New and facile synthesis of thiosulfonates from sulfinate/disulfide/I2 system

Article abstract of DOI:10.1055/s-2002-20031

Thiosulfonates were prepared by the iodine oxidative sulfenylation of sulfinates with various disulfides in good yields both in the presence and absence of solvent. One of the important biological applications of sulfenylation is the reaction of cyclic disulfides.

Full text of DOI:10.1055/s-2002-20031

PAPER
343
New and Facile Synthesis of Thiosulfonates from Sulfinate/Disulfide/I2 System
New
and Facile
S
y
i
nthesis
y
of Thiosulf
o
S
k
ulfinate/Dis
o
ulfide/I2 System Fujiki,* Naoki Tanifuji, Yohei Sasaki, Taku Yokoyama
Department of Agricultural Chemistry, Meiji University, Kawasaki 214-8571, Japan
Fax +81(44)9347831; E-mail: fujiki@isc.meiji.ac.jp
Received 27 July 2001; revised 30 October 2001
iodine to a solution of sodium sulfinate and disulfide in
dichloromethane results in the formation of thiosulfonate
(Equation 2).
Abstract: Thiosulfonates were prepared by the iodine oxidative
sulfenylation of sulfinates with various disulfides in good yields
both in the presence and absence of solvent. One of the important
biological applications of sulfenylation is the reaction of cyclic dis-
ulfides.
Key words: thiosulfonates, sulfinates, sulfenylation, cyclic disul-
fides, solvent free synthesis
Thiosulfonates have shown biological interest due to their
antimicrobial1 and fungicidal activities. They block the
normal metabolism of the microorganism by sulfenyla-
tion of the enzyme’s thiol groups.2 Furthermore, the thio-
sulfonates have a wide industrial application both in
polymer production and in photographic processes.3 Due
to their stronger sulfenylating power, thiosulfonates have
also been extensively utilized in organic syntheses for sul-
fide and disulfide formation or aromatic thiocyanation
with the thiolate anion.4 Several synthetic methods for the
preparation of unsymmetrical thiosulfonates possessing
various substituents at the sulfenyl sulfur atom have been
reported. One of the most general procedures is the reac-
tion of sulfinic acid with sulfenyl derivatives based on the
nucleophilicity of the sulfinate anion toward electrophilic
sulfenylating species such as sulfenyl chlorides,5
disulfides6 and thiosulfinates.7 An example of disulfides
as a sulfenylating species includes the reaction of sodium
methanesulfinate with alkyl disulfides in the presence of
AgNO3,6a which easily cleaves alkyl disulfides to form
thiosulfonates (Equation 1).
Equation 2
The thiosulfonates 3 were obtained in good to excellent
yields under reasonable reaction times when excess sulfi-
nates and iodine were used to completely consume the
disulfides. The best molar ratio of sulfinates 1 to disul-
fides 2 to iodine was 3.2:1:2 at room temperature
(Table 1). What is truly remarkable is the fact that this re-
action gave good results even in the absence of solvent
(Table 2).
When taking into account the nucleophilicity of the sulfi-
nate anion, it seems reasonable to postulate that the reac-
tion pathway is similar to that of bromine.6b Iodine first
reacted with sulfinate 1 (not with disulfide), and generated
the sulfonyl iodide 4, followed by nucleophilic sulfenyla-
tion on the sulfonyl sulfur with disulfide 2, and the pro-
duction of the thiosulfonate 3 and the unstable sulfenyl
iodide 5. The unstable sulfenyl iodide then reacted with
another sulfinate to give an additional thiosulfonate 3
(Scheme 1). Thus two thiosulfonates are produced for
each disulfide used. Iodine does not react with disulfide
though bromine does.9 In contrast, iodine rapidly reacts
with sulfinate to give sulfonyl iodide.10 To confirm this re-
action pathway the following two reactions were carried
out. In the first reaction, the bromine color rapidly faded
when it was dropped into a dichloromethane solution of
diphenyldisulfide, but iodine did not react with diphenyl-
disulfide under both solvent and solvent-free conditions.
In the second reaction, reaction of p-toluenesulfonyl io-
dide, (prepared from p-toluenesulfinate and iodine), with
an equivalent of diphenyldisulfide proved that unless an-
other sulfinate is added, the disulfide was not completely
consumed. More sulfinate was necessary to remove the
resulting sulfenyl iodide and to promote the reaction since
the reaction had attained equilibrium. For the final step,
(reaction with another sulfinate molecule), a longer reac-
tion time was needed until the disulfide completely disap-
peared.
Equation 1
Recently a similar example was reported in the literature,8
where aryl diselenides were oxidized to areneselenosul-
fonates in the presence of asulfinates under phase transfer
conditions. These two examples led to the preparation of
arenethiosulfonates from activated disulfides by bromine
in the presence of arenesulfinates.6b We decided to deter-
mine whether the effect of iodine (a stable oxidizing
agent) would be comparable to bromine as reported in the
previous example. We were able to confirm that adding
Synthesis 2002, No. 3, 18 02 2002. Article Identifier:
1437-210X,E;2002,0,03,0343,0348,ftx,en;F064SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881

344
K. Fujiki et al.
PAPER
Table 1 Preparation of Unsymmetrical Thiosulfonatesa at Room
O
O
O
S
Temperature (R1SO2SR2)
+
+
I2
I-
S
R1
R1
O-
I
Compound R1
No.
R2
Reaction Yieldb
Time (h) (%)
4
1
O
O
3a-1
3a-2
3a-3
3a-4
3a-5
3a-6
3a-7
3b-1
3b-2
3b-3
3b-4
3b-5
3b-6
3b-7
3b-8
3c-1
3c-2
3c-3
3c-4
3c-5
3c-6
3c-7
3d-1
3d-2
3d-3
3d-4
Ph
Me
2
2
90
86
89
96
90
85
85
85
91
91
85
85
88
80
88
84
88
93
89
80
90
89
90
86
93
90
O
R1
R2
O-
I
R2 -S-S- R2
S
4
+
S
+S
+
S
R2
I
R1
SR2
2
Ph
Heptyl
Cy
5
S
R2
3
Ph
10
48
O
O
Ph
Bn
O
I-
+
5
+
S
S
R1
SR2
R1
O-
Ph
p-Tolyl
p-F-Ph
2-Pyridyl
Me
1.5
3
1
Ph
2
3
Scheme 1
Ph
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
p-Cl-Ph
p-Cl-Ph
p-Cl-Ph
p-Cl-Ph
p-Cl-Ph
p-Cl-Ph
p-Cl-Ph
Me
3
Table 2 Solvent-free Synthesis of Unsymmetrical Thiosulfonatesa
i-Pr
42
3
(R1SO2SR2)
Heptyl
Cy
Compound R1
No.
R2
Reaction
Time (h)
Yieldb
(%)
9
p-F-Ph
MeOPh
2-Pyridyl
2-Naphthyl
Me
6
3a-1
3a-4
3a-5
3a-6
3b-1
3b-2
3b-3
3b-4
3b-5
3c-1
3c-4
3c-6
Ph
Me
1.5c
3c
93
70
89
80
90
90
95
86
90
85
85
95
3
Ph
Bn
2
Ph
p-Tolyl
p-F-Ph
Me
2e
24
3
Ph
4c
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
p-Cl-Ph
p-Cl-Ph
p-Cl-Ph
2c
Heptyl
Cy
2
i-Pr
4c
2
Heptyl
Cy
10c
9d
p-Tolyl
p-Br-Ph
p-F-Ph
2-Naphthyl
Heptyl
p-F-Ph
p-MeOPh
2-Naphthyl
1
4
p-F-Ph
Me
6d
6
2c
18
24
24
12
144
p-Tolyl
p-F-Ph
2e
5d
a Reaction conditions: The molar ratio of sodium sulfinate to disulfide
to iodine was 2.8:1.0:2.0.
Me
b Isolated yield is based on amount of disulfide used.
c Reaction temperature was maintained at 30 °C.
d Reaction temperature was maintained at 40 °C.
e Reaction temperature was maintained at 45 °C.
Me
Me
a Reaction conditions: The molar ratio of sodium sulfinate to disulfide
to iodine was 3.2:1.0:2.0.
b Isolated yield is based on amount of disulfide used.
(CH2)n
2
R
SO2Na +
+
I2
Under solvent free conditions, (in some cases mild warm-
ing was necessary), the thiosulfonates were produced in
higher yields. The molar ratio of sodium sulfinate to dis-
ulfide to iodine was 2.8:1.0:2.0 (Table 2). The reaction
proceeded more rapidly in the aromatic sulfinates than in
the aliphatic sulfinates. Moreover, we report that the sym-
metric thiosulfinates, bis(arylsulfonylthio)alkanes 7, (pre-
pared from cyclic disulfides 6)11 were successfully
prepared in a similar way under solvent-free conditions
(Scheme 2). To facilitate a smooth reaction, the reaction
S _S
6
O
O
O O
S
(CH2)n
S
R
+ 2NaI
R
S
S
7a: R = H
7b: R = CH3
7c: R = Cl
Scheme 2
Synthesis 2002, No. 3, 343–348 ISSN 0039-7881 © Thieme Stuttgart · New York

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New and Facile Synthesis of Thiosulfonates from Sulfinate/Disulfide/I2 System
345
Procedure for the Preparation of Bis(arylsulfonylthio)alkanes
7b; General Procedure
temperature of 45 °C was ideal except in the case of 1,2
dithiepane (Table 3). It is noted that in the presence of sol-
vent, the reaction did not go to completion, only by prod-
ucts were produced.
A mixture of sodium p-toluenesulfinate (499 mg, 2.8 mmol), 1,2-
dithiolane (106.2 mg, 1 mmol) and I2 (507.6 mg, 2 mmol) was al-
lowed to stand at 45 °C and occasionally stirred until the 1,2-dithi-
olane was consumed. The reaction mixture was added to Et2O (100
mL). After the work up was carried out as described above, 1,3-bis
(p-toluenesulfonylthio)propane 7b-1 was obtained as colorless
crystals.
Table 3 Solvent-Free Synthesis of Bis(arylsulfonylthio)alkane at
45 °Ca[RSO2S(CH2)nSSO2R]
Compound
No.
R
n
Reaction time
(h)
Yieldb
(%)
S-Methyl Benzenethiosulfonate 3a-112
Colorless oil.
IR: 1331.05, 1145.86, 1078.35 cm–1.
1H NMR: = 7.93 (d, 2 H, J = 7.5 Hz), 7.65 (t, 1 H, J = 7.5 Hz), 7.57
(t, 2 H, J = 7,5 Hz), 2.52 (s, 3 H).
13C NMR: = 143.72, 133.72, 129.29, 127.09, 18.06.
7a-1
7a-2
7b-1
7b-2
7c-1
7c-2
Ph
4
5
3
4
3
4
2
82
78
75
91
72
86
Ph
1.5c
2
p-Tolyl
p-Tolyl
p-Cl-Ph
p-Cl-Ph
2
MS (EI): m/z (%) = 188 (34.94).
2
Anal. Calcd for C7H8O2S2: C, 44.66; H, 4.28. Found: C, 44.74; H,
4.35.
2
a Reaction conditions: The molar ratio of sodium sulfinate to disulfide
to iodine was 2.8:1.0:2.0.
S-Heptyl Benzenethiosulfonate 3a-2
Colorless oil.
IR: 1327.19, 1145.86, 1978.35 cm–1.
b Isolated yield is based on amount of disulfide used.
c Reaction temperature was maintained at 30 °C.
1H NMR: = 7.94 (d, 2 H, J = 7.5 Hz), 7.61 (t, 1 H, J = 7.5 Hz), 7.56
(t, 2 H, J = 7.5 Hz), 3.00 (t, 2 H, J = 7.0 Hz), 1.57 (quintet, 2 H,
J = 7.0 Hz), 1.26–1.20 (m, 8 H), 0.86 (t, 3 H, J = 7.0 Hz).
13C NMR: = 144.99, 133.55, 129.24, 126.96, 36.12, 31.50, 28.58,
28.54, 28.45, 22.49, 14.01.
In summary, we have described a simple and efficient
method for preparing a wide variety of thiosulfonates, es-
pecially unsymmetrical ones, from sodium sulfinates, us-
ing easily available disulfides and iodine at room
temperature both in the presence and absence of solvent.
This indicates that this system is useful for both scale-up
and for practical applications.
MS (EI): m/z (%) = 272 (0.48).
Anal. Calcd for C13H20O2S2: C, 57.32; H, 7.40. Found: C, 57.51; H,
7.48.
This system (solvent-free reaction) can be used with bio-
logically important cyclic disulfides such as, lipoic acid.
S-Cyclohexyl Benzenethiosulfonate 3a-3
Colorless oil.
IR: 1323.34, 1143.93, 1078.35(m) cm–1.
1H NMR: = 7.95 (d, 2 H, J = 8.0 Hz), 7.62 (t, 1 H, J = 8.0 Hz), 7.55
(t, 2 H, J = 8.0 Hz), 3.37 (nonet, 1 H, J = 3.5 Hz), 1.94–1.89 (m, 2
H), 1.68–1.63 (m, 2 H), 1.55–1.20 (m, 6 H).
13C NMR: = 145.78, 133.43, 129.21, 126.82, 50.46, 33.43, 25.67,
25.15.
Melting points were determined using a Yanagimoto micro melting
1
point apparatus (Mp-S3), and are uncorrected. H and 13C NMR
spectra were measured on a JMM-GSX 500N (JOEL) NMR spec-
trometer (500 and 125 MHz respectively, CDCl3). NMR data are re-
ported in parts per million downfield from tetramethylsilane as an
internal standard ( = 0.0) and coupling constants are given in
Hertz. IR spectra were measured on a Hitachi-Nicolet FT-IR 5020
spectrometer. KBr tablets were used for solid products and thin
films for oily products. Mass spectra were measured on a JMS SX-
102 (JOEL) (and recorded either in the EI or FAB mode). The start-
ing materials, cyclic disulfides 6, were prepared according to the lit-
erature procedures.11 All products were obtained as colorless oil or
crystals. Elemental analyses were performed at the Analysis Center,
The University of Tsukuba on a Perkin Elmer 2400.
MS (EI): m/z (%) = 256 (26.45).
Anal. Calcd for C12H20O2S2:, C, 56.22; H, 6.29. Found: C, 56.25; H,
6.37.
S-Benzyl Benzenethiosulfonate 3a-414
Mp 39–41 °C (Lit.14 43 °C).
MS (EI): m/z (%) = 264 (1.38).
S-p-Tolyl Benzenethiosulfonate 3a-515
Procedure for the Preparation of Unsymmetrical
Thiosulfonates 3a; General Procedure
Mp: 52–53 °C (Lit.15 54 °C).
MS (EI): m/z (%) = 264 (60.96).
To a mixture of sodium benzenesulfinate (525.3 mg, 3.2 mmol) and
di p-tolyl disulfide (246.4 mg, 1 mmol) in CH2Cl2 (5 mL) was added
I2 (507.6 mg, 2 mmol) with mixing. The mixture was stirred until
the disulfide was consumed, then CH2Cl2 (100 mL) was added fol-
lowed by aq Na2S2O3 (1 M) with stirring until the I2 color disap-
peared. The organic layer was washed with H2O (2 200 mL) and
dried over Na2SO4. After the solvent was removed at reduced pres-
sure, S-p-tolyl benzenethiosulfonate 3a-5 was obtained as colorless
crystals.
S-p-Fluorophenyl Benzenethiosulfonate 3a-6
Mp 52–53 °C.
IR: 1321.41, 1143.93, 1076.42 cm–1.
1H NMR: = 7.60 (t, 1 H, J = 7.5 Hz), 7.58 (d, 2 H, J = 7.5 Hz),
7.45 (t, 2 H, J = 7.5 Hz), 7.34 (dd, 2 H, JH –F = 5.5 Hz, J = 9.0 Hz),
7.03 (dd, 2 H, JH –F = 9.0 Hz, J = 9.0 Hz).m
O
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K. Fujiki et al.
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13C NMR: = 164.83(J4C–F = 253.0 Hz), 142.79, 138.84 (Jm
S-2-Pyridyl p-Toluenethiosulfonate 3b-716
C–
F = 9.1 Hz), 133.80, 128.93, 127.59, 123.44 (JpC–F = 3.6 Hz),
Mp: 47.5–49 °C (Lit.16 50–51 °C).
116.81(JoC–F = 21.9 Hz).
MS (EI): m/z (%) = 265 (-).
MS (EI): m/z (%) = 268 (74.77).
S-2-Naphthyl p-toluenethiosulfonate 3b-84d
Anal. Calcd for C12H9FO2S2: C, 53.72; H, 3.38. Found: C, 53.56; H,
3.41.
Mp: 88 °C (Lit.4d 87–88 °C).
MS (EI): m/z (%) = 314 (82.07).
S-2-Pyridyl Benzenethiosulfonate 3a-7
Mp: 38–40 °C.
IR: 1307.90, 1151.65, 1045.55 cm–1.
S-Methyl p-chlorobenzenethiosulfonate 3c-112
Mp: 31–32 °C (Lit.12 35–37 °C).
MS (EI): m/z (%) = 222 (42.33).
1H NMR: = 8.50 (d, 1 H, J = 5.0 Hz), 7.76–7.70 (m, 2 H), 7.68 (d,
2 H, J = 8.0 Hz), 7.57 (t, 1 H, J = 8.0), 7.44 (t, 2 H, J = 8.0 Hz), 7.33
(t, 1 H, J = 5.0 Hz).
13C NMR: = 150.94, 150.70, 144.12, 137.84, 133.87, 131.91,
129.04, 127.41, 124.94.
S-Heptyl p-Chlorobenzenethiosulfonate 3c-2
Colorless oil.
IR: 1331.05, 1145.86, 1078.35 cm–1.
1H NMR: = 7.87 (d, 2 H, J = 8.0 Hz), 7.53 (d, 2 H, J = 8.0 Hz),
3.00 (t, 2 H, J = 7.5 Hz), 1.60 (quintet, 2 H, J = 7.5 Hz), 1.27–1.19
(m, 8 H), 0.87 (t, 3 H, J = 7.5 Hz).
13C NMR: = 143.45, 140.18, 129.54, 128.42, 36.26, 31.52, 28.58,
28.55, 28.46, 22.50, 14.01.
MS (EI): m/z (%) = 251 (0.06).
Anal. Calcd for C11H9 NO2S2: C, 52.57; H, 3.61. Found: C, 52.58;
H, 3.67.
S-Methyl p-Toluenethiosulfonate 3b-1
Mp: 54–55 °C (Lit.12 57–58 °C).
MS (EI): m/z (%) = 306 (0.60).
MS (EI): m/z (%) = 202 (36.92).
Anal. Calcd for C13H13ClO2S2: C, 50.88; H, 6.24. Found: C, 50.73;
H, 6.32.
S-Isopropyl p-Toluenethiosulfonate 3b-213
Colorless oil.
S-Cyclohexyl p-Chlorobenzenethiosulfonate 3c-3
Mp 55–56 °C.
IR: 1321.41, 1142.00, 1076.42 cm–1.
1H NMR: = 7.88 (d, 2 H, J = 8.7 Hz), 7.52 (d, 2 H, J = 8.7 Hz),
3.37 (nonet, 1 H, J = 3.5 Hz), 1.96–1.91 (m, 2 H), 1.70–1.63 (m, 2
H), 1.58–1.22 (m, 6 H).
13C NMR: = 144.30, 140.02, 129.51, 128.28, 50.72, 33.44, 25.67,
25.13.
IR: 1325.27, 1142.00, 1078.35 cm–1.
1H NMR: = 7.83 (d, 2 H, J = 8.5 Hz), 7.34 (d, 2 H, J = 8.5 Hz),
3.49 (heptet, 1 H, J = 7.0 Hz), 2.45 (s, 3 H), 1.32 (d, 6 H, J = 7.0
Hz).
13C NMR: = 144.56, 142.71, 129.80, 126.99, 42.57, 23.54, 21.63.
MS (EI): m/z (%) = 230 (30.05).
Anal. Calcd for C10H14O2S2: C, 52.14; H, 6.13. Found: C, 51.91; H,
6.18.
MS (EI): m/z (%) = 290 (23.91).
Anal. Calcd for C12H15ClO2S2: C, 49.56; H, 5.20. Found: C, 49.31;
H, 5.13.
S-Heptyl p-Toluenethiosulfonate 3b-31a
Colorless oil.
IR: 1327.19, 1143.93, 1078.35 cm–1.
1H NMR: = 7.81 (d, 2 H, J = 8.0 Hz), 7.34 (d, 2 H, J = 8.0 Hz),
2.98 (t, 2 H, J = 7.0 Hz), 2.45 (s, 3H), 1.58 (quintet, 2 H, J = 7.0
Hz), 1.27–1.19 (m, 8 H), 0.86 (t, 3 H, J = 7.0 Hz).
13C NMR: = 144.62, 142.19, 129.81, 127.03, 36.04, 31.52, 28.59,
28.55, 28.46, 22.55,21.62, 14.01.
S-p-Tolyl p-Chlorobenzenethiosulfonates 3c-415
Mp125–126 °C (Lit.15 130 °C).
MS (EI): m/z (%) = 298 (58.13).
S-p-Bromophenyl p-Chlorobenzene-thiosulfonate 3c-5
Mp: 148–149 °C.
IR: 1323.34, 1145.86, 1091.85 cm–1.
1H NMR: = 7.53 (d, 2 H, J = 9.0 Hz), 7.51 (d, 2 H, J = 8.5 Hz),
7.43 (d, 2 H, J = 9.0 Hz), 7.24 (d, 2 H, J = 8.5 Hz)
MS (EI): m/z (%) = 286 (1.03).
Anal. Calcd for C14H22O2S2: C, 58.70; H, 7.74. Found: C, 58.31; H,
7.79.
13C NMR: = 141.38, 140.59, 137.84, 132.93, 129.30, 128.95,
127.01, 126.68.
S-Cyclohexyl p-Toluenethiosulfonate 3b-44d
Mp: 51 °C (Lit.4d 50–51 °C).
MS (EI): m/z (%) = 362 (24.74).
MS (EI): m/z (%) = 270 (26.67).
Anal. Calcd for C12H8BrClO2S2: C, 39.63; H, 2.22. Found: C, 39.32;
H, 2.08.
S-p-Fluorophenyl p-Toluenethiosulfonate 3b-54d
Mp: 91 °C (Lit.4d 93–95.5 °C).
S-p-Fluorophenyl p-Chlorobenzenethiosulfonate 3c-6
Mp 87.5–88.5 °C.
IR: 1327.19, 1147.79, 1093.78 cm–1.
1H NMR: = 7.51 (d, 2 H, J = 8.5 Hz), 7.42 (d, 2 H, J = 8.5 Hz),
7.37 (dd, 2 H, JmH–F = 5.0 Hz, J = 9.0 Hz), 7.07 (dd, 2 H, JoH–F = 9.0
Hz, J = 9.0 Hz).
MS (EI): m/z (%) = 282 (42.69).
S-p-Methoxyphenyl p-Toluenethiosulfonate 3b-615
Mp: 53–55 °C (Lit.15 58 °C).
MS (EI): m/z (%) = 294 (24.96).
Synthesis 2002, No. 3, 343–348 ISSN 0039-7881 © Thieme Stuttgart · New York

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New and Facile Synthesis of Thiosulfonates from Sulfinate/Disulfide/I2 System
347
13C NMR: = 164.96 (J4C–F = 253.0 Hz), 141.30, 140.53, 138,85
(JmC–F = 9.1 Hz), 129.25, 128.98, 123.18 (JpC–F = 3.8 Hz), 117.01
(JoC–F = 22.0 Hz).
S-2-Naphthyl Methanethiosulfonate 3d-4
Mp 111–112 °C.
IR: 1317.55, 1134.20 cm–1.
MS (EI): m/z (%) = 302 (43.26).
1H NMR: = 8.26 (s, 1 H), 7.93 (d, 1 H, J = 8.0 Hz), 7.90 (t, 2 H,
J = 8.0 Hz), 7.72 (dd, 1 H, J = 2.0 Hz, J = 8.0 Hz), 7.63–7.57 (m, 2
H), 3.20 (s, 3 H).
Anal. Calcd for C12H8ClFO2S2: C, 47.61; H, 2.66. Found: C, 47.58;
H, 2.70.
13C NMR: = 137.07, 134.24, 133.48, 131.49, 129.73, 128.48,
128.44, 127.88, 127.26, 124.99, 47.49.
S-2-Naphthyl p-Chlorobenzenethiosulfonate 3c-7
Mp 122–123 °C.
IR: 1319.48, 1140.08, 1081.27 cm–1.
1H NMR: = 7.90 (s, 1 H), 7.87 (d, 1 H, J = 8.0 Hz), 7.82 (d, 1 H,
J = 8.0 Hz), 7.78 (d, 1 H, J = 8.0 Hz), 7.61 (t, 1 H, J = 8.0 Hz), 7.56
(t, 1 H, J = 8.0 Hz), 7.47 (d, 2 H, J = 8.5 Hz), 7.39 (dd, 1 H, J = 8.0
Hz, J = 2.0 Hz), 7.34 (d, 2 H, J = 8.5 Hz).
13C NMR: = 141.52, 140.29, 137.63, 134.16, 133.31, 131.66,
129.35, 129.12, 128.98, 128.43, 127.82, 127.13, 124.66.
MS (EI): m/z (%) = 238 (37.92).
Anal. Calcd for C11H10O2S2: C, 55.44; H, 4.23. Found: C, 55.35; H,
4.28.
1,4-Bis(benzenesulfonylthio)butane 7a-117
Mp 94–95 °C (Lit.17 93–94 °C).
MS-FAB: m/z (%) [M + H]+= 403 (19.21).
MS (EI): m/z (%) = 334 (42.33).
1,5-Bis(benzenesulfonylthio)pentane 7a-217
Mp 66 °C (Lit.17 66–67 °C).
Anal. Calcd for C16H11ClO2S2: C, 57.39; H, 3.31. Found: C, 57.03;
H, 3.31.
MS (EI): m/z (%) = 416 (-).
S-Heptyl Methanethiosulfonate 3d-1
Colorless oil.
1,3-Bis(p-toluenesulfonylthio)propane 7b-117
Mp 66–67 °C (Lit.17 69 °C).
IR: 1325.27, 1136.22 cm–1.
MS-FAB: m/z (%) [M + H]+= 417 (2.64).
1H NMR: = 3.32 (s, 3 H), 3.17 (t, 2 H, J = 7.5 Hz), 1.77 (quintet,
2 H, J = 7.5 Hz), 1.42 (quintet, 2 H, J = 7.5 Hz), 1.34–1.28 (m, 6 H),
0.89 (t, 3 H, J = 7.5 Hz).
13C NMR: = 50.64, 36.50, 31.58, 29.48, 28.63, 28.55, 22.53,
14.02.
1,4-Bis(p-toluenesulfonylthio)butane 7b-217
Mp 117–118 °C (Lit.17 119.5 °C).
MS-FAB: m/z (%) [M + H]+= 431 (19.2).
1,3-Bis(p-chlorobenzenesulfonylthio)propane 7c-1
Mp108–109 °C.
MS (EI): m/z (%) = 210 (0.46).
IR: 1319.48, 1140.08, 1081.27 cm–1.
1H NMR: = 7.85 (d, 4 H, J = 8.8 Hz), 7.54 (d, 4 H, J = 8.8 Hz),
3.05 (t, 4 H, J = 6.9 Hz), 2.11 (quintet, 2 H, J = 6.9 Hz).
Anal. Calcd for C8H18O2S2: C, 45.68; H, 8.62. Found: C, 45.63; H,
8.67.
S-p-Fluorophenyl Methanethiosulfonate 3d-2
Mp 59–60 °C.
13C NMR: = 142.82, 140.68, 129.77, 128.45, 34.11, 28.31.
IR: 1309.83, 1134.29 cm–1.
MS (EI): m/z (%) = 456 (-).
1H NMR: = 7.71 (dd, 2 H, JmH–F = 5.2 Hz, J = 9.0 Hz), 7.18 (dd, 2
Anal. Calcd for C13H14Cl2O4S4: C, 39.38; 3.08. Found: C,39.56; H,
3.14.
H, JoH–F = 9.0 Hz, J = 9.0 Hz). 3.19 (s, 3 H).
13C NMR: = 164.94 (J4C–F = 253.1 Hz), 138,53 (JmC–F = 9.1 Hz),
123.45 (JpC–F = 3.6 Hz), 117.30 (JoC–F = 21.9 Hz), 47.40.
1,4-Bis(p-chlorobenzenesulfonylthio)butane 7c-2
Mp 136–137 °C.
IR: 1323.34, 1142.00 cm–1.
1H NMR: = 7.85 (d, 4 H, J = 8.8 Hz), 7.54 (d, 4 H, J = 8.8 Hz),
2.96 (t, 4 H, J = 7.0 Hz), 1.72 (quintet, 4 H, J = 7.0 Hz).
MS (EI): m/z (%) = 206 (36.55).
Anal. Calcd for C7H7FO2S2: C, 40.76, H, 3.42. Found: C, 40.71; H,
3.47.
S-p-Methoxyphenyl Methanethiosulfonate 3d-3
13C NMR: = 143.04, 140.49, 129.70, 128.40, 35.24, 27.54
Mp 75–76 °C.
IR: 1311.76, 1134.29 cm–1.
1H NMR: = 7.62 (d, 2 H, J = 9.0 Hz), 6.98 (d, 2 H, J = 9.0 Hz),
MS (EI): m/z (%) = 471 (1.5).
Anal. Calcd for C16H16Cl2O4S4: C, 40.76; H, 3.42. Found: C, 40.70;
H, 3.55.
3.86 (s, 3 H), 3.15 (s, 3 H).
13C NMR: = 162.51, 138.06, 118.57, 115.47, 55.56 46.93.
References
MS (EI): m/z (%) = 218 (36.01).
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Anal. Calcd for C8H10O3S2: C, 44.02; H, 4.62. Found: C, 43.96; H,
4.67.
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