Iodosobenzene dichloride, a convenient reagent for chloro- and iodomethoxylation of double and triple bonds

Full text of DOI:10.1023/A:1020320011241

Russian Journal of Organic Chemistry, Vol. 38, No. 6, 2002, pp. 902 904. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 6, 2002,
pp. 944 945.
Original Russian Text Copyright
2002 by Yusubov, Yusubova, Filimonov, Chi Ki-Whan.
SHORT
COMMUNICATIONS
Iodosobenzene Dichloride, a Convenient Reagent for Chloro-
*
and Iodomethoxylation of Double and Triple Bonds
1
,2
2
2
3
M. S. Yusubov , R. Ya. Yusubova , V. D. Filimonov , and Chi Ki-Whan
1
Siberian State Medical University, Tomsk, 634050 Russia
2
3
Tomsk Polytechnic University, Chi Ki-Whan, University of Ulsan, Republic of Korea
Received January 16, 2002
Iodosobenzene dichloride (I), an organic com-
pound of polyvalent iodine, is extensively used in
organic synthesis for chlorination and oxidation of a
wide range of compounds [1 3]. However published
reports on application of the compound to haloalk-
oxylation are lacking.
formation of reaction product X is an evidence of a
contribution from free-radical chlorination of the
methyl group in compound IX [or in initial -methyl-
styrene (VIII)] effected by PhICl2.
It turned out that reaction of styrene (II) with
PhICl in methanol in the presence of iodine took
2
We established that the reaction of PhICl with
another route easily providing a product of iodo-
methoxylation of the double bond XI in 80% yield.
Obviously here the iodosobenzene dichloride acted as
2
styrene derivatives II IV in methanol at room
temperature easily gave rise to products of electro-
philic chloromethoxylation V VII in 68 90% yield.
oxidant for iodine providing its electrophilic inter-
+
mediates (I , ICl, or CH OI). This reaction is
The chloromethoxylation proceeded as a typical
electrophilic addition, and therewith, as was shown
by an example of trans-stilbene (III), occurred pre-
dominantly anti-addition to furnish erythro-diastereo-
mer VI in 64% yield (the yield of threo-isomer VI
was 36%).
3
perhaps the first example of a simple iodoalkoxylation
of alkenes with the use of compounds of polyvalent
iodine, and it opens new opportunities for the syn-
thesis of commonly less available iodoalkoxyalkanes
[
4, 5].
Phenylacetylene (XII) reacted with two moles of
The reaction with -methylstyrene (VIII) was less
selective and afforded in 70% overall yield an in-
separable mixture of two isomers IX and X in 75: 25
compound I in methanol furnishing 1,1-dimethoxy-1-
phenyl-2,2-dichloroethane (XIII) in 65% yield.
Compound XIII was formerly prepared by reaction of
1
ratio according to GC-MS and H NMR data. The
R = R = H (II, V); R = R = Ph (III, VI); R = Ph, R = H (IV, VII).
*
The study was carried out under financial support of the Russian Foundation for Basic Research (grant no. 00-03-32812a).
1
070-4280/01/3806-902$27.00 2002 MAIK Nauka/Interperiodica

IODOSOBENZENE DICHLORIDE, A CONVENIENT REAGENT
903
phenylacetylene with chlorine or N-chlorosuccinimide
1-Methoxy-1,1-diphenyl-2-chloroethane (VII).
in methanol (yield 70 81%) [6].
Yield 72%, mp 47 49 C (publ. oily substance [8]).
1
H NMR spectrum (CCl CDCl , 3: 1, , ppm):
4
3
Thus iodosobenzene dichloride provides a pos-
sibility to perform both chloro- and iodomethoxyla-
tion of aromatic alkenes and alkynes under mild
conditions.
3
7
.12 s (3H, OCH ), 4.22 s (2H), 7.19 t (4H arom)
.22t (6H arom), 7.30(4Harom). C NMR spectrum
3
13
(
CCl CDCl , 3: 1, , ppm): 48.36 (CH Cl), 50.57
4 3 2
(
OCH ), 81.69 (COCH ), 127.14, 127.30, 128.05,
3
3
General procedure of the synthesis. To a solu-
tion of 2.0 mmol of alkene in 8.0 ml of MeOH was
added 2.02 mmol of iodosobenzene dichloride (I),
and the mixture was stirred at room temperature for
142.43 (C arom). Found, %: C 72.96; H 6.47; Cl
13.70. C15H15ClO. Calculated, %: C 73.02; H 6.13;
Cl 14.37.
1
, 1-Dimethoxy-1-phenyl-2,2-dichloroethane
2
0 min. The mixture was poured into 30 ml of water,
(
6
3
XIII). Yield 65%, mp 68 69 C (publ. mp 66
extracted with ether (2 30 ml), the extract was
washed with water (2 50 ml), with saturated NaCl
solution (50 m), and dried on Na SO . On removing
1
7.5 C [6]). H NMR spectrum (CDCl , , ppm):
3
.34 s (6H, OCH ), 5.97 s (1H), 7.39 m (3H arom)
3
1
3
2
4
7.62 m (2H arom). C NMR spectrum (CDCl , ,
3
the ether the residue was dissolved in benzene (2 ml)
and applied to a column packed with silica gel. Elu-
tion with hexane afforded 390 mg of iodobenzene
ppm): 49.89 (OCH3), 73.10 (CCl2), 102.81
[
(
C(OCH ) ],
127.86, 128.89, 129.22, 133.84
3
2
C arom). Found, %: C 50.87; H 5.05; Cl 29.87.
(
95%) (bp 188 C [7]). The reaction products V, VII,
C H Cl O . Calculated, %: C 51.09; H 5.14;
1
0
12
2
2
XIII were eluted with hexane benzene, 4: 1.
Cl 30.16.
1
-Methoxy-1-phenyl-2-chloroethane (V). Yield
8%, oily substance, bp 82 85 C/hexane benzene
mixture, 4: 1. 6 mm Hg (publ. bp 79 82 C/4 mm Hg
2
-Iodo-1-methoxy-1-phenylethane (XI). To a
6
solution of 267 mg (1.05 mmol) of iodine in 8 ml of
MeOH was added 275 mg (1.0 mmol) of iodoso-
benzene dichloride, and the mixture was stirred for
5 min at room temperature. The mixture was poured
into a solution of 208 mg (2.0 mmol) of styrene (II)
in 2.0 ml of MeOH, and the mixture was stirred at
room temperature for 10 min. Then it was poured
into 30 ml of 5% Na S O . Further workup was as
1
[
8]). HNMR spectrum (500MHz, CCl CDCl , 3: 1,
ppm, J, Hz): 3.27 s (3H, OCH ), 3.50 d.d (1H,
3
4 3
,
CH , J 4.5, 11.5), 3.60 d.d (1H, CH , J 7.5, 11.5),
a
b
4
.27 d.d (1H, J 4.5, 7.5), 7.26 7.34 m (5H arom).
C NMR spectrum (500 MHz, CCl CDCl , 3:1, ,
ppm): 47.80(CH ), 56.99(OCH ), 83.79 (CH),
1
3
4
3
2
3
2
2
3
1
26.76, 128.35, 128.50, 138.72 (C arom). Found, %:
described above. We obtained 420 mg (80%) of oily
compound (publ. oily compound [5]). H NMR spec-
1
C 63.40; H 6.43; Cl 20.04. C H ClO. Calculated,
1
1
11
%
: C 63.35; H 6.50; Cl 20.78.
-Methoxy-1,2-diphenyl-2-chloroethane
Yield 90%. erythro-(VI) mp 98 100 C (publ. mp
trum [400MHz, CCl (CD ) CO, 3: 1, , ppm, J, Hz]:
4
3 2
3
.21 s (3H, OCH ), 3.23 m (2H, CH ), 4.21 d.d (1H,
3 2
1
(VI).
13
J 5.0, 8.0), 7.26 7.34 m (5H arom). C NMR spec-
trum [CCl (CD ) CO, 3: 1, , ppm]: 10.10 (CH I),
1
4
3 2
2
9
,
4
5 97 C [8]). H NMR spectrum (500 MHz, CDCl ,
3
5
6.94 (OCH ), 83.55 (CH), 126.51, 128.23, 128.53,
3
ppm, J, Hz): 3.18s (3H, OCH ), 4.53d (1H, J7.0),
+
3
139.98 (C arom). Found: m/z 261.98537 [M] .
C H IO. Calculated: M 261.98564. Mass spectrum
1
3
.97d (1H, J7.0), 7.24 7.29m (10Harom). CNMR
9
11
spectrum (CDCl3, , ppm): 57.35 (OCH ), 65.32
3
(Electron impact, 70 ev), m/z (I , %): 262 (>1),
rel
(
CHCl), 87.14 (CHOCH ), 127.89, 127.95, 128.24,
3
135 (14), 121 (100), 104 (10), 103 (9), 91 (10), 77
1
7
28.14, 137.71, 138.22 (C arom). Found, %: C
3.05; H 6.24; Cl 13.97. C H ClO. Calculated, %:
(
13).
1
5
15
NMR spectra were registered on spectrometer Bruker
C 73.02; H 6.13; Cl 14.37. threo-(VI) oily substance
1
13
1
AM-400 (400.13 MHz for H, 100.61 MHz for
C
(
(
publ. oily substance [8]). H NMR spectrum
500 MHz, CDCl3, , ppm, J, Hz): 3.31 s (3H,
spectra) for compound XI, the NMR spectra of all
other compounds were registered on spectrometer
OCH ), 4.46 d (1H, J 8.0), 4.95 d (1H, J 8.0), 7.17
7
ppm):57.21(OCH ), 66.75(CHCl), 87.66(CHOCH ),
3
1
1
3
Bruker DRX-500 (500.13 MHz for H, 125.76 MHz
.22 m (10H arom). C NMR spectrum (CDCl , ,
3
1
3
for
C spectra). NMR and mass spectra were
3
3
1
(
27.58, 127.94, 127.99, 128.21, 137.47, 138.15
C arom). Found, %: C 73.27; H 6.37; Cl 13.90.
C H ClO. Calculated, %: C 73.02; H 6.13; Cl
measured and elemental analyses were carried out at
TsKP, Siberian Division, Russian Academy of
Sciences (grant of the Russian Foundation for Basic
Research no. 00-03-40135).
1
5
15
1
4.37.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

9
04
YUSUBOV et al.
5. Iranpoor, N. and Shekarriz, M., Tetrahedron, 2000,
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