzene (10 ml) was
added to a solution of sodium hydroxide (84 mg, 0.20 mmol) in water
(8 ml) at room temperature. After stirring for 2 h, phenylchlorodithio-
formate (400 mg, 2.10 mmol) was then added dropwise to the above mix-
ture at room temperature over a period of 30 min, the reaction mixture

2410
I. El-Sayed et al.
was kept for 7 days. The benzene solution was washed successively with
three times water. The organic layer was dried over anhydrous CaCl2,
filtrated and then concentrated under reduced pressure to leave an oily
substance, which was treated with n-hexane to give a yellow solid. The
solid product crystallized from n-hexane, in 92% yield as yellow crys-
tals; m.p. 80–82◦C. IR (KBr) cm−1: 1565, 1470, 1453, 1385, 1095 (νC S),
854, 745, 685; 1H NMR (CDCl3-d6) ppm: 7.44 (s, 2H), 7.49–7.52 (m, 3H),
7.54–7.56 (m, 4H); 13C NMR (CDCl3-d6) ppm: 128.92, 129.60, 129.83,
130.30, 130.87, 135.55, 136.83, 137.28, 224.03 (C S); MS: m/z (%) 296
(22, M, C13H9ClS3), 219 (1, C7H4ClS3), 187 (35, C7H4ClS2), 153 (100,
C7H5S2), 111 (27, C6H4Cl), 77 (42, C6H5); Anal. Calcd for C13H9ClS3
(296.50): C, 52.61; H, 3.03; S, 32.37. Found: C, 52.60; H, 3.32; S, 32.05%.
p-Chlorophenyl(pentachlorophenyl)trithiocarbonate 3b
The p-chlorothiophenol (158 mg, 1.10 mmol) in benzene (10 ml) and a
solution of sodium hydroxide (44 mg, 1.10 mmol) in water (4 ml) was
added at room temperature. After stirring for 2 h, pentachlorophenyl
chlorodithioformate (400 mg, 1.10 mmol) was then added dropwise to
the above mixture at room temperature over a period of 30 min, the re-
action mixture was stirred for 7 days at room temperature. The benzene
solution was washed successively three times with water. The organic
layer was dried over anhydrous CaCl2, filtrated and then concentrated
under reduced pressure to leave a yellow solid. The product was recrys-
tallized from n-hexane, in 89% yield as yellow crystals; m.p. 93–96◦C.
IR (KBr) cm−1: 1345, 1305, 1095, 1082 (νC S), 1015, 880, 692; 1H NMR
(CDCl3-d6) ppm: 7.48–7.55 (m, 4H); 13C NMR (CDCl3-d6) ppm: 128.60,
130.48, 131.12, 133.11, 137.09, 137.48, 138.29, 139.21, 216.53 (C S);
MS: m/z (%) 326, C13H4Cl2S3), 247 (12, C6C15), 219 (1, C7H4ClS3), 187
(100, C7H4ClS2), 143 (24, C6H4ClS), 111 (72, C6H4Cl), 76 (6, C6H4);
Anal. Calcd. for C13H4Cl6S3 (469): C, 33.26; H, 0.85; S, 20.47. Found: C,
33.24; H, 0.89; S, 20.42%.
p-Chlorophenylthio(phenylthio)sulfine 4a
To a stirred solution of 3a (300 mg, 1.01 mmol) in chloroform (5 ml)
at 0◦C, a single portion of m-chloroperbenzoic acid (75%, 230 mg,
1.33 mmol) was added. The mixture was stirred at 0◦C for 1 h. The
chloroform solution was washed successively with saturated aqueous
sodium hydrogen carbonate three times. The organic layer was dried
over anhydrous CaCl2, filtrated and then concentrated under reduced
pressure to leave an oily substance, which was dissolved in diethyl
ether (3 ml) and cooled overnight to give a yellow solid. The solid

Trithiocarbonate-S-Oxides
2411
product crystallized from n-hexane, in 84% yield as yellow crystals; m.p.
83–85◦C. IR (KBr) cm−1: 1470, 1390, 1110, 1088, 1110 (νC
O), 815,
S
1
750, 690; H NMR (CDCl3-d6) ppm: 6.96–6.99 (m, 2H), 7.20–7.33 (m,
4H), 7.41–7.45 (m, 2H), 7.37–7.42 (m, 1H); 13C NMR (CDCl3-d6) ppm:
129.03, 129.27, 130.03, 130.21, 131.16, 134.82, 135.63, 136.77, 187.11
>
( C S O); MS: m/z (%): 312 (29, M, C13H9ClOS3), 235 (1, C7H4ClOS3),
55 (57, C7H4ClS), 121 (62, C7H5S), 109 (100, C6H5S), 77 (66, C6H5);
Anal. Calcd. For C13H9ClOS3 (312.52): C, 49.92; H, 2.88; S, 30.72. Found:
C, 49.62; H, 2.60; S, 30.58%.
p-Chlorophenylthio(pentachlorophenylthio)sulfine 4b
To a stirred solution of 3b (100 mg, 2.10 mmol) in chloroform (5 ml) at
0◦C, m-chloroperbenzoic acid (75%, 49 mg, 2.80 mmol) was added as a
single portion. The mixture was stirred at 0◦C for 1 h. The chloroform
solution was washed successively with saturated sodium hydrogen car-
bonate solution three times.The organic layer was dried over anhydrous
CaCl2, filtrated, and then concentrated under reduced pressure to leave
a yellow solid. The solid product crystallized from CH2Cl2/n-hexane
(1:3), in 80% yield as yellow crystals; m.p. 86–89◦C. IR (KBr) cm−1
:
1
1480, 1332, 1300, 1115, 1095 (νC
O), 820, 685; H NMR (CDCl3-d6)
S
ppm: 7.02–7.05 (m, 2H), 7.24–7.25 (m, 2H); 13C NMR (CDCl3-d6) ppm:
128.69, 129.57, 129.74, 130.86, 131.80, 132.46, 136.00, 138.77, 180.99
(C S O); MS: m/z (%) 447 (4, C13H4Cl5OS3), 323 (4, C7Cl5S2), 279 (26,
C6Cl5S), 219 (27, C7H4ClS3), 203 (2, C7H4ClOS2), 187 (64, C7H4ClS2),
143 (100, C6H4ClS), 111 (63, C6H4Cl). Anal. Calcd. for C13H4Cl6OS3
(485): C, 32.16; H, 0.82; S, 19.79. Found: C, 32.40; H, 1.00; S,
19.56%.
5,6-Dihydro-3,4-dimethyl-6-( p-chlorophenylthio)-6-
(phenylthio)-2H-thiopyran-S-oxide 5a
A large excess of 2,3-dimethyl-1,3-butadiene was added to a solution
of 4a (150 mg, 4.80 mmol) in dry chloroform (5 ml) and the mixture
was stirred in dark at room temperature until the yellow color had
been disappeared after 2 weeks. After the removal of the solvent under
reduced pressure, colorless oil of 5a as a mixture of two diasteriomers
was formed, in 72% yield.
Mixture of two isomers: 1H NMR (CDCl3-d6) ppm: 1.64 (s, 6H), 2.08
(d, 1H, J = 3.2 Hz), 2.13 (d, 1H, J = 2.4 Hz), 3.53 (d, 1H, J = 17.2 Hz),
3.63 (d, 1H, J= 16 Hz), 7.29–7.40 (m, 10H), 7.51–7.66 (m, 8H); 13C NMR
(CDCl3-d6) ppm: 19.17, 19.22, 19.33, 19.46, 36.55, 37.25, 52.27, 52.53,
75.01, 76.25, 117.69, 118.12, 124.72, 128.25, 128.42, 128.48, 128.60,
128.68, 128.83, 128.91, 128.95, 128.99, 129.80, 129.94, 135.34, 136.49,

2412
I. El-Sayed et al.
136.84, 137.63, 138.13, 138.92; Anal. Calcd for: C19H19ClOS3 (394.5):
C, 57.79; H, 4.82; S, 24.33 Found: C, 58.06; H, 4.65; S, 24.46%.
5,6-Dihydro-3,4-dimethyl-6-( p-chlorophenylthio)-
6(pentachlorophenylthio)-2H-thiopyran-S-oxide 5b
A large excess of 2,3-dimethyl-1,3-butadiene was added to a solution
of 4b (200 mg, 4.10 mmol) in dry chloroform (5 ml) and the mixture
was stirred in dark at room temperature until the yellow color had had
disappeared after 2 weeks. After the removal of the solvent under a
reduced pressure, an oily substance was formed, which upon treating
with petroleum ether and cooling it gave a solid residue which was
recrystallized from chloroform/ether (1:3), in 77% yield as a colorless
crystals of 5b as a mixture of two diasteriomers; m.p. 59–61◦C.
Mixture of two isomers: 1H NMR (CDCl3-d6) ppm: 1.63 (s, 3H), 1.66
(s, 3H), 1.88 (s, 3H), 1.93 (s, 3H), 2.44 (d, 1H, J = 16 Hz), 2.61 (d, 1H, J =
18.4 Hz), 2.93 (d, 1H, J = 16 Hz), 2.61 (d, 1H, J = 18.4 Hz), 2.93 (d, 1H,
J = 16 Hz), 3.26 (d, 1H, J = 19.2 Hz), 3.53 (d, 1H, J = 17.2 Hz), 3.78 (d,
1H, J = 16 Hz), 4.12 (d, 1H, J = 16 Hz), 7.54 (d, 2H, J = 8.4 Hz), 7.58 (d,
2H, J = 12 Hz), 7.80 (d, 2H, J = 8.4 Hz), 7.83 (d, 2H, J = 12.2 Hz); 13
C
NMR (CDCl3-d6) ppm: 17.95, 19.27, 19.39, 19.96, 24.52, 35.29, 36.29,
52.45, 52.71, 65.32, 79.09, 79.82, 116.72, 118.89, 124.59, 124.84, 125.79,
128.86, 128.99, 129.44, 130.45, 131.67, 132.02, 132.30, 136.46, 136.89,
137.86, 139.03, 140.47, 141.30; MS m/z (%) 564 (4, M, C19H14Cl6OS3,
421 (2, C13H10Cl5OS2), 281 (23, C13H10ClOS2), 266 (100, C12H7ClOS2),
247 (55, C6Cl5), 143 (85, C6H4Cl5); Anal. Calcd. for C19H14Cl6OS3 (567):
C, 40.21; H, 2.47; S, 16.93 Found: C, 40.60; H, 2.64; S, 16.91%.
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Trithiocarbonate-S-Oxides
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