Oxyhalogenation of thiols and disulfides into sulfonyl chlorides/bromides using oxone-KX (X = Cl or Br) in water

Article abstract of DOI:10.1039/c4gc00246f

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides by oxyhalogenation of thiols and disulfides with oxone-KX (X = Cl or Br) using water as the solvent is described. This journal is the Partner Organisations 2014.

Full text of DOI:10.1039/c4gc00246f

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PAPER
Oxyhalogenation of thiols and disulfides into
sulfonyl chlorides/bromides using oxone-KX
(X = Cl or Br) in water†
Cite this: Green Chem., 2014, 16,
3125
Sridhar Madabhushi,*a Raveendra Jillella,a Vinodkumar Sriramojua and Rajpal Singhb
Received 13th February 2014,
Accepted 21st March 2014
DOI: 10.1039/c4gc00246f
A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides by oxyhalogenation of
thiols and disulfides with oxone-KX (X = Cl or Br) using water as the solvent is described.
www.rsc.org/greenchem
toxic, inexpensive, and abundantly available solvent. In the lit-
erature, many organic transformations were known to proceed
Introduction
Organic sulfonyl chlorides are highly important as protecting very efficiently in water medium. Application of water as a reac-
agents in organic synthesis1 and they are also useful precur- tion medium also has several other advantages. For example, it
sors for preparation of sulfonic acids, sulfonamides and sulfo- enables more control on exothermic reactions due to its high
nates. In addition, they are industrially important building specific heat capacity. In a biphasic reaction system, organic
blocks for manufacture of elastomers, pharmaceuticals, dyes, products can be easily isolated by phase separation or by simple
detergents, ion exchange resins, herbicides, etc.2 Sulfonyl filtration. Water, with its dense network of hydrogen bonds, can
chlorides are generally prepared by oxychlorination of thiols highly influence the reactivity of a substrate. Water has a high
and disulphides using aqueous chlorine.3 Many methods are dielectric constant and low molecular size and hence, it can dis-
available in the literature to accomplish this reaction using a solve polar and ionic compounds such as salts, surfactants,
variety of reagents such as SOCl2–H2O2,4 POCl3–H2O2,5 TiCl4– cyclodextrins, etc. very efficiently. For this reason, water is often
H2O2,6 and Me3SiCl–KNO3.7 The other important approaches used as a co-solvent for carrying out reactions between an
for preparation of sulfonyl chlorides include chlorination of organic substrate and a reactive inorganic salt such as peroxy-
sulfonic acid using reagents such as 2,4,6-trichloro-1,3,5-tri- sulfates, permanganates, perhalates, nitrates, etc.
azine,8 thionylchloride, and trichloroacetonitrile-triphenylphos-
phene9 and reactions of Grignard reagents with sulfur dioxide
and thionyl chloride.10 In most of these methods, toxic and
Results and discussion
highly corrosive reagents were used and reaction was carried
out using organic solvents. These methods also suffer from
Oxone or potassium peroxymonosulfate [2KHSO5·KHSO4·
one or more disadvantages such as vigorous reaction con-
K2SO4] is an inexpensive, environmentally benign and widely
ditions, formation of side products, long reaction times and
used stable oxidant. It has been extensively studied in the lit-
tedious workup procedures for isolation of the pure products.
erature for a variety of oxidative transformations and some
Therefore, development of a milder and practical method for
other important reactions such as oxidation of alkenes to epox-
the synthesis of sulfonyl chlorides is highly desirable.
ides,12 thioethers to sulfones,13 aldehydes to carboxylic
The growing usage of volatile organic solvents in industry
acids,14 tertiary amines to amine oxides,15 etc. It is also shown
has become a major environmental concern, and in recent
to be useful for promoting aromatic bromination,16 hydroxy-
years, studies on development of ‘green’ processes by replacing
bromination,17 and benzylic oxidation18 reactions in the pres-
toxic-organic solvents with alternative non-toxic media have
ence of salts such as NH4Br, KBr, etc. Recently we found that
gained high importance.11 Water is a non-flammable, non-
alkynes undergo efficient oxyhalogenation with oxone-KX (X =
Cl, Br or I) and convert into α,α-dihaloketones.19 In continu-
aFluoroorganics Division, CSIR-Indian Institute of Chemical Technology,
Hyderabad-500007, India. E-mail: smiict@gmail.com; Fax: +91 40 27160387;
Tel: +91 40 27191772
ation of our research interest on oxone mediated oxyhalogena-
tion reactions, we herein report a new application of oxone-KX
(X = Cl or Br) for efficient preparation of sulfonyl chlorides
(68–98%) and sulfonyl bromides (89–96%) from thiols and dis-
ulfides by oxyhalogenation reaction under mild conditions
using water as a reaction medium as shown in Scheme 1.
bCentre for Fire Explosives and Environmental Safety, DRDO, Timarpur,
New Delhi-110054, India
†Electronic supplementary information (ESI) available: Characterization data
and copies of NMR spectra. See DOI: 10.1039/c4gc00246f
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Table 2 Reaction of thiophenol and KCl with various oxidants
%Yielda
PhSSPh
S. no.
Oxidant
Reaction time (h)
PhSO2Cl
1
2
3
4
5
IBX
NaIO4
H2O2
m-CPBA
TBHP
10
10
10
10
10
68
98
22
0
No reaction
No reaction
No reaction
a Isolated yields. Reactions were studied at room temperature using 2.5
equiv. of oxidant and 1 equiv. of KCl in water.
Scheme 1 Synthesis of sulfonyl halides from thiols and disulfides with
oxone-KX in water.
In our preliminary experiments, reaction of thiophenol with
0.5 equivalent of oxone and 0.5 equivalent of KCl in water at
room temperature was found to produce diphenyl disulfide in
a quantitative yield. However, when 1.0 equivalent of oxone
and 1.0 equivalent of KCl were used in this reaction, we
obtained a mixture of diphenyl disulfide and sulfonyl chloride
and with 2.5 equivalents of oxone and 1.0 equivalent of KCl,
we obtained phenylsulfonyl chloride in 98% yield. In our
study, oxone was found to promote this reaction effectively
also with other halogen sources such as aq. HCl, NaCl, KBr,
KI, aq. HBr, AlCl3, FeCl3, ZnCl2 and NH4Br, which gave benzene-
sulfonyl halide in 88–98% yields in 10–20 minutes. These
results are shown in Table 1.
to be highly unstable and decomposed rapidly at room temp-
erature. We also studied the scope of oxyhalogenation of a
thiol with other oxidants such as 2-iodoxybenzoic acid (IBX),
sodium periodate, 30% hydrogen peroxide, m-chloroperbenzoic
acid (mCPBA) and t-butyl hydrogen peroxide (TBHP). For
example, results observed in the reaction of thiophenol with
these oxidants in the presence of KCl at room temperature
using water as the solvent are shown in Table 2. In this study,
IBX was found to produce a mixture of disulphenyl disulfide
and phenyl sulfonyl chloride in a 2 : 1 ratio and with sodium
periodate, we obtained only diphenyl disulfide in a quantita-
tive yield and no reaction was observed with the other oxidants,
i.e. H2O2, mCPBA and TBHP, under the reaction conditions.
In the study of screening of halogen sources (Table 1), we
found formation of sulfonyl chlorides and bromides in
maximum yields with KCl and KBr respectively. Next, we
studied oxychlorination of a variety of aliphatic, aromatic and
heteroaromatic thiols 1a–n with oxone-KCl in water and
obtained the corresponding sulfonyl chlorides 2a–n in 68–95%
yields as shown in Table 3. Using a similar procedure, we
studied oxybromination of thiols 1a–f with oxone-KBr and
observed formation of the corresponding sulfonyl bromines
3a–f in 89–96% yields as shown in Table 4. Chloride and, at
the end of reaction, no disulfide was observed and only sulfo-
nyl chloride formed. In a control experiment, reaction of thio-
phenol with 0.5 equivalent of oxone and 0.5 equivalent of KCl
gave diphenyl disulfide in 96% yield in 10 min. It shows that
oxone-KCl initially oxidizes thiol into disulfide, which under-
goes further reaction and converts into sulfonyl chloride. We
prepared a variety of symmetrical disulfides, which were found
to undergo efficient oxyhalogenation with 2 equivalents of
oxone and 2 equivalents of KCl in water at room temperature
producing sulfonyl chlorides in 82–98% yields as shown in
Table 5.
Here, though we could prepare phenyl sulfonyl iodide in
high yield (90%) by this method using oxone-KI, it was found
Table 1 Screening of various halogen sources
Halogen
source
Reaction time
(min)
S. no.
1
Product
%Yielda
98
KCl
10
10
15
10
15
12
10
12
10
—
2
KBr
97
90
95
90
90
98
89
88
—
3
KI
4
NaCl
5
NaBr
6
NH4Br
AlCl3
7
The plausible mechanism for transformation of thiols into
sulfonyl halides via disulfides by reaction with oxone-KX is
shown in Scheme 2. In this mechanism, oxone initially reacts
with KX in water and produces hypohalous acid (HOX).20 Next,
hypohalous acid reacts with thiol to produce sulfinyl halide,
which converts into a disulfide by reaction with another mole-
cule of thiophenol. In the subsequent steps, disulfide reacts
with HOX and converts into RS(O)-S(O)R. It is amply reported
in the literature that RS(O)-S(O)R rapidly rearranges into RSO2-
8
50% aq. HCl
48% aq. HBr
9
10
N.R.
a Isolated yields.
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Table 3 Synthesis of sulfonyl chloride from thiols with oxone-KCI
Entry
a
RSH 1
RSO2Cl 2
Reaction time (min)
10
%Yielda
98
b
c
15
12
97
95
d
e
12
15
96
92
f
10
15
15
89
95
92
g
h
i
j
12
10
90
88
k
10
20
15
90
93
88
1
m
n
12
68
a Isolated yields. All products gave satisfactory spectral data.
SR,21 which upon reaction with HCl cleaves into RSO2X and by oxyhalogenation of thiols and disulfides with oxone-KX (X =
RSH. RSH undergoes a few more similar reaction cycles and Cl or Br) under mild conditions using water as a solvent.
converts into RSO2X. In our study, we found that the present
General information
oxyhalogenation of a thiol into sulfonyl halide requires 2.5
equivalents of oxone and 1.0 equivalent of KX and it is in
accordance with the proposed mechanism.
Oxone, N-chlorosuccinimide, NH4Br, and KBr were purchased
from Sigma-Aldrich Ltd, India. HCl, HBr, NaCl, KCl, KI, AlCl3,
and solvents used in this study were procured from SD Fine
Chem. Ltd, India. Melting points of the compounds were
recorded on Veego programmable melting point apparatus in
open capillaries and are uncorrected. IR spectra were recorded
on a PerkinElmer FT-IR 240-C spectrophotometer using KBr
Conclusions
In conclusion, we showed an efficient and rapid method for and neat optics. 1H NMR spectra were recorded on a Bruker AV
preparation of sulfonyl chlorides and bromides in high yields 300 MHz in CDCl3 using TMS as the internal standard. All the
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Table 4 Oxybromination of thiols with oxone-KBr
Reaction
time (min)
Entry
a
RSH 1
RSO2Br 3
%Yielda
96
10
b
c
10
12
95
92
d
e
10
15
89
90
Scheme 2 Plausible mechanism for transformation of thiols and
disulfides into sulfonyl halides with oxone-KX.
f
10
95
(8.6 mmol), KCl (3.4 mmol), and water (10 mL) was taken in a
round bottomed flask and stirred at room temperature. This
reaction is slightly exothermic and the temperature of the
mixture rose to 45 °C. After completion of the reaction (TLC),
a lsolated yields. All products gave satisfactory spectral data.
reactions were monitored by thin layer chromatography (TLC) the reaction mixture was extracted with ethyl acetate (4 ×
on precoated silica gel 60 F254 (mesh); spots were visualized 5 mL). The combined organic layer was dried over anhydrous
with UV light or by charring with anisaldehyde solution. Na2SO4 and concentrated under reduced pressure. The crude
Merck silica gel (60–120 mesh) was used for column product obtained was purified by normal column chromato-
chromatography.
graphy (silica gel 60–120 mesh, n-hexane) to obtain the corres-
General procedure for the preparation of sulfonyl chlorides ponding sulfonyl chloride. A similar procedure was used for
with oxone-KX. A mixture of thiol (3.4 mmol), oxone preparation of sulfonyl bromides with oxone-KBr.
Table 5 Preparation of sulfonyl chlorides from disulfides with oxone-KCl
S. no.
1
R–S–S–R
RSO2Cl
Reaction time (min)
10
%Yielda
95
2
3
4
5
10
12
10
15
96
94
82
98
6
7
10
10
90
91
a Isolated yields. All products gave satisfactory spectral data.
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General procedure for the preparation of sulfonyl chlorides
4-Fluorobenzene-1-sulfonyl chloride (2g). Colorless oil
from disulfides. A mixture of disulfide (1.7 mmol), oxone (0.28 g, 95%). 1H NMR (300 MHz, CDCl3): δ = 8.10–8.07 (m,
(3.5 mmol) KCl (3.5 mmol), and water (10 mL) was taken in a 2H), 7.33–7.28 (m, 2H); 13C NMR (75 MHz, CDCl3): δ = 168.1,
round bottomed flask and stirred at room temperature. After 130.1, 130.0, 117.2, 116.9; IR (neat): ν 3108, 3073, 2928, 1589,
completion of the reaction (TLC), the reaction mixture was 1492, 1380, 1182, 840, 569 cm−1. EI-HRMS: exact mass
extracted with ethyl acetate (4 × 5 mL) and the combined observed for C6H4ClFO2S: 193.9601 (calculated: 193.9604).
organic layer was dried over anhydrous Na2SO4 and concen-
3-Chloro-4-fluorobenzene-1-sulfonyl chloride (2h). Colorless
1
trated under reduced pressure. The crude product obtained oil (0.25 g, 92%). H NMR (300 MHz, CDCl3): δ = 8.14 (dd, J =
was purified by normal column chromatography (silica gel 2.4 Hz, 1H), 8.01–7.92 (m, 1H), 7.43–7.39 (m, 1H); 13C NMR
60–120 mesh, n-hexane) to obtain the corresponding sulfonyl (75 MHz, CDCl3): δ = 163.7, 130.1, 127.8, 127.6, 118.2, 117.8;
chloride.
IR (neat): ν 2927, 2757, 1593, 1474, 1228, 1163, 1101,
884 cm−1. EI-MS: 227, 224, 195, 193, 129. 129, 109, 94, 79;
EI-HRMS: exact mass observed for C6H3Cl2FO2S: 227.9211 (cal-
culated: 227.9214).
Characterization data of sulfonyl halides 2a–n and 3a–f
Benzenesulfonyl chloride (2a). Colorless oil (0.31 g, 98%).
3,4-Dimethoxybenzene-1-sulfonyl chloride (2i). White solid
1H NMR (300 MHz, CDCl3): δ = 8.05–8.04 (m, 2H), 7.76 (t, J = (0.24 g, 90%). 1H NMR (300 MHz, CDCl3): δ = 7.68 (dd, J =
7.3 Hz, 1H), 7.62 (t, J = 7.7 Hz, 2H); 13C NMR (75 MHz, CDCl3): 2.2 Hz, 1H), 7.44 (d, J = 2.2 Hz, 1H), 7.68 (d, J = 8.5 Hz, 1H),
δ = 136.4, 133.6, 131.3, 129.3, 128.7, 127.4; IR (neat): ν 3065, 3.99 (s, 3H), 3.97 (s, 3H); 13C NMR (75 MHz, CDCl3): δ = 154.6,
2926, 2855, 1444, 1326, 1144, 1077, 750, 593 cm−1. EI-MS 176, 149.2, 135.8, 121.6, 110.4, 108.9, 56.4, 56.3; IR (neat): ν 2929,
159, 112, 95, 75, 57; EI-HRMS: exact mass observed for 2862, 1461, 1406, 1229, 1183, 1119, 1034, 819 cm−1. EI-MS:
C6H5ClO2S: 175.9695 (calculated: 175.9698).
236, 201, 153, 137, 94, 79; EI-HRMS: exact mass observed for
4-Chlorobenzene-1-sulfonyl chloride (2b). White solid C8H10ClO4S: 235.9916 (calculated: 235.9910).
1
(0.28 g, 97%). H NMR (300 MHz, CDCl3): δ = 7.98 (d, J = 8.6
Pyridine-2-sulfonyl chloride (2j). Colorless oil (0.28 g, 88%).
Hz, 2H) 7.60 (d, J = 8.6 Hz, 2H), 13C NMR (75 MHz, CDCl3): δ = 1H NMR (300 MHz, CDCl3): δ = 8.64–8.55 (m, 1H), 7.98–7.85
142.4, 140.4, 137.6; IR (neat): ν 3109, 3052, 1573, 1474, 1184, (m, 3H); 13C NMR (75 MHz, CDCl3 + DMSO-D6): δ = 155.2,
1088, 825, 755, 559 cm−1. EI-MS 212, 201, 177, 175, 111, 75, 146.0, 140, 126.1, 123.3; IR (neat): ν 3029, 1453, 1028,
69; EI-HRMS: exact mass observed for C6H4Cl2O2S: 209.9319 638 cm−1. EI-MS 177, 175, 159, 111, 69, 57; EI-HRMS: exact
(calculated: 209.9309).
mass observed for C5H4ClO2S: 176.96526 (calculated:
3-Fluorobenzene-1-sulfonyl chloride (2c). Pale yellow solid 176.96513).
1
(0.28 g, 95%). H NMR (300 MHz, CDCl3): δ = 7.98 (d, J = 8.1
4-(Trifluoromethyl)benzene-1-sulfonyl chloride (2k). Colour-
1
Hz, 2H), 7.30 (d, J = 8.1 Hz, 2H), 6.69 (s, 1H), 2.44 (s, 3H); less oil (0.24 g, 90%). H NMR (300 MHz, CDCl3): δ = 8.20 (d,
13C NMR (75 MHz, CDCl3): δ = 163.5, 131.4, 122.7, 122.4, J = 8.3 Hz, 2H), 7.92 (d, J = 8.3 Hz, 2H); 13C NMR (75 MHz,
114.1, 113.7; IR (neat): ν 3108, 3056, 2927, 2757, 1593, 1474, CDCl3): δ = 147.0, 136.9, 136.4, 136.1, 127.6, 127.0, 126.9; IR
1368, 1228, 1163, 884, 595 cm−1. EI-HRMS: exact mass (neat): ν 3026, 1454, 1242, 1145, 1014, 940, 780 cm−1
;
observed for C6H4ClFO2S: 193.9602 (calculated: 193.9604).
EI-HRMS: exact mass observed for C7H4ClF3O2S: 243.9569 (cal-
4-Methylbenzene-1-sulfonyl chloride (2d). White solid culated: 243.9572).
1
(0.29 g, 96%). H NMR (300 MHz, CDCl3): δ = 7.89 (d, J = 8.4
4-Methoxybenzene-1-sulfonyl chloride (2l). Colorless oil
Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 2.59 (s, 3H); 13C NMR (0.27 g, 93%). 1H NMR (300 MHz, CDCl3): δ = 7.97 (d, J =
(75 MHz, CDCl3): δ = 146.8, 130.2, 126.9, 21.7; IR (KBr): ν 3009, 9.0 Hz, 2H), 7.04 (d, J = 9.0 Hz, 2H), 3.92 (s, 3H); 13C NMR
1690, 1598, 1481, 1231, 993, 796 cm−1. EI-MS 191, 175, 128, (75 MHz, CDCl3): δ = 159.8, 132.6, 128.3, 114.5, 55.3; IR (neat):
111, 75, 55; EI-HRMS: exact mass observed for C7H7ClO2S: ν 3052, 3007, 2926, 2854, 1574, 1463, 1367, 1281, 1171,
189.9854 (calculated: 189.9855).
1088, 944 cm−1. EI-MS 206, 190, 175, 142, 75, 55; EI-HRMS:
Naphthalene-1-sulfonyl chloride (2e). White solid (0.25 g, exact mass observed for C7H7ClO3S: 205.9803 (calculated:
1
92%). H NMR (300 MHz, CDCl3): δ = 8.61 (s, 1H), 8.08–7.96 205.9804).
(m, 4H), 7.78–7.67 (m, 2H); 13C NMR (75 MHz, CDCl3): δ =
1-Methyl-1H-tetrazole-5-sulfonyl chloride (2m). Colorless oil
130.3, 130.2, 129.8, 128.9, 128.3, 128.1, 121.2; IR (neat): ν 3108, (0.27 g, 88%). 1H NMR (300 MHz, CDCl3): δ = 40.18 (s, 3H); 13
C
3073, 2928, 1589, 1492, 1380, 1182, 1081, 840 cm−1. EI-MS: NMR (75 MHz, CDCl3): δ = 143.08; IR (neat): ν 2928, 2858,
226, 210, 208, 146, 127, 115, 77, 57; EI-HRMS: exact mass 1633, 1343, 1056, 771 cm−1. Mass: ESI-MS: 181 (M + H), 203
observed for C10H7ClO2S: 225.9854 (calculated: 225.9855).
(M + Na).
Cyclohexanesulfonyl chloride (2f). Colorless oil (0.27 g,
Hexane-1-sulfonyl chloride (2n). Colorless oil (0.21 g, 68%).
89%). 1H NMR (300 MHz, CDCl3): δ = 3.56–3.46 (m, 1H), 1H NMR (300 MHz, CDCl3): δ = 3.38 (t, J = 7.3, 7.4 Hz, 2H),
2.42–2.37 (m, 2H), 2.01–1.95 (m, 2H), 1.75–1.62 (m, 3H), 1.69–1.62 (m, 2H), 1.41–1.30 (m, 6H), 0.89 (t, J = 6.6, 6.7 Hz,
1.48–1.18 (m, 3H); 13C NMR (75 MHz, CDCl3): δ = 74.7, 27.0, 3H); 13C NMR (75 MHz, CDCl3): δ = 62.5, 36.1, 31.0, 23.3, 22.3,
24.8, 24.5; IR (neat): ν 2938, 2859, 1451, 1369, 1219, 1160, 751, 13.8; IR (neat): ν 2929, 2857, 1463, 1378, 1256, 988, 725 cm−1
.
589 cm−1; EI-MS: m/z. 182, 118, 99, 83, 67, 55; EI-HRMS: exact EI-MS: 184, 141, 125, 109, 77, 69, 57; EI-HRMS: exact mass
mass observed for C6H11ClO2S: 182.0164 (calculated:182.0168). observed for C6H13ClO2S: 184.0322 (calculated: 184.0324).
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Benzenesulfonyl bromide (3a). Colorless oil (0.38 g, 96%).
503–507, pp. 736–739; (b) P. J. Kociensky, Protecting Groups,
Thieme, New York, 1994, 96–102; (c) G. Theodoridis, Tetra-
hedron, 2000, 56, 2339–2358.
1H NMR (300 MHz, CDCl3): δ = 8.02–7.99 (m, 2H), 7.76 (t, J =
7.3 Hz, 1H), 7.63 (t, J = 7.7 Hz, 2H); 13C NMR (75 MHz, CDCl3):
δ = 136.4, 133.6, 131.3, 129.3, 128.7, 127.4; IR (neat): ν 3022,
2919, 1489, 1329, 1143, 806, 653 cm−1. EI-MS 220, 171, 158,
137, 97, 69; EI-HRMS: exact mass observed for C6H5ClO2S:
219.91920 (calculated: 219.91936).
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4-Chlorobenzene-1-sulfonyl bromide (3b). White solid
(0.35 g, 95%). 1H NMR (300 MHz, CDCl3): δ = 7.98 (d, J =
8.6 Hz, 2H), 7.60 (d, J = 8.6 Hz, 2H); 13C NMR (75 MHz,
CDCl3): δ = 142.4, 140.4, 130.0; IR (neat): ν 3109, 3052, 1573,
1474, 1184, 1088, 825, 755, 559 cm−1. EI-MS 256, 254, 177,
175, 113, 111, 75, 76; EI-HRMS: exact mass observed for
C6H4Cl2O2S: 253.87998 (calculated: 253.88039).
3-Fluorobenzene-1-sulfonyl bromide (3c). Colorless oil
(0.34 g, 92%). 1H NMR (300 MHz, CDCl3): δ = 7.84–7.80 (m, 2H),
7.72–7.60 (m, 2H), 7.49–7.43 (m, 1H); 13C NMR (75 MHz,
CDCl3): δ = 163.5, 131.4, 122.7, 122.4, 114.1, 113.7; IR (neat):
ν 3073, 2938, 1564, 1485, 1378, 1192, 846 cm−1. EI-HRMS: exact
mass observed for C6H4BrFO2S: 237.9096 (calculated: 237.9099).
4-Methylbenzene-1-sulfonyl chloride (3d). White solid
(0.33 g, 89%). 1H NMR (300 MHz, CDCl3): δ = 7.87 (d, J =
8.0 Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 2.46 (s, 3H); 13C NMR
(75 MHz, CDCl3): δ = 142.20, 136.81, 130.06, 126.40, 21.80;
IR (KBr): ν 3010, 2923, 1584, 1457, 1027, 696 cm−1. EI-MS 234,
202, 186, 171, 139, 123, 107, 92, 77; EI-HRMS: exact mass
observed for C7H7BrO2S: 233.9348 (calculated: 233.9350).
Naphthalene-2-sulfonyl bromide (3e). Pale yellow solid
(0.30 g, 90%). 1H NMR (300 MHz, CDCl3): δ = 8.62 (s, 1H), 10 (a) W. Holly, G. R. Carlos, M. Isabel, A. L. Thompson and
8.10–7.99 (m, 4H), 7.80–7.70 (m, 2H); 13C NMR (75 MHz,
CDCl3): δ = 135.6, 132.1, 130.3, 130.1, 129.9, 128.3, 128.1, 121.0;
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IR (neat): ν 3063, 2946, 1589, 1455, 1237, 1025, 840 cm−1
.
EI-MS: 270, 185, 149, 139, 123, 69, 57; EI-HRMS: exact mass 11 (a) J. Zhang, C. Wei and C. J. Li, Tetrahedron Lett., 2002, 43,
observed for C10H7ClO2S: 269.93500 (calculated: 269.93501).
Cyclohexanesulfonyl bromide (3f). Colorless oil (0.37 g,
95%). 1H NMR (300 MHz, CDCl3): δ = 3.54–3.44 (m, 1H),
2.40–2.36 (m, 2H), 1.97–1.94 (m, 2H), 1.73–1.60 (m, 3H),
1.45–1.12 (m, 3H); 13C NMR (75 MHz, CDCl3): δ = 74.7, 27.0,
24.8, 24.5; IR (neat): ν 2938, 2859, 1451, 1369, 1219, 1160, 751,
589 cm−1; EI-MS: m/z. 227, 225, 191, 163, 148, 111, 97, 83, 69,
55; EI-HRMS: exact mass observed for C6H11BrO2S: 225.9661
(calculated: 225.9663).
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Acknowledgements
S.M. is thankful to CSIR, New Delhi for the financial support
through the XII five year plan project DITSF (code: CSC0204).
R.J. is thankful to CSIR, New Delhi for the financial support in
the form of a Senior Research Fellowship.
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