2-[PYRIDIN-2(4)-YL]-N-[ω-VINYLOXYALKYL]ETHANAMINES
1421
Scheme 2.
H
N
OH
HC CH
≡
Ib
+
HOCH2CH2NH2
IIIc
N
IV
V
2
3
1560, 1470, 1415, 1350, 1310, 1190, 1140, 1120, 1065,
1030, 980, 950, 800, 720, 615, 590, 510, 490. 1H NMR
spectrum, δ, ppm: 1.95 br.s (1H, NH), 2.90 t (2H,
CH=C, J = 2.0, J = 6.9 Hz), 4.16 d.d (1H, trans-
CH=C, 2J = 2.0, 3J = 14.3 Hz), 6.44 d.d (1H, OCH=C,
3Jcis = 6.9, Jtrans = 14.3 Hz), 7.12 d.d (2H, 3-H, 5-H,
3
3
NCH2CH2O, J = 5.2 Hz), 3.0 m (4H, 2-CH2CH2),
4J = 1.4, 3J = 4.5 Hz), 8.48 d.d (2H, 2-H, 6-H, 4J = 1.6,
3J = 4.5 Hz). 13C NMR spectrum, δC, ppm: 35.01
(4-CH2), 48.17 (4-CH2CH2), 49.62 (NCH2CH2O),
66.81 (CH2O), 86.45 (=CH2), 123.86 (C3, C5), 148.77
(C4), 149.47 (C2, C6), 151.32 (OCH=). Found, %:
C 68.95; H 8.27; N 14.17. C11H16N2O. Calculated, %:
C 68.72; H 8.39; N 14.57.
3
3.76 t (2H, CH2O, J = 5.2 Hz), 3.96 d.d (1H, cis-
2
3
CH=C, J = 1.7, J = 6.8 Hz), 4.15 d.d (1H, trans-
CH=C, 2J = 1.7, 3J = 14.2 Hz), 6.43 d.d (1H, OCH=C,
3
3Jcis = 6.8, Jtrans = 14.2 Hz), 7.09 m (1H, 5-H), 7.16 d
3
(1H, 3-H, J3,4 = 7.6), 7.56 m (1H, 4-H), 8.51 d (1H,
3
6-H, J5,6 = 4.1 Hz). 13C NMR spectrum, δC, ppm:
38. 39 (2-CH2), 48. 37 (2-CH2CH2), 49. 13
(NCH2CH2O), 67.18 (NCH2CH2O), 86.49 (=CH2),
121.08 (C5), 123.09 (C3), 136.13 (C4), 149.14 (C6),
151.58 (OCH=), 160.01 (C2). Found, %: C 68.63;
H 8.32; N 14.36. C11H16N2O. Calculated, %: C 68.72;
H 8.39; N 14.57.
2-(Pyridin-4-yl)-N-(3-vinyloxypropyl)ethan-
amine (IIId). Yield 49%, bp 172–175°C (8 mm), d420 =
1.0179, nD20 = 1.5190. IR spectrum, ν, cm–1: 3285,
3115, 3075, 3020, 2940, 2880, 2820, 1620, 1610,
1600, 1560, 1495, 1470, 1405, 1370, 1310, 1290,
1190, 1125, 1080, 990, 965, 890, 800, 735, 585, 550,
510, 505, 490. 1H NMR spectrum, δ, ppm: 1.77 m (2H,
CH2CH2CH2), 2.17 br.s (1H, NH), 2.69 t (2H, 4-CH2,
2-(Pyridin-2-yl)-N-(3-vinyloxypropyl)ethan-
amine (IIIb). Yield 51%, bp 165–166°C (8 mm), d420 =
1.0161, nD20 = 1.5140. IR spectrum, ν, cm–1: 3280,
3115, 3070, 3005, 2935, 2880, 2820, 1630, 1610,
1590, 1570, 1475, 1425, 1380, 1310, 1190, 1140, 1120,
1075, 1045, 990, 960, 890, 805, 745, 620, 595, 520,
3
3J = 6.9 Hz), 2.74 t (2H, 4-CH2CH2, J = 6.9 Hz),
3
2.85 t (2H, NCH2CH2CH2O, J = 6.8 Hz), 3.68 t (2H,
OCH2, 3J = 6.1 Hz), 3.93 d.d (1H, cis-CH=C, 2J = 2.0,
2
3
3J = 6.6 Hz), 4.10 d.d (1H, trans-CH=C, J = 2.0, J =
1
3
3
490. H NMR spectrum, δ, ppm: 1.83 m (2H,
14.3 Hz), 6.37 d.d (1H, OCH=C, Jcis = 6.6, Jtrans
=
4
3
CH2CH2CH2), 2.35 br.s (1H, NH), 2.75 t (2H, NCH2,
3J = 7.0 Hz), 2.99 m (4H, 2-CH2CH2), 3.72 t (2H,
OCH2, 3J = 6.1 Hz), 3.96 d.d (1H, cis-CH=C, 2J = 2.0,
14.3 Hz), 7.09 d.d (2H, 3-H, 5-H, J = 1.3, J =
4.6 Hz), 8.45 d.d (2H, 2-H, 6-H, 4J = 1.5, 3J = 4.4 Hz).
13C NMR spectrum, δC, ppm: 28.96 (CH2CH2O), 35.32
(4-CH2), 46.32 (4-CH2CH2), 49.60 (NCH2CH2CH2O),
65.80 (CH2O), 86.02 (=CH2), 123.70 (C3, C5), 148.72
(C4), 149.34 (C2, C6), 151.27 (OCH=). Found, %:
C 69.62; H 8.93; N 13.77. C12H18N2O. Calculated, %:
C 69.87; H 8.80; N 13.58.
2
3
3J = 6.9 Hz), 4.14 d.d (1H, trans-CH=C, J = 2.0, J =
3
3
14.3 Hz), 6.42 d.d (1H, OCH=C, Jtsis = 6.9, Jtrans
14.3 Hz), 7.10 m (1H, 5-H), 7.16 d (1H, 3-H, J3,4
=
=
=
3
3
7.9 Hz), 7.58 m (1H, 4-H), 8.51 d (1H, 6-H, J5,6
4.6 Hz). 13C NMR spectrum, δC, ppm: 29.40
(CH2CH2O), 38.40 (2-CH2), 46.62 (2-CH2CH2), 49.31
(NCH2), 66.24 (CH2O), 86.29 (=CH2), 121.15 (C5),
123.23 (C3), 136.26 (C4), 149.28 (C6), 151.74 (OCH=),
160.22 (C2). Found, %: C 69.99; H 8.45; N 13.54.
C12H18N2O. Calculated, %: C 69.87; H 8.80; N 13.58.
2-[2-(Pyridin-4-yl)ethyl]aminoethanol (V). Yield
69%, bp 168–170°C (5 mm); published data [7]:
bp 188–193°C (15 mm), d240 = 1.0652, nD20 = 1.5341.
Vinylation of amino alcohol (V). A mixture of
100 ml of benzene, 33.2 g (0.2 mol) of amino alcohol
V, and 6.6 g of potassium hydroxide was placed into
a 1-l steel high-pressure reactor, saturated with acety-
lene under a pressure of 14 atm, and heated for 6 h at
120°C. Vacuum distillation of the mixture gave 18.1 g
(47%) of compound IIIc, bp 154–156°C (8 mm),
n2D0 = 1.5175.
2-(Pyridin-4-yl)-N-(2-vinyloxyethyl)ethanamine
(IIIc). Yield 51%, bp 152–156°C (8 mm), d420
=
1.0315, nD20 = 1.5180. IR spectrum, ν, cm–1: 3285,
3120, 3070, 3025, 2925, 2840, 1620, 1610, 1600,
1555, 1495, 1470, 1410, 1370, 1360, 1315, 1190,
1135, 1075, 1030, 990, 970, 800, 730, 590, 505, 490.
1H NMR spectrum, δ, ppm: 1.85 br.s (1H, NH), 2.78 t
1
The H and 13C NMR spectra were recorded at
3
(2H, 4-CH2, J = 7.1 Hz), 2.90 m (4H, CH2NCH2),
3
3.75 t (2H, OCH2, J = 5.1 Hz), 3.98 d.d (1H, cis-
26°C on a Bruker DPX-400 instrument (400 MHz for
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009