5138
P.A. Koutentis, S.I. Mirallai / Tetrahedron 66 (2010) 5134e5139
879m, 847w, 831w, 797m, 777s, 725m, 712m; dH(300 MHz; CDCl3)
7.79 (2H, d, J 6.9, Ar H), 7.52e7.37 (4H, m, Ar H), 7.08 (1H, d, J 2.1, Ar
H), 6.81 (1H, dd, J 8.4, 2.1, Ar H), 4.77 (2H, br s, NH2); dC(75 MHz;
CDCl3) 155.6, 149.2, 135.0, 133.0, 131.0 (CH), 130.9 (CH), 128.6 (CH),
126.8 (CH), 126.3, 123.6 (CH), 121.5 (CH); m/z (EI) 268 (Mþþ4, 8%),
266 (Mþþ2, 51), 264 (Mþ, 78), 250 (13), 248 (23), 163 (38), 161 (57),
147 (12), 145 (18), 109 (20), 104 (100), 97 (10), 77 (54), 52 (23).
CDCl3) 156.4, 155.7, 147.8, 141.7, 131.0 (CH), 127.3 (CH), 122.7 (CH),
117.1 (CH), 116.6, 116.5 (CH), 114.8 (CH), 55.5 (OCH3); m/z (EI) 241
(Mþ, 71%), 224 (10), 209 (7), 181 (3), 154 (2), 123 (66), 119 (40), 108
(100), 92 (27), 80 (12), 65 (19), 52 (6).
6.1.13. (Z)-2-Amino-N-(4-fluorophenyl)benzamidine 3n. Similar treat-
mentof anthranilonitrile1b(531 mg, 4.50 mmol) withAlCl3 (593 mg,
4.50 mmol) and 4-fluoroaniline (432 mL, 4.50 mmol) heated at ca.
6.1.10. (Z)-2-Amino-(N-phenyl)benzamidine 3j. Similar treatment of
anthranilonitrile 1b (634 mg, 5.37 mmol) with AlCl3 (708 mg,
100 ꢀC for 6 h gave the title compound 3n (593.5 mg, 58%) as col-
ourless plates, mp 143.4e145 ꢀC (cyclohexane/EtOH, 95:05); Rf (t-
BuOMe) 0.67; (found: C, 68.18; H, 5.35; N,18.21. C13H12FN3 requires C,
5.37 mmol) and aniline (489 m
L, 5.37 mmol) heated at ca. 100 ꢀC for
6 h gave the title compound 3j (722 mg, 64%) as colourless plates,
68.11; H, 5.28; N,18.33%); lmax(DCM)/nm 232 (log 3 4.35), 283 (3.82),
mp 146e147 ꢀC (lit.,4c 146e147 ꢀC) (PhH); Rf (t-BuOMe) 0.62;
330 (3.71); nmax/cmꢁ13495w, 3435wand3377w(NH2), 3204w,1610s,
1572m, 1537m, 1495s, 1450w, 1406w, 1375m, 1327m, 1267w, 1234w,
1211s, 1159m, 1088w, 1009w, 872w, 839m, 789m, 744s, 710w;
dH(300 MHz; CDCl3) 7.39 (1H, d, J 7.5, Ar H), 7.22e7.17 (1H, m, Ar H),
7.08e7.02 (2H, m, ArH), 6.95e6.90(2H, m, ArH), 6.73e6.66 (2H, m, Ar
H), 5.78 (2H, br s, NH2), 4.91 (2H, br s, NH2); dC(75 MHz; CDCl3) 159.1
(d,1JCF 241.6, CF),156.5,147.7,144.5,131.2(CH),127.3(CH),123.0(d, 3JCF
7.6, CH), 117.1 (CH), 116.6 (CH), 116.3, 116.2 (d, 2JCF 21.9, CH); m/z (EI)
229 (Mþ, 52%), 212 (19),185 (3), 119 (61), 111 (100), 92 (31), 84 (9), 75
(15), 65 (27), 57 (5).
lmax(DCM)/nm 232 (log
3
3.56), 327 (2.92); nmax/cmꢁ1 3493w and
3433m (NH2), 3385w, 3205w, 1600s (Ar CH), 1579m, 1568m, 1539m,
1483m, 1446m, 1375m, 1325m, 1271m, 1238m, 1149m, 1072m,
1022m, 908m, 839m, 781m, 740s, 700m; dH(300 MHz; CDCl3)
7.43e7.35 (3H, m, Ar CH), 7.22e7.17 (1H, m, Ar CH), 7.12e7.06 (1H, m,
Ar CH), 7.02e6.99 (2H, m, Ar CH), 6.74e6.67 (2H, m, Ar CH), 5.99 (2H,
s, NH2), 4.81 (2H, s, NH2); dC(75 MHz; CDCl3) one peak missing 155.8,
148.8, 147.8, 131.1 (CH), 129.5 (CH), 127.3 (CH), 123.1 (CH), 121.8 (CH),
117.1 (CH), 116.6 (CH); m/z (EI) 211 (Mþþ1, 63%), 210 (25), 196 (27),
167 (4), 119 (40), 105 (4), 93 (100), 92 (24), 77 (19), 65 (22), 51 (16).
6.1.14. (Z)-2-Amino-N-(4-chlorophenyl)benzamidine 3o. Similar treat-
ment of anthranilonitrile 1b (463 mg, 3.92 mmol) with AlCl3 (517 mg,
3.92 mmol) and 4-chloroaniline (500 mg, 3.92 mmol) heated at ca.
100 ꢀC for 6 h gave the title compound 3o (461 mg, 48%) as colourless
plates, mp 162e163 ꢀC (lit.,4c 161e162 ꢀC) (cyclohexane/EtOH, 95:05);
6.1.11. (Z)-2-Amino-N-(4-methylphenyl)benzamidine
3k. Similar
treatment of anthranilonitrile 1b (551 mg, 4.66 mmol) with AlCl3
(615 mg, 4.66 mmol) and p-toluidine (500 mg, 4.66 mmol) heated
at ca. 100 ꢀC for 6 h gave first tricycloquinazoline 5 (60 mg, 12%) as
yellow cotton like fibres, mp 322e323 ꢀC (lit.,24 322e323 ꢀC); Rf
(DCM) 0.51; nmax/cmꢁ1 3480w, 3360m (NH), 1630m, 1597m, 1587m,
1506w, 1470m, 1445w, 1294s, 1182m, 1111s, 841m, 754m;
dH(300 MHz; CDCl3) 8.50 (3H, d, J 8.1, Ar CH), 7.63 (1H, dd, J 7.5, 7.5,
Ar CH), 7.55 (1H, d, J 8.1, Ar CH), 7.37 (1H, dd, J 7.5, 7.5, Ar CH); m/z
(EI) 320 (Mþ,18%), 311 (27), 293 (78),167 (41),149 (13),127 (89),118
(11), 97 (56), 91 (27), 77 (19), 71 (25). Further elution (t-BuOMe)
gave the title compound 3k (688.5 mg, 66%) as colourless plates,
mp 150e151 ꢀC (lit.,4c 152e153 ꢀC) (cyclohexane/EtOH, 95:05); Rf
Rf (t-BuOMe) 0.78; lmax(DCM)/nm 230 (log
3 4.30), 242 (4.21), 272
(3.69); nmax/cmꢁ1 3495w, 3435w and 3381w (NH2), 3206w (Ar CH),
1611s, 1580m, 1566m, 1537m, 1481m, 1400w, 1375m, 1327w, 1265w,
1240m, 1159m, 1088m, 1009m, 868w, 847w, 824w, 766w, 746m;
dH(300 MHz; CDCl3) 7.39 (1H, dd, J 7.8, 0.9, Ar CH), 7.31 (2H, d, J 8.7, Ar
CH), 7.20 (1H, dd, J 7.7, 1.5, Ar CH), 6.93 (2H, d, J 8.7, Ar CH), 6.74e6.66
(2H, m, Ar CH), 5.82 (2H, br s, NH2), 4.79 (2H, br s, NH2); dC(75 MHz;
CDCl3) 156.3, 147.7, 147.2, 131.4 (CH), 129.6 (CH), 128.4, 127.3 (CH),
123.3 (CH), 117.2 (CH), 116.7 (CH), 116.2; m/z (EI) 247 (Mþþ2, 15%), 245
(Mþ, 51), 230 (9), 228 (27), 209 (3), 192 (3), 166 (3), 136 (24), 129 (29),
127 (100), 119 (97), 105 (14), 92 (53), 75 (15), 65 (33).
(t-BuOMe) 0.33; lmax(DCM)/nm 232 (log
3 4.51), 285 (3.84), 326
(3.91); nmax/cmꢁ1 3493w, 3433w and 3387w (NH2), 3179w, 1609s,
1572m, 1537m, 1504m, 1448w, 1375m, 1325m, 1271w, 1238m,
1157m, 1105w, 1053w, 1034w, 1015w, 868w, 849w, 825m, 779w,
741s, 712w; dH(300 MHz; CDCl3) 7.41 (1H, dd, J 7.8, 1.2, Ar H),
7.22e7.15 (3H, m, Ar H), 6.90 (2H, J 8.1, Ar H), 6.74e6.66 (2H, m, Ar
H), 5.81 (2H, br s, NH2), 4.86 (2H, br s, NH2), 2.35 (3H, s, CH3);
dC(75 MHz; CDCl3) 156.1, 147.7, 146.0, 132.5, 131.0 (CH), 130.1 (CH),
127.3 (CH), 121.7 (CH), 117.1 (CH), 116.6, 116.6 (CH), 20.8 (CH3); m/z
(EI) 226 (Mþþ1,10%), 225 (Mþ, 99), 208 (16),119 (22),107 (100),106
(94), 92 (27), 77 (11), 65 (28).
6.1.15. (Z)-2-Amino-N-(4-bromophenyl)benzamidine 3p. Similar treat-
ment of anthranilonitrile 1b (344 mg, 2.91 mmol) with AlCl3
(3.84 mg, 2.91 mmol) and 4-bromoaniline (500 mg, 2.91 mmol)
heated at ca. 100 ꢀC for 6 h gave the title compound 3p (358 mg, 43%)
as colourless plates, mp 167e168 ꢀC (lit.,4c 167e168 ꢀC) (cyclohexane/
EtOH, 95:05); Rf (t-BuOMe) 0.76; lmax(DCM)/nm 232 (log 3 4.48), 241
(4.46), 280 (4.13), 331 (3.88); nmax/cmꢁ1 3495w, 3433w and 3383w
(NH2), 3211w (Ar CH), 1609s, 1574m, 1566m, 1537m, 1479m, 1396w,
1375m, 1327w, 1242m, 1159m, 1095w, 1070m, 1005m, 868w, 847w,
822w, 766w, 746s, 710w; dH(300 MHz; CDCl3) 7.46 (2H, d; J 8.4, Ar H),
7.39 (1H, d, J 7.8, Ar H), 7.23e7.16 (1H, m, Ar H), 6.87 (2H, d, J 8.4, Ar
H), 6.74e6.66 (2H, m, Ar H), 5.80 (2H, br s, NH2), 4.80 (2H, br s, NH2);
dC(75 MHz; CDCl3) one peak missing 156.3, 147.8, 132.6 (CH), 131.4
(CH), 127.4 (CH), 123.8 (CH), 117.2 (CH), 116.8 (CH), 116.2, 116.1; m/z
(EI) 291 (Mþþ2, 34%), 289 (Mþ, 35), 274 (14), 272 (14), 236 (17), 209
(4), 193 (5), 173 (54), 171 (56), 119 (100), 105 (18), 92 (57), 76 (16), 65
(52), 52 (10).
6.1.12. (Z)-2-Amino-N-(4-methoxyphenyl)benzamidine 3l. Similar
treatment of anthranilonitrile 1b (959 mg, 8.12 mmol) with AlCl3
(535 mg, 4.06 mmol) and p-anisidine (500 mg, 4.06 mmol) heated
at ca. 100 ꢀC for 8 h gave first tricycloquinazoline 5 (260 mg, 30%) as
yellow cotton like fibres, mp 322e323 ꢀC (lit.,24 322e323 ꢀC);
identical to that described above. Further elution (t-BuOMe) gave
the title compound 3l (545 mg, 56%) as cream coloured plates, mp
148e149 ꢀC (PhH); Rf (t-BuOMe) 0.41; (found: C, 69.66; H, 6.30; N,
17.37. C14H15N3O requires C, 69.69; H, 6.27; N, 17.41%); lmax(DCM)/
nm 231 (log
3
5.26), 296 (4.70), 327 (4.67); nmax/cmꢁ1 3482w,
6.1.16. (Z)-2-Amino-N-(3,4-dichlorophenyl)benzamidine 3r. Similar
treatment of anthranilonitrile 1b (364 mg, 3.09 mmol) with AlCl3
(407 mg, 3.09 mmol) and 3,4-dichloroaniline (500 mg, 3.09 mmol)
heated at ca. 100 ꢀC for 6 h gave the title compound 3r (305.5 mg,
35%) as colourless plates, mp 129e130 ꢀC (lit.,4c 130e131 ꢀC) (cy-
clohexane/EtOH, 95:05); Rf (t-BuOMe) 0.90; (found: C, 55.64; H,
3.98; N, 14.98. C13H11Cl2N3 requires C, 55.73; H, 3.96; N, 15.00%);
3441w and 3383w (NH2), 3192w (Ar CH), 2962w, 2926w and
2835w (CH3), 1606s, 1574m, 1537m, 1500s, 1470m, 1456w, 1414w,
1373m, 1327m, 1285m, 1234s, 1182m, 1169m, 1155m, 1099m,
1032m, 932m, 901m, 870m, 849m, 827m, 783m, 737s, 714m;
dH(300 MHz; CDCl3) 7.41 (1H, dd, J 8.0, 1.1, Ar H), 7.18 (1H, ddd, J 7.7,
7.7,1.5, Ar H), 6.92 (4H, br s, Ar H), 6.73e6.66 (2H, m, Ar H), 5.99 (2H,
br s, NH2), 4.86 (2H, br s, NH2), 3.81 (3H, s, CH3O); dC(75 MHz;
lmax(DCM)/nm 230 (log
3
4.35), 242 (4.27), 287 (3.75); nmax/cmꢁ1