A new synthesis of alkane and polyfluoroalkanesulfonyl chlorides

Article abstract of DOI:10.1002/hc.20559

This study describes a new and advantageous procedure for the synthesis of alkanesulfonyl chlorides (2) by the reaction of alkyl thiocyanates (1) with sulfuryl chloride in a mixture of acetic acid and water. The alkanesulfonyl chlorides were obtained in good yields.

Full text of DOI:10.1002/hc.20559

Heteroatom Chemistry
Volume 20, Number 6, 2009
A
New Synthesis of Alkane and
Polyfluoroalkanesulfonyl Chlorides
1
1
2
Zohra Benfodda, Franck Guillen, H e´ l e` ne Arnion,
Abdelkader Dahmani, and Hubert Blancou
1
1
1
Institut des Biomol e´ cules Max Mousseron (IBMM) UMR CNRS 5247 Universit e´ de Montpellier I
et de Montpellier II, CC1706, Place Eug e` ne Bataillon 34095 Montpellier cedex 05, France
2
S3F Chimie Universit e´ de Montpellier II, CC01706, Place Eug e` ne Bataillon 34095 Montpellier
cedex 05, France
Received 3 July 2009; revised 4 September 2009
A number of methods for the preparation of alka-
ABSTRACT: This study describes a new and ad-
nesulfonyl chlorides have been described. Amongst
these methods, the more important involve the aque-
ous chlorination of disulfides and thiols [8]. Different
sulfur compounds have also been converted to alka-
nesulfonyl chlorides, e.g., thiols [8], sulfides [9], thio-
cyanates [10], isothiouronium salts [11], S,S-dialkyl
dithiocarbonates [12], thiol esters [8], thiosulfonates
vantageous procedure for the synthesis of alkane-
sulfonyl chlorides (2) by the reaction of alkyl thio-
cyanates (1) with sulfuryl chloride in a mixture of
acetic acid and water. The alkanesulfonyl chlorides
were obtained in good yields. ꢀC 2009 Wiley Periodicals,
Inc. Heteroatom Chem 20:355–361, 2009; Published on-
line in Wiley InterScience (www.interscience.wiley.com).
[8], sulfinyl chlorides [13], and sulfinic acids [14].
DOI 10.1002/hc.20559
However, the disadvantages of the most of these
methods are the preparation of starting materials,
or unsatisfactory reaction yields or the production
of side products. Thus limiting convenient access to
alkanesulfonyl chlorides.
INTRODUCTION
Alkanesulfonyl chlorides are known for their utility
in imparting functionality into various compounds
or as intermediates to modify various compounds
including pharmaceuticals, agricultural chemicals,
photographic chemicals, and the like, to increase
their efficacy, to protect sensitive functional groups
during certain processing steps, or to improve the
recovery and purity during isolation procedures [1].
The use of alkanesulfonyl chlorides as the impor-
tant precursors has been frequently encountered for
the preparation of many diverse functional groups
including sulfonates esters [2], sulfonamides [3], sul-
fonyl fluorides [4], sulfones [5], sulfinic acids [6], and
others [7].
In this paper, we describe a new preparation
of alkanesulfonyl chloride starting from alkyl thio-
cyanates with sulfuryl chloride in acetic acid/ water
media, which is a very effective and new pathway to
synthesize these derivatives in good yields.
RESULTS AND DISCUSSION
A number of papers have been published on the syn-
thesis of sulfonyl chlorides from thiocyanates using
chlorine [10]. Chlorine gas in aqueous acetic acid
has been used in the method. However, the use of
chlorine gas is tedious and quite often causes a trou-
ble. In the Table 1, we described a comparison of
sulfuryl chloride and chlorine as chlorination agents
of the alkyl thiocyanates [10].
Correspondence to: Hubert Blancou; e-mail: hubert.blancou@
univ-montp2.fr
ꢀ
c 2009 Wiley Periodicals, Inc.
355

356 Benfodda et al.
TABLE 1 Comparison between SO Cl2 and Cl2 as Chlori-
2
120
00
nation Agents of Alkyl Thiocyanates
1
Chlorination Reactant
80
60
40
20
0
Sulfuryl Chloride
Chlorine
Yield
Quantity of
reactant
Reaction time
Manipulation
Very good (max 99%)
10 equiv
Good (max 79%)
Large excess,
not precise
Not precise
Tedious
5
5
0°C, 10 eq.
0°C, 8 eq.
Rapid (30 min—1 h)
Easy
50°C, 5 eq.
0°C, 2 eq.
5
0
20
40
60
80 100 120 140 160
Reaction time (min)
The present method gives better reaction yields
to the chlorine gas method with a much easier ma-
nipulation.
The alkanesulfonyl chlorides were prepared
from alkyl bromide or chloride, in two steps, in good
yields according to a method developed in our labo-
ratory (Scheme 1).
FIGURE 1 Effects of the equivalent amounts of sulfuryl chlo-
ride (1 equiv/min) on the conversion of 1g. Reactions condi-
◦
tions: solvent: acetic acid, reaction temperature: 50 C. Note
1
that the percentage of formation of 2g was determined by H
NMR (acetone-d ) by the relative integration of the functional
6
CH2 signal of 1g compared with that of the functional CH2
signal of 2g.
The reaction of alkyl bromide or chloride with
◦
potassium thiocyanate in absolute ethanol at 90 C
gave the alkyl thiocyanates (1) in good yields.
We have now found that various alkyl thio-
cyanates and polyfluoroalkyl thiocyanates (1) re-
acted with sulfuryl chloride in the presence of a
mixture of acetic acid and water at 50 C to lead to
the corresponding sulfonyl chlorides (2) in excellent
yields without any side products.
Influence of the Reaction Temperature
We studied the effect of the variation of the tempera-
ture on rates of the chlorination. 1g was chlorinated
with 10 equiv of sulfuryl chloride (1 equiv/min) in a
mixture of water and acetic acid.
◦
Increases of the temperature resulted in in-
creases of the formation of 2g as could be seen in
To find out optimum conditions, the reactions of
◦
◦
Fig. 2. At 25 C and 40 C, there were no more than,
respectively, 83% and 94% of the chlorination of 1g
in 160 min.
1g with sulfuryl chloride in the presence of a mix-
ture of water and acid were examined under various
reaction conditions. In each case, we studied the con-
version of 1g in 160 min.
1
20
00
80
60
Influence of the Sulfuryl Chloride Molar Amount
1
When more than 5 equiv of sulfuryl chloride were
◦
used in a mixture of water and acetic acid at 50 C,
2
g was obtained in high yield. However, the chlo-
rination reaction was achieved more rapidly with
0 equiv (1 equiv/min). With 2 equiv of sulfuryl chlo-
1
5
2
0°C
5°C
4
2
0
0
0
ride, we obtained 50% of formation of 2g in 160 min.
We used 10 equiv of sulfuryl chloride for the prepa-
ration of the others alkanesulfonyl chlorides. The
results are summarized in Fig. 1.
40°C
0
20
40
60
80 100 120 140 160
Reaction time (min)
SO Cl2
KSCN
EtOH
100°C
2
R SO Cl
R Br or R Cl
R SCN
H
H
H
H
2
FIGURE 2 Effects of the reaction temperature on the conver-
sion of 1g. Reactions conditions: sulfuryl chloride = 10 equiv
H O/ CH CO H
2
3
2
1a–k
2a–k
5
0°C
RH = Alkyl, or
R (CH )
(1 equiv/min), solvent: acetic acid. Note that the percentage
F
2 2
1g: RH =C H
2g: R =C H
1
8
17
H
8
17
of formation of 2g was determined by H NMR (acetone-d )
6
by the relative integration of the functional CH signal of 1g
2
SCHEME 1
compared with that of the functional CH2 signal of 2g.
Heteroatom Chemistry DOI 10.1002/hc

A New Synthesis of Alkane and Polyfluoroalkanesulfonyl Chlorides 357
1
1
20
00
120
100
80
8
6
4
2
0
0
0
0
0
60
1
0
0
eq/min
Acetic acid
4
2
0
0
.33 eq/min
.1 eq/min
Propionic acid
0
0
20
40
60
80
100
120
140
160
0
20
40
60
80
100
120
140
160
Reaction time (min)
Reaction time (min)
FIGURE 3 Effects of the addition rate of sulfuryl chloride on
FIGURE 4 Effects of the solvent (propionic or acetic acid) on
the conversion of 1g. Reactions conditions: sulfuryl chloride =
the conversion of 1g. Reactions conditions: sulfuryl chloride =
◦
◦
1
0 equiv, solvent: acetic acid, reaction temperature: 50 C.
10 equiv (1 equiv/min), reaction temperature: 50 C. The% of
1
Note that the percentage of formation of 2g was determined
formation of 2g was determined by H NMR (acetone-d6)
1
by H NMR (acetone-d ) by the relative integration of the
by the relative integration of the functional CH signal of 1g
6
2
functional CH2 signal of 1g compared with that of the func-
compared with that of the functional CH signal of 2g.
2
tional CH signal of 2g.
2
that were added at the rate of 1 equiv/min, in a mix-
◦
ture of acetic acid/ water at 50 C.
Influence of the Sulfuryl Chloride Rate
We introduced 10 equiv of sulfuryl chloride that were
added at different rates in a mixture of water and
acetic acid at 50 C.
The chlorination reaction was achieved more
rapidly with 10 equiv, which were added at the rate
of 1 equiv/min. When the sulfuryl chloride was added
at 0.33 equiv/min, the conversion of 1g was not fin-
ished: There was 92% of formation of 2g in 160 min.
In the same conditions, when the sulfuryl
chloride was added more slowly, at the rate of
CONCLUSION
In summary, we have developed a new and effi-
cient method for the synthesis of alkanesulfonyl
chlorides and polyfluoroalkanesulfonyl chlorides
starting from, respectively, alkyl thiocyanates and
polyfluoroalkyl thiocyanates with sulfuryl chloride
in a mixture of acetic acid and water. All alkanesul-
fonyl chlorides and polyfluoroalkanesulfonyl chlo-
◦
1
rides have been identified by comparison of their H
13
and C NMR spectra with those authentic samples
of analytical purity.
0.1 equiv/min, there was only 76% of formation of
2g. The results are summarized in Fig. 3.
1
1
20
00
80
Influence of the Solvent
In addition the chlorination of 1g is carried out in
the presence of different solvents at 50 C along with
◦
1
0 equiv of sulfuryl chloride (1 equiv/min).
6
0
With water
When we used propionic acid instead of acetic
acid, there was less chlorination of 1g and there was
2% of chlorination with propionic acid (Fig. 4).
40
Without water
9
2
0
0
Influence of the Water
0
20
40
60
80
100
120
140
160
The reaction was performed in the absence or the
presence of water. Without water, there was not the
conversion of 1g. The results are depicted in Fig. 5.
The water is essential for the chlorination of thio-
cyanates that is an oxidation.
Reaction time (min)
FIGURE 5 Effects of the water on the conversion of 1g. Re-
action conditions: sulfuryl chloride = 10 equiv (1 equiv/min),
◦
solvent: acetic acid, reaction temperature: 50 C. Note: The%
1
of formation of 2g was determined by H NMR (acetone-d )
6
The best conditions for the chlorination of thio-
cyanates were the use of 10 equiv of sulfuryl chloride
by the relative integration of the functional CH signal of 1g
compared with that of the functional CH2 signal of 2g.
2
Heteroatom Chemistry DOI 10.1002/hc

358 Benfodda et al.
EXPERIMENTAL
General
potassium thiocyanate, and 4.15 g of 1b was ob-
tained (99%).
1
H NMR (300.13 MHz, d
), 1.40 (m, 2H, CH
), 2.96 (t, J = 7.2 Hz, 2H,
SCN); C NMR (75.46 MHz, d -acetone): δ 13.68
), 32.78 (CH CH SCN), 34.15
SCN), 112.84 (SCN).
6
-acetone): δ 0.85
Different alkyl bromides (R
H
Br) or alkyl iodides
(t, J = 7.4 Hz, 3H, CH
3
3
CH ),
2
(
R
H
I) were purchased from Aldrich (Saint Quentin
1.69 (m, 2H, CH CH CH
3
2
2
13
Fallavier, France). Different polyfluoroalkyl iodides
CH
2
6
(
(
R
F
(CH
2
)
2
I) were purchased from Elf Atochem
(CH
(CH
3
), 21.70 (CH
3
CH
2
2
2
Pierre B e´ nite, France). Solvents were distilled from
2
the appropriate drying agents immediately prior
to use.
Synthesis of 2-Methylpropyl Thiocyanate (1c).
Five grams (36.49 mmol) of 2-methylpropyl bromide
in 40 mL of absolute ethanol was refluxed with 5.31 g
(54.73 mmol) of potassium thiocyanate, and 4.15 g
of 1c was obtained (99%).
1
19
13
H, F, and C NMR spectra were recorded at
00.13, 282.37, and 75.46 MHz, respectively, with a
Bruker Avance 300 spectrometer; therefore, chem-
ical shifts were given in ppm relative to Me Si,
CCl F, respectively, as internal standards. Coupling
constants are given in hertz.
3
4
1
3
H NMR (300.13 MHz, d -acetone): δ 0.94
6
(d, J = 6.7 Hz, 6H, 2CH
3
), 1.95 (m, 1H, CH), 2.90
13
Melting points were recorded at atmospheric
pressure unless otherwise stated on a Stuart sci-
entific SMP3 apparatus and remained without any
correction.
(d, J = 6.81 Hz, 2H, CH ); C NMR (75.46 MHz,
2
6
d -acetone): δ 21.23 (2CH ), 30.09 (CH), 42.75
3
(CH SCN), 113.14 (SCN).
2
Identifications of all the products, which are al-
ready known, were performed according to the liter-
ature by comparison with authentic samples.
Note that for each kinetic of formation of 2g we
used 5 g of 1g.
Synthesis of 3-Methylbutyl Thiocyanate (1d).
Five grams (33.10 mmol) of 3-methylbutyl bromide
in 40 mL of absolute ethanol was refluxed with 4.81 g
(49.66 mmol) of potassium thiocyanate, and 3.12 g
of 1d was obtained (73%).
1
H NMR (300.13 MHz, d
6
-acetone): δ 0.81
),
); C NMR (75.46
(
2
d, J = 6.4 Hz, 6H, 2CH
3
), 1.63 (m, 3H, CH, CH
2
Synthesis of Alkyl Thiocyanates (1a–1j)
13
.99 (t, J = 7.5 Hz, 2H, CH
2
General Procedure for the Synthesis of Alkyl
MHz, d -acetone): δ 22.40 (CH ), 27.61 (CH), 32.64
6
3
Thiocyanates. To a solution of R
H
Br or R
F
(CH
2
)
2
I
(CH
2
SCN), 39.69 (CH
2
CH
2
SCN), 112.81 (SCN).
(1 equiv) dissolved in absolute ethanol, potassium
thiocyanate (1.5 equiv) was added. The reaction mix-
ture was refluxed for 5 h. After cooling, all volatile
parts of the mixture were removed in vacuo. The
residue was dissolved in EtOAc and washed succes-
sively with water and brine. The organic layer was
Synthesis of Hexyl Thiocyanate (1e). Twenty
grams (122 mmol) of hexyl bromide in 100 mL of ab-
solute ethanol was refluxed with 17.74 g (183 mmol)
of potassium thiocyanate, and 16.1 g of 1e was ob-
tained (92%).
1
dried over anhydrous Na
2
SO
4
, filtered, and evap-
H NMR (300.13 MHz, d -acetone): δ 0.81
6
orated under reduced pressure to yield the corre-
sponding alkyl thiocyanates, which were used in the
next step without any purification.
(t, 3H, CH ), 1.32 (m, 4H, CH (CH ) ), 1.55 (m, 2H,
3
3
2 2
CH (CH ) SCN), 1.69 (m, 2H, CH CH SCN), 2.95
2
2
2
2
2
13
(t, J = 7.25, 2H, CH SCN); C NMR (75.46 MHz,
2
d
6
-acetone): δ 14.35 (CH
3
), 23.18, 31.86 (2CH ),
2
Synthesis of Propyl Thiocyanate (1a). Five
grams (29.41 mmol) of propyl iodide in 40 mL of ab-
solute ethanol was refluxed with 4.28 g (44.12 mmol)
of potassium thiocyanate, and 2 g of 1a was obtained
30.76 (CH
2
(CH
2
)
2
SCN), 28.27 (CH
2
CH SCN), 34.50
2
(CH SCN), 117.98 (SCN).
2
Synthesis of Octyl Thiocyanate (1f). Twenty-
three grams (120 mmol) of octyl bromide in 100 mL
of absolute ethanol was refluxed with 17.34 g
(180 mmol) of potassium thiocyanate, and 18 g of
1g was obtained (88%).
(
67%).
1
H NMR (300.13 MHz, d
t, J = 7.3 Hz, 3H, CH ), 1.72 (m, 2H, CH
t, J = 7 Hz, 2H, CH
-acetone): δ 17.93 (CH
1.54 (CH SCN), 118.03 (SCN).
6
-acetone): δ 0.90
CH ), 3.02
SCN); C NMR (75.46 MHz,
CH ), 29.38 (CH CH ),
(
(
d
3
3
2
13
2
1
6
3
2
3
2
H NMR (300.13 MHz, d -acetone): δ 0.91 (t,
6
4
2
J = 6.9 Hz, 3H, CH ), 1.40 (m, 10H, CH (CH ) ),
3
3
2 5
1.86 (m, 2H, CH
2
CH
2
SCN) 3.10 (t, J = 7.2 Hz, 2H,
6
13
Synthesis of Butyl Thiocyanate (1b). Five grams
36.49 mmol) of butyl iodide in 40 mL of absolute
ethanol was refluxed with 5.31 g (54.73 mmol) of
CH
(CH
(CH
2
SCN); C NMR (75.46 MHz, d
3
-acetone): δ 14.46
), 23.35, 28.60, 29.65, 30.80, 32.54 (5CH ), 29.88
CH SCN), 34.49 (CH SCN), 112.77 (SCN).
(
2
2
2
2
Heteroatom Chemistry DOI 10.1002/hc

A New Synthesis of Alkane and Polyfluoroalkanesulfonyl Chlorides 359
Synthesis of Decyl Thiocyanate (1g). Five grams
(75.46 MHz, d
6
-acetone): δ 25.70 (CH SCN), 32.42
2
(22.61 mmol) of decyl bromide in 40 mL of abso-
(CF CH ), 111.98 (SCN), 111–124 (C F17).
2
2
8
lute ethanol was refluxed with 3.29 g (33.91 mmol)
of potassium thiocyanate, and 4.46 g of 1g was ob-
tained (99%).
Synthesis of Alkanesulfonyl Chloride (2a–2j)
1
General Procedure for the Synthesis of Alkane-
sulfonyl Chloride. Alkyl thiocyanates (1 equiv) dis-
H NMR (300.13 MHz, d
), 1.25 (m, 14H, CH
CH
SCN), 3.02 (t, J = 7.25 Hz,
SCN); C NMR (75.46 MHz, d -acetone): δ
4.44 (CH ), 23.38, 28.58, 29.67, 30.02, 30.07, 30.28,
2.66 (7CH ), 30.79 (CH CH SCN), 34.46 (CH SCN),
11.06 (SCN).
6
-acetone): δ 0.78 (t,
J = 6.5 Hz, 3H, CH
3
3
(CH ),
2 7
)
solved in a mixture of acetic acid (5 equiv) and water
1
2
1
3
1
.71 (m, 2H, CH
2
2
◦
13
(
1.5 equiv) were stirred for 30 min at 50 C. Sulfuryl
H, CH
2
6
chloride (SO
2
Cl
2
, 10 equiv) was added dropwise to
3
◦
the reaction mixture at 50 C. This reaction was ac-
2
2
2
2
companied by a strong emission of gases (SO
Cl ), which were trapped with an aqueous solution
of NaOH (1 M). The excess of SO Cl , present in
2
and
2
2
2
Synthesis of 3,3,4,4,5,5,6,6,6-Nonafluorohexyl
Thiocyanate (1h). Forty grams (107 mmol) of
(CH I in 300 mL of absolute ethanol was re-
the media, was hydrolyzed by dropwise addition of
water. The crude product was extracted three times
with EtOAc. The combined organic extracts were
washed three times with water, dried over anhy-
C
4
F
9
)
2 2
fluxed with 16 g (160 mmol) of potassium thio-
cyanate, and 32 g of 1h was obtained (98%).
drous Na
2
SO , filtered, and concentrated giving a
4
1
H NMR (300.13 MHz, d
CH ), 3.48 (m, 2H, C
NMR (282.37 MHz, d
-acetone): δ −126.84 (m, 2F,
CF CF CF CF ), −114.74 (m,
), −125.02 (m, 2F, CF
F, CF (CF CF ); C NMR
), −82.2 (m, 3F, CF
75.46 MHz, d -acetone): δ 25.61 (CH
CF CH ), 111.83 (SCN), 111–124 (C
6
-acetone): δ 2.85
crude material alkanesulfonyl chloride, which could
be used without further purification.
19
(
m, 2H, C
4
F
9
2
4
F
9
CH
2
CH
2
);
F
6
3
2
3
2
2
Synthesis of Propanesulfonyl Chloride (2a).
13
2
(
(
3
2
)
2
2
3
1.22 g (12.08 mmol) of 1a dissolved in a mixture
6
2
SCN), 32.37
).
of 3.5 mL (60.4 mmol) of acetic acid and 0.32 mL
2
2
4
F
9
◦
(
18.1 mmol) of water was stirred 30 min at 50 C with
9.8 mL (120.8 mmol) of SO
2
Cl
2
. The excess of SO
2
Cl
2
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecaflu-
orooctyl Thiocyanate (1i). Sixty grams (127 mmol)
of C I in 450 mL of absolute ethanol was
refluxed with 18.4 g (190 mmol) of potassium thio-
cyanate, and 46.20 g of 1i was obtained (90%).
was hydrolyzed by the addition of water (10 mL).
The crude product was extracted with 3 × 5 mL of
6
F
13(CH
2
)
2
EtOAc, and 1.70 g of 2a [15] was obtained (99%).
1
H NMR (300.13 MHz, d
6
-acetone): δ 1.05 (t,
CH ), 3.88
Cl); C NMR (75.46 MHz, d
acetone): δ 12.27 (CH CH ), 19.11 (CH CH ), 67.37
(CH SO Cl).
J = 7.4 HZ; 3H, CH
3
), 1.95 (m, 2H, CH
3
2
◦
1
13
mp
-acetone):
m, 2H, C
=
40–41 C.
δ
H
NMR (300.13 MHz,
2.85 (m, 2H, ), 3.48
); F NMR (282.37 MHz,
CF
), −123.93
), −123.44 (m, 2F, CF (CF CF ),
122.45 (m, 2F, CF (CF CF
), −114.35 (m, 2F,
(CF CF ); C NMR
), −81.75 (m, 3F, CF
-acetone): δ 26.13 (CH SCN), 32.78
), 112.42 (SCN), 111–124 (C
(m, 2H, CH SO
2
2
6
-
d
(
6
C
6
F
13CH
2
3
2
3
2
1
9
6
F13CH
2
CH
2
2
2
d
6
-acetone): δ −126.77 (m, 2F, CF
3
2
Synthesis of Butanesulfonyl Chloride (2b). Two
grams (17.39 mmol) of 1b dissolved in a mixture
(
m, 2F, CF CF CF
3
2
2
3
2
)
2
2
−
3
2
)
3
2
13
of 5 mL (86.96 mmol) of acetic acid and 0.47 mL
CF
3
2
)
4
2
3
◦
(
26.09 mmol) of water was stirred 30 min at 50 C
(
(
75.46 MHz, d
CF CH
6
2
with 14.1 mL (173.9 mmol) of SO
2
Cl
2
. The excess
2
2
6
F13).
of SO Cl was hydrolyzed by the addition of water
2
2
(
5
(
10 mL). The crude product was extracted with 3 ×
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
Heptadecafluorodecyl Thiocyanate (1j). Sixty grams
105 mmol) of C I in 450 mL of absolute
ethanol was refluxed with 15.21 g (157 mmol) of
potassium thiocyanate, and 52.27 g of 1j was ob-
tained (99%).
mL of EtOAc, and 2.64 g of 2b [16] was obtained
97%).
(
8
F
17(CH
2
)
2
1
H NMR (300.13 MHz, d
m, 3H, CH ), 1.49 (m, 2H, CH CH
CH CH
), 3.90 (t, J = 7 Hz, 2H, CH
NMR (75.46 MHz, d -acetone): δ 13.74 (CH
CH CH ), 27.20 (CH CH SO Cl), 65.70 (CH
6
-acetone): δ 0.85
(
3
3
2
), 1.90 (m, 2H,
13
CH
3
2
2
2
SO
2
Cl);
), 21.37
SO Cl).
C
6
3
◦
1
mp
-acetone):
m, 2H, C
=
67–68 C.
δ
H
NMR (300.13 MHz,
2.85 (m, 2H, ), 3.48
), F NMR (282.37 MHz,
CF
), −123.91
), −123.2 (m, 2F, CF (CF CF ),
122.32 (m, 6F, CF (CF (CF
), −114.27 (m,
(CF CF ); C NMR
), −81.60 (m, 3F, CF
(
3
2
2
2
2
2
2
d
(
6
C
8
F
17CH
2
1
9
6
F17CH
2
CH
2
Synthesis of 2-Methylpropanesulfonyl Chloride
d
6
-acetone): δ −126.70 (s, 2F, CF
3
2
(2c). One gram (8.69 mmol) of 1c dissolved in a
mixture of 2.5 mL (43.45 mmol) of acetic acid and
0.23 mL (13 mmol) of water was stirred 30 min at
50 C with 7 mL (86.95 mmol) of SO
(
m, 2F, CF CF CF
3
2
2
3
2
)
2
2
−
3
2
)
3
2
)
3
13
◦
2
F, CF
3
2
)
6
2
3
2
2
Cl . The excess
Heteroatom Chemistry DOI 10.1002/hc

360 Benfodda et al.
of SO
2
Cl
2
was hydrolyzed by the addition of water
Synthesis of Decanesulfonyl Chloride (2g). Four
grams (20.10 mmol) of 1g dissolved in a mixture of
5.75 mL (100.5 mmol) of acetic acid and 0.54 mL of
(
5
10 mL). The crude product was extracted with 3 ×
mL of EtOAc, and 1.35 g of 2c [17] was obtained
◦
(
95%).
water (30.15 mmol) was stirred 30 min at 50 C with
1
H NMR (300.13 MHz, d
J = 6.77 Hz, 6H, 2CH ), 2.32 (m, 1H, CH), 3.85
d, J = 6.47 Hz, 2H, CH
MHz, d -acetone): δ 19.55 (2CH
Cl).
6
-acetone): δ 1.05 (d,
16.29 mL (201 mmol) of SO Cl . The excess of SO Cl
2
2
2
2
3
was hydrolyzed by the addition of 10 mL of water.
The crude product was extracted with 3 × 5 mL of
EtOAc, and 4.6 g of 2g was obtained (95%).
13
(
2
SO
2
Cl); C NMR (75.46
), 24.62 (CH), 71.28
6
3
1
(
CH
2
SO
2
H NMR (300.13 MHz, d -acetone): δ 0.78 (d,
6
J = 6.5 Hz, 3H, CH
3
), 1.37 (m, 14H, CH
3
(CH
2
)
7
),
Synthesis of 3-Methylbutanesulfonyl Chloride
2d). Two grams (15.51 mmol) of 1d dissolved in a
1.99 (m, 2H, CH CH SO Cl), 3.99 (t, J = 7.8 Hz,
2
2
2
13
(
2H, CH SO Cl); C NMR (75.46 MHz, d -acetone): δ
2
2
6
mixture of 4.4 mL (77.55 mmol) of acetic acid and
14.39 (CH ), 22.63, 24.27, 27.55, 28.87, 29.15, 29.19,
3
0
.42 mL (23.3 mmol) of water was stirred 30 min
29.38, 31.81 (8CH ), 65.78 (CH SO Cl).
2
2
2
◦
at 50 C with 12.6 mL (155.1 mmol) of SO
2
Cl
was hydrolyzed by the addition of
water (10 mL). The crude product was extracted with
× 5 mL of EtOAc, and 2.17 g of 2d was obtained
82%).
2
. The
excess of SO
2
Cl
2
Synthesis of 3,3,4,4,5,5,6,6,6-nonafluorohexane-
sulfonyl Chloride (2h). Twenty-nine grams
(95 mmol) of 1h dissolved in a mixture of 27 mL
3
(
(475 mmol) of acetic acid and 2.6 mL (142.5 mmol)
1
◦
H NMR (300.13 MHz, d
6
-acetone): δ 0.90 (d, J =
), 1.80 (m, 3H, CH, CH ), 3.90 (m,
-acetone):
CH SO Cl),
of water was stirred 1.5 h at 50 C with 77 mL
6.5 Hz, 6H, 2CH
3
1
2
(950 mmol) of SO Cl . The excess of SO Cl was
2
2
2
2
3
2H, CH
2
SO
2
Cl); C NMR (75.46 MHz, d
6
hydrolyzed by the addition of water (60 mL). The
crude product was extracted with 3 × 20 mL of
EtOAc, and 29.64 g of 2h was obtained (90%). The
compound 2h synthesized previously was com-
δ 22.35 (2CH
3
), 27.67, 33.61 (CH and CH
Cl).
2
2
2
64.55 (CH SO
2
2
1
Synthesis of Hexanesulfonyl Chloride (2e). Two
pared by H NMR spectroscopy with pure sample
grams (13.98 mmol) of 1e dissolved in a mixture
furnished by Elf-Atochem.
1
of 4 mL (69.9 mmol) of acetic acid and 0.38 mL
H NMR (300.13 MHz, d -acetone): δ 3.05 (m,
6
◦
19
of water (20.98 mmol) was stirred 30 min at 50 C
2H, C F CH ), 4.45 (m, 2H, C F CH CH );
F
4
9
2
4
9
2
2
with 11.3 mL (139.86 mmol) of SO
2
Cl
2
. The excess
NMR (282.37 MHz, d -acetone): δ −126.70 (m, 2F,
6
of SO Cl was hydrolyzed by the addition of water
2
2
CF CF ), −124.65 (m, 2F, CF CF CF ), −113.80 (m,
3
2
3
2
2
13
(
5
10 mL). The crude product was extracted with 3 ×
2F, CF (CF ) CF ), −82.10 (m, 3F, CF ); C NMR
3
2
2
2
3
mL of EtOAc, and 2.4 g of 2e [16] was obtained
(75.46 MHz, d -acetone): δ 27.52 (CF CH ), 57.05
6
2
2
(
93%).
(CH SO Cl), 111–124 (C F ).
2
2
4
9
1
H NMR (300.13 MHz, d
H, CH ), 1.35 (m, 4H, CH (CH
CH (CH SO Cl), 2.00 (m, 2H, CH
m, 2H, CH
acetone): δ 14.23 (CH
4.87 (CH CH SO Cl), 65.92 (CH
6
-acetone): δ 0.90 (m,
), 1.57 (m, 2H,
CH SO Cl), 4.00
Cl); C NMR (75.46 MHz, d
), 22.97, 27.72, 31.78 (3CH
SO Cl).
3
3
3
2
)
2
2
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecaflu-
orooctanesulfonyl Chloride (2i). Thirty grams
(74 mmol) of 1i dissolved in a mixture of 21 mL
(370 mmol) of acetic acid and 2 mL (111 mmol)
2
2
)
2
2
2
2
13
(
2
SO
2
6
-
),
3
2
◦
2
2
2
2
2
2
of was stirred 1.5 h at 50 C with 60 mL of SO Cl
2
2
(740 mmol). The excess of SO
2
2
Cl was hydrolyzed by
Synthesis of Octanesulfonyl Chloride (2f). Two
the addition of water (60 mL). The crude product
grams (11.69 mmol) of 1f dissolved in a mixture
was extracted with 3 × 25 mL of EtOAc, and
of 3.3 mL (58.45 mmol) of acetic acid and 0.32 mL
32.98 g of 2i was obtained (100%). The compound
◦
1
(
17.54 mmol) of water was stirred 30 min at 50 C
2i synthesized previously was compared by
H
with 9.48 mL (116.90 mmol) of SO
2
Cl
2
. The excess
NMR spectroscopy with pure sample furnished by
Elf-Atochem.
of SO Cl was hydrolyzed by the addition of water
2
2
◦
1
(
5
10 mL). The crude product was extracted with 3 ×
mp = 28 C. H NMR (300.13 MHz, d
δ 3.10 (m, 2H, C ), 4.48 (m, 2H, CH
F NMR (282.37 MHz, d
-acetone): δ −127.04
(m, 2F, CF CF CF (CF ),
−122.62 (m, 2F, CF
CF (CF CF
(75.46 MHz, d
(CH SO Cl), 111–124 (C
6
-acetone):
mL of EtOAc and 2.15 g of 2f [16] was obtained
6
F13CH
2
2
CH ),
2
19
(
86%).
6
1
H NMR (300.13 MHz, d
H, CH ), 1.52 (m, 10H, CH
CH CH SO Cl), 3.80 (m, 2H, CH
75.46 MHz, d -acetone): δ 14.5 (CH
5.60, 27.80, 29.60, 32.60 (6CH ), 65.80 (CH
6
-acetone): δ 0.91 (m,
3
2
), −123.87 (m, 4F, CF
3
2
2 2
)
3
3
3
(CH ), 2.04 (m, 2H,
2
)
5
3
(CF
2
)
3
CF
2
), −113.70 (m, 2F,
13
13
2
2
2
2
SO
2
Cl); C NMR
), 23.40, 25.4,
SO Cl).
3
2
)
4
2
), −82.12 (m, 3F, CF
3
); C NMR
2
(
6
3
6
-acetone): δ 27.64 (CF
CH ), 57.11
2
2
2
2
2
2
2
6
F13).
Heteroatom Chemistry DOI 10.1002/hc

A New Synthesis of Alkane and Polyfluoroalkanesulfonyl Chlorides 361
Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
Heptadecafluorooctanesulfonyl Chloride (2j). Thirty-
four grams (67 mmol) of 1j dissolved in a mixture
of 19 mL (335 mmol) of acetic acid and 2 mL (100.5
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[
[
[
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1
[
[
[
H NMR spectroscopy with pure sample furnished
by Elf-Atochem.
◦
1
mp = 65 C. H NMR (300.13 MHz, d
δ 3.05 (m, 2H, C ), 4.40 (m, 2H, CH
F NMR (282.37 MHz, d
-acetone): δ −126.81
s, 2F, CF CF CF CF ),
), −123.62 (m, 2F, CF
123.31 (m, 2F, CF (CF CF
), −122.33 (m, 6F,
CF (CF (CF (CF CF ),
), −113.36 (m, 2F, CF
81.81 (m, 3F, CF ); C NMR (75.46 MHz, d
acetone): δ 27.33 (CF CH ), 57.11 (CH SO Cl), 111–
22 (C
6
-acetone):
6
0, 1486–1489.
8
F17CH
2
2
CH );
2
[
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2
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3
2
)
3
3
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2
2
2
1
8
F17).
ACKNOWLEDGEMENT
We gratefully acknowledge the “Minist e` re de
l’Education Nationale et de la Recherche” for its
financial support (Ph.D. grant to Z. Benfodda), the
University of Montpellier 1&2, and the French CNRS
(Centre National de la Recherche Scientifique).
Heteroatom Chemistry DOI 10.1002/hc