SYNTHESIS OF 4-VINYLMORPHOLINE BASED ON ACETYLENE
Vinylation of 4-morpholine 7 with acetylene at atmospheric pressure
345
Discharge of condensate, g L–1 h–1
(content of 4-vinylmorpholine,%, in
condensate)
Amount of KOH,
by weight of morpholine
Consumption of acetylene,
Т, °C
%
L/(Lcat.sol h)
1
00
10
8
8
350
400
450
500
15–20 (30)
25–30 (25)
20–25 (20)
30–35 (15)
1
115
10
10
1
25
Found, %: C 47.31, H 7.48, N 9.28. C H NO. Calculated,
receiver 6, and uncondensed gases, mainly acetylene,
6
11
%
: C, 47.05. H, 7.18, N, 9.15.
-Acetylpiperidine (5). It was prepared in a
manner similar to the previous example from 8.5 g
0.1 mole) piperidine and 46.7 g (0.5 mole) VA. Yield
were released into atmosphere.
1
The yield and reaction conditions for the morpholine
vinylation with acetylene are given in the table. Bp 103–
110°C (680 mmHg), n D2 0 1.4965 [1]. IR spectrum, ν, cm :
–1
(
1
of 1-acetylpiperidine 5 9.9 g (78%), bp 99°C (3 mmHg),
nD20 1.4750. IR spectrum, ν, cm : 1650 (C = O). H NMR
1100 (C–O–C), 1640 (C=O). H NMR spectra, δ, ppm
–1
1
(J, Hz): 2.47 m (4H, O–CH ), 3.66 m (4H, N–CH ), 4.52 d
2
2
spectra, δ, ppm (J, Hz): 1.44–1.68 m (6H, 3CH ), 1.96 s
(1H, J 15.6, =CH ), 5.35 d (1H, J 8.8, =CH ), 6.55 d.d
(1H, J 15, 6.88 =CH).
2
2
2
(
3H, CH ), 3.36–3.44 m [4H, N–(CH )–]. 13C NMR
3
2
spectra, δ ppm: 20.7 (CH ), 24.0 (CH ), 25.0 (CH ),
3
2
2
2
5.9 (CH ), 41.5 (N–CH ), 46.5 (N–CH ), 166.7 (C =
CONCLUSIONS
2
2
2
O ). Found, %: C 66.31, H 10.00, N 11.28. C H NO.
7
13
Calculated, %: C 66.14, H 10.23, N 11.02.
It has been shown that earlier attempts to synthesize
-vinylmorpholine without the use of acetylene have
4
1-Acetylpyrrolidine (6). Pyrrolidine [7.1 g (0.1 mol)]
not been successful. Technologically more acceptable
conditions for the vinylation of morpholine with acetylene
at atmospheric pressure in a solution of dimethylsulfoxide
in the presence of caustic potassium were developed.
and VA [46.7 g (0.5 mol)] were obtained in a manner
analogous to the previous example. Yield of 1-acetylpyr-
2
0
rolidine 9.0 g (80%), bp 80°C (3 mmHg), n 1.4740. IR
D
–1
1
spectrum, ν, cm : 1640 (C = O). H NMR spectra, δ, ppm
(
1
J, Hz): 1.78–1.88 (2H, CH ), 1.88–1.99 m (2H, CH ),
2 2
REFERENCES
.92 s (3H, CH ), 3.30 t (2H, J 6.8, NCH ), 3.41 t (2H,
3 2
13
J 6.7, NCH ). C NMR spectra, δ, ppm: 21.8 (CH ), 24.0
2
3
1
2
3
4
. Pivnenko, V.P., Chem. Het. Compd., 1971, vol. 7, no. 8,
(CH ), 25.6 (CH ), 47.7 (N–CH ), 46.4 (N–CH ), 166.9
2 2 2 2
p. 963.
(C=O). Found, %: C, 63.51; H, 9.96; N, 12.11. C H NO.
6 11
. Markosyan, A.J., Baghdasaryan, G.A.,Oganesyan, G.P.,
et al., Russ. J. Gen. Chem., 2012, vol. 82, no. 2, pp. 344–345.
Calculated, %: C 63.71, H 9.73, N 12.38.
4-Vinylmorpholine (7). Morpholine 1 (100 mL) from
. Baghdasaryan, G.A., J. Arm. Chem., 2016, vol. 69, no. 4,
measuring point 2 and dimethyl sulfoxide from measuring
point 3 containing 8–10% of potassium hydroxide (in
terms of morpholine) were charged to the bottom of the
reactor 1 with a volume of 300 mL. The mixture was
heated to 100–125°C and acetylene was passed through
it at a rate of 350–500 L/(Lcat.sol h). During the reaction
at the top of the reactor, the leaving vapors [unreacted
morpholine 1 and 4-vinylmorpholine 7 with excess
acetylene stream were condensed through condensers 4
and 5. The condensate discharged into the raw material
pp. 534–538.
. Shekhirev, Yu.P., Lopatinskii, V.P., Sutyagin, V.P., and
Tuzovskaya, С.А., Khim. Geterotsikl. Soedin., 1983, no. 11,
pp. 1504–1508.
5
6
. Attryan H. S., Baltayan S. G., Sahatelyan R. F., Takma-
zyan K. C., Russ. J. Gen. Chem., 2007. V. 77. N 12.
P. 2031–2033.
. Buzilova, S.R., Shul’gina, V.M., Sakovnya, G.V., and
Vereshchagin, L.I., Khim. Geterotsikl. Soedin., 1981, no. 9,
p. 1279.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 91 No. 2 2018