ADDITION OF CYCLIC AMINES TO α,β-UNSATURATED ACIDS
1959
CHCH , J = 14.9, 7.5 Hz), 2.42 d.d (1H, CHCH , J =
[4H, O(CH ) ], 10.60 br.s (2H, COOH). Found, %: C
2
2
2 2
1
4.9, 6.8 Hz), 2.43–2.56 m [4H, N(CH ) ], 2.93–3.06
47.09; H 6.71; N 6.95. C H NO . Calculated, %: C
2
2
8
15
5
m (1H, CH-CH ), 3.53–3.64 m [4H, O(CH ) ], 12.23
47.29; H 6.45; N 6.89.
3
2 2
br.s (1H, COOH). Found, %: C 56.85; H 8.43; N 8.26.
C H NO . Calculated, %: C 56.47; H 8.73; N 8.09.
b. Prepared similarly from 5.8 g (0.05 mol) of
fumaric acid and 5.3 g (0.06 mol) of morpholine in
8
15
3
b. 11.3 g (0.13 mol) of morpholine 4 was added
dropwise in the course of 1 h to a mixture of 8.6 g
0.1 mol) of crotonic acid and 20 mL of water, at
stirring and heating to 70–75°C. The mixture was
stirred for 10 h, cooled down, and extracted with
chloroform. The aqueous layer was separated and
concentrated in vacuum. The formed crystals were
crystallized from dioxane. Yield 11.5 g (66%).
2
5 mL of water. Yield 3.5 g (35%).
2
-(Piperidin-1-yl)succinic acid (10). а. Prepared
(
similarly from 5.8 g (0.05 mol) of maleic acid and
5
1
.1 g (0.06 mol) of piperidine. Yield 6.1 g (60%), mp
–
1
1
99–200°C. IR spectrum, ν, cm : 1690 (COOH). H
NMR spectrum, δ, ppm: 1.41–1.69 m [6H, (CH2)3],
2
.43 d.d (2H, NCHCH , J = 16.0, 5.6 Hz), 2.54–2.79
2
m (4H, NCH ), 3.55 d.d (1H, NCH J = 9.0, 5.6 Hz),
2
,
3
-(Piperidin-1-yl)butanoic acid (7) was prepared
8
7
7
.0–13.0 br.s (2H, COOH). Found, %: C 53.43; H
.65; N 6.75. C H NO . Calculated, %: C 53.72; H
similarly via procedure b from 8.6 g (0.1 mol) of
crotonic acid and 12.7 g (0.15 mol) of piperidine 5.
Yield 7.7 g (45%), mp 153°C (from dioxane). IR
9
17
4
.51; N 6.96.
–
1
spectrum, ν, cm : 1680 (C=O), 3000–3400 (COOH);
b. Prepared similarly from 5.8 g (0.05 mol) of
1
H NMR spectrum, δ, ppm: 1.03 d (3H, CHCH , J =
fumaric acid and 5.1 g (0.06 mol) of piperidine in
25 mL of water. Yield 4.0 g (40%).
3
6
.7 Hz), 1.45–1.70 m (6H, (CH ) ,), 2.09 d.d (1H,
2 3
CHCH , J = 15.9, 5.9 Hz), 2.37 d.d (1H, CHCH , J =
2
2
2
-(Pyrrolidin-1-yl)succinic acid (11). A mixture
1
5.9, 9.3 Hz), 2.45–2.54 m (2H, NCH ), 2.62–2.71 m
2
of 5.8 g (0.05 mol) of maleic acid and 4.3 g (0.06 mol)
pyrrolidine in 25 mL of water was heated to reflux for
h; water was removed in vacuum; the residue was
crystallized from isopropanol. Yield 4.1 g (44%), mp
(
(
2H, NCH ), 2.99-3.11 m (1H, CHCH ), 11.48 br.s
1H, COOH). Found, %: C 63.31; H 10.35; N 8.41.
2
3
6
C H NO . Calculated, %: C 63.13; H 10.01; N 8.18.
9
17
2
–
1
1
3
-(Pyrrolidin-1-yl)butanoic acid (8). A mixture of
200°C. IR spectrum, ν, cm : 1680 (COOH). H NMR
8
1
.6 g (0.1 mol) of crotonic acid, 20 mL of water, and
0.7 g (0.15 mol) of pyrrolidine was refluxed for 6 h.
spectrum, δ, ppm: 1.80–1.87 m (4H, 2CH ), 2.44–2.63
2
a
b
m (1H , CHCH CH ), 2.72 d.d (1H , CHCH CH , J =
2
2
2
2
Water and excess of pyrrolidine were removed in
vacuum, the formed crystals were filtered and washed
with diethyl ether. Yield 14.1 g (90%), mp 134–135°C.
15.8, 9.1 Hz), 2.80–3.02 m (4H, 2NCH ), 3.79 d.d (1H,
NCH, J = 9.1, 4.8 Hz), 1.0–5.0 br.s (2H, 2COOH).
2
Found, %: C 51.53; H 6.78; N 7.65. C H NO .
8
13
4
–1
IR spectrum, ν, cm : 1670 (C=O), 3000–3400 (COOH).
Calculated, %: 51.33; H 7.00; N 7.48.
1
H NMR spectrum, δ, ppm: 1.11 d (3H, CHCH , J =
3
b. Prepared similarly from 5.8 g (0.05 mol) of
fumaric acid and 4.3 g (0.06 mol) of pyrrolidine in
6
.5 Hz), 1.73–1.85 m (4H, (CH ) ,), 2.19 d.d (1H,
2 2
CHCH , J = 15.5, 6.9 Hz), 2.35 d.d (1H, CHCH , J =
2
2
2
5 mL of water. Yield 2.9 g (30.8%).
1
5.5, 6.1 Hz), 2.61–2.72 m (4H, N(CH ) ), 2.90–3.01
2 2
m (1H, CHCH ), 9.81 br.s (1H, COOH). Found, %: C
2
Morpholine cinnamate (12). A Mixture of 7.4 g
0.05 mol) of cinnamic acid and 5.3 g (0.06 mol) of
6
6
1.45; H 9.85; N 8.58. C H NO . Calculated, %: C
8 15 2
(
1.12; H 9.62; N 8.91.
-Morpholinosuccinic acid (9). а. A mixture of
.8 g (0.05 mol) of maleic acid, 5.3 g (0.06 mol) of
morpholine in 25 mL of water was refluxed for 2.5 h
and then concentrated in vacuum. The residue was
crystallized from isopropanol. Yield 10.3 g (87.5%),
2
5
–
1
morpholine, and 25 mL of water was refluxed for 7 h
and then concentrated in vacuum. The residue was
crystallized from a 1 : 1 dioxane–water mixture. Yield
mp 160–162°C. IR spectrum, ν, cm : 1530 (Ph), 1640
+
1
(C=C), 2000–2800 (NH ). H NMR spectrum, δ, ppm:
2
2.74–2.78 m (4H, 2CH O), 3.63–3.67 m (4H,
2
–
1
6
1
.6 g (65%), mp 210–215°C. IR spectrum, ν, cm :
2HHCH O), 6.37 d (1H, =CH, J = 16.0 Hz), 6.68 br.s
2
1
680 (COOH). H NMR spectrum, δ, ppm: 2.39 d.d
(2H, NH ), 7.2–7.40 m (3H, Ph), 7.52–7.56 m (2H,
2
(
1H, CH , J=16.0, 6.0 Hz), 2.44–2.52 m (2H) and 2.64–
Ph), 7.51 d (1H, =CH, J = 16.0 Hz). Found, %: C
2
2
8
.72 m [2H, N(CH ) ], 2.66 d.d (1H, CH , J = 16.0,
.7 Hz), 3.48 d.d (1H, CH, 8.7, 6.0 Hz), 3.50–3.61 m
66.51; H 7.08; N 5.78. C H NO . Calculated, %:
66.38; H 7.29; N 5.95.
2
2
2
13 17
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016