Clean and economic synthesis of alkanesulfonyl chlorides from S-alkyl isothiourea salts via bleach oxidative chlorosulfonation

Article abstract of DOI:10.1055/s-0033-1338567

A simple procedure for clean and economic synthesis of alkanesulfonyl chlorides via bleach-mediated oxidative chlorosulfonation of S-alkyl isothiourea salts is disclosed. This procedure is environment- and worker-friendly with the advantages of readily accessible materials and reagents, simple and safe operations, easy purification without chromatography, and affords high yields of up to 99%.

Full text of DOI:10.1055/s-0033-1338567

PAPER
▌225
paper
Clean and Economic Synthesis of Alkanesulfonyl Chlorides from S-Alkyl
Isothiourea Salts via Bleach Oxidative Chlorosulfonation
Clean Synthesis of Alkanesulfonyl Chlorides
Zhanhui Yang, Bingnan Zhou, Jiaxi Xu*
State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, Faculty of Science, Beijing University of Chemical
Technology, Beijing 100029, P. R. of China
Fax +86(10)64435565; E-mail: jxxu@mail.buct.edu.cn
Received: 11.10.2013; Accepted after revision: 08.11.2013
Bleach has been widely applied in bleaching, disinfection,
Abstract: A simple procedure for clean and economic synthesis of
and water treatment. In synthetic chemistry, it is common-
alkanesulfonyl chlorides via bleach-mediated oxidative chlorosul-
ly used in chlorination5 and oxidation.6 Among the many
chlorinating and oxidizing reagents, it is regarded as one
fonation of S-alkyl isothiourea salts is disclosed. This procedure is
environment- and worker-friendly with the advantages of readily
accessible materials and reagents, simple and safe operations, easy of the most environment-friendly and atom-economic re-
purification without chromatography, and affords high yields of up
to 99%.
agents, according to the reagent guide developed by Dunn
and co-workers.7 Thus, it has the potential to replace other
Key words: bleach, sulfonyl chloride, S-alkyl isothiourea, chloro-
sulfonation, oxidation
unsatisfactory chlorinating and oxidizing reagents in syn-
thetic chemistry, and presents simple and green proce-
dures. Based on these facts, we planned the direct
oxidative chlorosulfonation of S-alkyl isothiourea salts,
Sulfonyl chlorides are an extraordinarily important class which are readily accessible from the reaction of corre-
of compounds that have been widely used as synthetic in- sponding alkyl halides or mesylates and thiourea. This
termediates and building blocks in both synthetic and me- procedure is supported by the fact that S-alkyl isothiourea
dicinal chemistry.1 As a result, many methods have been salts and sulfonyl chlorides have distinctly different solu-
developed for their syntheses.1,2 Among the starting mate- bilities in most organic solvents, and the by-products urea
rials involved, S-alkyl isothiourea salts are considered as and sodium salts are well soluble in water (Scheme 1).
easily accessible, inexpensive, and green. They can be Therefore, the products can be easily isolated and purified
converted into the corresponding sulfonyl chlorides via by extraction with suitable organic solvents. In continua-
the oxidative chlorosulfonation. Chlorine gas,3a,b H2O2– tion of our work on simple and green syntheses of sulfonic
HCl,3c,d KMnO4/HCl,3e HCl-treated silica gel and acid derivatives, especially sulfonyl chlorides, herein, we
PhIO,3f,g and NaClO3/HCl3i have been applied in the oxi- present the bleach-mediated oxidative chlorosulfonation
dative chlorosulfonation. Recently, we successfully real- of S-alkyl isothiourea salts to synthesize alkanesulfonyl
ized the oxidative chlorosulfonation of S-alkyl isothiourea chlorides.
salts into the corresponding sulfonyl chlorides with N-
chlorosuccinimide3h and NaClO23j as the oxidative chlori-
nating reagents under acidic conditions. In the N-chloro-
succinimide method, organic by-product succinimide is
generated three times the amount of sulfonyl chlorides.
Although it can be converted to N-chlorosuccinimide with
sodium hypochlorite in acetic acid, it interferes with the
purification of desired products in some cases. To over-
come the drawbacks, the best way is to use the inorganic,
clean, and atom-economic reagents, among which
NaClO2 is a choice. After analyzing its oxidative chloro-
sulfonation mechanism, we rationalized that NaClO
should be another clean and atom-economic reagent for
the oxidative chlorosulfonation of S-alkyl isothiourea
salts. Thus, we turned to the ubiquitous household chem-
ical bleach, which was reported to mediate oxidative chlo-
rosulfonation of odious starting materials, heteroaryl
thiols, alkyl thiols, and disulfides, into the corresponding
sulfonyl chlorides.4
soluble in most
organic solvents
H2N
RSO2Cl
bleach, H+
3
CS(NH2)2
NH X–
R
X
+
EtOH
reflux, 1 h
R
S
H2O, 0–20 °C
2
1
CO(NH2)2 + NaCl
soluble in H2O
insoluble in most
organic solvents
Scheme 1 Synthesis and purification of alkanesulfonyl chlorides
from S-alkyl isothiourea salts via NaClO oxidative chlorosulfonation
The reaction optimization commenced with the treatment
of S-benzyl isothiouronium chloride (2a) as an example
with bleach and hydrochloric acid (Table 1, entries 1–3).
The results suggest that, to add the accurate amount of the
bleach, it should better be titrated prior to use for both the
bench-stored bleach and the freshly manufactured sample
to afford good results. For the highest yield, the oxidative
chlorosulfonation of 2a was carried out with 30 mL of
freshly manufactured 5% bleach and 2 mL of 6 M H2SO4.
During the optimization, we found that the starting mate-
rial 2a did not completely dissolve in water; thus, when
the product 3a was generated, it was contaminated with
trace amount of 2a. As a result, purification of 3a by direct
SYNTHESIS 2014, 46, 0225–0229
Advanced online publication: 28.11.2013
DOI: 10.1055/s-0033-1338567; Art ID: SS-2013-H0637-OP
© Georg Thieme Verlag Stuttgart · New York
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1
1
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226
Z. Yang et al.
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Table 1 Optimization of Reaction Conditionsa
Table 2 Synthesis of Diverse Important Sulfonyl Chloridesa
H2N
H2N
bleach, 6 M H2SO4
H2O, 0–20 °C
conditions
NH2 X–
NH2 Cl–
RSO2Cl
BnSO2Cl
0–20 °C, 30 min
R
S
Bn
S
2
3
2a
3a
Entry Substrate
2
Product
3
Yield
(%)
Entry
Conditions
Yield (%)
1b
2c
3d
4d
10% bleach (30 mL), 2 M HCl (10 mL)
5% bleach (30 mL), 3 M HCl (10 mL)
5% bleach (30 mL), concd HCl (2 mL)
5% bleach (30 mL), 6 M H2SO4 (2 mL)
39
65
88
93
NH X–
SO2Cl
S
NH2
R1
R1
1
2
3
4
5
6
R1 = H, X = Cl
R1 = F, X = Cl
R1 = Cl, X = Cl
R1 = CN, X = Cl
R1 = NO2, X = Br
2a
R1 = H
3a 93
3b 99
3c 99
3d 99
3e 85
3f 87
a Reactions conducted on a 5 mmol scale.
2b R1 = F
2c
R1 = Cl
2d R1 = CN
b The bleach was 1 year and 4 months old. A series of optimizations
using different volumes up to 30 mL of bleach and different concen-
trations of HCl gave poor results.
c Freshly purchased bleach was used, but the sample was 6 months
old.
d Freshly purchased bleach manufactured within 2 months was used.
2e
2f
R1 = NO2
R1 = Me
R1 = Me, X = Cl
NH2 X–
filtration upon completion of the reaction seemed to be
not so satisfactory; consequently, further purification such
as recrystallization is required. This problem was also en-
countered by Sprague and co-workers who employed
chlorine gas to mediate the oxidative chlorosulfonation of
isothiourea salts. To solve this problem and to get the
highly pure product by simple purification, we decided to
add diethyl ether to the reaction vessel. When 3a was gen-
erated, it would be extracted immediately into the ethereal
phase, leaving 2a as a suspension in the aqueous phase to
react with NaClO. As expected, 3a was easily separated in
high purity by partition of the ethereal phase, which could
be isolated by the usual workup procedure. Moreover, the
extraction of 3a into diethyl ether minimized its hydroly-
sis, and thus gave a good 93% yield after the usual workup
(see experimental).
SO2Cl
n
S
NH2
n
7
n = 2, X = Br
n = 4, X = Br
n = 6, X = Br
n = 10, X = Br
n = 14, X = Br
2g
n = 2
3g 98
3h 93
3i 96
3j 97
3k 98
8
2h n = 4
9
2i
2j
n = 6
10
11
n = 10
2k n = 14
NH2 Br–
12
2l
3l 80
3m 71
3n 94
SO2Cl
S
NH2
H2N
2–
13b
14
2m MeSO2Cl
NH2
SO4
MeS
2
NH2 MsO–
NH2
MeO
With this simple procedure in hand, we decided to synthe-
size various significantly important sulfonyl chlorides.
Phenylmethanesulfonyl chloride and its phenyl-modified
congeners have been extensively used as sulfene precur-
sors in mechanistic studies,8 and as building blocks for the
antibacterial medicines and enzyme inhibitors.9 These
privileged structures became our preferred synthetic tar-
gets. To our delight, the substituted phenylmethanesulfo-
nyl chlorides were obtained in good (Table 2, entries 5, 6)
to excellent yields (entries 2–4), regardless of the elec-
tron-donating or electron-withdrawing substituents. The
relatively low yield (85%) of 4-nitrophenylmethanesulfo-
nyl chloride is attributed to its high reactivity to water,
while that of 4-tolylmethanesulfonyl chloride (87%) to its
intrinsic property to decompose because of the electron-
donating methyl group. The alkanesulfonyl chlorides, es-
pecially those with long chains, are widely applied in the
production of fine chemicals such as detergents and
dyes.10 In synthetic chemistry, they also have powerful
functions, which have been exemplified by the asymmet-
ric synthesis of β-sultones1d and β-sultams1e as reported by
2n
SO2Cl
MeO
S
NH2 Br–
S
NH2 Br–
NH2
ClO2S
SO2Cl
n
H2N
S
n
15c n = 1
16c n = 2
2o
n = 1
3o 60
3p 83
2p n = 2
a Reactions conducted in a 5 mmol scale. For entries 1−4, 6, and 14,
30 mL of 5% bleach (4 equiv) was used; for entries 5 and 7−12, 37.5
mL of 5% bleach (5 equiv) was used.
b Conditions: 6 M H2SO4 (4 mL) and 5% bleach (60 mL, 8 equiv).
c Conditions: 6 M H2SO4 (4 mL) and 5% bleach (75 mL, 10 equiv).
Peters and co-workers. Satisfactory results in synthesizing
these compounds were realized. The alkanesulfonyl chlo-
rides, whether having branched or straight chains, were
synthesized in good to excellent yields, regardless of the
chain lengths (entries 7–12). Additionally, methanesulfo-
nyl chloride (3m) was also synthesized in 71% yield from
Synthesis 2014, 46, 225–229
© Georg Thieme Verlag Stuttgart · New York

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Clean Synthesis of Alkanesulfonyl Chlorides
227
NaClO + H+
HOCl + H+
HOCl + Na+
Cl+ + H2O
S-methyl isothiouronium sulfate (2m), which was pre-
pared from the inexpensive dimethyl sulfate and thiourea
(entry 13). Not only the isothiouronium halides and sulfo-
nates, but also the mesylates are suitable substrates for this
method (entry 14), delivering the desired product 3n in an
excellent 94% yield. This example extends the sources of
isothiourea salts from alkyl halides to compounds with
other good leaving groups. Next, we tried to use our sim-
ple procedure to synthesize alkanedisulfonyl dichlorides,
which were usually synthesized by chlorination of the cor-
responding disodium alkanedisulfonates and purified
through a tedious sequence.11 Presumably due to the diffi-
cult accesses to these compounds, their applications are
very limited.12 In contrast, by our method, propane-1,3-di-
sulfonyl dichloride (3o) and butane-1,4-disulfonyl dichlo-
ride (3p) were readily obtained in moderate 60% and good
83% yield, respectively (entries 15 and 16). It can be pre-
dicted that alkanedisulfonyl dichlorides with longer
chains are also accessible by this method.
O
Cl
R
S
Cl+
S
H2O
R
S+ +NH2 X–
+NH2 X–
R
+NH2 X–
– H+, – HCl
H2N
H2N
NH2
O
O
1. Cl+
2. H2O
O
O
R
S
H2O
R
S
NH2
OH
+NH2 X–
– H+, – HCl
– HX
H2N
H2N
4
O
O
O
H+
Cl+
– H+
S
R
S
OH
R
Cl
– OC(NH2)2, – H+
5
3
Scheme 3 Proposed mechanism for the bleach oxidative chlorosul-
fonation of S-alkyl isothiourea salts
alkanedisulfonyl chlorides. Additionally, this method is
environment- and worker-friendly, simple, and safe to op-
erate. Easy purification of the products without chroma-
tography affords high yields of up to 99%. All these
advantages make this procedure a good choice for the syn-
thesis of structurally diverse alkanesulfonyl chlorides and
alkanedisulfonyl chlorides.
In an attempt to extend the current method to a large-scale
preparation, p-chlorophenylmethanesulfonyl chloride
was smoothly synthesized in 96% yield after simple puri-
fication on a 50 mmol scale (Scheme 2).
1. SC(NH2)2, EtOH, reflux, 1 h
Cl
SO2Cl
All starting materials, solvents, and reagents were used directly as
received, without further purification. Petroleum ether (PE) used re-
fers to the fraction boiling in the 60–90 °C range. Melting points
were obtained on a Yanaco MP-500 melting point apparatus and are
uncorrected. 1H and 13C NMR spectra were recorded on Bruker 400
spectrometer with TMS as an internal standard in CDCl3 solution.
2. bleach, 6 M H2SO4, H2O
0–20 °C, 30 min
Cl
Cl
1c
3c
on 50-mmol scale,
yield: 10.85 g, 96%.
Scheme 2 Large-scale synthesis of sulfonyl chlorides
Sulfonyl Chlorides 3a–h,m–p; General Procedure
The appropriate alkyl halide (or mesylate) (5 mmol) and thiourea
(0.381 g, 5 mmol) were refluxed in EtOH (5 mL) for 1 h. After re-
moval of the solvent in vacuum and washing with Et2O (3 × 5 mL),
the corresponding S-alkyl isothiourea salt was obtained as a white
solid or sticky oil in an almost quantitative yield. Without purifica-
tion, the product was transferred into a three-necked round-bot-
tomed flask equipped with a thermometer and an addition funnel in
an ice-bath. Then, 6 M H2SO4 (2 mL), followed by Et2O (30 mL)
were added. To the resultant vigorously stirred mixture was added
dropwise 5% bleach (for alkyl chlorides and mesylates, 30 mL; for
alkyl bromides, 37.5 mL) by keeping the inner temperature 0–20 °C
The reaction of hypochlorite and hydrochloric acid can
give rise to chlorinium ion (Cl+) and chlorine gas. Both
chlorinium ion and chlorine gas can convert S-alkyl iso-
thiourea salts into the corresponding sulfonyl chlorides.
However, the reaction of hypochlorite and sulfuric acid
can generate chlorinium ion only, revealing that the chlo-
rinium ion is the key oxidant and shows higher reactivity
than chlorine gas in the oxidative chlorosulfonation.
The oxidative chlorosulfonation mechanism, similar to
that of NCS/HCl method,3h is proposed and depicted in (for the preparation of alkanedisulfonyl dichlorides, 0.762 g, 10
mmol thiourea, 4 mL of 6 M H2SO4, 50 mL of Et2O, and 75 mL of
Scheme 3. In the presence of aqueous acidic solution, hy-
pochlorite is converted into chlorinium ion. The S-alkyl
isothiourea salt is oxidized into the corresponding alkyl-
sulfonyl methanimidamide salt 4 via two consecutive
5% bleach were used). After the addition, the mixture was stirred
for another 30 min. The mixture was partitioned in a separatory fun-
nel, and the ethereal phase was washed with brine (25 mL), dried
(Na2SO4), and evaporated in vacuum to afford the desired product.
chlorinium ion oxidation steps. Through a sequence of at-
tack by water, leaving of X– anion, proton transfer, and
leaving of protonated urea, 4 gives rise to the correspond-
ing sulfinic acid 5, which subsequently undergoes a fur-
ther oxidation to produce the corresponding sulfonyl
chloride 3.
The oily products were extracted with CHCl3 (3 × 2.5 mL) and
evaporated to remove the by-product, bromine. If necessary, the
products can be dissolved in minimal PE–EtOAc (5:1) and filtered
through a column of silica gel (h = 5 cm) with PE–EtOAc (5:1) as
eluent to remove the impurities (Table 2).
Sulfonyl Chlorides 3i–l; General Procedure
The corresponding S-alkyl isothiourea salt was prepared as de-
scribed above and was transferred to 6 M H2SO4 (2 mL) kept in a
three-necked round-bottomed flask equipped with a thermometer
and an addition funnel at r.t. To the resultant vigorously stirred mix-
ture was added dropwise 5% bleach (45 mL) by keeping the inner
temperature less than 40 °C. After 1 h, the mixture was cooled to r.t.
and Et2O (30 mL) was added. The same workup as described above
afforded the desired product in each case (Table 2).
In conclusion, a simple procedure for clean and economic
synthesis of alkanesulfonyl chlorides via bleach-mediated
oxidative chlorosulfonation of S-alkyl isothiourea salts is
described. The materials and reagents involved are readily
accessible, rendering this method the versatility in synthe-
sizing structurally diverse alkanesulfonyl chlorides and
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 225–229

228
Z. Yang et al.
PAPER
All the sulfonyl chlorides synthesized are known compounds. Their
1H NMR spectra and melting points of the solid products are iden-
tical with those reported.
Dodecane-1-sulfonyl Chloride (3j)
Yield: 1.304 g (97%); white solid; mp 40–41 °C (Lit.3b 42–43 °C).
1H NMR (400 MHz, CDCl3): δ = 3.88–3.72 (m, 2 H), 2.14–1.98 (m,
2 H), 1.56–1.46 (m, 2 H), 1.37–1.27 (m, 16 H), 0.88 (t, J = 6.7 Hz,
3 H).
Phenylmethanesulfonyl Chloride (3a)
Yield: 0.886 g (93%); colorless crystals; mp 92–94 °C (Lit.2i mp
91–93 °C).
13C NMR (101 MHz, CDCl3): δ = 65.5, 31.9, 29.55, 29.53, 29.4,
29.3, 29.1, 28.9, 27.6, 24.3, 22.7, 14.1.
1H NMR (400 MHz, CDCl3): δ = 7.45–7.40 (m, 5 H), 4.83 (s, 2 H).
13C NMR (101 MHz, CDCl3): δ = 131.4, 130.3, 129.2, 126.1, 70.9.
Hexadecane-1-sulfonyl Chloride (3k)
Yield: 1.628 g (98%); white solid; mp 50–52 °C (Lit.3f 51–52 °C).
(4-Fluorophenyl)methanesulfonyl Chloride (3b)
Yield: 1.066 g (99%); colorless crystals; mp 68–69 °C (Lit.3f mp
66–67 °C).
1H NMR (400 MHz, CDCl3): δ = 7.49–7.13 (m, 4 H), 4.84 (s, 2 H).
13C NMR (101 MHz, CDCl3): δ = 163.85 (d, JC,F = 251.2 Hz),
133.34 (d, JC,F = 8.8 Hz), 122.1 (d, JC,F = 3.4 Hz), 116.40 (d,
1H NMR (400 MHz, CDCl3): δ = 3.75–3.51 (m, 2 H), 2.06–2.02 (m,
2 H), 1.49–1.26 (m, 26 H), 0.88 (t, J = 6.2 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 65.5, 31.9, 29.8, 29.7, 29.6, 29.5,
29.4, 29.2, 28.9, 28.9, 27.6, 24.3, 22.7, 14.1.
3-Methylbutane-1-sulfonyl Chloride (3l)3h
Yield: 0.680 g (80%); yellowish oil.
JC,F = 22.1 Hz), 69.94.
1H NMR (400 MHz, CDCl3): δ = 3.76–3.65 (m, 2 H), 1.96–1.88 (m,
2 H), 1.84–1.74 (m, 1 H), 0.99 (d, J = 6.4 Hz, 6 H).
13C NMR (101 MHz, CDCl3): δ = 64.0, 32.5, 26.9, 22.0, 21.9.
(4-Chlorophenyl)methanesulfonyl Chloride (3c)
Yield: 1.114 g (99%) on a 5 mmol scale and 10.85 g (96%) on a 50
mmol scale; colorless crystals; mp 96–97 °C (Lit.2i mp 92–93 °C).
1H NMR (400 MHz, CDCl3): δ = 7.46–7.42 (m, 4 H), 4.83 (s, 2 H).
13C NMR (101 MHz, CDCl3): δ = 136.8, 132.6, 129.5, 124.6, 70.0.
Methanesulfonyl Chloride (3m)3h
Yield: 0.808 g (71%); colorless oil.
1H NMR (400 MHz, CDCl3): δ = 3.68 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 52.5.
(4-Cyanophenyl)methanesulfonyl Chloride (3d)
Yield: 1.090 g (99%); colorless crystals; mp 102–103 °C (Lit.13 mp
102–103 °C).
1H NMR (400 MHz, CDCl3): δ = 7.78–7.62 (m, 4 H), 4.91 (s, 2 H).
13C NMR (101 MHz, CDCl3): δ = 132.9, 132.1, 131.1, 117.8, 114.4,
69.8.
2-Methoxyethanesulfonyl Chloride (3n)3h
Yield: 0.746 g (94%); yellowish oil.
1H NMR (400 MHz, CDCl3): δ = 3.97–3.94 (m, 4 H), 3.43 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 65.8, 64.9, 59.1.
(4-Nitrophenyl)methanesulfonyl Chloride (3e)
Yield: 1.001 g (85%); colorless crystals; mp 88–89 °C (Lit.2i mp
92–93 °C).
1H NMR (400 MHz, CDCl3): δ = 8.33 (d, J = 8.7 Hz, 2 H), 7.70 (d,
J = 8.7 Hz, 2 H), 4.96 (s, 2 H).
Propane-1,3-disulfonyl Dichloride (3o)
Yield: 0.718 g (60%); white solid; mp 46–48 °C (Lit.14 mp 46.5–
47.0 °C).
1H NMR (400 MHz, CDCl3): δ = 4.04–3.94 (m, 4 H), 2.80–2.67 (m,
2 H).
13C NMR (101 MHz, CDCl3): δ = 149.0, 133.2, 132.6, 124.3, 73.2.
13C NMR (101 MHz, CDCl3): δ = 49.5, 19.7.
p-Tolylmethanesulfonyl Chloride (3f)
Yield: 0.899 g (87%); colorless crystals; mp 80–81 °C (Lit.3f mp
84–85 °C).
1H NMR (400 MHz, CDCl3): δ = 7.38–7.26 (m, 4 H), 4.83 (s, 2 H),
Butane-1,4-disulfonyl Dichloride (3p)
Yield: 1.000 g (83%); colorless crystals; mp 90–91 °C (Lit.3f mp
89–90 °C).
1H NMR (400 MHz, CDCl3): δ = 3.85–3.75 (m, 4 H), 2.32–2.27 (m,
2.39 (s, 3 H).
4 H).
13C NMR (101 MHz, CDCl3): δ = 140.6, 131.2, 129.9, 123.0, 70.8,
21.3.
13C NMR (101 MHz, CDCl3): δ = 64.0, 22.5.
Butane-1-sulfonyl Chloride (3g)3h
Yield: 0.768 g (98%); yellowish oil.
Acknowledgment
1H NMR (400 MHz, CDCl3): δ = 3.89–3.65 (m, 2 H), 2.10–1.97 (m,
2 H), 1.61–1.50 (m, 2 H), 1.01 (t, J = 7.4 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 65.2, 26.2, 20.9, 13.3.
The project was supported by The National Basic Research Pro-
gram of China (No. 2013CB328905) and National Natural Science
Foundation of China (Nos. 21172017 and 20092013).
Hexane-1-sulfonyl Chloride (3h)3h
Supporting Information for this article is available online at
Yield: 0.855 g (93%); yellowish oil
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
m
tgioSrantnugIifoop
r
itmnatr
1H NMR (400 MHz, CDCl3): δ = 3.76–3.65 (m, 2 H), 2.08–1.98 (m,
2 H), 1.50–1.35 (m, 6 H), 0.91 (t, J = 6.2 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 65.5, 31.0, 27.2, 24.2, 22.2, 13.8.
References
Octane-1-sulfonyl Chloride (3i)3h
(1) (a) Opitz, G. Angew. Chem., Int. Ed. Engl. 1967, 6, 107.
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W. X.; Xu, J. X. Org. Lett. 2009, 11, 3922.
Yield: 0.958 g (96%); yellowish oil.
1H NMR (400 MHz, CDCl3): δ = 3.76–3.64 (m, 2 H), 2.08–1.98 (m,
2 H), 1.53–1.46 (m, 2 H), 1.33–1.29 (m, 8 H), 0.85 (t, J = 6.8 Hz, 3
H).
13C NMR (101 MHz, CDCl3): δ = 65.5, 31.6, 28.8, 27.3, 24.6, 22.5,
14.0.
Synthesis 2014, 46, 225–229
© Georg Thieme Verlag Stuttgart · New York

PAPER
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