The melting points were determined on a PTP instrument (Khimlaborpribor, Russia). The 3-formyl-
-hydroxycoumarin was synthesized according to the method described in [12]. The reactions were monitored
by TLC on Silufol UV-254 plates in the following solvent systems: a) CHCl ; b) CHCl –acetone, 16:1.
4
3
3
Compounds 5a,b and 6a-c (General Method). A mixture of 3-formyl-4-hydroxycoumarin 4 and the
diamine in alcohol (6-15 ml) was heated for 1-3 h and then cooled to 25°C. The precipitate was filtered off,
washed with water, recrystallized from EtOH, and dried.
3
-{[(4-Aminophenyl)amino]methylidene}-2H-chromene-2,4(3H)-dione (5a). This compound was
obtained from the aldehyde 4 (100 mg, 0.526 mmol) and p-phenylenediamine (57 mg, 0.526 mmol). Yield
-
1
1
(
18 mg (80%). Dark-yellow crystals; mp 240-242 °С. IR spectrum, ν, cm : 1612 (С=O), 1683 (O–С=O), 3212
1
NH), 3347 (N–H), 3449 (H–N–H). H NMR spectrum, δ, ppm (J, Hz): 13.61 (0.73Н, d, J , = 13.5, NH (E));
9 10
1
1.82 (0.27Н, d, J , = 14.8, NH (Z)); 8.70 (0.27Н, br. s, Н-9 (Z)); 8.66 (0.73Н, d, J = 13.5, Н-9 (E)); 7.97
9 10 9,10
(
1H, dd, J5,6 = 7.8, J5,7 = 1.5, Н-5); 7.70-7.66 (1H, m, Н-7); 7.38-7.30 (4Н, m, Н-6,8,2',6'); 6.61-6.65 (2Н, m,
+
·
+
Н-3',5'); 5.49 (2Н, s, NH ). Mass spectrum, m/z (I , %): 280 [М] (100), 173 [M-C H N ] (35), 121
2
rel
6
7
2
+
+
+·
[M-C H N -C O] (17), 108 [M-C H O ] (20), 92 [M-C H N -C O-CHO] (13). Found, %: С 68.75; Н 4.36;
6 7 2 3 10 4 3 6 7 2 3
N 10.07. C H N O . Calculated, %: С 68.57; Н 4.32; N 9.99.
1
6
12
2
3
3
-{[(2-Aminophenyl)amino]methylidene}-2H-chromene-2,4(3H)-dione (5b). This compound was
obtained from the aldehyde 4 (100 mg, 0.526 mmol) and o-phenylenediamine (114 mg, 1.052 mmol). Yield
1
1
10 mg (75%). Yellow crystals; mp 208-211°C. H NMR spectrum, δ, ppm (J, Hz): 13.43 (0.51Н, d,
J9,10 = 13.1, NH (E, s-cis)); 13.25 (0.16Н, br. s, NH (E, s-trans)); 11.99 (0.11Н, br. s, NH (Z, s-trans)); 11.65
(
(
0.22Н, br. s, NH (Z, s-cis); 8.76 (0.22Н, br. s, Н-9 (Z, s-cis)); 8.73 (0.51Н, d, J9,10 = 13.1, Н-9 (E, s-cis)); 8.61
0.11Н, br. s, Н-9 (Z, s-trans)); 8.57 (0.16Н, br. s, Н-9 (E, s-trans)); 8.02-7.93 (1H, m, Н-5); 7.76-7.67 (1H, m,
Н-7); 7.57-7.46 (1H, m, Н-6'); 7.43-7.32 (2Н, m, Н-6,8); 7.13-7.08 (1H, m, Н-4'); 6.94-6.89 (1H, m, Н-3');
+
·
+
6
[
[
.78-6.74 (1H, m, Н-5'); 5.28 (2Н, s, NH ). Mass spectrum, m/z (I , %): 280 [М] (50), 279 [М-Н] (55), 262
2 rel
+
·
+
+
+
М-Н-ОН] (4), 173 [М-С Н N ] (5), 121 [M-C H N -C O] (33), 119 [M-H-C H O ] (100), 108
6 7 2 6 7 2 3 9 4 3
М-С Н О ] (12), 105 [M-H-C H O -N] (14), 92 [М-С H N -C O-СНО] (31). Found, %: С 68.42; Н 4.38;
+
·
+·
+·
1
0
4
3
9
4
3
6
7
2
3
N 9.93. C H N O . Calculated, %: С 68.57; Н 4.32; N 9.99.
1
6
12
2
3
3
,3'-[1,2-Phenylenebis(iminomethylidene)]bis(2H-chromene-2,4(3H)-dione) (6a). This compound
was obtained from the aldehyde 4 (300 mg, 1.578 mmol) and o-phenylenediamine (114 mg, 0.526 mmol). Yield
-
1
2
3
14 mg (90%). Yellow crystals; mp 279-281°C. IR spectrum, ν, cm : 1620 (С=O), 1720 (O–С=O), 3062 (N–H),
1
435 (br., N–H). H NMR spectrum, δ, ppm (J, Hz): 13.26 (0.90Н, d, J9 = 13.8, NH (E,E)); 13.24 (0.42Н, d,
,10
J9,10 = 13.8, NH (E-part E,Z)); 12.00 (0.42Н, d, J9,10 = 14.8, NH (Z-part E,Z)); 11.98 (0.26Н, d, J9,10 = 14.8, NH
Z,Z)); 8.61 (0.42H, J9,10 = 14.8, H-9 (Z-part E,Z)); 8.59 (0.26Н, d, J9,10 = 14.8, H-9 (Z,Z)); 8.57 (0.9Н, d,
(
J9,10 = 13.8, H-9 (E,E)); 8.55 (0.42Н, d, J9,10 = 13.8, Н-9 (E-part E,Z)); 8.03-7.93 (2Н, m, Н-5); 7.79-7.67 (4Н,
m, Н-7,4',5'); 7.56-7.47 (2Н, m, Н-3',6'); 7.39-7.32 (4Н, m, Н-6,8). Mass spectrum, m/z (I , %): 304 [М-
rel
+
·
+·
+
+·
+·
С Н O ] (5), 303 [М-С Н O ] (5), 291 [М-С Н O ] (17), 278 [M-C H O ] (100), 212 [M-2C H O ] (2),
11 [M-C H O -C H O ] (4), 184 [M-2C H O -CO] (3), 183 [М-С Н O -С Н O -СО] (1), 173
M-C H O N ] (7), 158 [M-C H O -C H O ] (10), 121 [M-C H O N -C O] (28). Found, %: С 69.10;
8
4
3
8
5
3
9
5
3
10
6
3
7
+·
4
2
+
·
+·
2
[
7
4
2
+
7
5
2
7
4
2
7
4
2
7
5
2
+·
+
1
6
11
3
2
10
6
3
7
4
2
16 11
3
2
3
Н 3.66; N 6.25. C H N O . Calculated, %: С 69.03; Н 3.56; N 6.19.
2
6
16
2
6
3
,3'-[Ethane-1,2-diylbis(iminomethylidene)]bis(2H-chromene-2,4(3H)-dione) (6b). This compound
was obtained from the aldehyde 4 (200 mg, 1.052 mmol) and 1,2-diaminoethane (35 μl, 0.526 mmol). Yield 189
-1
mg (89%). Colorless crystals; mp 364-365°C. IR spectrum, ν, cm : 1631 (С=O), 1711 (O–С=O), 3253 (N–H),
1
3
434 (br., N–H). H NMR spectrum, δ, ppm (J, Hz): 11.57 (1.51Н, br. s, NH (E,E+E-part E,Z)); 10.38 (0.49Н,
br. s, NH (Z,Z+Z-part E,Z)); 8.55 (0.31Н, d, J9,10 = 15.1, Н-9 (Z-part E,Z)); 8.51 (0.18Н, d, J9,10 = 15.1, H-9
Z,Z)); 8.44 (1.20Н, d, J9,10 = 14.5, Н-9 (E,E)); 8.41 (0.31Н, d, J9,10 = 14.5, Н-9 (E-part E,Z)); 7.93-7.84 (2Н, m,
Н-5); 7.68-7.61 (2Н, m, Н-7); 7.34-7.23 (4Н, m, Н-6,8); 3.91 (4Н, s, СН СН ). Mass spectrum, m/z (I , %): 404
(
2
2
rel
+·
+·
+·
+·
+·
[
2
М] (6), 230 [M-C H O ] (9), 217 [М-С H NO ] (13), 215 [М-С H NO ] (33), 203 [М-С H NO ] (55),
1
0
6
3
10
5
+
3
10
7
3
11
7
3
+
+
+
02 [M-C H NO ] (55), 190 [М-С Н NO ] (17), 188 [M-C H NO ] (17), 175 [M-C H N O ] (54), 173
11 8 3 12 8 3 12 10 3 12 9 2 3
1
791