N-(1-NITROALKYLMETHYL)-2(3)-VINYLOXYALKYLAMINES
1249
3
1
J 5.2 Hz), 3.02 s (2H, NCH CNO ), 3.72 t (2H,
687, 525, 495. H NMR spectrum, δ, ppm: 1.45–2.35 m
2
2
3
OCH CH N, J 5.2 Hz), 3.99 d.d (1H, cis-CH=CO,
2
[12H, (CH ) , OCH CH CH N], 2.70 t (3H,
2
2
2 5
2
2
2
3
3
Jgem 2.1, J 6.8 Hz), 4.17 d.d (1H, trans-CH=CO,
Jgem 2.1, J
OCH CH CH N, J 6.7 Hz), 2.95 s (2H, NCH CNO ),
cis
2 2 2 2 2
2
3
14.3 Hz), 6.44 d.d (1H, C=CHO,
3.33 br.s (1H, NH), 3.72 t (2H, OCH CH CH N,
2 2 2
J 6.7 Hz), 3.97 d.d (1H, cis-CH=CO, J 1.9, J 6.8 Hz),
4.17 d.d (1H, trans-CH=CO, J 1.9, 3Jtrans 14.3 Hz),
6.44 d.d (1H, C=CHO, J 6.8, J
spectrum, δ, ppm: 22.26 (C , C cyclohexyl), 25.22 (C
cyclohexyl), 31.16 (C , C cyclohexyl), 49.38
trans
3Jcis 6.8, 3J
14.3 Hz). 13C NMR spectrum, δ, ppm:
3
2
3
trans
gem cis
2
2
6
1
3.80 (CMe ), 48.82 (OCH CH N), 57.34 (NCH CNO ),
2
2
2
2
2
gem
3
3
13
7.05 (OCH CH N), 86.53 (=CH ), 88.29 (CMe ),
14.3 Hz). C NMR
2
2
2
2
cis
trans
3
5
4
51.31 (=CHO). Found, %: C 51.14; H 8.69; N 14.62.
2
6
C H N O . Calculated, %: C 51.05; H 8.57; N 14.88.
8
16
2
3
(
(
OCH CH CH N), 57.53 (NCH CNO ), 67.68
[
3-(Vinyloxy)propyl]-2-methyl-2-nitropropane-1-
2 2 2 2 2
1
OCH CH CH N), 86.62 (CH =), 92.39 (C cyclohexyl),
amine (IIIb). Yield 35%, bp 118–120°C (3 mm Hg),
2
2
2
2
2
0
20
–1
152.01 (=CHO). Found, %: C 59.64; H 9.08; N 11.23.
C H N O . Calculated, %: C 59.48; H 9.15; N 11.56.
d 1.0293, n 1.4610. IR spectrum, ν, cm : 3347, 3107,
033, 2933, 2867, 1620, 1602, 1523, 1459, 1389, 1357,
335, 1307, 1187, 1120, 1059, 953, 876, 844, 800, 749,
93, 627, 548. H NMR spectrum, δ, ppm: 1.75 s (6H,
CMe ), 1.95 m (2H, OCH CH CH N), 2.70 br.s (1H,
NH), 2.91 t (2H, OCH CH CH N, J 6.2 Hz), 3.16 s
2H, NCH CNO ), 3.91 t (2H, OCH CH CH N,
2 2 2 2 2
J6.2 Hz), 4.15 d.d (1H, cis-CH=CO, J 1.9, J 6.7 Hz),
.35 d.d (1H, trans-CH=CO, J 1.9, 3Jtrans 14.2 Hz),
.61 d.d (1H, C=CHO, J 6.7, J
spectrum, δ, ppm: 24.20 (CMe ), 29.45
OCH CH CH N), 47.21 (OCH CH CH N), 57.81
NCH CNO ), 66.11(OCH CH CH N), 86.52 (CH =),
8.29 (CMe ), 151.80 (=CHO). Found, %: C 53.21;
4
D
3
1
6
12 22
2
3
N-[2-(Vinyloxy)ethyl]-N,2-dimethyl-2-nitro-
propan-1-amine (IIIe). Yield 44%, bp 90–92°C (1 mm
Hg), d 1.0219, n 1.4580. IR spectrum, ν, cm : 3400,
3120, 2989, 2947, 2877, 2800, 1625, 1612, 1526, 1455,
1396, 1367, 1340, 1315, 1193, 1115, 1053, 1013, 989, 980,
960, 900, 848, 833, 800, 653. H NMR spectrum, δ, ppm:
1.54 s (6H, CMe ), 2.34 s (3H, NMe), 2.75 t (2H,
OCH CH N, J 5.1 Hz), 2.94 s (2H, CH NCH CH O),
1
20
20
–1
2
2
2
2
3
4 D
2
2
2
(
3
2
3
1
gem
cis
2
4
6
gem
2
3
3
13
3
14.2 Hz). C NMR
cis
trans
2
2
2
2
2
3
3.70 t (2H, OCH , J 5.1 Hz), 3.98 d.d (1H, cis-CH=CO,
2
2
2
2
3
3
(
(
Jgem 1.9, J 6.8 Hz), 4.16 d.d (1H, trans-CH=CO,
cis
Jgem 1.9, J
2
2
2
2
2
2
3
3
14.3 Hz), 6.46 d.d (1H, CHO, J 6.3,
2
2
2
2
2
2
trans cis
8
Jtrans 14.3 Hz). Found, %: C 53.02; H 8.51; N 13.29.
2
H 9.08; N 13.63. C H N O . Calculated, %: C 53.45;
C H N O . Calculated, %: C 53.45; H 8.97; N 13.85.
9
18
2
3
9 18 2 3
H 8.97; N 13.85.
-(Vinyloxy)(1-nitrocyclohexylmethyl)ethan-
amine (IIIc). Yield 38%, bp 136–139°C (2 mm Hg),
1
13
H and C NMR spectra were registered on a spec-
2
trometer Bruker DPX-400 (400 and 100 MHz) in CDCl3
at 26°C, internal reference HMDS. IR spectra were
recorded on a spectrophotometer Specord 75IR from thin
films.
2
0
–1
n
1.4915. IR spectrum, ν, cm : 3346, 3107, 3033, 2923,
D
2853, 1615, 1602, 1513, 1433, 1331, 1307, 1180, 1113, 1053,
1
979, 944, 893, 800, 683, 640, 587, 525. H NMR spectrum,
δ, ppm: 1.58–2.36 m [10H, (CH ) ], 2.78 t (2H,
REFERENCES
2
5
3
OCH CH N, J 5.4 Hz), 3.00 s (2H, NCH CNO ),
2
2
2
2
1
. Trofimov, B.A., Geteroatomnye proizvodnye atsetilena
3
3
3
4
6
.50 br.s (1H, NH), 3.78 t (2H, OCH CH N, J 5.4 Hz),
.99 d.d (1H, cis-CH=CO, J
.16 d.d (1H, trans-CH=CO, J
.45 d.d (1H, C=CHO, J 6.9, J
spectrum, δ, ppm: 22.17 (C , C cyclohexyl), 24.89
C cyclohexyl), 32.30 (C , C cyclohexyl), 49.05
OCH CH N), 57.28 (NCH CNO ), 66.43
2
2
2
3
(Heteroatomic Derivatives ofAcetylene), Moscow: Nauka,
1981; Shostakovskii, M.F., Trofimov, B.A.,Atavin,A.S., and
Lavrov, V.I., Usp. Khim., 1968, vol. 37, p. 2070; Kukha-
rev, B.F., Stankevich, V.K., and Klimenko, G.R., Usp. Khim.,
1995, vol. 64, p. 562.
1.5, J 6.9 Hz),
gem
1.5, 3J
cis
2
14.3 Hz),
gem
trans
3
3
13
14.3 Hz). C NMR
cis
trans
5
3
4
2
6
(
(
(
2
. The Chemistry of the Nitro and Nitroso Groups, Feuer, H.,
Ed., New York: Wiley-Interscience, 1969; Novikov, S.S.,
Shvekhgeimer, G.A., Sevost’yanova, V.V., and
Shlyapochnikov, V.A., Khimiya alifaticheskikh i alitsikli-
cheskikh nitrosoedinenii (Chemistry of Aliphatic and
Alicyclic Nitrocompounds), Moscow: Khimiya, 1974.
3. Grillot, G.F. and Bashford, R.I., J. Am. Chem. Soc., 1951,
vol. 73, p. 5598.
2
2
2
2
1
OCH CH N), 86.54 (CH =), 91.87 (C cyclohexyl),
2 2 2
1
51.62 (=CHO). Found, %: C 57.91; H 8.94; N 12.08.
C H N O . Calculated, %: C 57.87; H 8.83; N 12.27.
11
20
2
3
3
-(Vinyloxy)(1-nitrocyclohexylmethyl)propan-1-
amine (IIId). Yield 40%, bp 138–140°C (1 mm Hg),
2
0
–1
n
1
1.4922. IR spectrum, ν, cm : 3347, 3113, 2933, 2853,
D
620, 1605, 1532, 1427, 1363, 1327, 1307, 1264, 1185,
1133, 1119, 1063, 993, 953, 913, 884, 859, 831, 800, 729,
4. Senkus, M., J. Am. Chem. Soc., 1946, vol. 68, p. 10.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 8 2009