Helvetica Chimica Acta – Vol. 97 (2014)
451
7-Amino-6-imino-9-phenyl-6H-benzo[c]chromene-8-carbonitrile (3a). Yield: 255 mg (82%). Yellow
powder. M.p. 3008. IR: 3438, 3349 (NH , NH), 2206 (CN), 1607 (C¼N), 1559, 1471, 1424 (Ar), 1261
2
1
(
CꢀO). H-NMR: 7.47 (t, J ¼ 7.6, 1 H); 7.51 (t, J ¼ 8.8, 1 H); 7.54 (s, 2 H); 7.57 (s, 1 H); 7.59 – 7.60 (m,
2
H); 7.70 (t, J ¼ 8.0, 1 H); 7.78 (t, J ¼ 8.0, 1 H); 8.34 (s, 1 H); 8.41 (d, J ¼ 7.6, 2 H); 8.58 (d, J ¼ 8.0, 1 H).
13
C-NMR: 102.5; 104.7; 116. 5; 117.3; 117.9; 124.8; 125.2; 125.3; 127.7; 128.7; 130.7; 133.1; 137.9; 138.6;
þ
1
51.7; 155.4; 159.9; 162.1. EI-MS (70 eV): 311.34 (17, M ), 272 (12), 236 (10), 171 (25), 149 (25), 105
(
100), 97 (33), 83 (62), 69 (96). Anal. calc. for C H N O (311.34): C 77.16, H 4.21, N 13.50; found: C
20 13 3
7
7.09, H 4.15, N 13.46.
-Amino-6-imino-9-(4-methylphenyl)-6H-benzo[c]chromene-8-carbonitrile (3b). Yield: 279 mg
7
(
1
2
86%). Yellow powder. M.p. 300 – 3028. IR: 3441, 3347, 3170 (NH , NH), 2206 (CN), 1603 (C¼N),
2
1
479, 1424 (Ar), 1265 (CꢀO). H-NMR: 2.41 (s, 3 H); 7.39 (d, J ¼ 7.6, 2 H); 7.40 (t, J ¼ 7.2, 1 H); 7.50 (s,
H); 7.52 (s, 1 H); 7.54 (d, J ¼ 7.2, 1 H); 7.71 (t, J ¼ 7.2, 1 H); 8.33 (d, J ¼ 7.6, 2 H); 8.34 (s, 1 H); 8.60 (d,
13
J ¼ 7.2, 1 H). C-NMR: 21.0; 102.4; 104.3; 116.5; 117.3; 117.9; 124.8; 125.2; 125.3; 127.7; 129.4; 133.1;
þ
þ
1
(
(
35.0; 138.4; 140.7; 151.7; 155.5; 159.1; 162.1. EI-MS (70 eV): 326 (29, [M þ 1] , 29), 325 (100, M ), 324
7), 311 (5), 149 (25), 118 (16), 105 (35), 95 (16), 81 (45), 69 (71), 55 (25). Anal. calc. for C H N O
21
15
3
325.37): C 77.52, H 4.65, N 12.91; found: C 77.49, H 4.72, N 12.81.
-Amino-6-imino-2-methoxy-9-phenyl-6H-benzo[c]chromene-8-carbonitrile (3c). Yield: 283 mg
7
(
1
83%). Yellow powder. M.p. 3008. IR: 3303, 3177 (NH and NH), 2203 (CN), 1596 (C¼N), 1480,
2
1
420 (Ar), 1261 (CꢀO). H-NMR: 3.91 (s, 3 H); 7.25 (d, J ¼ 7.6, 1 H); 7.44 (d, J ¼ 7.6, 1 H); 7.47 (s, 2 H);
13
7
1
.55 – 7.70 (m, 4 H); 8.00 (s, 1 H); 8.34 (s, 1 H); 8.42 (d, J ¼ 7.2, 1 H). C-NMR: 57.7; 103.8; 106.3; 109.0;
18.1; 119.2; 120.6; 122.1; 129.4; 130.3; 132.2; 139.5; 140.1; 147.4; 157.1; 158.0; 160.6; 163.1; 163.3. EI-MS
þ
(
70 eV): 341 (M ), 239 (3), 200 (83), 185 (12), 168 (100), 140 (43), 128 (35), 102 (35), 77 (25). Anal.
calc. for C H N O (341.37): C 73.89, H 4.43, N 12.31; found: C 73.97, H 4.34, N 12.20.
21
15
3
2
6-Amino-13,14-dihydro-7-imino-7H-phenanthro[2,1-c]chromene-5-carbonitrile (3d). Yield: 269 mg
(
80%). Yellow powder. M.p. > 3008. IR: 3464, 3354, 3184 (NH , NH), 2209 (CN), 1605 (C¼N), 1548,
2
1
1
1
1
1
1
478 (Ar), 1226 (CꢀO). H-NMR: 2.84 – 2.90 (m, 2 H); 3.00 – 3.07 (m, 2 H); 7.18 (s, 2 H); 7.37 (d, J ¼ 7.6,
H); 7.42 (t, J ¼ 7.6, 1 H); 7.45 (d, J ¼ 7.6, 1 H); 7.50 (t, J ¼ 7.6, 1 H); 7.57 (t, J ¼ 7.6, 1 H); 7.64 (t, J ¼ 7.6,
13
H); 7.95 (d, J ¼ 7.6, 1 H); 7.98 (d, J ¼ 7.6, 1 H); 8.12 (s, 1 H). C-NMR: 27.6; 30.6; 101.6; 115.7; 117.1;
19.3; 122.5; 124.4; 125.1; 126.1; 126.5; 127.0; 128.4; 128.9; 130.7; 131.3; 131.9; 132.7; 151.3; 154.8; 160.1;
þ
63.1. EI-MS (70 eV): 336 ([M – 1] ), 300 (13), 236 (100), 209 (48), 181 (75), 171 (58), 140 (30), 127
(
38), 115 (37), 91 (36), 77 (16). Anal. calc. for C H N O (337.38): C 78.32, H 4.48, N 12.45; found: C
22 15 3
7
8.45, H 4.61, N 12.34.
-Amino-13,14-dihydro-7-imino-9-methoxy-7H-phenanthro[2,1-c]chromene-5-carbonitrile (3e).
6
Yield: 267 mg (73%). Green-yellow powder. M.p. > 3008. IR: 3450, 3344, (NH , NH), 2212 (CN),
2
1
1
3
1
3
1
632 (C¼N), 1552, 1474 (Ar), 1275, 1207 (CꢀO). H-NMR: 2.94 – 2.97 (m, 2 H); 3.02 – 3.17 (m, 2 H);
.94 (s, 3 H); 7.03 (d, J ¼ 7.6, 1 H); 7.13 (s, 2 H); 7.18 (d, J ¼ 7.6, 1 H); 7.24 (t, J ¼ 7.6, 1 H); 7.32 (t, J ¼ 7.6,
13
H); 7.42 (t, J ¼ 7.2, 1 H); 7.90 (d, J ¼ 7.2, 1 H); 8.14 (d, J ¼ 7.2, 1 H); 8.36 (br. s, 1 H). C-NMR: 28.4;
0.7; 55.9; 103.3; 111.5; 113.7; 114.5; 119.5; 120.7; 126.5; 127.0; 127.4; 128.9; 129.4; 129.7; 130.7; 132.6;
þ
33.8; 148.1; 151.5; 153.8; 158.5; 162.5. EI-MS (70 eV): 367 (100, M ), 350 (30), 334 (16), 304 (20), 267
(
37), 243 (16), 201 (16), 167 (15), 126 (15). Anal. calc. for C H N O (367.40): C 75.19, H 4.66, N 11.44;
23 17 3 2
found: C 75.33, H 4.71, N 11.35.
6
-Amino-13,14-dihydro-7-imino-11-methoxy-7H-phenanthro[2,1-c]chromene-5-carbonitrile (3f).
Yield: 321 mg (85%). Yellow powder. M.p. > 3008. IR: 3394, 3336, 3221 (NH , NH), 2221, 2185
2
1
(
3
1
1
CN), 1655 (C¼N), 1582, 1498 (Ar), 1208 (CꢀO). H-NMR: 2.82 – 2.90 (m, 2 H); 3.00 – 3.04 (m, 2 H);
.73 (s, 3 H); 7.27 (d, J ¼ 8.00, 1 H); 7.36 (d, J ¼ 8.00, 1 H); 7.39 (s, 2 H); 7.44 (t, J ¼ 7.2, 1 H); 7.55 (t, J ¼ 7.2,
13
H); 7.64 (s, 1 H); 7.72 (d, J ¼ 7.6, 1 H); 7.89 (d, J ¼ 7.6, 1 H); 8.30 (s, 1 H). C-NMR: 23.3; 25.2; 55.5;
02.5; 111.4; 113.4; 114.4; 120.9; 122.9; 126.2; 126.7; 128.2; 128.6; 129.1; 129.4; 131.6; 133.3; 133.8; 149.8;
þ
1
51.5; 155.6; 158.7; 163.5. EI-MS (70 eV): 367 (100, M ), 350 (30), 336 (20), 304 (20), 279 (20), 267 (37),
1
67 (6), 139 (13), 126 (15). Anal. calc. for C H N O (367.40): C 75.19, H 4.66, N 11.44; found: C 75.33,
23
17
3
2
H 4.78, N 11.33.
7-Amino-6-imino-9-phenyl-6H-benzo[c]chromene-6a,8(10aH)-dicarbonitrile (7a). Yellow powder.
M.p. 2848. IR: 3444, 3216 (NH , NH), 2360, 2207 (CN), 1602 (C¼N), 1525, 1414, 1424 (Ar), 1255 (CꢀO).
2
þ
EI-MS (70 eV): 338 (27, M ), 336 (100), 311 (10), 301 (20), 272 (30), 168 (12), 104 (10), 91 (11), 77 (22).