254
BONDARENKO et al.
2
3
2
3
solutions were dried over sodium sulfate. On evaporating
the solvent the residue was subjected to chromatography
on silica gel (eluent ethyl acetatepetroleum ether, 1:3).
J 17.4, J 7.5), 3.46 d.d (1Í, ÑÍ , J 17.4, J 11.3),
2
3
3
5.55 d.d (1Í, ÑÍÎ, J 7.5, J 11.3), 7.18 br.s (1Í, CHN),
3
3
7.29 d (2Harom, J 7.8), 7.44 d (2H , J 8.2), 7.80 d
arom
(
2Harom, 3J 7.8), 7.91 d (2Íarom, J 8.2). Ñ NMR spec-
3
13
The yields of compounds obtained are given in
Table 1. Physical constants of separated aldehydes and
acrylonitriles were consistent with the published data [17].
trum, d, ppm: 21.43 (ÑÍ ), 43.75, 78.63, 126.35, 127.57,
1
Mass spectrum, m/z (I , %): [M] 301 (40), 258 (14)
3
27.89, 129.85, 138.33, 141.57, 144.22, 145.22, 146.36.
+
rel
b. At the end of the required reaction time 5 ml of
dichloromethane cooled to the reaction temperature was
added to the reaction mixture, and the solution was quickly
evaporated on a rotary evaporator.
+
[M HCNO] , 233 (23), 151 (25), 139 (100), 91 (34),
7
7 (14).
Conversion of 2-benzylsulfophenylcyclopropane
Ij). After the reaction of 0.12 g (0.45 mmol) of cyclo-
propane Ij and 0.14 g (2.2 mmol) of NOCl at 20°Ñ for
6 h the workup of the reaction mixture by procedure à
(
Conversion of 4-cyanophenylcyclopropane (Ig).
After the reaction of 0.07g (0.5 mmol) cyclopropane Ig
and 0.18 g (2.5 mmol) of nitrosyl chloride for 24 h at
9
and chromatographic separation on a plate (SiO , ethyl
acetatepetroleum ether, 1:1) afforded 0.10 g (85%) of
2
(12%) of 5-(2-benzylsulfophenyl)isoxazoline (IIj),
R 0.75, mp 121122°Ñ (ethyl acetatepetroleum ether).
IR spectrum (film), cm : 3070, 3040, 2985, 2930, 2860,
1
2
2
0°Ñ the workup of the reaction mixture by procedure à
afforded 0.06 g of products mixture. The chromatographic
-benzylsulfophenylcyclopropane (Ij) and 0.016 g
separation on plates with SiO , (eluent ethyl acetate
2
petroleum ether, 1:3) gave the following compounds:
f
0
.005 g (7%) of 3-(4-cyanophenyl)acrylonitrile (IVg)
1
(
mixture of isomers cis:trans = 1:2). Oily substance,
600, 1500, 1320 (SO ), 1290, 1160 (SO ), 1125, 780.
2 2
1
R 0.45. IR spectrum (mull in mineral oil), cm : 2230
2
1
1
2
3
3
3
f
Í NMR spectrum, d, ppm (J, Hz): 2.77 d.d.d (1Í, ÑÍ ,
2
+
220 (CN). Mass spectrum, m/z (I , %), cis-(IVg): [M]
3
3
2
rel
J 18.4, J 7.1, J 1.8), 3.54 d.d.d (1Í, ÑÍ , J 18.4,
2
54 (100), 127 (50), 100 (10), 76 (10), 50 (10); trans-
3
J 11.4, J 1.5), 4.30 s (2H, CH ), 5.78 d.d (1Í, ÑÍÎ,
2
+
3
(
IVg): [M] 154 (100), 127 (50), 100 (10), 75 (10),
J 7.1, J 11.4), 7.11 br.s (1Í, CHN), 7.05 d (2Harom,
13
57 (10), 50 (10); 0.008 g (10%) of trans-4-cyanocin-
J 7.25), 7.237.74 (7Harom). Ñ NMR spectrum, d, ppm:
namic aldehyde (IIIg), R 0.33. IR spectrum (film),
45.53, 63.51, 76.26, 126.80, 127.32, 128.26, 128.62, 128.99,
130.73, 130.88, 134.14, 134.40, 142.34, 145.65. Mass
spectrum, m/z (I , %): [M] 301 (1.25), 146 (15) [M
f
1
cm : 2235 (CN), 1690 (C=O), 1130; 0.04 g (46%) 5-(4-
cyanophenyl)isoxazoline (IIg). Colorless oily sub-
stance, R 0.17. IR spectrum (film), cm : 3085, 2940,
+
rel
1
+
+
SO CH Ph] , 116 (34) [M SO CH Ph NO] ,
f
2 2 2 2
2
860, 2240 (CN), 1615, 1510, 1440, 1420, 1290, 855.
91 (100), 65 (10).
1
Í
NMR spectrum, d, ppm (J, Hz): 2.95 d.d.d (1Í, ÑÍ ,
2
Conversion of 4-bromophenylcyclopropane (Id).
After the reaction of cyclopropane Id with a 7-fold
excess of NOCl in the liquid sulfur dioxide at 55 to
60°Ñ for 2 h the workup of the reaction mixture by
procedure b furnished an oily blue substance containing
compounds Id, IId, and Vd in a ratio 8:10:8 (according
2
3
3
3
2
J 17.6, J 7.5, J 1.8), 3.53 d.d.d (1Í, ÑÍ , J 17.6,
2
3
3
3
J 11.4, J 1.8), 5.60 d.d (1Í, ÑÍÎ, J 11.4, J 7.5),
3
3
7
(
.23 t (1Í, CHN, J 1.8), 7.45 d (2Í , J 8.3) 7.68 d
arom
2Íarom, J8.3). 13Ñ NMR spectrum, d, ppm: 43.89, 78.77,
3
4
112.01 (Ñ àð-CN), 118.50 (ÑN), 126.35, 132.62, 146.30,
1
1
45.26 (ÍÑ=N). Found, %: Ñ 69.83; Í 4.77; N 16.11.
to Í NMR data). Mass spectrum of compound Vd, m/z
+
Ñ H N O. Calculated, %: C 69.77; H 4.65; N 16.28.
(I , %): [M] 261/259 (8), 245/243 (10), 233/231 (3),
1
0
8
2
rel
2
05/203 (100), 129 (16), 124 (11), 117 (10), 102 (26), 89
Conversion of 4-tosylphenylcyclopropane (Ii).
(
59), 63 (41), 51 (25), 32 (71).
After the reaction of 0.11g (0.4 mmol) of cyclopropane
Ii and 0.13 g (2.0 mmol) of NOCl at 20°Ñ for 96 h the
workup of the reaction mixture by procedure à and
Conversion of phenylcyclopropane (Ia). After the
reaction of cyclopropane Ia with a 5-fold excess of NOCl
in the liquid sulfur dioxide at 55...60°Ñ for 2 h the
workup of the reaction mixture by procedure b furnished
an oily blue substance containing compounds Ià, IIà, and
Và in a ratio 2:1:1 (according to Í NMR data). Mass
spectrum of compound Và, m/z (I , %): [M] 181 (10),
chromatographic separation on a plate (SiO , ethyl
2
acetatepetroleum ether, 1:1) afforded 0.06 g (59%)
-tosylphenylcyclopropane (Ii) and 0.02 g (17%)
4
5
1
(
1
1
-(4-tosylphenyl)isoxazoline (IIi), R 0.39, mp 122
f
+
23°Ñ (ethyl acetatepetroleum ether). IR spectrum
rel
1
165 (10), 138 (3), 125 (100), 103 (10), 89 (8), 40 (30).
film), cm : 3070, 2930, 2860, 1600, 1500, 1320 (SO ),
2
1
310, 1290, 1160 (SO ), 1115, 750. Í NMR spectrum
,
The study was carried out under financial support of
the Russian Foundation for Basic Research (grant no.
2
d, ppm (J, Hz): 2.30 s (3H, CH ), 2.90 d.d (1Í, ÑÍ ,
3
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 2 2006