TARASOVA et al.
1178
Ketoxime 2c with different substituents R and R'
washed with water (3 × 20 mL), dried with MgSO4,
and distilled.
was obtained as a single configuration isomer. From
the values of the chemical shifts in 13С NMR spectrum
of Me group (12.8 ppm) and atom Ci of the phenyl
group (136.1 ppm) it follows that ketoxime 2c exists in
the Е-form [9].
N-[(2-Chloroprop-2-en-1-yl)oxy]propan-2-imine
(2а). Yield 3.91 g (53%), colorless mobile liquid, bp
72°С (37 mmHg), nD24 1.4532. IR spectrum, cm–1:
3111 w, 2992, 2950, 2920 s, 2867, 1651 s, 1638 s,
1459 sh, 1436 s, 1376 sh, 1370 s, 1349 sh, 1260, 1237
w, 1174, 1148 w, 1077 s, 1057 s, 1019 s, 1003 s, 952
w, 909 sh, 881 s, 828 s, 721 s, 641, 582 w, 533 w, 476
w, 450 w, 411. 1Н NMR spectrum, δ, ppm: 1.87 s, 1.89
Cl
Me
O
N
4
s (6Н, CMe2), 4.54 d.d (2Н, OCH2, J 1.1, 0.98 Hz),
2
5.35 d.t (1Н, СCl=CH-cis, J 1.3 Hz), 5.40 d.t (1Н,
СCl=CH-trans). 13С NMR spectrum, δ, ppm: 15.62,
21.67 (Me2C), 75.03 (OCH2), 113.06 (=CH2), 138.39
(ClC=), 156.13 (C=N). Found, %: С 48.70; Н 6.79; Cl
23.95; N 9.40. C6H10ClNO. Calculated, %: С 48.82; Н
6.83; Cl 24.02; N 9.49.
2c
Considering the simplicity of the experiment, the
availability of initial ketoximes and 2,3-dichloroprop-
1-ene it is expectable that О-(2-chloroprop-2-enyl)
ketoximes will attract attention as promising
precursors of heterocyclic compounds and
multipurpose building blocks for organic synthesis.
N-[(2-Chloroprop-2-en-1-yl)oxy]cyclohexanimi-
ne (2b). Yield 5.44 g (55%), colorless mobile liquid,
bp 92°С (3 mmHg), nD24 1.4916. IR spectrum, cm–1:
3117 w, 2934 s, 2860, 1650, 1638, 1449, 1438, 1388
w, 1368 w, 1347 w, 1318 w, 1279 w, 1253, 1221 w,
1173, 1140 w, 1107 w, 1062 s, 1019, 1002, 989, 951
2,3-Dichloroprop-1-ene. To a mixture of 442.3 g
(3 mol) of 1,2,3-trichloropropane and 120 mL of
DMSO was added at vigorous stirring a solution of
240 g (6 mol) of NaOH in 300 mL of water at 55–65°С
within 2.5 h. The reaction mixture was stirred at this
temperature for 5 h more and was left overnight. The
organic layer was separated, from the water layer the
reaction product was extracted with ether (3 × 30 mL).
Combined organic solutions were washed with water
(3 × 20 mL), dried with MgSO4. The residue after
distilling off ether was distilled using an efficient
Vigreux column in the presence of hydroquinone.
1
w, 914, 886, 866, 836, 784 w, 720, 662 w, 638 w. Н
NMR spectrum, δ, ppm: 1.65 m (6Н, С3(4,5)Н2), 2.19 m
(2Н, С2Н2), 2.50 m (2Н, С6Н2), 4.54 s (2Н, СН2), 5.34
br.s (1Н, СCl=CH-cis), 5.38 br.s (1Н, СCl=CH-trans).
13С NMR spectrum, δ, ppm: 25.41 (С6), 25.69 (С4),
25.77 (С5), 26.99 (С3), 31.99 (С2), 74.85 (ОСН2),
112.92 (СН2=), 138.41 (ClC=), 161.71 (C=N). Found,
%: С 57.52; Н 7.47; Cl 18.80; N 7.43. C9H14ClNO.
Calculated, %: С 57.60; Н 7.52; Cl 18.89; N 7.46.
1
Yield 245.3 g (74%), bp 94°С [10]. Н NMR spec-
(1Е)-N-[(2-Chloroprop-2-en-1-yl)oxy]-1-phenyl-
ethanimine (2с). Yield 7.13 g (68%), colorless mobile
liquid, bp 117–118°С (2 mmHg), nD24 1.5476. IR spec-
trum, cm–1: 3105 w, 3083 w, 3058 w, 3026 w, 2921, 2870
w, 1650, 1637, 1613 w, 1600 sh, 1573 w, 1496, 1445,
1430, 1387 w, 1370, 1348 w, 1314, 1265, 1173, 1142 w,
1094, 1077 sh, 1055 v.s, 1019 s, 1001 s, 955 w, 905 sh,
883 s, 781 w, 760 s, 720, 693 s, 653 w, 639, 589 w, 560,
516 w. 1Н NMR spectrum, δ, ppm: 2.56 s (3Н, Me), 4.71
s (2H, OCH2), 5.36 br.s (1Н, СCl=CH-cis), 5.42 br.s (1Н,
СCl=CH-trans), 7.33 m (3Н, Hm,p), 7.61 m (2Н, Ho). 13С
NMR spectrum, δ, ppm: 12.82 (Me), 75.86 (OCH2),
113.50 (CH2=), 126.10 (Co), 128.35 (Cm), 129.24 (Cp),
136.14 (Ci), 138.14 (ClC=), 155.85 (C=N). Found, %:
С 62.88; Н 5.72; Cl 16.81; N 6.64. C11H12ClNO.
Calculated, %: С 63.01; Н 5.77; Cl 16.91; N 6.68.
4
trum, δ, ppm: 4.15 d (2H, CH2Cl, J 1.0 Hz), 5.40 d
4
[1H, CH=, J(=CH, CH2Cl) 1.83 Hz], 5.57 d.t (1H,
CH=, Jhem 1.0 Hz).
О-(2-Chloroprop-2-enyl)ketoximes (2а–2с). A mix-
ture of 3.25 g (50 mmol) of KOH·0.5H2O and 50 mmol
of ketoxime in 50 mL of DMSO was stirred at room
temperature till the precipitate completely dissolved
(25 min). Then 5.91 g (53 mmol) of 2,3-dichloroprop-
1-ene was added dropwise within 5 min maintaining
temperature at the level of 20–23°С with external
cooling. After 15 min the cooling was removed, the
reaction mixture was stirred at room temperature for
1 h. О-(2-Chloroprop-2-enyl)oxime 2 was extracted
from the reaction mixture with hexane (12 × 20 mL),
without diluting with water. The hexane extract was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015