Reaction of polyfluoroarenesulfonyl bromides with allyl bromide. Synthesis of allyl polyfluoroaryl sulfones

Article abstract of DOI:10.1134/S1070428011030080

Reactions of polyfluoroarenesulfonyl bromides 4-XC₆F ₄SO₂Br (X = F, H, Cl, Br, CF₃) with allyl bromide gave 84-94% of the corresponding allyl polyfluoroaryl sulfones.

Full text of DOI:10.1134/S1070428011030080

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 3, pp. 374–378. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © R.A. Bredikhin, A.M. Maksimov, V.E. Platonov, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 3,
pp. 380–384.
Reaction of Polyfluoroarenesulfonyl Bromides with Allyl
Bromide. Synthesis of Allyl Polyfluoroaryl Sulfones
R. A. Bredikhin, A. M. Maksimov, and V. E. Platonov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: platonov@nioch.nsc.ru
Received July 18, 2010
Abstract—Reactions of polyfluoroarenesulfonyl bromides 4-XC6F4SO2Br (X = F, H, Cl, Br, CF3) with allyl
bromide gave 84–94% of the corresponding allyl polyfluoroaryl sulfones.
DOI: 10.1134/S1070428011030080
We previously developed a procedure for the syn-
thesis of polyfluoroarenesulfonyl bromides Ia–Ie
which are poorly studied compounds [1]. On the other
hand, the chemical properties of nonfluorinated arene-
sulfonyl bromides were studied in sufficient detail; for
example, addition of these compounds to alkenes [2, 3]
and alkynes [4] and 1,4-addition to conjugated dienes
[5] were reported. Reactions of arenesulfonyl bromides
with olefins give rise to the corresponding bromoalkyl
sulfones which can be converted into aryl vinyl sul-
fones as potential monomers for the preparation of
polymeric compounds [2]. Reactions of arenesulfonyl
bromides with allyl halides were not reported. Non-
fluorinated arenesulfonyl chlorides reacted with allyl
bromide (II) in the presence of indium compounds [6]
to afford the corresponding allyl aryl sulfones which
are used in organic synthesis [7–9]. The goal of the
present work was to study the reaction of fluorinated
arenesulfonyl bromides Ia–Ie with allyl bromide (II)
with a view to obtain allyl polyfluoroaryl sulfones.
By heating sulfonyl bromides Ia–Ie with allyl
bromide (II) at 145–155°C we obtained the corre-
sponding allyl polyfluoroarylsulfones IIIa–IIIe in high
yield (Scheme 1). In addition, 1,2,3-tribromopropane
(IV) was formed as by-product. Presumably, thermally
induced homolytic dissociation of the S–Br bond in
polyfluoroarenesulfonyl bromide generates polyfluoro-
arenesulfonyl radical A which adds at the terminal
double-bonded carbon atom of compound II, yielding
secondary radical B (Scheme 2). This reaction direc-
tion is consistent with the data reported for the reaction
of allyl bromide (II) with trichloromethyl radical [10].
Analogous scheme was recently proposed for the ad-
dition of SF5Br to 1,2-dibromoethylene, which resulted
in the formation of F5SCH=CHBr and CHBr2CHBr2
[11]. Elimination of bromine atom from radical B
gives double C=C bond. The reaction of bromine atom
with compound II produces radical C which abstracts
bromine atom from sulfonyl bromide I, thus being
converted into 1,2,3-tribromopropane (IV).
Scheme 2.
Scheme 1.
Δ
II
·
·
SO2Br
ArFSO2Br
ArFSO2
ArFSO2CH2CHCH2Br
·
–Br
Br
+
F
H2C
Ia–Ie
A
B
X
ArFSO2CH2CH=CH2
·
–Br
Ia–Ie
II
IIIa–IIIe
Hc
O
O
·
Br
Ia–Ie
S
Hb
·
145–155°C
84–94%
II
BrCH2CHCH2Br
BrCH2CHBrCH2Br
–A
F
Ha
C
IV
X
IIIa–IIIe
Allyl polyfluoroaryl sulfone III is also capable of
X = F (a), H (b), Cl (c), Br (d), CF3 (e).
acting as bromine acceptor. Using as an example the
374

REACTION OF POLYFLUOROARENESULFONYL BROMIDES WITH ALLYL BROMIDE.
375
reaction of pentafluorobenzenesulfonyl bromide (Ia)
with compound II we showed that reduction of the
amount of II with respect to Ia favors formation of
a mixture of allyl pentafluorophenyl sulfone (IIIa) and
2,3-dibromopropyl pentafluorophenyl sulfone (V). The
latter may result from the reaction of allyl sulfone IIIa
with bromine by analogy with the formation of tri-
bromopropane IV from allyl bromide (II). In fact, by
heating compound IIIa with bromine at 145–155°C we
obtained dibromo derivative V in almost quantitative
yield (Scheme 3), whereas no C–S bond cleavage was
observed.
ible process which is likely to follow Scheme 5. Re-
versible addition of thiyl radicals to allyl halides was
observed previously [10].
Scheme 5.
·
4-XC6F4SO2
·
Br
4-XC6F4SO2Br
+
·
4-XC6F4SO2
+
4-YC6F4SO2CH2CH=CH2
·
4-YC6F4SO2CH2CHCH2SO2C6F4X-4
·
4-YC6F4SO2
+
H2C=CHCH2SO2C6F4X-4
4-YC6F4SO2Br
·
·
4-YC6F4SO2
+
Br
Scheme 3.
X, Y = F, CF3.
Br
O
O
S
Br
Unlike published data on the addition of arenesul-
fonyl bromides at double bonds, according to which
the addition products contained both sulfonyl group
and bromine atom [2], in our case the resulting sulfone
contains a double C=C bond but no bromine atom.
Polyfluoroarenesulfonyl bromides turned out to be
more reactive toward allyl bromide (II) than the cor-
responding polyfluoroarenesulfonyl chlorides. This is
consistent with the proposed reaction mechanism and
energies of the S–Cl (S2Cl2, 61 kcal/mol) and S–Br
bonds (S2Br2, 51 kcal/mol) [13]. Homolytic dissocia-
tion of the S–Cl bond in polyfluoroarenesulfonyl
chlorides should be more difficult than dissociation of
the S–Br bond in polyfluoroarenesulfonyl bromides.
145–155°C
99%
IIIa
+
Br2
F
V
We also found that allyl polyfluoroaryl sulfones can
be formed at room temperature on prolonged keeping
of the reaction mixture. In this case, scattered daylight
accelerated the process, which suggests radical nature
of the reaction. After exposure to daylight over a peri-
od of 15 days, the conversion of sulfonyl bromide Ia
was 94% (44% in the dark). Addition of hydroquinone
inhibited the reaction [12]: after 17 days in the dark,
the conversion of Ia did not exceed 10%.
When a mixture of compound IIIa and 4-trifluoro-
methyl-2,3,5,6-tetrafluorobenzenesulfonyl bromide
(Ie) was heated at 145–155°C (under the same con-
ditions as in the reaction of sulfonyl bromides Ia–Ie
with allyl bromide), compound Ia and allyl 4-trifluoro-
methyl-2,3,5,6-tetrafluorophenyl sulfone (IIIe) were
formed. Likewise, heating of Ia with allyl sulfone IIIe
resulted in the formation of compound Ie and allyl
sulfone IIIa (Scheme 4). We can conclude that the
formation of allyl polyfluoroaryl sulfones is a revers-
It is known [2, 5] that copper(I) salts catalyze
radical addition of nonfluorinated arenesulfonyl
halides to multiple bonds. In fact, addition of copper(I)
iodide to the reaction mixture considerably shortened
the reaction time. The conversion of sulfonyl bromide
Ia in the reaction with allyl bromide (II) in the pres-
ence of 20 mol % of copper(I) iodide at 145–155°C
was complete in 3 h, whereas in the absence of cop-
per(I) salt the conversion of Ia was 80%, other con-
ditions being equal.
Scheme 4.
EXPERIMENTAL
O
O
SO2Br
S
The NMR spectra of the reaction mixtures and
isolated individual compounds were recorded on
a Bruker AV-300 spectrometer at 282.4 (19F) and
300.13 MHz (1H) from solutions in CCl4 with addition
of acetone-d6. The chemical shifts were determined
relative to C6F6 (δF –162.9 ppm) or hexamethyldi-
siloxane (δ 0.04 ppm). The IR spectra were measured
on a Bruker Vector 22 instrument from samples pre-
pared as KBr pellets. The UV spectra were recorded
CH2
+
F
F
F3C
Ie
IIIa
O
O
SO2Br
S
145–155°C
CH2
+
F
F
F3C
Ia
IIIe
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011

BREDIKHIN et al.
376
from solutions in hexane on a Hewlett–Packard 8453
spectrophotometer. The molecular weights and ele-
mental compositions were determined from the high-
resolution mass spectra (electron impact, 70 eV) which
were obtained on a DFS instrument (ion source tem-
perature 110°C). Gas chromatographic–mass spectro-
metric analysis was performed on a Hewlett–Packard
G1801A GC–MS system consisting of an HP 5890
Series II gas chromatograph and an HP 5971 mass-
selective detector (electron impact, 70eV; HP-5 capil-
lary column, 30 m×0.25 mm, stationary phase 5% of
diphenyl- and 95% of dimethylpolysiloxane copoly-
mer; carrier gas helium, flow rate 1ml/min; oven tem-
perature 50–280°C; ion source temperature 173°C).
The melting points were determined on a Kofler
melting point apparatus.
zenesulfonyl bromide (Ia) with 1.22 g (10.08 mmol) of
allyl bromide (II) gave 2.05 g of a mixture of com-
pounds IIIa and IV containing a small amount (<2%)
of dibromo derivative V. Yield of IIIa 94%, mp 67–
68°C. IR spectrum, ν, cm–1: 2978, 2920, 1643, 1519,
1503, 1383, 1356, 1294, 1243, 1158, 1095, 996, 952,
883, 781, 727, 657, 547. UV spectrum, λmax, nm
1
(logε): 209 (3.97), 243 (2.50), 270 (3.12). H NMR
spectrum, δ, ppm: 3.96 d (2H, CH2, J = 7.4 Hz),
5.29 d.d (1H, Ha, Jac = 17.0, Jab ≈ 1 Hz), 5.41 d.d (1H,
Hb, Jbc = 10.1, Jab ≈ 1 Hz), 5.89 m (1H, Hc). 19F NMR
spectrum, δF, ppm: 2.9 m (2F, 3-F, 5-F), 17.2 t.t
3
4
(1F, 4-F, JFF = 20.7, JFF = 7.3 Hz), 26.6 m (2F, 2-F,
6-F). Found, %: C 40.03; H 1.80; F 34.74; S 11.86.
m/z 271.9911 [M]+. C9H5O2F5S. Calculated, %:
C 39.71; H 1.85; F 34.90; S 11.78. M 271.9925.
4-Bromo-2,3,5,6-tetrafluorobenzenesulfonyl
bromide (Id) was synthesized by reaction of 3.92 g
(15.02 mmol) of 4-bromo-2,3,5,6-tetrafluorobenzene-
thiol with a mixture of 9.10 g (92.43 mmol) of 64%
nitric acid, 17.76 g (166.59 mmol) of 92% sulfuric
acid, and 9.84 g (61.58 mmol) of bromine at 80°C
(reaction time 5 h) [1]. Yield 4.66 g (83%), mp 54–
56°C. IR spectrum, ν, cm–1: 1622, 1493, 1448, 1392,
1381, 1372, 1356, 1263, 1253, 1166, 1150, 978, 930,
798, 722, 619, 563, 533, 498. UV spectrum, λmax, nm
(logε): 235 (4.10), 258 (3.87), 287 (3.50). 19F NMR
spectrum, δF, ppm: 27.0 m (2F, 2-F, 6-F), 34.1 m (2F,
3-F, 5-F). Found, %: C 19.44; Br 42.92; F 20.26;
S 8.84. m/z 369.7914 [M]+. C6Br2F4O2S. Calculated,
%: C 19.38; Br 42.97; F 20.43; S 8.62. M 369.7916.
1-Allylsulfonyl-2,3,5,6-tetrafluorobenzene (IIIb).
The reaction of 2.18 g (7.44 mmol) of 2,3,5,6-tetra-
fluorobenzenesulfonyl bromide (Ib) with 3.80 g
(31.41 mmol) of allyl bromide (II) gave 3.73 g of
a mixture of allyl sulfone IIIb and compound IV.
Yield of IIIb 85%, mp 58–61°C. IR spectrum, ν, cm–1:
3084, 2972, 2911, 1640, 1614, 1496, 1433, 1379,
1342, 1302, 1248, 1181, 1152, 1085, 998, 957, 930,
894, 866, 777, 714, 633, 548, 469. UV spectrum, λmax
nm (logε): 215 (3.71), 281 (3.20). H NMR spectrum,
δ, ppm: 3.97 d (2H, CH2, J = 7.4 Hz), 5.29 d.d (1H, Ha,
,
1
Jac = 17.1, Jab ≈ 1 Hz), 5.39 d.d (1H, Hb, Jac = 10.0,
3
Jab ≈ 1 Hz), 5.89 m (1H, Hc), 7.38 t.t (1H, 4-H, JHF
=
9.1, JHF = 7.1 Hz). 19F NMR spectrum, δF, ppm:
25.7 m (2F), 26.1 m (2F). Found, %: C 42.64; H 2.34;
F 29.63; S 12.51. m/z 254.0021 [M]+. C9H6F4O2S.
Calculated, %: C 42.52; H 2.38; F 29.89; S 12.61.
M 254.0019.
4
Allyl polyfluoroaryl sulfones IIIa–IIIe (general
procedure). A glass ampule was charged under argon
with polyfluoroarenesulfonyl bromide Ia–Ie and allyl
bromide II. The ampule was heated for 25 h at 145–
155°C on an oil bath and cooled to room temperature.
The reaction mixture was dissolved in ~10 ml of
methylene chloride, and the solvent and unreacted allyl
bromide were distilled off under reduced pressure. The
residue was a dark solid containing (according to the
1H NMR data) allyl polyfluoroaryl sulfone IIIa–IIIe
and 1,2,3-tribromopropane (IV) at a ratio of ~1:1. The
structure of compound IV was confirmed by compar-
ing the 1H NMR spectrum of the reaction mixture with
the spectrum of an authentic sample of IV [14] pre-
pared as described in [15]. Tribromopropane IV was
removed by washing with hexane (3×10 ml), and the
crude product was purified by vacuum sublimation at
80–100°C (2 mm).
1-Allylsulfonyl-4-chloro-2,3,5,6-tetrafluoroben-
zene (IIIc). The reaction of 1.52 g (4.64 mmol) of
4-chloro-2,3,5,6-tetrafluorobenzenesulfonyl bromide
(Ic) with 2.89 g (23.89 mmol) of allyl bromide (II)
gave 2.34 g of a mixture of allyl sulfone IIIc and com-
pound IV. Yield of IIIc 84%. By washing with hexane
(3×10 ml) we isolated 0.81 g of individual compound
1
IIIc (according to the 19F and H NMR data). Yield
60% (isolated product), mp 74.5–75.5°C. IR spectrum,
ν, cm–1: 2981, 2913, 1629, 1482, 1457, 1400, 1388,
1350, 1336, 1264, 1195, 1151, 1089, 995, 975, 959,
776, 727, 646, 551, 498, 463. UV spectrum, λmax, nm
1
(logε): 217 (4.10), 227 (4.09), 281 (3.32). H NMR
spectrum, δ, ppm: 3.98 d (2H, CH2, J = 7.4 Hz),
5.30 d.d (1H, Ha, Jac = 17.1, Jab ≈ 1 Hz), 5.41 d.d (1H,
Hb, Jbc = 10.1, Jab ≈ 1 Hz), 5.88 m (1H, Hc). 19F NMR
spectrum, δF, ppm: 24.1 m (2F), 26.4 m (2F). Found,
(Allylsulfonyl)pentafluorobenzene (IIIa). The
reaction of 1.25 g (4.02 mmol) of pentafluoroben-
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REACTION OF POLYFLUOROARENESULFONYL BROMIDES WITH ALLYL BROMIDE.
377
%: C 37.55; H 1.78; Cl 12.07; F 26.07; S 11.40.
m/z 287.9637 [M]+. C9H5ClF4O2S. Calculated, %:
C 37.45; H 1.75; Cl 12.28; F 26.33; S 11.11.
M 287.9629.
bath. The mixture was cooled to room temperature,
dissolved in 5 ml of carbon tetrachloride, and analyzed
by GC–MS and 19F and 1H NMR. According to the 19F
and 1H NMR data, the ratio Ia:Ie:IIIa:IIIe was about
0.4:1.5:1.7:1.0, and the ratio IIIa:IIIe was estimated
at 1.7:1.0 (according to the GC–MS data).
1-Allylsulfonyl-4-bromo-2,3,5,6-tetrafluoroben-
zene (IIId). The reaction of 1.45 g (3.90 mmol) of
4-bromo-2,3,5,6-tetrafluorobenzenesulfonyl bromide
(Id) and 2.34 g (19.34 mmol) of allyl bromide (II)
gave 2.16 g of a mixture of allyl sulfone IIId and com-
pound IV. Yield of allyl sulfone IIId 87%. By washing
with hexane (20 + 15 + 5 ml) we isolated 0.79 g (62%)
Likewise, sulfonyl bromide Ia, 0.25 g (0.80 mmol),
reacted with sulfone IIIe, 0.25 g (0.78 mmol);
1
Ia:Ie:IIIa:IIIe ≈ 2.6:0.6:1.0:1.5 (19F, H NMR);
IIIa:IIIe = 1.0:1.5 (GC–MS).
Effect of daylight on the reaction of arensulfonyl
bromide Ia with allyl bromide (II). a. An ampule was
charged with 1.60 g (5.14 mmol) of sulfonyl bromide
Ia and 1.83 g (15.13 mmol) of allyl bromide (II), and
the mixture was kept at 17–21°C in the dark.
19
of individual compound IIId (according to the F and
1H NMR data), mp 95–96.5°C (from EtOH). IR spec-
trum, ν, cm–1: 2982, 2913, 1626, 1485, 1447, 1398,
1385, 1347, 1337, 1258, 1195, 1149, 1088, 994, 970,
954, 929, 878, 802, 773, 724, 643, 588, 550, 492. UV
spectrum, λmax, nm (logε): 224 (4.16), 237 (4.09), 281
b. Another ampule was charged with 1.38 g
(4.44 mmol) of compound Ia and 1.54 g (12.73 mmol)
of allyl bromide (II), and the mixture was exposed to
scattered daylight at the same temperature.
1
(3.35). H NMR spectrum, δ, ppm: 4.01 d (2H, CH2,
J = 7.2 Hz), 5.34 d.d (1H, Ha, Jac = 17.0, Jab ≈ 1 Hz),
5.42 d.d (1H, Hb, Jbc = 10.2, Jab ≈ 1 Hz), 5.89 m (1H,
Hc). 19F NMR spectrum, δF, ppm: 26.9 m (2F, 2-F,
6-F), 31.9 m (2F, 3F, 5-F). Found, %: C 32.23; H 1.87;
Br 23.50; F 22.70; S 9.60. m/z 331.9122 [M]+.
C9H5BrF4O2S. Calculated, %: C.45; H 1.51; Br 23.99;
F 22.81; S 9.63. M 331.9124.
After 10 days, colorless needles of tribromopropane
IV separated from the mixture kept under daylight.
After 15 days, the reaction mixtures in both ampules
were dissolved in methylene chloride, and the solu-
tions were analyzed by 19F NMR spectroscopy. The
mixtures contained initial compound Ia and allyl sul-
fone IIIa at a ratio of 1:0.78 (a) or 1:17 (b); the con-
version of Ia was 44% (a) or 94% (b).
1-Allylsulfonyl-2,3,5,6-tetrafluoro-4-trifluoro-
methylbenzene (IIIe). The reaction of 1.76 g
(4.87 mmol) of 2,3,5,6-tetrafluoro-4-trifluoromethyl-
benzenesulfonyl bromide (Ie) with 3.04 g
(25.13 mmol) of allyl bromide (II) gave 4.71 g of
a mixture containing allyl sulfone IIIe, initial allyl
bromide (II), and 1,2,3-tribromopropane (IV) at a ratio
Effect of hydroquinone on the reaction of arene-
sulfonyl bromide Ia with allyl bromide (II). An am-
pule was charged with 1.37 g (4.40 mmol) of sulfonyl
bromide Ia, 2.49 g (20.58 mmol) of allyl bromide (II),
and 0.12 g (1.09 mmol, 25 mol %) of hydroquinone,
and the mixture was kept at 20–23°C in the dark. After
17 days, the mixture was dissolved in carbon tetra-
chloride, and the solution was analyzed by 19F NMR.
The conversion of bromide Ia did not exceed 10%.
1
of ~1:2.6:1 (according to the 19F and H NMR data).
Yield of allyl sulfone IIIe 90%, mp 58–59°C. IR spec-
trum, ν, cm–1: 2976, 2920, 1607, 1497, 1428, 1401,
1354, 1327, 1246, 1190, 1163, 1148, 1083, 990, 912,
878, 781, 716, 677, 620, 548, 492. UV spectrum, λmax
,
1
nm (logε): 214 (3.92), 287 (3.40). H NMR spectrum,
δ, ppm: 4.02 d (2H, CH2, J = 7.4 Hz), 5.35 d.d (1H, Ha,
Jac = 17.0, Jab ≈ 1 Hz), 5.45 d.d (1H, Hb, Jbc = 10.2,
Jab ≈ 1 Hz), 5.91 m (1H, Hc). 19F NMR spectrum, δF,
ppm: 104.7 t (3F, CF3, 4JFF = 22.0 Hz), 28.0 m (2F, 2-F,
6-F), 24.6 m (2F, 3-F, 5-F). Found, %: C 37.10;
H 1.68; F 41.03; S 10.05. m/z 321.9892 [M]+.
C10H5F7O2S. Calculated, %: C 37.28; H 1.56; F 41.27;
S 9.95. M 321.9893.
Effect of copper(I) iodide on the reaction of
arenesulfonyl bromide Ia with allyl bromide (II).
An ampule was charged with 1.37 g (4.40 mmol) of
sulfonyl bromide Ia, 2.10 g (17.36 mmol) of allyl
bromide (II), and 0.1672 g (0.88 mmol, 20 mol %) of
copper(I) iodide, and the ampule was heated for 3 h at
145–155°C. The mixture was then dissolved in meth-
ylene chloride, and the solution was analyzed by
19F NMR. The mixture contained sulfone IIIa, while
compound Ia was absent. When a mixture of 1.37 g
(4.40 mmol) of compound Ia and 2.11 g (17.44 mmol)
of allyl bromide (II) was heated in an ampule for 3 h at
150°C, the resulting mixture contained 20% of initial
bromide Ia and 80% of sulfone IIIa (19F NMR data).
Reaction of polyfluoroarenesulfonyl bromides
with allyl polyfluoroaryl sulfones. An ampule was
charged with 0.06 g (0.22 mmol) of sulfone IIIa and
0.08 g (0.22 mmol) of sulfonyl bromide Ie, and the
mixture was heated for 25 h at 145–155°C on an oil
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BREDIKHIN et al.
378
2. Ermoshkin, A.A., Kasatochkin, A.N., and Boyar-
1-(2,3-Dibromopropyl)pentafluorobenzene (V).
skii, V.P., Russ. J. Org. Chem., 2007, vol. 43, p. 990.
An ampule was charged with 0.57 g (2.09 mmol) of
sulfone IIIa and 0.96 g (6.01 mmol) of bromine, and
the ampule was heated for 5 h at 145–150°C. The
mixture was cooled to room temperature and dissolved
in 5 ml of methylene chloride, and the solvent and
excess bromine were removed under reduced pressure.
Yield 0.90 g (99%), mp 53–57°C. The crude product
was purified by vacuum sublimation at 110–115°C
(2 mm), mp 54–56°C. IR spectrum, ν, cm–1: 3016,
2897, 1649, 1521, 1500, 1440, 1404, 1387, 1366,
1334, 1300, 1274, 1250, 1157, 1147, 1099, 991, 889,
842, 779, 750, 652, 535, 483. UV spectrum, λmax, nm
3. De Riggi, I., Surzur, J.-M., and Bertrand, M.P., Tetra-
hedron, 1988, vol. 44, p. 7119.
4. Pelter, A., Ward, R.S., and Little, G.M., J. Chem. Soc.,
Perkin Trans. 1, 1990, p. 2775.
5. Tanaskov, M.M. and Stadnichuk, M.D., Zh. Obshch.
Khim., 1977, vol. 47, p. 1813.
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p. 588.
7. Cheng, W.-C., Halm, C., Evarts, J.B., Olmstead, M.M.,
and Kurth, M.J., J. Org. Chem., 1999, vol. 64, p. 8557.
8. Kisanga, P.B. and Verkade, J.G., J. Org. Chem., 2002,
1
(logε): 220 (4.38), 274 (4.07). H NMR spectrum, δ,
vol. 67, p. 426.
ppm: 3.78 d.d (1H, J = 11.0, 7.7 Hz), 3.87 d.d (1H, J =
15.6, 8.0 Hz), 3.98 d.d (1H, J = 11.0, 4.3 Hz), 4.11 d.d
(1H, J = 15.6, 4.4 Hz), 4.64 m (1H, CH). 19F NMR
spectrum, δF, ppm: 3.3 m (2F, 3-F, 5-F), 18.1 t.t (1F,
4-F, J = 20.8, J = 7.7 Hz), 26.5 m (2F, 2-F, 6-F).
Found: m/z 429.8286 [M]+. C9H5Br2F5O2S. Calculated:
M 429.8292.
9. Katritzky, A.R., Abdel-Fattah, A.A.A., and Wang, M.,
J. Org. Chem., 2003, vol. 68, p. 1443.
10. Nonhebel, D., Tedder, J., and Walton, J., Radicals,
Cambridge: Cambridge Univ., 1979. Translated under
the title Radikaly, Moscow: Mir, 1982, p. 141.
3
4
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Reaction of pentafluorobenzenesulfonyl chloride
with allyl bromide (II). An ampule was charged with
1.20 g (4.52 mmol) of pentafluorobenzenesulfonyl
chloride and 2.67 g (22.07 mmol) of compound II, and
the ampule was heated for 25.5 h at 135–150°C. The
mixture was cooled to room temperature and dissolved
in 5 ml of carbon tetrachloride. The 19F NMR spectrum
of the solution contained mainly signals from the
initial compound.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011