Synthesis of S-Aryl arenethiosulfonates from N,N-Di(arenesulfonyl) hydrazines: Reduction of sulfonyl chlorides with an organic reagent

Article abstract of DOI:10.1002/hc.21088

N,N-Di(arenesulfonyl)-N′,N′-dimethyl-hydrazines, readily prepared from arenesulfonyl chlorides and N,N-dimethylhydrazine, were heated at 120°C in chlorobenzene to give S-aryl arenethiosulfonates, ArSSO ₂Ar, in good yields.

Full text of DOI:10.1002/hc.21088

Heteroatom Chemistry
Volume 24, Number 4, 2013
Synthesis of S-Aryl Arenethiosulfonates from
N,N-Di(arenesulfonyl)hydrazines: Reduction
of Sulfonyl Chlorides with an Organic Reagent
Satoshi Iwata, Masato Senoo, Takeshi Hata, and Hirokazu Urabe
Department of Biomolecular Engineering, Graduate School of Bioscience and Biotechnology,
Tokyo Institute of Technology, Yokohama, Kanagawa 226-8501, Japan
Received 8 January 2013; revised 15 March 2013
such as metallic Sm or Fe(CO)5 are usually neces-
ABSTRACT: N,N-Di(arenesulfonyl)-Nꢀ,Nꢀ-dimethyl-
sary for this type of transformation [5]. To our best
knowledge, other methods replacing these transi-
tion metal–based reductions have not been reported.
During our study on sulfonamides [7], we found that
a sulfonyl derivative of hydrazine 2 afforded S-aryl
arenethiosulfonates 3 in good yields upon simple
heating in chlorobenzene, formally achieving a tran-
sition metal–free reduction of sulfonyl chlorides 1
with an organic reagent as shown in Eq. (1).
hydrazines, readily prepared from arenesulfonyl chlo-
rides and N,N-dimethylhydrazine, were heated at
120◦C in chlorobenzene to give S-aryl arenethiosul-
ꢁC
fonates, ArSSO2Ar, in good yields. 2013 Wiley Pe-
riodicals, Inc. Heteroatom Chem 24:336–344, 2013;
View this article online at wileyonlinelibrary.com.
DOI 10.1002/hc.21088
INTRODUCTION
S-Aryl arenethiosulfonates, ArSSO2Ar, are interest-
ing organosulfur compounds [1] and have found
use as a sulfenylating agent in organic synthesis
[2]. They are prepared by a variety of methods
[1b,c], typically including (i) substitution of sul-
fonyl halides with thiolates or vice versa [3], (ii)
oxidation of thiols or disulfides [4], and (iii) re-
duction of sulfonyl chlorides [5]. As arenesulfonyl
chlorides are primary organosulfur products read-
ily prepared from parent arenes and chlorosulfonic
acid [6], their reduction (i.e., the method (iii) above)
should be one of the most straightforward meth-
ods to prepare thiosulfonates. However, as sulfonic
acid derivatives belong to the most stable class of
organosulfur compounds, strong reducing agents
(1)
RESULTS AND DISCUSSION
N,N-Di-p-toluenesulfonyl-Nꢀ,Nꢀ-dimethylhydrazine
(5) was readily prepared by standard methods
(Eq. (2)) [8], involving (i) monosulfonylation of
N,N-dimethylhydrazine with p-TolSO2Cl (Tol =
CH3C6H4–) in the presence of Et3N and DMAP and
(ii) the second sulfonylation with NaH as a base. This
procedure was conveniently carried out in one pot.
The resultant disulfonylhydrazine 5 was then heated
in various solvents, the results of which are summa-
rized in Table 1. While higher reaction temperature
than 100◦C appears essential (entries 1–3), the kind
of solvents also influenced the smooth reaction (en-
tries 4–6). Among the conditions examined, heating
in chlorobenzene at 120◦C for 4 h was found opti-
mal to give a desired product 6 in the highest yield
(entry 8). Careful analysis of the crude reaction
Correspondence to: H. Urabe; e-mail: hurabe@bio.titech.ac.jp.
Contract grant sponsor: Grant-in-Aid for Challenging Ex-
ploratory Research from JSPS, Japan.
Contract grant number: 22655014.
2013 Wiley Periodicals, Inc.
ꢁC
336

Synthesis of S-Aryl Arenethiosulfonates from N,N-Di(arenesulfonyl)hydrazines 337
TABLE 1 Optimization of the Thermal Decomposition of 5
TABLE 2 Preparation of Various S-Aryl Arenethiosulfonates
1
2
3
Entry
Ar
Yield (%)a
Yield (%)a
1
2
3
7
4
8
14
5
84
92
74
21
6
75
71
71
Temperature Period
Entry Solvent
(◦C)
Reflux
(h)
6 (%)a 5 (%)a
1
2
3
4
5
6
7
8
THF
(CICH2)2 80
6
6
6
6
6
6
5
4
(0)
(0)
(Quant.)
(Quant.)
15
22
Toluene
DMSO
Xylenes
PhCI
PhCI
PhCI
Reflux
(21) (79)
120
120
120
120
120
30
(Trace)
4
9
16
87
23
82
(46) (17)
60
67
71
(Trace)
(6)
(Trace)
5
6
10
11
17
18
66
76
24
25
65
68
aIsolated yields. Values in parentheses were determined by 1H NMR
analysis.
7
12
13
19
20
74
85
26
27
66
75
mixture did not show the presence of other isolable
organosulfur compounds of a higher or lower
oxidation state such as a vic-disulfone, thiosulfinate,
disulfide, or thiol.
8
aIsolated yields.
not suffer the reduction (entries 6 and 7). Some addi-
tional observations are in order (Eqs. (3)–(6)). While
commercially available N,N-dimethylhydrazine was
routinely used as the reductant, its higher ho-
molog, N,N-dioctylhydrazine, was also valid for
this reaction to give the desired product 6 in
good yield via 28 (Eq. (3)). A mixed disulfonyl-
hydrazine, N-p-toluenesulfonyl-N-p-anisolesulfonyl-
Nꢀ,Nꢀ-dimethylhydrazine (29) afforded all possible
products 6, 24, 30, and 31 in almost equal amounts
(Eq. (4)). This fact clearly suggests that the reduc-
tive coupling of two arenesulfonyl groups took place
in an intermolecular manner. To the contrary, an
aliphatic sulfonyl derivative, N,N-dibutanesulfonyl-
Nꢀ,Nꢀ-dimethylhydrazine (32), did not give the
desired product 33, even though the starting ma-
terial was consumed (Eq. (5)). Finally, N,Nꢀ-di-p-
toluenesulfonylhydrazine (34) did not give 6, either
(Eq. (6)), showing that the sulfonimide structure of
2 appears essential.
(2)
Table 2 summarizes both results of the prepa-
ration of starting disulfonylhydrazines 2 (accord-
ing to Eq. (2)) and their subsequent conversion to
various thiosulfonates 3 (according to entry 8 in
Table 1). The preparation of starting materials 5
and 14–20 proceeded in good yields. The thiosul-
fonates having an electron-rich (entries 2–5 and 8)
or -poor (entries 6 and 7) aromatic group could be
prepared in good yields. The chloro substituent did
(3)
Heteroatom Chemistry DOI 10.1002/hc

338 Iwata et al.
(4)
(5)
(6)
Although arenesulfonylhydrazine-based reductions
are well known, their reactions result in the for-
mation of a sulfinic acid, accompanied by another
reduced organic fragment and nitrogen gas, as rep-
resented by Scheme 1 [9]. Thus, the present reac-
tion forming thiosulfonates is a new entry, which is
in stark contrast to the existing protocol shown in
Scheme 1.
To gain mechanistic insight, we attempted
to identify products resulting from the hydrazine
residue rather than the arenesulfonyl group. How-
ever, even in the reaction of dioctyl derivative 28
(Eq. (3)), only intractable mixtures, except for
desired 6, were always recovered, in which we could
not find any useful compounds for the elucidation
of a mechanism.
reaction, indicating that a radical chain mechanism
is not involved.
galvinoxyl (5 mol%)
(p-TolSO2)2N-NMe2
(5)
p-TolSSO2-p-Tol
(6) 63%
−−−−−−−−−−→
PhCl,120◦C
(7)
Thus, Scheme 2 shows a proposed mechanism, in
which the sterically congested sulfonimide moiety
of 35 thermally isomerizes to less bulky hydroxy-
lamine O-sulfinate derivatives 36 or 37 [10a]. During
this process, the scrambling of the sulfur groups via
the intermolecular addition may take place, which
is consistent with the observation of Eq. (4). The
resultant 37 should then collapse to the putative
vic-disulfoxide 39, whose well-known, spontaneous
disproportionation [4i,5a,10b,11] finally gives the
thiosulfonate 40. However, as mentioned above, the
Alternatively, as shown in Eq. (7), the presence
of galvinoxyl, a radical scavenger, did not block the
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of S-Aryl Arenethiosulfonates from N,N-Di(arenesulfonyl)hydrazines 339
SCHEME 1 Known arenesulfonylhydrazine-based reductions.
SCHEME 2 A proposed mechanism.
vent (CDCl3) (δ 77.00 ppm for 13C NMR) as an in-
ternal standard. Signal patterns are indicated as br,
broad; s, singlet; d, doublet; t, triplet; q, quartet; m,
multiplet. Coupling constants (J) are given in hertz.
Infrared (IR) spectra were recorded on a JASCO
A-100 spectrometer (Tokyo, Japan) and are reported
in wavenumbers (cm−1). High-resolution mass spec-
tra (HRMS) were obtained on a Bruker micrOTOF
II by the electron ionization (EI) or positive elec-
trospray ionization (ESI) method calibrated with
sodium formate at the Suzukake-dai Material Anal-
ysis Center, Technical Department, Tokyo Institute
of Technology. Dry solvents (THF, diethyl ether,
and CH2Cl2) were purchased from Kanto Chemicals
(Tokyo, Japan). Chemicals were purified or dried in
a standard manner, if necessary. All reactions were
carried out under argon.
isolation of the key by-product 38 [10c] is not so far
successful.
At any event, the hydrazine moiety should accept
two oxygen atoms from two sulfonyl groups to effect
their reduction to the thiosulfonate stage, and the
mechanistic rationale must await further research.
CONCLUSIONS
In conclusion, we reported herein a new prepa-
ration of S-aryl arenethiosulfonates from N,N-
di(arenesulfonyl)hydrazines. This reduction of the
sulfonyl group does not need a metallic reductant,
but instead it utilizes an organic reducing agent in
the same molecule.
EXPERIMENTAL
General Information
N,N-Bis(4-methylbenzenesulfonyl)-Nꢀ,
1H and 13C NMR spectra were taken on an Agilent
400-MR spectrometer at 400 and 100 MHz, respec-
tively. For NMR spectra, CDCl3 was used as the
solvent and chemical shifts are reported in parts
per million shift (δ value) from Me4Si (δ 0 ppm
for 1H) or based on the middle peak of the sol-
Nꢀ-dimethylhydrazine (5)
This was prepared according to the literature [8a].
To
a
mixture of p-toluenesulfonyl chlo-
ride (4) (0.687 g, 3.60 mmol) and DMAP
(37.2 mg, 0.304 mmol) in THF (12.0 mL),
Heteroatom Chemistry DOI 10.1002/hc

340 Iwata et al.
N,N-Di(benzenesulfonyl)-Nꢀ,
N,N-dimethylhydrazine (0.228 mL, 3.00 mmol) and
NEt3 (0.499 mL, 3.60 mmol) were added in this or-
der at 0◦C. After stirring at room temperature for
30 min, the mixture was cooled to 0◦C and NaH
(0.265 g of a 60% dispersion in oil, 6.63 mmol) was
added. After the mixture was stirred at room tem-
perature for 20 min and cooled to 0◦C, an additional
p-toluenesulfonyl chloride (4) (0.685 g, 3.59 mmol)
was added. After the mixture was stirred at room
temperature for 15 h, it was cooled to 0◦C and was
quenched with water. To the resultant mixture, ethyl
acetate was added and the organic layer was sepa-
rated. The aqueous layer was extracted with ethyl
acetate. The combined organic layers were washed
successively with brine, dried over Na2SO4, and con-
centrated in vacuo to give a crude oil, which was
chromatographed on silica gel (hexane–ethyl ac-
etate) to afford the title compound (1.02 g, 92%) as
a white solid.
Nꢀ-dimethylhydrazine (14)
1H NMR (400 MHz) δ 2.77 (s, 6H), 7.54 (t, J = 7.6 Hz,
4H), 7.65 (t, J = 7.6 Hz, 2H), 7.95 (d, J = 7.6 Hz, 4H).
13C NMR (100 MHz) δ 45.10 (two carbons), 128.58
(four carbons), 128.87 (four carbons), 133.82 (two
carbons), 139.34 (two carbons). IR (KBr) 3075, 3064,
2993, 2960, 2931, 2896, 1583, 1447, 1363, 1165, 1080,
908 cm−1. Anal. Calcd for C14H16N2O4S2: C, 49.40;
H, 4.74. Found: C, 49.49; H, 4.70. mp 115–116◦C.
N,N-Bis(4-tert-butylbenzenesulfonyl)-Nꢀ,
Nꢀ-dimethylhydrazine (15)
1H NMR (400 MHz) δ 1.35 (s, 18H), 2.78 (s, 6H),
7.53 (d, J = 8.8 Hz, 4H), 7.87 (d, J = 8.8 Hz, 4H).
13C NMR (100 MHz) δ 31.01 (six carbons), 35.23
(two carbons), 45.13 (two carbons), 125.79 (four car-
bons), 128.43 (four carbons), 136.39 (two carbons),
157.71 (two carbons). IR (KBr) 3073, 2961, 2903,
2869, 1593, 1477, 1370, 1181, 908 cm−1. HRMS (ESI)
Calcd for C22H32N2O4S2Na [M + Na]+: 475.1696.
Found: 475.1695. mp 145–146◦C.
1H NMR (400 MHz) δ 2.42 (s, 6H), 2.75 (s, 6H),
7.30 (d, J = 8.4 Hz, 4H), 7.81 (d, J = 8.4 Hz, 4H). 13C
NMR (100 MHz) δ 21.63 (two carbons), 45.07 (two
carbons), 128.61 (four carbons), 129.43 (four car-
bons), 136.58 (two carbons), 144.81 (two carbons).
IR (KBr) 3067, 3051, 2992, 2961, 2931, 2897, 1595,
1365, 1162, 911 cm−1. Anal. Calcd for C16H20N2O4S2:
C, 52.15; H, 5.47. Found: C, 51.94; H, 5.54. mp 156–
157 ◦C.
N,N-Bis(3-methylbenzenesulfonyl)-Nꢀ,
Nꢀ-dimethylhydrazine (16)
S-(4-Methylphenyl) (4-methylbenzene)
1H NMR (400 MHz) δ 2.43 (s, 6H), 2.78 (s, 6H),
7.42 (t, J = 7.2 Hz, 2H), 7.45 (d, J = 7.2 Hz, 2H),
7.72 (s, 2H), 7.75 (d, J = 7.2 Hz, 2H). 13C NMR
(100 MHz) δ 21.29 (two carbons), 45.09 (two car-
bons), 125.74 (two carbons), 128.67 (two carbons),
128.76 (two carbons), 134.55 (two carbons), 139.06
(two carbons), 139.18 (two carbons). IR (KBr) 3093,
3065, 3004, 2962, 2926, 2891, 1477, 1366, 1180, 1084,
902 cm−1. Anal. Calcd for C16H20N2O4S2: C, 52.15;
H, 5.47. Found: C, 52.19; H, 5.58. mp 91–92◦C.
thiosulfonate (6) [5a,11–13]
A solution of N,N-bis(4-methylbenzenesulfonyl)-
Nꢀ,Nꢀ-dimethylhydrazine (5) (59.4 mg, 0.160 mmol)
in chlorobenzene (0.8 mL) was stirred in an oil bath
maintained at 120◦C for 4 h. After being cooled to
room temperature, the mixture was concentrated
in vacuo to give a crude oil, which was chro-
matographed on silica gel (hexane–ethyl acetate) to
afford the title compound (31.6 mg, 71%) as a white
solid.
1H NMR (400 MHz) δ 2.38 (s, 3H), 2.42 (s, 3H),
7.14 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H),
7.24 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H). 13C
NMR (100 MHz) δ 21.46, 21.64, 124.57, 127.58 (two
carbons), 129.34 (two carbons), 130.17 (two car-
bons), 136.48 (two carbons), 140.45, 142.01, 144.54.
IR (KBr) 3082, 3066, 3034, 2917, 2862, 1590, 1488,
1323, 1138, 806 cm−1. MS (EI, 70 eV) m/z (rel. inten-
sity): 278 ([M]+, 85), 155 (28), 139 (100), 123 (31),
91 (38). HRMS (EI, 70 eV) Calcd for C14H14O2S2
[M]+: 278.0435. Found: 278.0429. Anal. Calcd for
C14H14O2S2: C, 60.40; H, 5.07. Found: C, 60.47; H,
5.15. mp 77–78◦C (lit. 71◦C [4i], 74–75◦C [11, 14],
75.5–77.0◦C [5b], 76–78◦C [15]).
N,N-Bis(4-methoxybenzenesulfonyl)-Nꢀ,
Nꢀ-dimethylhydrazine (17)
1H NMR (400 MHz) δ 2.77 (s, 6H), 3.89 (s, 6H),
6.99 (d, J = 8.8 Hz, 4H), 7.88 (d, J = 8.8 Hz, 4H).
13C NMR (100 MHz) δ 45.06 (two carbons), 55.68
(two carbons), 113.94 (four carbons), 130.87 (four
carbons), 130.95 (two carbons), 163.69 (two car-
bons). IR (KBr) 3075, 3000, 2965, 2898, 1593, 1498,
1355, 1257, 1150, 1018, 911 cm−1. Anal. Calcd for
C16H20N2O6S2: C, 47.99; H, 5.03. Found: C, 47.97;
H, 4.97. mp 144–145◦C.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of S-Aryl Arenethiosulfonates from N,N-Di(arenesulfonyl)hydrazines 341
41◦C [4i], 40–41◦C [3e], 43.0–45.0◦C [5b], 44–45◦C
[15]).
Spectral properties of this compound were same
as those of an authentic sample from a commercial
source.
N,N-Bis(4-chlorobenzenesulfonyl)-Nꢀ,
Nꢀ-dimethylhydrazine (18)
1H NMR (400 MHz) δ 2.78 (s, 6H), 7.53 (td, J =
2.4, 8.8 Hz, 4H), 7.91 (td, J = 2.4, 8.8 Hz, 4H). 13C
NMR (100 MHz) δ 45.22 (two carbons), 129.31 (four
carbons), 130.06 (four carbons), 137.68 (two car-
bons), 140.73 (two carbons). IR (KBr) 3098, 3027,
2988, 2961, 2926, 2896, 1575, 1473, 1370, 1187, 1090,
907, 759 cm−1. Anal. Calcd for C14H14Cl2N2O4S2: C,
41.08; H, 3.45. Found: C, 41.29; H, 3.36. mp 167–
168◦C.
S-(4-tert-Butylphenyl) (4-tert-butylbenzene)
thiosulfonate (22) [5c,16,17]
1H NMR (400 MHz) δ 1.31 (s, 9H), 1.33 (s, 9H),
7.28 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.8 Hz,
2H), 7.40 (d, J = 8.8 Hz, 2H), 7.49 (d, J = 8.8
Hz, 2H). 13C NMR (100 MHz) δ 31.01 (three car-
bons), 31.11 (three carbons), 34.90, 35.23, 124.60,
125.63 (two carbons), 126.42 (two carbons), 127.41
(two carbons), 136.28 (two carbons), 140.18, 154.99,
157.51. IR (KBr) 3064, 2959, 2869, 1589, 1486, 1399,
1364, 1328, 1147, 1105, 1076, 826 cm−1. HRMS
(ESI) Calcd for C20H26O2S2Na [M + Na]+: 385.1266.
Found: 385.1271. mp 155–156◦C (lit. 143–145◦C [16],
147.5–149.5◦C [17], 150–151◦C [5c]).
N,N-Bis(3-chlorobenzenesulfonyl)-Nꢀ,
Nꢀ-dimethylhydrazine (19)
1H NMR (400 MHz) δ 2.80 (s, 6H), 7.52 (t, J = 8.0
Hz, 2H), 7.64 (d, J = 8.0 Hz, 2H), 7.87 (d, J = 8.0
Hz, 2H), 7.90 (s, 2H). 13C NMR (100 MHz) δ 45.23
(two carbons), 126.73 (two carbons), 128.55 (two
carbons), 130.26 (two carbons), 134.16 (two car-
bons), 135.17 (two carbons), 140.66 (two carbons).
IR (KBr) 3088, 3069, 2999, 2969, 2944, 2897, 1579,
1458, 1421, 1373, 1299, 1170, 899 cm−1. Anal. Calcd
for C14H14Cl2N2O4S2: C, 41.08; H, 3.45. Found: C,
41.29; H, 3.36. mp 62–63◦C.
S-(3-Methylphenyl) (3-methylbenzene)
thiosulfonate (23) [15]
1H NMR (400 MHz) δ 2.30 (s, 3H), 2.34 (s, 3H), 7.15
(d, J = 7.6 Hz, 1H), 7.15 (s, 1H), 7.22 (t, J = 7.6
Hz, 1H), 7.28 (d, J = 7.6 Hz, 1H), 7.31 (d, J = 7.6 Hz,
1H), 7.33–7.40 (m, 3H). 13C NMR (100 MHz) δ 21.09,
21.11, 124.71, 127.58, 127.98, 128.51, 129.10, 132.13,
133.59, 134.27, 137.16, 138.97, 139.36, 142.73. IR
(neat) 3058, 3024, 2953, 2923, 1592, 1474, 1330,
1141, 1079, 783 cm−1. MS (EI, 70 eV) m/z (rel. in-
tensity): 278 ([M]+, 80), 153 (100), 139 (81), 89 (58),
77 (82). HRMS (EI, 70 eV) Calcd for C14H14O2S2
[M]+: 278.0435. Found: 278.0437. Anal. Calcd for
C14H14O2S2: C, 60.40; H, 5.07. Found: C, 60.47; H,
5.15.
N,N-Di(2-naphthalenesulfonyl)-Nꢀ,
Nꢀ-dimethylhydrazine (20)
1H NMR (400 MHz) δ 2.82 (s, 6H), 7.61 (t, J = 7.6 Hz,
2H), 7.68 (t, J = 7.6 Hz, 2H), 7.88–7.99 (m, 8H), 8.49
(s, 2H). 13C NMR (100 MHz) δ 45.28 (two carbons),
123.03 (two carbons), 127.62 (two carbons), 127.90
(two carbons), 129.09 (two carbons), 129.48 (two
carbons), 129.59 (two carbons), 130.67 (two car-
bons), 131.82 (two carbons), 135.25 (two carbons),
136.08 (two carbons). IR (KBr) 3063, 2996, 2965,
2935, 2899, 1591, 1365, 1156, 1066, 899 cm−1. Anal.
Calcd for C22H20N2O4S2: C, 59.98; H, 4.58. Found:
C, 59.67; H, 4.80. mp 144–145◦C.
S-Phenyl benzenethiosulfonate (21) [3e,4h,4i]
S-(4-Methoxyphenyl) (4-methoxybenzene)
thiosulfonate (24) [4i,5b,18]
1H NMR (400 MHz) δ 7.30–7.38 (m, 4H), 7.39–7.50
(m, 3H), 7.57 (d, J = 8.0 Hz, 2H), 7.58 (t, J = 8.0
Hz, 1H). 13C NMR (100 MHz) δ 127.56 (two car-
bons), 127.83, 128.78 (two carbons), 129.42 (two car-
bons), 131.40, 133.60, 136.58 (two carbons), 142.96.
1H NMR (400 MHz) δ 3.83 (s, 3H), 3.87 (s, 3H), 6.85
(d, J = 8.8 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 7.27 (d, J
= 8.8 Hz, 2H), 7.50 (d, J = 8.8 Hz, 2H). 13C NMR (100
MHz) δ 55.45, 55.68, 113.80 (two carbons), 114.89
(two carbons), 118.91, 129.89 (two carbons), 134.92,
138.35 (two carbons), 162.18, 163.49. IR (KBr) 3060,
IR (neat) 3062, 1474, 1446, 1327, 1146, 1077 cm−1
.
MS (EI, 70 eV) m/z (rel. intensity): 250 ([M]+, 100),
141 (38), 125 (90), 109 (40), 77 (60). HRMS (EI, 70
eV) Calcd for C12H10O2S2 [M]+: 250.0122. Found:
250.0129. Anal. Calcd for C12H10O2S2: C, 57.57; H,
4.03. Found: C, 57.47; H, 4.19. mp 38–39◦C (lit. 39–
2941, 2836, 1590, 1494, 1323, 1260, 1139, 1020 cm−1
Anal. Calcd for C14H14O4S2: C, 54.17; H, 4.55. Found:
C, 54.18; H, 4.79. mp 83–84◦C (lit. 86–88◦C [18],
89.0–89.5◦C [5b], 89–90◦C [4i].
.
Heteroatom Chemistry DOI 10.1002/hc

342 Iwata et al.
S-(4-Chlorophenyl) (4-chlorobenzene)
thiosulfonate (25) [4h,12]
N,N-Bis(4-methylbenzenesulfonyl)-Nꢀ,
Nꢀ-dioctylhydrazine (28)
1H NMR (400 MHz) δ 7.31 (d, J = 8.8 Hz, 2H), 7.36
(d, J = 8.8 Hz, 2H), 7.42 (d, J = 8.8 Hz, 2H), 7.52
(d, J = 8.8 Hz, 2H). 13C NMR (100 MHz) δ 126.01,
128.93 (two carbons), 129.27 (two carbons), 129.92
(two carbons), 137.68 (two carbons), 138.56, 140.56,
141.28. IR (KBr) 3086, 2924, 1570, 1473, 1322, 1145,
1092, 1010, 823 cm−1. Anal. Calcd for C12H8Cl2O2S2:
C, 45.15; H, 2.53. Found: C, 44.99; H, 2.54. mp 137–
138◦C (lit. 134–136◦C [4i], 135–136◦C [15].
1H NMR (400 MHz) δ 0.89 (t, J = 7.2 Hz, 6H), 1.01–
1.35 (m, 24H), 2.45 (s, 6H), 2.98 (t, J = 8.0 Hz, 4H),
7.32 (d, J = 8.4 Hz, 4H), 7.87 (d, J = 8.4 Hz, 4H). 13C
NMR (100 MHz) δ 14.10 (two carbons), 21.64 (two
carbons), 22.63 (two carbons), 26.98 (two carbons),
28.62 (two carbons), 29.23 (two carbons), 29.34 (two
carbons), 31.81 (two carbons), 57.21 (two carbons),
128.98 (four carbons), 129.34 (four carbons), 136.71
(two carbons), 144.75 (two carbons). IR (neat) 3068,
3029, 2955, 2926, 2855, 1597, 1466, 1371, 1165, 1084
cm−1. Anal. Calcd for C30H48N2O4S2: C, 63.79; H,
8.57. Found: C, 63.71; H, 8.40.
S-(3-Chlorophenyl) (3-chlorobenzene)
thiosulfonate (26) [19,20]
1H NMR (400 MHz) δ 7.30 (td, J = 1.6, 7.6 Hz, 1H),
7.34 (t, J = 7.6 Hz, 1H), 7.34 (t, J = 1.6 Hz, 1H), 7.41
(t, J = 7.6 Hz, 1H), 7.46 (td, J = 1.6, 7.6 Hz, 1H),
7.49 (td, J = 1.6, 7.6 Hz, 1H), 7.55 (t, J = 1.6 Hz, 1H),
7.59 (td, J = 1.6, 7.6 Hz, 1H). 13C NMR (100 MHz)
δ 125.56, 127.61, 129.00, 130.16, 130.57, 131.90,
134.01, 134.62, 135.14, 135.28, 136.08, 143.96. IR
(neat) 3087, 1573, 1460, 1402, 1336, 1150, 1074, 784
cm−1. Anal. Calcd for C12H8Cl2O2S2: C, 45.15; H,
2.53. Found: C, 45.12; H, 2.65.
N-(4-Methoxybenzenesulfonyl)-N-(4-
methylbenzenesulfonyl)-Nꢀ,Nꢀ-dimethylhydrazine
(29)
1H NMR (400 MHz) δ 2.45 (s, 3H), 2.77 (s, 6H), 3.89
(s, 3H), 6.99 (d, J = 9.2 Hz, 2H), 7.32 (d, J = 8.4
Hz, 2H), 7.82 (d, J = 8.4 Hz, 2H), 7.88 (d, J = 9.2
Hz, 2H). 13C NMR (100 MHz) δ 21.64, 45.05 (two
carbons), 55.67, 113.94 (two carbons), 128.55 (two
carbons), 129.41 (two carbons), 130.87 (three car-
bons), 136.55, 144.77, 163.72. IR (KBr) 3070, 2965,
2845, 1595, 1498, 1360, 1268, 1160, 1084, 1027, 897
cm−1. HRMS (ESI) Calcd for C16H20N2O5S2Na [M +
Na]+: 407.0706. Found: 407.0703. mp 97–98◦C.
S-(2-Naphthyl) 2-naphthalenethiosulfonate (27)
[4i,5b]
1H NMR (400 MHz) δ 7.34 (dd, J = 1.6, 8.0 Hz,
1H), 7.44–7.69 (m, 7H), 7.73 (d, J = 8.0 Hz, 1H),
7.83 (d, J = 8.0 Hz, 1H), 7.83 (s, 1H), 7.88 (d, J
= 8.0 Hz, 2H), 7.93 (d, J = 1.6 Hz, 1H). 13C NMR
(100 MHz) δ 122.38, 125.13, 126.87, 127.64, 127.69,
127.85, 128.21, 128.37, 129.09, 129.30 (two car-
bons), 129.36, 129.43, 131.57, 131.81, 133.22, 134.07,
135.08, 137.68, 139.63. IR (KBr) 3056, 1587, 1500,
1322, 1142, 1063, 860, 811 cm−1. MS (EI, 70 eV)
m/z (rel. intensity): 350 ([M]+, 87), 175 (100), 159
(51), 127 (57), 115 (59). HRMS (EI, 70 eV) Calcd
for C20H14O2S2 [M]+: 350.0435. Found: 350.0434.
Anal. Calcd for C20H14O2S2: C, 68.54; H, 4.03. Found:
C, 68.56; H, 3.93. mp 111–112◦C (lit. 104.5–106.5◦C
[5b], 104–106◦C [4i].
Reaction of N-(4-Methoxybenzenesulfonyl)-
N-(4-methylbenzenesulfonyl)-Nꢀ,
Nꢀ-dimethylhydrazine (29)
A
solution of N-(4-methoxybenzenesulfonyl)-N-
(4-methylbenzenesulfonyl)-Nꢀ,Nꢀ-dimethylhydrazine
(29) (76.9 mg, 0.200 mmol) in chlorobenzene
(1.0 mL) was stirred in an oil bath maintained at
120◦C for 8 h. After being cooled to room tem-
perature, the mixture was concentrated in vacuo
to give a crude oil, which was chromatographed
on silica gel (hexane–ethyl acetate) to afford S-(4-
methylphenyl)
(6) (12.1 mg, 22%) as
methoxyphenyl) (4-methoxybenzene)thiosulfonate
(24) (10.0 mg, 16%) as white solid, and
47:53 mixture of S-(4-methylphenyl) (4-
methoxybenzene)thiosulfonate (30), and S-(4-
(4-methylbenzene)thiosulfonate
a
white solid, S-(4-
a
N,N-Dioctylhydrazine
a
This was prepared according to the literature
method [21].
methoxyphenyl)
(4-methylbenzene)thiosulfonate
1H NMR (400 MHz) δ 0.89 (t, J = 8 Hz, 6H),
1.18–1.40 (m, 22H), 1.54 (br s, 4H), 2.44 (t, J = 8 Hz,
4H).
(31) (15.9 mg, 27%) as a solid by 1H NMR analysis.
The spectral data for 6 or 24 have been already
shown.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of S-Aryl Arenethiosulfonates from N,N-Di(arenesulfonyl)hydrazines 343
[5] With Sm metal: (a) Liu, Y.; Zhang, Y. Tetrahedron
Lett 2003, 44, 4291–4294. With Fe(CO)5: (b) Alper,
H. Tetrahedron Lett 1969, 1239–1242. See also (c)
Lehto, E. A.; Shirley, D. A. J Org Chem 1957, 22, 1254–
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42, 3265–3270; (e) Armarego, W. L. F.; Turner, E. E.
J Chem Soc 1956, 3668–3673. For a review on the
reduction of sulfonic acid derivatives, see (f) Firouz-
abadi, H.; Jamalian, A. J Sulfur Chem 2008, 29, 53–
97.
S-(4-methylphenyl) (4-methoxybenzene) thiosul-
fonate (30). 1H NMR (400 MHz) (characteristic
peaks are shown) : 2.38 ppm (Me) and 3.87 ppm
(MeO).
S-(4-methoxyphenyl) (4-methylbenzene) thiosul-
fonate (31). 1H NMR (400 MHz) (characteristic
peaks are shown) : 2.42 ppm (Me) and 3.83 ppm
(MeO).
The characteristic peaks of 30 and 31 were as-
signed on the basis of the assumption that the Me or
MeO group bearing the SO2Ar group should show
low-field shifts.
[6] Smith, M. B.; March, J. March’s Advanced Or-
ganic Chemistry, 6th ed.; Wiley: Hoboken, NJ, 2007;
p 697.
[7] (a) Yamagishi, M.; Nishigai, K.; Ishii, A.; Hata, T.;
Urabe, H. Angew Chem, Int Ed 2012, 51, 6471–6474;
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(b) Abramovitch, R. A.; Bailey, T. D.; Takaya, T.; Uma,
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N,Nꢀ-Bis(4-methylbenzenesulfonyl)hydrazine
(34) [22]
1H NMR (400 MHz) δ 2.43 (s, 6H), 6.28 (s, 2H), 7.17
(d, J = 8.0 Hz, 4H), 7.59 (d, J = 8.0 Hz, 4H). IR (KBr)
3206 (NH), 3065, 2929, 1597, 1331, 1166, 1090, 813,
695 cm−1
.
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