Aliphatic sulfonation, 16: Sulfonation of alkenes by chlorosulfuric acid, acetyl sulfate, and trifluoroacetyl sulfate

Article abstract of DOI:10.1002/(sici)1099-0690(199901)1999:1<91::aid-ejoc91>3.0.co;2-j

An exploratory study has been made on the reaction of a number of non- branched alkenes in [D]chloroform as an aprotic solvent, using chlorosulfuric acid as reagent both in the presence and the absence of [D₈]1,4-dioxane as complexing agent. Reaction of cyclopentene (1a) with 1.1 mol-equiv. of chlorosulfuric acid in [D]chloroform in the presence of 2.2 mol-equiv, of [D₈]1,4-dioxane at 0 °C yielded quantitatively 1,2-cyclopentanesultone (2a). Under similar reaction conditions, the linear alkenes 1b-g afforded the corresponding β-sultones 2b-g. The ClSO₃H-dioxane complex acted as a sulfonating reagent with the alkenes to yield the corresponding β-sultones in a syn cycloaddition of SO₃ to the carbon-carbon double bond. In the absence of [D₈]1,4-dioxane the reaction of the linear alkenes 1a-1k in [D]chloroform with chlorosulfuric acid at -40 °C led to the formation of the sec-alkyl chlorosulfates 5a-i, which were formed after initial protonation of the alkene by the strongly acidic ClSO₃H. Cyclopentyl chlorosulfate (5a) in [D]chloroform at 0 °C was quantitatively converted into 1,2- cyclopentanesultone (2a). The sec-alkyl chlorosulfates 5b-i at 0 °C gave rise to a mixture of the internal trans- and cis-β-sultones 2b-m. Reaction of 1-octene (1g) with both acetyl sulfate (6a) and trifluoroacetyl sulfate (6b) as reagent in [D]chloroform at -20 °C directly afforded the products 1,2-octanesultone (2g), and the (E) and (Z) isomer of 2-octene-1-sulfonic acid (4g).

Full text of DOI:10.1002/(sici)1099-0690(199901)1999:1<91::aid-ejoc91>3.0.co;2-j

FULL PAPER
Aliphatic Sulfonation, 16[°]
Sulfonation of Alkenes by Chlorosulfuric Acid, Acetyl Sulfate, and
Trifluoroacetyl Sulfate
Bert H. Bakker[a] and Hans Cerfontain*[a]
Keywords: Alkenes / Electrophilic additions / β-Sultones / sec-Alkyl chlorosulfate / 2-Chloro-1-alkanesulfonic acid
An exploratory study has been made on the reaction of a
number of non-branched alkenes in [D]chloroform as an
aprotic solvent, using chlorosulfuric acid as reagent both in
the presence and the absence of [D8]1,4-dioxane as
complexing agent. Reaction of cyclopentene (1a) with 1.1
mol-equiv. of chlorosulfuric acid in [D]chloroform in the
presence of 2.2 mol-equiv. of [D8]1,4-dioxane at 0 °C yielded
quantitatively 1,2-cyclopentanesultone (2a). Under similar
reaction conditions, the linear alkenes 1b–g afforded the
corresponding β-sultones 2b–g. The ClSO3H–dioxane
complex acted as a sulfonating reagent with the alkenes to
yield the corresponding β-sultones in a syn cycloaddition of
SO3 to the carbon–carbon double bond. In the absence of
[D8]1,4-dioxane the reaction of the linear alkenes 1a–1k in
[D]chloroform with chlorosulfuric acid at –40 °C led to the
formation of the sec-alkyl chlorosulfates 5a–i, which were
formed after initial protonation of the alkene by the strongly
acidic ClSO3H. Cyclopentyl chlorosulfate (5a) in [D]chlo-
roform at
0 °C was quantitatively converted into 1,2-
cyclopentanesultone (2a). The sec-alkyl chlorosulfates 5b–i
at 0 °C gave rise to a mixture of the internal trans- and cis-
β-sultones 2b–m. Reaction of 1-octene (1g) with both acetyl
sulfate (6a) and trifluoroacetyl sulfate (6b) as reagent in
[D]chloroform at –20 °C directly afforded the products 1,2-
octanesultone (2g), and the (E) and (Z) isomer of 2-octene-1-
sulfonic acid (4g).
With diethyl ether as solvent the reaction of chlorosulfuric
acid with alkenes proceeds differently,[13] since the chloro-
sulfuric acid adds to diethyl ether to form the correspond-
ing oxonium complex.[15] Reaction of chlorosulfuric acid
with an α-olefin in diethyl ether as solvent leads to the for-
mation of 1- and 2-alkene-1-sulfonic acids in high yield via
2-chloroalkane-1-sulfonic acid as intermediate.[16]
We now report on a study of the reaction of chlorosul-
furic acid with non-branched alkenes in chloroform as sol-
vent both in the presence and the absence of dioxane at
temperatures ranging from Ϫ40 to 25°C. In addition we
have studied the reaction of 1-octene with both acetyl sul-
fate and trifluoroacetyl sulfate in CDCl3 within the same
temperature range. The objective of these exploratory stu-
dies was to obtain information as to the initial reaction
products and their subsequent chemistry.
Introduction
As a sequel to our studies on the reaction of simple and
monofunctionalized alkenes with sulfur trioxide,[1Ϫ5] we
now report on the reaction of a series of olefins with chloro-
sulfuric acid and two related sulfuric acid derivatives, viz.
acetyl sulfate and its trifluoro derivative. Sulfur trioxide re-
acts vigorously with alkenes to form β-sultones as the pri-
mary unstable products, which at room temperature eventu-
ally yield a complex mixture of alkenesulfonic acids and γ-
and δ-sultones.[6,7] The very high reactivity of neat sulfur
trioxide can be moderated by complexation with Lewis
bases such as 1,4-dioxane and pyridine.[8,9] Another type of
moderated sulfur trioxide donors are the complexes com-
posed of SO3 and protic species such as hydrochloric acid,
acetic acid, and water.[10] Reagents of the latter group are
very strong acids and may thus also act as proton donors.
In fact, alkenes are protonated by sulfuric acid to give sub-
sequently alkyl hydrogen sulfates in a reversible reaction.[11]
Acetyl sulfate, i.e. the adduct of SO3 and acetic acid, reacts
with alkenes to afford the corresponding β-sultones in a
stereospecific fashion.[12] In nonpolar solvents like chloro-
form alkenes are protonated by chlorosulfuric acid to give
the corresponding chlorosulfonate esters.[13] However, the
reaction of chlorosulfuric acid with 2-pentene in chloro-
form was reported to afford a mixture of 2-pentene-2-sul-
fonic acid and 2-pentene-3-sulfonic acid in a 4:1 ratio.[14]
Results and Discussion
Sulfonation of Alkenes with Chlorosulfuric Acid in the
Presence of Dioxane
Reaction of the alkenes 1a؊g with 1.1 mol-equiv. of chlo-
rosulfuric acid and 2.2 mol-equiv. of [D8]1,4-dioxane
(further referred to as [D8]dioxane or dioxane) were studied
in [D]chloroform as solvent. In order to obtain information
on the primary sulfonation products, the reactions were car-
ried out at low temperatures. The composition of the homo-
geneous reaction mixtures were determined by 1H- and 13C-
NMR spectroscopy. The 1H- and 13C-NMR assignments of
the various sulfonation products are compiled in the Exper-
imental Section.
[°]
Part 15: H. Cerfontain, J. B. Kramer, R. M. Schonk, B. H.
Bakker, Recl. Trav. Chim. Pays-Bas 1995, 114, 410Ϫ420.
[a]
Laboratory of Organic Chemistry, University of Amsterdam,
Nieuwe Achtergracht 129, NL-1018 WS Amsterdam, The
Netherlands
Eur. J. Org. Chem. 1999, 91Ϫ96
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
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91

B. H. Bakker and H. Cerfontain
FULL PAPER
Addition of cyclopentene (1a) to a mixture of 1.1 mol-
equiv. of chlorosulfuric acid in [D]chloroform as solvent in
the presence of 2.2 mol-equiv. of [D8]dioxane at 0°C gives Treatment of 1-butene (1d) with 1.1 mol-equiv. of chlorosul-
1,2-cyclopentanesultone (2a). At temperatures Յ Ϫ20°C furic acid in the presence of 2.2 mol-equiv. of [D8]dioxane
the rate of the β-sultone formation is very small, but after in [D]chloroform as solvent at 0°C for 3.0 h leads to the
raising the temperature to 0°C it takes about 2 h to com- formation of a mixture of 1,2-butanesultone (2d), 2-chloro-
pletely convert the cyclopentene into the β-sultone 2a. The 1-butanesulfonic acid (3d), and 2-butene-1-sulfonic acid
rate of reaction of cyclopentene with chlorosulfuric acid in (4d) in a molar ratio of 4:2:1. The 1,2-alkanesultones are
the presence of [D8]dioxane in [D]chloroform as solvent ap- much more reactive than the internal cis-β-sultones,
pears to be much smaller than that with the SO3Ϫdioxane whereas the latter are more reactive than the corresponding
complex, which reacts very rapidly with cyclopentene at trans-β-sultones. It is therefore proposed that 2-chloro-1-
temperatures as low as Ϫ40°C to afford the β-sultone 2a[17]
.
butanesulfonic acid (3d) is formed by reaction of the 1,2-
This is in line with the pK values of the dissociation con- butanesultone (2d) with HCl, as shown in Scheme 2. The
stants of the SO3Ϫdioxane complex (pK ϭ 1.9) and chloro- 2-butene-1-sulfonic acid [4d, (E)/(Z) ϭ 1:1] is also thought
sulfuric acid (pK ϭ 4.2) which were measured in a potentio- to be a secondary product formed by thermal rearrange-
metric study[18]. Apparently, the complex of chlorosulfuric ment of the 1,2-butanesultone (2d). Our conclusion that the
acid with [D8]dioxane[19] releases SO3 slowly, which reacts 1,2-butanesultone (2d) is the primary product differs from
with cyclopentene to afford the corresponding β-sultone 2a. an earlier report[16] that the primary product upon reaction
At room temperature the solution of 1,2-cyclopentanesul- of chlorosulfuric acid with α-olefins in the presence of di-
tone in [D]chloroform in the presence of [D8]dioxane is ethyl ether would be the chlorinated alkanesulfonic acid 3.
rather stable, the content of the β-sultone after 24 h still The reaction of 1-octene (1g) with 1.1 mol-equiv. of the
being > 90%.
chlorosulfuric acidϪdioxane complex in [D]chloroform at
Reaction of (E)-2-butene (1b) with 1.1 mol-equiv. of chlo- 0°C for 2.0 h similarly affords a mixture of 50% of 1,2-
rosulfuric acid in [D]chloroform in the presence of 2.2 mol- octanesultone (2g), 18% of 2-chloro-1-octanesulfonic acid
equiv. of [D8]dioxane for 2 h at room temperature affords (3b), 16% of a mixture of (E)- and (Z)-2-octene-1-sulfonic
solely trans-2,3-butanesultone (2b). Similarly, reaction of acid [4b, (E)/(Z) ϭ 4:3], and 16% of the starting 1-octene.
(E)-4-octene (1e) with 1.1 mol-equiv. of the chlorosulfuric
Thus, it appears that the primary reaction of alkenes with
acidϪdioxane complex at room temperature for 2 h leads to the chlorosulfuric acidϪdioxane complex in [D]chloroform
the quantitative formation of trans-4,5-octanesultone (2e). as solvent is the formation of the corresponding β-sultones.
Furthermore, reaction of both (Z)-2-butene (1c) and (Z)- The rate of reaction of alkenes with the chlorosulfuric acid-
4-octene (1f) with 1.1 mol-equiv. of chlorosulfuric acid in Ϫdioxane complex is much slower than with the SO3Ϫdi-
[D]chloroform in the presence of 2.2 mol-equiv. of [D8]di- oxane complex; it is, however, of the same order of magni-
oxane for 1.0 h at room temperature exclusively yields cis- tude as upon using trimethylsilyl chlorosulfate[20,21] as re-
2,3-butanesultone (2c) and cis-4,5-octanesultone (2f), agent. The chlorosulfuric acidϪdioxane complex is a sul-
respectively. The complex of chlorosulfuric acid and fonating agent that slowly releases SO3, which upon
[D8]dioxane thus reacts with the alkenes 1 by syn cycload- stereospecific cycloaddition to the alkenes affords the ob-
dition to afford the β-sultones 2, as depicted in Scheme 1. served β-sultones.
92
Eur. J. Org. Chem. 1999, 91Ϫ96

Aliphatic Sulfonation, 16
FULL PAPER
upon reaction of 2-hexene [(E)/(Z) ϭ 3:1] with 1.1 mol-
equiv. of ClSO3H in [D]chloroform at Ϫ20°C, viz. 63% of
5e and 37% of 5f. Reaction of 1-octene (1g) with 1.1 mol-
equiv. of ClSO3H in [D]chloroform at Ϫ40°C affords a mix-
ture of 2-octyl chlorosulfate (5g), 3-octyl chlorosulfate (5h),
and 4-octyl chlorosulfate (5i) in yields of 70, 18 and 12%,
respectively. The composition of the three sec-octyl chloros-
ulfates does not change when the temperature is raised to
0°C and kept at that temperature for 50 min. On the other
hand, treatment of (E)-4-octene (1e) or (Z)-4-octene (1f)
with 1.1 mol-equiv. of ClSO3H in [D]chloroform at Ϫ40°C
yields a mixture of 4-octyl chlorosulfate (5i) and 3-octyl
chlorosulfate (5h) in a ratio of 4:1, with possibly in addition
at most 3% of 2-octyl chlorosulfate (5g). The general
scheme for the reaction of the linear α-alkenes with chloros-
ulfuric acid in [D]chloroform at Ϫ40°C is shown in Scheme
3. From the obtained results it appears that the addition of
ClSO3H to linear alkenes in [D]chloroform as solvent only
affords the internally substituted linear alkyl chlorosulfates,
but not any 1-alkyl derivative. Remarkably, in the tempera-
ture range of Ϫ40 to 0°C the addition of chlorosulfuric acid
to the linear alkenes does not yield the thermodynamically
most stable mixture of sec-alkyl chlorosulfates, but the com-
position is mainly determined by the original position of
the double bond in the alkene.
Scheme 1. Formation of β-sultones from the alkenes 1a؊g with
chlorosulfuric acid and [D8]dioxane in CDCl3
Scheme 2. Conversion of the 1,2-alkanesultones 2 in the presence
of HCl into the corresponding 1-alkane-2-chlorosulfonic acids 3,
and the (E)- and (Z)-2-alkene-1-sulfonic acids 4
Reaction of Alkenes with Chlorosulfuric Acid in the
Absence of Dioxane
Addition of cyclopentene (1a) to 1.1 mol-equiv. of chlo-
rosulfuric acid in [D]chloroform at Ϫ40°C leads immedi-
ately to the quantitative formation of cyclopentyl chloro-
sulfate (5a). Thus, chlorosulfuric acid in [D]chloroform
without dioxane acts as a strong protic acid to give the
chlorosulfate 5a by initial protonation.[22,23] Addition of 1-
butene (1d) to 1.1 mol-equiv. of ClSO3H in [D]chloroform
at Ϫ40°C only leads to the formation of sec-butyl
chlorosulfate (5b), the corresponding 1-butyl derivative not
1
being present beyond the limit of detection by H NMR.
The same chlorosulfate 5b was formed quantitatively when
either (E)-2-butene (1b) was added to 1.1 mol-equiv. of
chlorosulfuric acid in [D]chloroform at Ϫ40°C, or (Z)-2-
butene (1c) was added to 1.1 mol-equiv. of chlorosulfuric
acid in [D]chloroform at Ϫ60°C. Reaction of 1-pentene (1h)
with 1.1 mol-equiv. of ClSO3H in [D]chloroform at Ϫ40°C
affords a mixture of 2-pentyl chlorosulfate (5c) and 3-pentyl
chlorosulfate (5d) in 80 and 20% yield, respectively. The ra-
tio of the two chlorosulfates 5c and 5d remained the same
Scheme 3. Reaction of the α-olefins 1b, 1g, and 1h with ClSO3H in
CDCl3 at Ϫ40°C
Although the chemistry of prim-alkyl chlorosulfates has
upon keeping the solution at 0°C for 45 min. Concentrated been studied extensively, sec- and tert-alkyl derivatives are
sulfuric acid reacts similarly with linear alkenes to afford virtually unknown due to their high instability.[24] We have
only the sec-alkyl hydrogen sulfates.[11] Reaction of (Z)-3- studied the fate of the unstable sec-alkyl chlorosulfates 5,
hexene (1k) with 1.1 mol-equiv. of ClSO3H in [D]chloro- which were obtained upon reaction of the alkenes 1aϪk
form at Ϫ40°C leads to a mixture of 46% of 2-hexyl chloro- with chlorosulfuric acid at Ϫ40°C in [D]chloroform. Cyclo-
sulfate (5e) and 54% of 3-hexyl chlorosulfate (5f). A differ- pentyl chlorosulfate (5a), obtained by reaction of cyclopen-
ent ratio of the two chlorosulfates 5e and 5f was obtained tene with ClSO3H at Ϫ40°C in [D]chloroform, is slowly
Eur. J. Org. Chem. 1999, 91Ϫ96
93

B. H. Bakker and H. Cerfontain
FULL PAPER
converted into 1,2-cyclopentanesultone (2a) upon raising then yields the corresponding β-sultones. From the preced-
the temperature to Ϫ10°C, the chlorosulfate 5a/β-sultone ing results it appears that in the absence of [D8]dioxane the
2a ratio after 3 h being 2:8. Upon further raising the tem- chlorosulfuric acid initially protonates the linear alkenes to
perature to 0°C and keeping it there for 20 min the 5a/2a afford sec-alkyl chlorosulfates, which are eventually con-
ratio had decreased to 1:9. Leaving the β-sultone solution verted into internal β-sultones.
subsequently at room temperature overnight resulted
mainly in decomposition, the remaining amount of the β-
Reaction of 1-Octene with Acetyl Sulfate and
Trifluoroacetyl Sulfate
sultone 2a being only 10%. Apparently, the stability of the
1,2-cyclopentanesultone (2a) in [D]chloroform is substan-
tially higher in the presence than in the absence of [D8]di-
oxane. Probably the [D8]dioxane reduces the protic acidity
of the reaction mixture, and thus the rate of decomposition
of the β-sultone. Reaction of each of the three linear but-
enes 1b, 1c and 1d with ClSO3H at Ϫ40°C in [D]chloroform
yielded sec-butyl chlorosulfate (5b), which after 1 h at room
temperature was gradually converted into a mixture of
trans- (2b) and cis-2,3-butanesultone (2c) in a 3:2 ratio. Re-
markably, only the internal β-sultones 2b and 2c were
formed, but not 1,2-butanesultone (1d). Upon reaction of
the 80:20 mixture of 2-pentyl (5c) and 3-pentyl chlorosul-
fate (5d, see before) in [D]chloroform at room temperature
for 24 h, the resulting solution was found to contain 40%
of trans-2,3-pentanesultone (2h), 12% of cis-2,3-pentanesul-
tone (2i), ca. 8% of trans-3,2-pentanesultone, 20% of the
starting 2-pentyl chlorosulfate (5c), and in addition small
amounts of various decomposition products of the β-sul-
tones. The 4:1 mixture of 4-octyl (5i) and 3-octyl chlorosul-
fate (5h) obtained from either (E)- or (Z)-4-octene (see be-
fore) was transformed after 10 min at room temperature
into a mixture of 60% of the trans isomers of 3,4-, 4,3-, and
4,5-octanesultone, and 20% of a mixture of the correspond-
ing cis-3,4-, -4,3-, and -4,5-octanesultone. The 1H-NMR
spectra of the trans-β-sultones show typical signals at δ ϭ
4.15 and 4.32, whereas those of the corresponding cis-β-
sultones appear at δ ϭ 4.57 and 4.78. The reaction mixture
consisting of 70% of 2-octyl chlorosulfate (5g), 18% of 3-
octyl chlorosulfate (5h), and 12% of 4-octyl chlorosulfate
(5i) in [D]chloroform (see before) afforded after 24 h at
room temperature 30% of trans-2,3-octanesultone (2l) and
10% of cis-2,3-octanesultone (2m) as the main products, be-
sides small amounts of the trans-3,4-, -4,5-, and -3,2-octane-
sultone. From the results presented it appears that the sec-
alkyl chlorosulfates 5 are transformed into a mixture of in-
ternal trans- and cis-β-sultones. The proposed mechanism
for this unexpected conversion is shown in Scheme 4. We
presume that ClSO3H is eliminated from the sec-alkyl chlo-
rosulfate in a cyclic process to afford a mixture of the (E)
and (Z) isomers of the internal alkenes, together with SO3
and HCl. Subsequent sulfonation of these alkenes by SO3
In the preceding section it was shown that chlorosulfuric
acid, which is formally a complex of SO3 and HCl, reacts
as a strong acid with alkenes leading to the formation of
sec-alkyl chlorosulfates. Both acetyl sulfate (6a) and its tri-
fluoro derivative 6b can also be considered as strongly
acidic sulfonating reagents. Therefore we were interested to
know whether the initial step of the acetyl sulfates 6a and
6b with an alkene would be protonation or sulfonation.
Reaction of 1-octene (1g) with 1.1 mol-equiv. of acetyl
sulfate (6a), made up from equimolar amounts of acetic
acid and SO3, in [D]chloroform at Ϫ40°C for 10 min leads
to the formation of 71% of 1,2-octanesultone (2g), 16% of
a mixture of (E)- and (Z)-2-octene-1-sulfonic acid [4g, (E)/
(Z) ϭ 4:3), leaving 13% of unreacted 1-octene. After 10 min
at 0°C, the remaining 1-octene had reacted to afford 81%
of 1,2-octanesultone (2g) and 19% of a mixture of (E)- and
(Z)-2-octene-1-sulfonic acid [4g, (E)/(Z) ϭ 4:3). Reaction of
1-octene (1g) with 1.1 mol-equiv. of trifluoroacetyl sulfate
(6b), made up from equimolar amounts of trifluoroacetic
acid and SO3, in [D]chloroform at Ϫ20°C for 10 min led to
the formation of 63% of 1,2-octanesultone (2g) and 37% of
a 3:2 mixture of (E)- and (Z)-2-octene-1-sulfonic acid (4g).
Thus, 1-octene reacts with both acetyl sulfate and trifluo-
roacetyl sulfate to afford rapidly the sulfonation products
1,2-octanesultone (2g) and (E)- and (Z)-2-octene-1-sulfonic
acid (4g) as depicted in Scheme 5. Although the acetyl sul-
fates 6a and 6b are strong acids there is no evidence for an
initial protonation of the 1-octene, since the only observed
procucts are the 1-sulfo compounds 2g and 4g. The sulfo-
nating behaviour of both the acetyl sulfate (6a)[12] and tri-
fluoroacetyl sulfate (6b) appears to be comparable with that
of the chlorosulfuric acidϪdioxane complex.
Scheme 5. Reaction of 1-octene (1g) with acetyl sulfate (6a) and
trifluoroacetyl sulfate (6b) in CDCl3
Experimental Section
General: Materials: The high-purity alkene substrates, chlorosul-
furic acid and trimethylsilyl chlorosulfate reagents, and [D]chloro-
form and [D8]dioxane solvents were obtained commercially. Sulfo-
Scheme 4. Mechanism for the conversion of sec-alkyl chlorosulfates
5 into the β-sultones 2 in CDCl3
94
Eur. J. Org. Chem. 1999, 91Ϫ96

Aliphatic Sulfonation, 16
FULL PAPER
1
nation procedures and analysis: These were analogous to those de-
scribed previously.[5,25,26] Ϫ 1H- and 13C NMR: Bruker AC-200 and
WM-250 spectrometers. Of the various types of the homogeneous
reaction mixtures the 1H- and 13C-NMR spectra were recorded ap-
plying APT (attached proton technique), COSY,[27] double reson-
ance, and CH correlation,[28] as appropriate. The structural assign-
ments of the components of the reaction mixtures were made on
the basis of the observed 1H-NMR chemical shifts, absorption ra-
tios and coupling constants in combination with the 1H-NMR-
shielding parameters of the ϪSO2ϪOϪ and SO3H substitu-
ents.[1,29] The product compositions of the various reaction mix-
tures were determined by multicomponent 1H-NMR analysis on
the basis of specific absorptions of the assigned components.[29]
2-Butyl Chlorosulfate (5b): H NMR (CDCl3): δ ϭ 5.04 (m, 1 H),
1.83 (m, 2 H), 1.54 (d, J ϭ 6.3 Hz, 3 H, 1-Me), 1.01 (t, J ϭ 7.4
Hz, 3 H, 4-Me). Ϫ 13C NMR (CDCl3): δ ϭ 19.7 (C-1), 90.8 (C-2),
29.1 (C-3), 9.4 (C-4).
1
2-Pentyl Chlorosulfate (5c): H NMR (CDCl3): δ ϭ 5.02 (m, 1 H),
1.80 (m, 2 H), 1.47 (d, J ϭ 6.3 Hz, 3 H, 1-Me), 1.42 (m, 2 H), 0.91
(t, J ϭ 7.2 Hz, 3 H, 5-Me).
1
3-Pentyl Chlorosulfate (5d): H NMR (CDCl3): δ ϭ 4.84 (m, 1 H),
1.65 (m, 4 H), 0.96 (t, J ϭ 7.4 Hz, 6 H).
1
2-Hexyl Chlorosulfate (5e): H NMR (CDCl3): δ ϭ 5.06 (m, 1 H),
1.80 (m, 2 H), 1.53 (d, J ϭ 6.2 Hz, 3 H, 1-Me), 1.35 (m, 4 H), 0.89
(3 H, 6-Me).
NMR-Spectroscopic Data of the Sulfo Products
1
3-Hexyl Chlorosulfate (5f): H NMR (CDCl3): δ ϭ 4.95 (m, 1 H),
1,2-Cyclopentanesultone (2a):[12] 1H NMR (CDCl3): δ ϭ 4.97 (m,
1 H), 4.91 (m, 1 H), 1.50Ϫ2.50 (m, 6 H).
1.80 (m, 4 H), 1.40 (m, 2 H), 0.99 (t, J ϭ 7.4 Hz, 3 H, 1-Me), 0.94
(t, J ϭ 7.1 Hz, 3 H, 6-Me).
trans-2,3-Butanesultone (2b):[30] 1H NMR (CDCl3): δ ϭ 4.33 (m, 1
H, CHS), 4.21 (m, 1 H, CHO), 1.59 (d, J ϭ 7.3, 3 H, 1-Me), 1.57
(d, J ϭ 7.3, 3 H, 4-Me).
2-Octyl Chlorosulfate (5g): H NMR (CDCl3): δ ϭ 5.08 (m, 1 H),
1
1.76 (m, 2 H), 1.54 (d, J ϭ 6.3 Hz, 3 H, 1-Me), 1.25Ϫ1.35 (m, 8
H), 0.84 ( 3 H, 8-Me).
cis-2,3-Butanesultone (2c):[30] 1H NMR (CDCl3): δ ϭ 4.88 (m, 1 H,
CHS), 4.76 (m, 1 H, CHO), 1.50 (d, J ϭ 7.2, 3 H, 1-Me), 1.48 (d,
J ϭ 6.3, 3 H, 4-Me).
1
3-Octyl Chlorosulfate (5h): H NMR (CDCl3): δ ϭ 4.98 (m, 1 H),
1.80 (m, 4 H), 1.35 (m, 6 H), 0.99 (t, J ϭ 7.3 Hz, 3 H, 1-Me), 0.85
(3 H, 8-Me).
1,2-Butanesultone (2d):[12] 1H NMR (CDCl3): δ ϭ 4.54 (dd, J ϭ
12.3, 7.5, 1 H, CHS), 4.40 (m, 1 H, CHO), 4.11 (dd, J ϭ 12.3, 5.5,
1 H, CHS), 1.90 (m, 2 H), 0.94 (t, J ϭ 7.3, Me).
1
4-Octyl Chlorosulfate (5i): H NMR (CDCl3): δ ϭ 4.98 (m, 1 H),
1.80 (m, 4 H), 1.35 (m, 6 H), 0.94 (m, 6 H).
trans-2,3-Pentanesultone (2h): 1H NMR (CDCl3): δ ϭ 4.34 (m, 1
H, CHS), 3.98 (m, 1 H, CHO), 1.89 (m, 2 H), 1.57 (d, J ϭ 7.1, 3
H, 1-Me), 0.96 (t, J ϭ 7.4, 3 H, 5-Me).
Acknowledgments
1
The authors wish to thank Dr. T. A. B. M. Bolsman and Dr. Ir. A.
van Zon for stimulating discussions, and Mrs. H. van der Laan-
Ctvrteckova for recording the NMR spectra. The financial support
by Shell Research B.V. is gratefully acknowledged.
cis-2,3-Pentanesultone (2i): H NMR (CDCl3): δ ϭ 4.85 (m, 1 H,
CHS), 4.45 (m, 1 H, CHO), 1.65 (m, 2 H), 1.43 (d, J ϭ 6.6, 3 H,
1-Me), 0.98 (t, J ϭ 7.4, 3 H, 5-Me).
trans-4,5-Octanesultone (2e):[1] 13C NMR (CDCl3): δ ϭ 77.7
(CHS), 72.5 (CHO), 36.5 (C-6, CH2), 30.4 (C-3, CH2), 19.9 (CH2),
18.1 (CH2), 13.5 (CH3), 13.4 (CH3).
[1]
B. H. Bakker, H. Cerfontain, Tetrahedron Lett. 1987, 28,
1699Ϫ1702.
[2]
cis-4,5-Octanesultone (2f):[1] 13C NMR (CDCl3): δ ϭ 75.0 (CHS),
70.0 (CHO), 31.7 (C-6, CH2), 26.3 (C-3, CH2), 20.6 (CH2), 18.3
(CH2), 13.5 (CH3), 13.4 (CH3).
B. H. Bakker, H. Cerfontain, Tetrahedron Lett. 1989, 30,
5451Ϫ5453.
[3]
R. M. Schonk, B. H. Bakker, H. Cerfontain, Recl. Trav. Chim.
Pays-Bas 1992, 111, 389Ϫ401.
[4]
R. M. Schonk, B. H. Bakker, H. Cerfontain, Recl. Trav. Chim.
1,2-Octanesultone (2g):[1] 13C NMR (CDCl3): δ ϭ 64.2 (CH2S),
65.6 (CHO), 34.9 (CH2), 31.4 (CH2), 28.5 (CH2), 24.5 (CH2), 22.4
(CH2), 14.0 (CH3).
Pays-Bas 1992, 111, 478Ϫ489.
[5]
H. Cerfontain, J. B. Kramer, R. M. Schonk, B. H. Bakker, Recl.
Trav. Chim. Pays-Bas 1995, 114, 410Ϫ420.
[6]
D. W. Roberts, D. L. Williams, Tetrahedron 1987, 43,
trans-2,3-Hexanesultone (2j): 1H NMR (CDCl3): δ ϭ 4.45 (m, 1 H,
CHS), 4.13 (m, 1 H, CHO), 1.88 (m, 2 H), 1.64 (d, J ϭ 7.1, Me),
1.43 (m, 2 H), 0.96 (t, J ϭ 7.3, Me).
1027Ϫ1062.
[7]
J. L. Boyer, J. P. Canselier, V. Castro, J. Am. Oil Chem. Soc.
1982, 59, 458Ϫ464.
[8]
C. M. Suter, B. P. Evans, J. M. Kiefer, J. Am. Chem. Soc. 1938,
1
60, 538Ϫ540.
cis-2,3-Hexanesultone (2k): H NMR (CDCl3): δ ϭ 4.97 (m, 1 H,
[9]
E. E. Gilbert, Chem. Rev. 1962, 62, 549Ϫ581.
CHS), 4.64 (m, 1 H, CHO).
[10]
H. Cerfontain, Mechanistic Aspects in Aromatic Sulfonation and
trans-2,3-Octanesultone (2l): 1H NMR (CDCl3): δ ϭ 4.38 (m, 1 H,
CHS), 4.07 (m, 1 H, CHO), 1.87 (m, 2 H), 1.60 (d, J ϭ 7.2, Me),
1.2Ϫ1.5 (m, 6 H), 0.86 (Me). Ϫ 13C NMR (CDCl3): δ ϭ 72.8
(CHS), 74.0 (CHO), 34.1 (CH2), 31.0 (CH2), 24.2 (CH2), 22.3
(CH2), 13.9 (C-8, CH3), 13.4 (C-1, CH3).
Desulfonation, John Wiley and Sons, Inc. New York, 1968, p.
6Ϫ7.
[11]
F. Asinger, B. Fell, U. Guhr, Chem. Ber. 1967, 100, 448Ϫ455.
[12]
W. A. Thaler, C. duBreuil, J. Polym. Sci. Polym. Chem. Ed.
1984, 22, 3905Ϫ3919.
[13]
E. E. Gilbert, Sulfonation and Related Reactions, Interscience,
New York, 1965, p. 18, 19 and 45.
1
[14]
cis-2,3-Octanesultone (2m): H NMR (CDCl3): δ ϭ 4.88 (m, 1 H,
S. Miron, G. Richter, J. Am. Chem. Soc. 1949, 71, 453Ϫ455.
[15]
L. Bert, C. R. Hebd. Seances Acad. Sci. 1946, 222, 898Ϫ900;
CHS), 4.57 (m, 1 H, CHO), 1.80 (m, 2 H), 1.53 (d, J ϭ 7.4, Me),
1.30 (m, 6 H), 0.87 (Me). Ϫ 13C NMR (CDCl3): δ ϭ 69.8 (CHS),
70.4 (CHO), 31.1 (CH2), 29.6 (CH2), 24.7 (CH2), 22.3 (CH2), 9.2
(C-1, CH3), 13.8 (C-8, CH3).
Chem. Abstr. 1946, 40, 40197.
[16]
H. R. Alul, Ind. Eng. Chem., Prod. Res. Develop. 1971, 10,
358Ϫ360.
[17]
B. H. Bakker, H. Cerfontain, Tetrahedron Lett. 1989, 30,
5451Ϫ5454.
1
[18]
Cyclopentyl Chlorosulfate (5a): H NMR (CDCl3): δ ϭ 5.46 (m, 1
H), 2.11 (m, 2 H), 1.97 (m, 2 H), 1.77 (m, 4 H).
Y. Auger, G. Delesalle, J. C. Fischer, M. Wartel, J. Electroanal.
Chem. 1980, 106, 149Ϫ159.
Eur. J. Org. Chem. 1999, 91Ϫ96
95

B. H. Bakker and H. Cerfontain
FULL PAPER
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978Ϫ981.
[20]
Both 1-butene (1d) and 1-octene (1g) were found to react with
1.1 mol-equiv. of trimethylsilyl chlorosulfate (ClSO3SiMe3)[21]
in chloroform at 0°C to afford the corresponding 1,2-alkanesul-
tones 2d and 2g, their respective yields after 60 and 10 min of
reaction being 57 and 75%.
[28]
[29]
[21]
K. Hofmann, G. Simchen, Justus Liebigs Ann. 1982, 282Ϫ297.
[22]
V. A. PalЈm, Dokl. Akad. Nauk S.S.S.R. 1956, 108, 270Ϫ273;
[30]
Chem. Abstr. 1957, 51, 814d.
M. Nagayama, O. Okumura, S. Noda, H. Mandai, A. Mori,
Bull. Chem. Soc. Jpn 1974, 47, 2158Ϫ2161.
Received June 25, 1998
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R. J. Gillespie, T. E. Peel, E. A. Robinson, J. Am. Chem. Soc.
1971, 93, 5083Ϫ5087.
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E. Buncel, Chem. Rev. 1970, 70, 323Ϫ337.
[O98280]
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Eur. J. Org. Chem. 1999, 91Ϫ96