REACTIONS OF CYCLOPROPANES WITH POTASSIUM DIHALOIODATES
349
[M + 2]+, 324 (0.3) [M]+, 199 (39.1), 197 (39.2),
117 (100), 115 (42.2), 91 (99.2), 83 (28.5); Vc:
280 (1.5) [M + 4]+, 278 (1.8) [M + 2]+, 276 (1.1) [M]+,
199 (44.6), 197 (44.9), 117 (81.3), 115 (38.5), 91
(100), 83 (25.5).
1-Chloro-2-iodomethyl-3-methyl-1-phenylbutane
(IXb) and 1,3-dichloro-4-methyl-1-phenylpentane
(Xb). H NMR spectrum (CDCl3), δ, ppm: IXb,
1
erythro isomer: 0.99 d and 1.11 d (3H each, CH3, J =
6.8 Hz), 2.05 m (1H, 3-H), 2.25 m (1H, 2-H), 3.20 d.d
(1H, ICH2, 2J = 10.4, 3J = 4.3 Hz), 3.32 d.d (1H, ICH2,
1
3-Chloro-1-iodo-3-phenylbutane (VII). H NMR
3
3
2J = 10.4, J = 6.8 Hz), 5.28 d (1H, 1-H, J = 6.3 Hz);
IXb, threo isomer: 0.93 d and 1.03 d (3H each, CH3,
J = 6.8 Hz), 1.96 m (1H, 3-H), 2.10 m (1H, 2-H),
3.47 d (1H, ICH2, J = 4.1 Hz), 3.48 d (1H, ICH2, J =
spectrum (CDCl3), δ, ppm: 2.00 s (3H, CH3),
2.76 d.d.d and 2.83 d.d.d (1H each, 2-H, 2J = 14.2, 3J =
9.6, 5.3 Hz), 3.07 d.d.d and 3.22 d.d.d (1H each, 1-H,
3
2J = 11.7, J = 9.6, 5.3 Hz), 7.30–7.60 m (5H, Harom).
3
13C NMR spectrum (CDCl3), δC, ppm: –1.5 (CI), 32.3
(CH3), 51.2 (C2), 74.4 (CCl), 125.8 (Cm), 127.8 (Cp),
128.6 (Co), 143.4 (Ci). Mass spectrum, m/z (Irel, %):
259 (2.7). 258 (26.9) [M – HCl]+, 131 (100), 129
(22.8), 115 (26.7), 103 (62.1), 91 (48.3).
5.1 Hz), 5.13 d (1H, 1-H, J = 7.0 Hz); Xb, erythro
isomer: 1.05 d and 1.12 d (3H each, CH3, J = 6.7 Hz),
2
3
2.05 m (1H, 4-H), 2.24 d.d.d (1H, 2-H, J = 15.0, J =
11.0, 2.4 Hz), 2.40 d.d.d (1H, 2-H, 2J = 15.0, 3J = 11.2,
2.0 Hz), 4.36 d.d.d (1H, 3-H, J = 11.0, 3.9, 2.0 Hz),
5.29 d.d (1H, 1-H, J = 11.2, 2.4 Hz); Xb, threo
3
3
1-Chloro-3-iodo-2-methyl-1-phenylpropane
1
isomer: 0.98 d and 1.00 d (3H each, CH3, J = 6.7 Hz),
(IXa). H NMR spectrum (CDCl3), δ, ppm: erythro
2
3
1.95 m (1H, 4-H), 2.49 d.d.d (1H, 2-H, J = 14.1, J =
isomer: 1.22 d (3H, CH3, J = 6.5 Hz), 3.00 d.d (1H,
10.4, 3.4 Hz), 2.60 d.d.d (1H, 2-H, 2J = 14.1, 3J = 10.8,
3-H, 2J = 9.8, 3J = 5.3 Hz), 3.31 d.d (1H, 3-H, 2J = 9.8,
3
3
3J = 5.9 Hz), 5.04 d (1H, 1-H, J = 6.3 Hz); threo
5.1 Hz), 3.42 d.d.d (1H, 3-H, J = 10.8, 3.5, 3.4 Hz),
5.20 d.d (1H, 1-H, 2J = 10.4, 3J = 5.1 Hz); 7.30–7.60 m
isomer: 0.92 d (3H, CH3, J = 6.5 Hz), 3.48 d.d (1H,
1
3-H, 2J = 9.6, 3J = 3.3 Hz), 3.66 d.d (1H, 3-H, 2J = 9.6,
(Harom in IXb and Xb). H NMR spectrum (C6D6), δ,
3
3J = 5.4 Hz), 4.75 d (1H, 1-H, J = 8.8 Hz); common
ppm: IXb, erythro isomer: 0.76 d and 0.99 d (3H each,
CH3, J = 7.0 Hz), 1.75 m (1H, 3-H), 2.12 m (1H, 2-H),
signals: 2.04 m and 2.17 m (1H each, 2-H), 7.35 m
(5H, Harom). 13C NMR spectrum (CDCl3), δC, ppm:
13.0 and 15.1 (CI), 17.0 and 18.7 (CH3), 41.9 and 42.9
(C2), 67.7 and 67.8 (CCl); 127.40, 128.42, 128.61,
128.78, 128.81, 128.90, 139.71, 139.86 (Carom). Mass
spectrum, m/z (Irel, %): 296 (3.9) [M + 2]+, 294 (12.9)
[M]+, 131 (17.3), 127 (42.8), 125 (100), 115 (16.7), 91
(29.3). Found, %: C 40.51; H 3.88. C10H12ClI. Cal-
culated, %: C 40.75; H 4.07. M 294.56
2
3
2.89 d.d (1H, ICH2, J = 10.4, J = 4.5 Hz), 3.10 d.d
2
3
(1H, ICH2, J = 10.4, J = 6.7 Hz), 5.26 d (1H, 1-H,
3J = 6.8 Hz); IXb, threo isomer: 0.72 d and 0.80 d (3H
each, CH3, J = 6.9 Hz), 1.85 m (1H, 3-H), 1.94 m (1H,
2
3
2-H), 3.27 d.d (1H, ICH2, J = 10.7, J = 3.9 Hz),
2
3
3.31 d.d (1H, ICH2, J = 10.7, J = 5.1 Hz), 4.99 d
(1H, 3-H, 3J = 7.2 Hz); Xb, erythro isomer: 0.86 d and
0.94 d (3H each, CH3, J = 6.7 Hz), 1.72 m (1H, 4-H),
2
3
2.11 d.d.d (1H, 2-H, J = 14.9, J = 10.8, 2.6 Hz),
1,3-Dichloro-1-phenylbutane (Xa) was isolated
and characterized in a mixture with compound IXa.
1H NMR spectrum (CDCl3), δ, ppm: erythro isomer:
1.84 d (3H, CH3, J = 6.7 Hz), 2.23 d.d.d (1H, 2-H, 2J =
15.1, 3J = 10.4, 2.7 Hz), 4.50 d.d.d (1H, 3-H, 3J = 10.4,
2
3
2.24 d.d.d (1H, 2-H, J = 14.9, J = 11.2, 2.2 Hz),
3
4.43 d.d.d (1H, 3-H, J = 10.8, 3.9, 2.2 Hz), 5.42 d.d
3
(1H, 1-H, J = 11.2, 2.6 Hz); Xb, threo isomer: 0.74 d
and 0.78 d (3H each, CH3, J = 6.7 Hz), 1.56 m (1H,
4-H), 2.36 d.d.d (1H, 2-H, 2J = 14.3, 3J = 10.4, 3.1 Hz),
3
6.5, 2.7 Hz), 5.30 d.d (1H, 1-H, J = 11.0, 2.7 Hz);
2
3
2.61 d.d.d (1H, 2-H, J = 14.3, J = 10.8, 5.1 Hz),
threo isomer: 1.74 d (3H, CH3, J = 6.3 Hz), 2.60 d.d.d
3
2
3
3.42 d.t (1H, 3-H, J = 10.8, 3.1 Hz), 5.25 d.d (1H,
(1H, 2-H, J = 14.3, J = 9.9, 6.0 Hz), 3.78 d.d (1H,
1-H, 3J = 10.4, 5.1 Hz); 7.10–7.35 m (Harom in IXb and
Xb). 13C NMR spectrum (CDCl3), δC, ppm: IXb,
erythro isomer: 5.2 (CI), 17.7 and 22.1 (CH3), 28.4
(C3), 52.6 (C2), 66.0 (CCl); IXb, threo isomer: 4.7
(CI), 17.2 and 19.6 (CH3), 29.7 (C3), 52.3 (C2), 66.3
(CCl); Xb, erythro isomer: 17.5 and 19.9 (CH3), 34.6
(C4), 46.1 (C2), 61.5 (C3), 67.1 (C1); Xb, threo isomer:
18.6 and 20.9 (CH3), 34.2 (C4), 45.7 (C2), 60.2 (C3),
66.3 (C1); 125.9–131.5, 140.0, 140.1, 141.6 (Carom in
IXb and Xb). Mass spectrum, m/z (Irel, %): IXb: 324
(0.1) [M + 2]+, 323 (0.1), 322 (0.3) [M]+, 198 (0.2),
3
3
3-H, J = 9.9, 5.1 Hz), 5.18 d.d (1H, 1-H, J = 9.4,
6.0 Hz), 2.45 m (2H, 2-H in erythro and threo iso-
mers), signals from aromatic protons were overlapped
by those of compound IXa. 13C NMR spectrum
(CDCl3), δC, ppm: 25.2 and 25.5 (CH3), 50.8 and 52.2
(C2), 55.2 and 55.8 (C3), 60.0 and 61.3 (C1); 127.0,
127.3, 128.0, 128.1, 128.9, 141.0 (Carom). Mass spec-
trum, m/z (Irel, %): 206 (2.6) [M + 4]+, 205 (2.2), 204
(19.2) [M + 2]+, 203 (3.4), 202 (29.1) [M]+, 169 (12.3),
167 (46.3), 131 (96.4), 127 (34.3), 125 (100), 91
(89.0), 32 (63.4), 28 (73.1).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011