V
R
SYNTHETIC COMMUNICATIONS
7
ꢀ
1 1
(
1
7
(
1
3
ATR) ꢀ
3417, 3342, 3190, 3023, 2945, 2198, 2172, 1613 cm . H NMR d 10.26 (s,
max
1
3
H, NH ), 9.13, 9.12 (d, J ¼ 3.2 Hz, 1H, NH ), 7.43, 7.41 (d, J ¼ 8.4 Hz, 2H, CHarom.),
.31, 7.29 (d, J ¼ 8.4 Hz, 2H, CH ), 6.43 (s, 2H, NH ), 6.33 (s, 2H, NH ), 5.67, 5.66
arom.
2
2
4
13
d, J ¼ 4.0 Hz, 1H, CH ). C NMR d 161.0, 156.5, 154.3, 150.0, 141.6, 133.0, 129.0,
28.9, 116.9 (2CN), 88.5, 70.6, 50.4. Anal. Calcd. for C H ClN (338.75): C, 53.18; H,
15 11 8
.27; N, 33.08. Found: C, 52.91; H, 3.22; N, 33.16.
5
,7-Diamino-6-cyano-2-cyanoimino-4-(2-thienyl)-3,4-dihydro-1H-pyrido[2,3-d]pyrimidine
ꢃ
(
3i). Yield (Method A 83%, Method B 87%); brown solid; m.p.: 300-302 C. IR (ATR)
ꢀ1 1
ꢀmax 3448, 3322, 3157, 3113, 3023, 2916, 2196, 2179, 1635 cm . H NMR d 10.32 (s,
1
3
1
7
2
1
H, NH ), 9.24, 9.23 (d, J ¼ 3.2 Hz, 1H, NH ), 7.40, 7.39 (d, J ¼ 4.8 Hz, 1H, CHarom.),
.06, 7.06 (d, J ¼ 2.7 Hz, 1H, CH ), 6.97–6.95 (t, J ¼ 4.1 Hz, 1H, CH ), 6.54 (s,
arom.
arom.
4
13
H, NH ), 6.35 (br. s., 2H, NH ), 5.97, 5.96 (d, J ¼ 3.7 Hz, 1H, CH ). C NMR d 161.0,
2
2
56.6, 154.2, 149.7, 147.0, 127.1, 125.9, 125.7, 116.8 (2CN), 89.8, 70.7, 47.1. Anal. Calcd.
for C H N S (310.33): C, 50.31; H, 3.25; N, 36.11. Found: C, 50.23; H, 3.10; N, 36.05.
1
3
10 8
0
0
0
0
f5,7-Diamino-6-cyano-2 -oxo-1 ,2 -dihydro-1H-spiro[pyrido[2,3-d]pyrimidine-4,3 indole]-
2
(3H)-ylidenegcyanamide (7). Yield (Method A 72%, Method B 77%); brown solid; m.p.:
ꢃ
ꢀ
>
310 C. IR (ATR) ꢀ
3440, 3368, 3334, 3291, 3220, 3062, 2191 (br.), 1748,
max
1
1
1
0
1
3
1
639 cm . H NMR d 12.38 (br. s, 1H, NH ), 10.53 (s, 1H, NH ), 9.88 (s, 1H, NH ),
.31–7.26 (m, 1H, CHarom.), 7.11, 7.09 (d, J ¼ 8.0 Hz, 1H, CHarom.), 7.02–6.97 (m, 2H,
7
13
CHarom.), 6.37 (s, 2H, NH ), 5.33 (s, 2H, NH ). C NMR d 176.1, 160.6, 156.9, 152.3,
2
2
137.2, 130.3, 125.8, 125.2, 122.2, 117.9, 117.1, 116.1, 115.3, 83.7, 70.0, 66.1. Anal. Calcd.
for C H N O (345.31): C, 55.65; H, 3.21; N, 36.51. Found: C, 55.55; H, 3.12; N, 36.47.
1
6
11 9
General procedures for synthesis of compounds 5a,b
A solution of 2-amino-4-aryl-buta-1,3-diene-1,1,3-tricarbonitrile (1, Ar ¼ 3-OCH -4-
3
OHC H -; 4-(CH ) N-C H -) (0.01 mol) with/without cyanoguanidine 2 (0.01 mol,
6
3
3 2
6
4
0.84 g) was refluxed in 60 mL sodium methoxide 0.5 M (0.69 g sodium metal in 60 mL
methanol) for about 10 h. After completion of the reaction (monitored using TLC), the
reaction mixture was cooled to room temperature, poured into ice-cold distilled water
and neutralized to pH ꢂ 6.5 with dilute hydrochloric acid. The formed precipitate was
collected, filtered, washed several times with distilled water, dried, and recrystallized
from ethanol.
4
-Amino-2-(4-hydroxy-3-methoxyphenyl)-6-methoxypyridine-3,5-dicarbonitrile (5a)
ꢃ
ꢃ
[26]
Yield 82%; gray solid; m.p.: 264–265 C (reported m.p. 266-267 C).
IR (ATR) ꢀmax
ꢀ
1
1
3
7
6
420, 3364, 3238, 3006, 2956, 2212, 1639 cm . H NMR d 9.70 (br. s, 1H, OH),
.52–7.51 (m, 3H, NH , 1 CHarom.), 7.46–7.43 (dd, J ¼ 1.7, 8.3 Hz, 1H, CHarom.), 6.94,
2
.92 (d, J ¼ 8.3 Hz, 1H, CH
), 4.03 (s, 3H, OCH ), 3.84 (s, 3H, OCH ). Anal. Calcd.
3 3
arom.
for C H N O (296.28): C, 60.81; H, 4.08; N, 18.91. Found: C, 60.75; H, 4.01;
1
5
12 4 3
N, 18.83.