2-ACYL(AROYL)-1,1,3,3-TETRACYANOPROPENIDES
1105
10.15 s and 10.26 s (2Н, NH2). Mass spectrum, m/z
(Irel, %): 287 (1), 286 (6) [M]+, 257 (2), 229 (27), 213
(25), 57 (45). Found, %: C 62.73; H 6.41; N 19.53.
C15H18N4O2. Calculated, %: C 62.92; H 6.34; N 19.57.
M 286.14.
(73%), mp 210–212°С. IR spectrum, ν, cm–1: 3390,
3117 (NH2), 2222 (C≡N), 1682 (C=O). Н NMR
1
spectrum, δ, ppm: 3.71 s (3Н, CH3), 3.72 s (3Н, CH3),
3
3.92 s (2Н, CH2), 6.74 d (1Нarom, J 8.3 Hz), 6.85 d
3
(1Нarom, J 8.3 Hz), 6.93 s (1Н, 1Нarom) 7.20 br.s (2Н,
NH2), 7.79 s (1Н, СОNH2), 8.11 s (1Н, СОNH2). 13С
NMR spectrum, δ, ppm: 36.64, 55.25, 66.25, 104.61,
111.59, 112.99, 116.29, 119.33, 120.83, 123.66,
129.38, 147.44, 148.34, 150.06, 156.85, 166.59. Mass
spectrum, m/z (Irel, %): 439 (1), 438 (6) [M]+, 263 (12),
136 (54), 127 (9). Found, %: C 43.98; H 3.53; N
12.88. C16H15IN4O3. Calculated, %: C 43.85; H 3.45;
N 12.79. M 438.02.
(Z)-2-(5-Amino-4-cyano-2-ethylidene-2,3-dihyd-
rofuran-3-ylidene)propanedinitrile (Vа). In 10 mL
of 1,4-dioxane was dissolved at heating 2.2 g (0.01 mol)
of sodium 2-propionyl-1,1,3,3-tetracyanopropenide
(Ic). Then dry HCl was bubbled through the solution at
50–60°С at a rate 0.5–1.0 mL s–1 till yellow color
disappeared (5–8 min); the mixture was poured into
20 mL of water, the separated precipitate was filtered
off and recrystallized from 2-propanol. Yield 1.72 g
(87%), t.decomp. > 230°С. IR spectrum, ν, cm–1: 3201
2-Amino-4-(2,5-dimethoxybenzyl)-6-iodo-5-
cyanopyridine-3-carboxamide (VIb) was similarly
prepared. Yield 77%, mp 218–220°С. IR spectrum, ν,
cm–1: 3386, 3120 (NH2), 2225 (C≡N), 1686 (C=O). 1Н
NMR spectrum, δ, ppm: 3.63 s (3Н, CH3), 3.74 s (3Н,
1
(NH2), 2250, 2225 (C≡N), 1685 (C=O). Н NMR
3
spectrum, δ, ppm: 1.98 d (3Н, CH3, J 7.3 Hz), 6.63 q
3
(1Н, CH, J 7.3 Hz), 10.21 br.s (1Н, NH2), 10.32 br.s
(1Н, NH2). 13С NMR spectrum (GATED), δ, ppm:
4
CH3), 3.93 s (2Н, CH2), 6.32 d (1Нarom, J 3.0 Hz),
1
12.67 q (CH3, J 129.87 Hz), 49.14 s (С4) 71.25 s
6.76 d.d (1Нarom, 3J 8.9, 4J 3.0 Hz), 6.88 d (1Н, 1Нarom
,
3J 8.9 Hz), 7.21 br.s (2Н, NH2), 7.66 s (1Н, СОNH2),
8.00 s (1Н, СОNH2). Mass spectrum, m/z (Irel, %): 439
(2), 438 (13) [M]+, 263 (20), 136 (65). Found, %: C
43.79; H 3.48; N 12.73. C16H15IN4O3. Calculated, %:
C 43.85; H 3.45; N 12.79. M 438.02.
[С(СN)2], 111.22 s (CN), 114.12 (CN), 116.32, 117.60
d.q (СН, 1J 162.8, 2J 7.5 Hz), 116.59 s (CN), 147.78 m
(С2), 153.29 s (С3), 169.74 s (С5). Mass spectrum, m/z
(Irel, %): 198 (31) [M]+, 171 (3), 143 (17). Found, %: C
60.51; H 3.11; N 28.12. C10H6N4O. Calculated, %: C
60.60; H 3.05; N 28.27. M 198.05.
4-Amino-6-iodo-3-oxo-1-(4-chlorophenyl)-2,3-di-
hydro-1H-pyrrolo[3,4-c]pyridine-7-carbonitrile
(VIIа). In 15 mL of conc. HI was carefully triturated
1.52 g (5 mmol) of propenide Ig, the reaction mixture
was heated at 100°С for 5 min, cooled, and diluted
with 10 mL of cold water. The separated oily
substance was decanted and triturated at heating with
10 mL of ethanol. The obtained slurry was filtered, the
precipitate was washed with ethanol to remove iodine,
then it was recrystallized from 25 mL of glacial acetic
acid. Yield of 4-amino-1- (4-chlorophenyl)-6-iodo-3-
oxo-1,3-dihydrofuro[3,4-c]-pyridine-7-carbonitrile
1.33 g (65%), mp 244–246°С {mp 244–246°С
(decomp.) [10]}. The filtrate was diluted with 10 mL
of water, the separated precipitate was filtered off and
recrystallized from a mixture acetic acid–2-propanol,
4 : 1. Yield of compound VIIа 0.14 g (7%), mp 258–
262°С (decomp.). IR spectrum, ν, cm–1: 3325 (NH),
3216 (NH2), 2215 (C≡N), 1655 (C=O). 1Н NMR
spectrum, δ, ppm: 5.85 s (1H, CH), 7.24 br.s (1H, NH2),
(Z)-2-(5-Amino-2-propylidene-4-cyano-2,3-di-
hydrofuran-3-ylidene)propanedinitrile (Vb) was
similarly prepared. Yield 79%, t.decomp. > 220°С. IR
spectrum, ν, cm–1: 3208 (NH2), 2251, 2230 (C≡N),
1
1686 (C=O). Н NMR spectrum, δ, ppm: 1.07 t (3Н,
CH3, 3J 7.5 Hz), 2.37–2.51 quintet (2Н, CH2, 3J 7.6 Hz),
6.57 t (1Н, CH, 3J 7.8 Hz), 10.28 br.s (2Н, NH2). Mass
spectrum, m/z (Irel, %): 213 (15) 212 (100) [M]+, 211
(34) [M – 1]+, 197 (17), 196 (13), 185 (36), 184 (29).
Found, %: C 62.33; H 3.91; N 26.27. C11H8N4O.
Calculated, %: C 62.26; H 3.80; N 26.40. M 212.07.
2-Amino-4-(3,4-dimethoxybenzyl)-6-iodo-5-
cyanopyridine-3-carboxamide (VIа). In 20 mL of
conc. HI (54–56%) was carefully triturated at room
temperature 3.28 g (0.01 mol) of sodium 2-(3,4-
dimethoxybenzoyl)-1,1,3,3-tetracyanopropenide (Ij).
The reaction mixture was heated to boiling and stirred
at this temperature for 2–3 min, then it was diluted
with 50 mL of water. The separated oily substance was
triturated till it solidified, and the liquid was decanted.
The solid residue was triturated in 20 mL of hot 2-
propanol, filtered off, washed with ethyl acetate, and
recrystallized from glacial acetic acid. Yield 3.19 g
3
3
7.29 d (2Harom, J 8.4 Hz), 7.45 d (2Harom, J 8.4 Hz),
8.46 br.s (1H, NH2), 9.13 s (1Н, NH). Mass spectrum,
m/z (Irel, %): 412 (3), 411 (1), 410 (10) [M]+, 127 (65).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 8 2014