Y. C. Kong et al. / Tetrahedron 56 (2000) 7153–7161
7159
3056, 1590, 1465 cmϪ1; MS (m/z) 274 (Mϩ, 54%), 153
(100), 121 (31). Anal. Calcd for C14H8F2N2S: C, 61.30; H,
2.94; N, 10.21; S, 11.69. Found: C, 61.25; H, 2.93; N, 10.16;
S, 11.48.
was added m-CPBA (57–86%, 0.11–0.45 mmol). The
mixture was stirred for an appropriate time at room tempera-
ture. After removal of the solvent in vacuo, the residue was
chromatographed on a silica gel column (2×8 cm). Elution
with a mixture of benzene and n-hexane (1:4) gave 8.
Elution with a mixture of EtOAc and acetone gave an
unknown mixture 9. Attempted purification of 9 by recrys-
tallization from a mixture of acetone and n-hexane has been
unsatisfactory. A mixture of CHCl3 and MeOH (10:1) was
used as a solvent for the reaction of 3h. Reaction time and
yields of 8 and 9, and melting points of 8 are summarized in
Table 2.
1-Amino-3,5-diphenyl-1,2,4,6-thiatriazine 1-oxide (5a).
Mp 242–243ЊC (CH2Cl2–n-hexane); 1H NMR (CDCl3–
DMSO-d6) d 7.47–7.58 (m, 6H), 7.62 (s, 2H), 8.51 (d,
J7.8 Hz, 4H); 13C NMR (CDCl3–DMSO-d6) d 128.9,
129.2, 133.1, 136.7, 169.6; IR (KBr) 3328, 3232, 1491,
1417, 1251 cmϪ1; FAB MS (m/z) 285 ((Mϩ1)ϩ, 76%),
136 ((C6H5CNSϩ1)ϩ, 67), 104 ((C6H5CNϩ1)ϩ, 18). Anal.
Calcd for C14H12N4OS: C, 59.14; H, 4.25; N, 19.70; S,
11.28. Found: C, 59.08; H, 4.19; N, 19.58; S, 11.09.
2-(3-Chlorophenyl)-4,6-diphenyl-1,3,5-triazine (8a). Mp
1
194–195ЊC (CH2Cl2–n-hexane); H NMR (CDCl3) d 7.53
1-Amino-3,5-di(t-butylphenyl)-1,2,4,6-thiatriazine 1-oxide
(5c). Mp 230–201ЊC (CH2Cl2–n-hexane); 1H NMR (CDCl3)
d 1.37 (s, 18H), 5.20 (s, 2H), 7.51 (d, J8.6 Hz, 4H), 8.42 (d,
J8.6 Hz, 4H); 13C NMR (CDCl3) d 31.1, 35.0, 125.2, 128.7,
133.4, 156.1, 169.5; IR (KBr) 3392, 3280, 1475, 1417,
1257 cmϪ1; FAB MS (m/z) 397 ((Mϩ1)ϩ, 100%), 192
(((CH3)3CC6H4CNSϩ1)ϩ, 0.3), 160 (((CH3)3CC6H4CNϩ1)ϩ,
43). Anal. Calcd for C22H28N4OS: C, 66.63; H, 7.12; N, 14.13;
S, 8.09. Found: C, 66.58; H, 7.01; N, 14.04; S, 7.98.
(dd, J7.7, 7.8 Hz, 1H), 7.58–7.66 (m, 7H), 8.68 (d,
J7.7 Hz, 1H), 8.76–8.82 (m, 5H); IR (KBr) 3056, 1584,
1516, 1440, 1360, 1020, 755, 684 cmϪ1; MS (m/z) 343 (Mϩ,
60%), 137 (63), 103 (100). Anal. Calcd for C21H14ClN3: C,
73.36; H, 4.10; N, 12.22. Found: C, 73.00; H, 4.09; N, 12.27.
2-(3-Chlorophenyl)-4,6-di(4-t-butylphenyl)-1,3,5-triazine
1
(8c). Mp 143–145ЊC (n-hexane); H NMR (CDCl3) d 1.43
(s, 18H), 7.53 (dd, J7.7, 7.8 Hz, 1H), 7.59 (d, J7.7 Hz,
1H), 7.62 (d, J8.5 Hz, 4H), 8.67 (d, J7.8 Hz, 1H), 8.69
(d, J8.5 Hz, 4H), 8.75 (s, 1H); IR (KBr) 3056, 2944, 1571,
1507, 1360, 1014, 819, 787 cmϪ1. Anal. Calcd for
C29H30ClN3: C, 76.38; H, 6.63; N, 9.21. Found: C, 76.19;
H, 6.55; N, 9.13.
1-Amino-3,5-di(4-bromophenyl)-1,2,4,6-thiatriazine 1-
1
oxide (5e). Mp (dec) 224–226ЊC (CH2Cl2–n-hexane); H
NMR (DMSO-d6) d 7.63 (d, J8.6 Hz, 4H), 7.75 (s, 2H),
8.37 (d, J8.6 Hz, 4H); 13C NMR (DMSO-d6) d 127.2,
130.3, 131.4, 135.0, 168.4; IR (KBr) 3360, 3216, 1577,
1478, 1417, 1248 cmϪ1; FAB MS (m/z) 441 ((Mϩ1)ϩ,
48%), 443 ((Mϩ1)ϩϩ2, 100), 445 ((Mϩ1)ϩϩ4, 58), 214
((BrC6H4CNSϩ1)ϩ, 0.6), 182 ((BrC6H4CNϩ1)ϩ, 36). Anal.
Calcd for C14H10Br2N4OS: C, 38.08; H, 2.28; N, 12.67; S,
7.25. Found: C, 38.14; H, 2.31; N, 12.59; S, 7.08.
2-(3-Chlorophenyl)-4,6-di(3,4-dimethylphenyl)-1,3,5-tri-
azine (8d). Mp 179–180ЊC (n-hexane); 1H NMR (CDCl3) d
2.40 (s, 6H), 2.45 (s, 6H), 7.34 (d, J8.0 Hz, 2H), 7.52 (dd,
J7.6, 7.9 Hz, 1H), 7.59 (d, J7.9 Hz, 1H), 8.50 (d,
J8.0 Hz, 2H), 8.51 (s, 2H), 8.66 (d, J7.6 Hz, 1H), 8.74
(s, 1H); IR (KBr) 3040, 1510, 1344, 1020, 780 cmϪ1; MS
(m/z) 399 (Mϩ, 18%), 207 (10), 139 (100), 111 (18). Anal.
Calcd for C25H22ClN3: C, 75.08; H, 5.54; N, 10.51. Found:
C, 75.16; H, 5.51; N, 10.38.
1-Amino-3,5-di(3-chlorophenyl)-1,2,4,6-thiatriazine 1-
1
oxide (5g). Mp 200–201ЊC (CH2Cl2–n-hexane); H NMR
(CDCl3) d 5.30 (s, 2H), 7.47 (dd, J8.0, 8.4 Hz, 2H), 7.59
(d, J8.4 Hz, 2H), 8.40 (d, J8.0 Hz, 2H), 8.48 (s, 2H); 13C
NMR (CDCl3) d 127.4, 129.0, 130.0, 132.8, 134.6, 138.2,
168.8; IR (KBr) 3376, 3264, 1491, 1430, 1276 cmϪ1; FAB
MS (m/z) 353 ((Mϩ1)ϩ, 100%), 355 ((Mϩ1)ϩϩ2, 70), 357
((Mϩ1)ϩϩ4, 15), 170 ((ClC6H4CNSϩ1)ϩ, 0.9), 138
((ClC6H4CNϩ1)ϩ, 34). Anal. Calcd for C14H10Cl2N4OS:
C, 47.60; H, 2.85; N, 15.86; S, 9.08. Found: C, 47.48; H,
2.78; N, 15.79; S, 8.96.
2,4,6-Tri(3-chlorophenyl)-1,3,5-triazine (8g). Mp 218–
1
219ЊC (CH2Cl2–n-hexane); H NMR (CDCl3) d 7.55 (t,
J7.7 Hz, 3H), 7.63 (d, J7.7 Hz, 3H), 8.66 (d,
J7.7 Hz, 3H), 8.72 (s, 3H); IR (KBr) 3056, 1619, 1516,
1440, 1350, 1065, 1024, 771, 710, 672 cmϪ1. Anal. Calcd
for C21H12Cl3N3: C, 61.12; H, 2.93; N, 10.18. Found: C,
60.04; H, 2.88; N, 10.06.
1-Amino-3,5-di(4-fluorophenyl)-1,2,4,6-thiatriazine 1-
oxide (5h). Mp 260–261ЊC (CH2Cl2–n-hexane); H NMR
2-(3-Chlorophenyl)-4,6-di(4-fluorophenyl)-1,3,5-triazine
(8h). Mp 225–226ЊC (n-hexane); 1H NMR (CDCl3) d 7.23–
7.29 (m, 4H), 7.52 (dd, J7.8, 7.9 Hz, 1H), 7.60 (d,
J7.8 Hz, 1H), 8.62 (d, J7.9 Hz, 1H), 8.69 (s, 1H),
8.74–8.79 (m, 4H); IR (KBr) 3088, 1593, 1516, 1408,
1356, 1011, 819, 784 cmϪ1; MS (m/z) 379 (Mϩ, 47%),
137 (51), 121 (100). Anal. Calcd for C21H12ClF2N3:
C, 66.41; H, 3.18; N, 11.06. Found: C, 66.29; H, 3.15; N,
11.08.
1
(CDCl3–DMSO-d6) d 6.66 (s, 2H), 7.13–7.18 (m, 4H),
8.49–8.54 (m, 4H); 13C NMR (CDCl3)
d
115.6
(J22 Hz), 131.7 (J9.2 Hz), 131.8, 166.2 (J255 Hz),
169.9; IR (KBr) 3363, 3236, 1601, 1501, 1434,
1267 cmϪ1; FAB MS (m/z) 321 ((Mϩ1)ϩ, 88%), 154
((FC6H4CNSϩ1)ϩ, 100), 122 ((FC6H4CNϩ1)ϩ, 20). Anal.
Calcd for C14H10F2N4OS: C, 52.50; H, 3.15; N, 17.49; S,
10.01. Found: C, 52.89; H, 3.74; N, 17.20; S, 10.34.
1
Unknown compound 9a. H NMR (DMSO-d6) d 7.43–
7.52 (m, 6H), 8.27 (d, J7.9 Hz, 4H); 13C NMR (DMSO-
d6) d 128.5, 128.8, 131.8, 137.3, 165.1; IR (KBr)
1500, 1446, 1401, 1132 cmϪ1; FAB MS (m/z) 329 (Mϩ,
100%).
General procedure for the preparation of 2,6-diaryl-4-
(3-chlorophenyl)-1,3,5-triazines 8
To a solution of 3 (0.074–0.22 mmol) in CHCl3 (6–10 mL)