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P. Woisel et al. / Tetrahedron 56 (2000) 377–380
1
Harom), 7.27–7.31 (2H, m, Harom), 7.43–7.46 (3H, m, Harom),
8.13 (1H, s, Harom), 8.46 (2H, s, Harom), 9.35 (1H, s, Harom);
m/z (%): 503 (Mϩ1, 8); 457 (Mϩ1ϪNO2, 100), 365 (10);
IR (KBr, cmϪ1): 2923, 1700, 1606, 1522, 1458, 1297, 1162,
1083, 711.
triazolo[3,4-a]isoindoles 10c. Mp 276–277ЊC; H NMR
(DMSO-d6, d, J Hz): 3.93 (3H, s, OCH3), 7.35 (2H, d,
J78.9 Hz, Harom), 7.45–7.60 (5H, m, Harom), 7.94 (2H, d,
J8.9 Hz, Harom), 8.72 (1H, s, Harom), 8.77 (1H, s, Harom),
9.72 (1H, s, Harom); 13C NMR (DMSO, d): C, 183.3, 160.4,
140.6, 139.2, 138.3, 136.0, 133.6, 124.1, 107.3, 107.2; CH,
131.9, 129.0, 127.2, 125.3, 123.1, 121.0, 115.5; CH3, 55.8;
m/z (%): 496 (MϩK, 15), 480 (MϩNa, 100), 458 (Mϩ1, 5),
295 (35), 36 (30); IR (KBr, cmϪ1): 3123, 1602, 1511, 1455,
1287, 1167, 1078, 1050, 840, 732; Anal. Calcd for
C23H15N5O6: C, 60.38; H, 3.31; N, 15.32; found: C, 60.09;
H, 3.27; N, 15.06.
1-(4-Methoxy-phenyl)-1H-[1,2,4]triazol-4-iumbenzoyl-
1
2,4,6-trinitrophenylmethylide 8c. Mp 109–110; H NMR
(CDCl3, d, J Hz): 3.90 (3H, s, OCH3), 7.06 (2H, d,
J9.1 Hz, Harom), 7.22–7.37 (5H, m, Harom), 7.64 (2H, d,
J9.1 Hz, Harom), 8.29 (1H, s, Harom), 8.53 (2H, s, Harom),
9.91 (1H, s, Harom); m/z (%): 527 (MϩNa, 80), 505 (Mϩ1,
100), 459 (Mϩ1ϪNO2, 20), 175 (25); IR (KBr, cmϪ1):
2945, 1606, 1520, 1519, 1259, 1257, 1165, 914, 831, 716.
1-(4-Methoxyphenyl)-5-(4-methoxy)benzoyl-6,8-dinitro-
1H-[1,2,4]triazolo[3,4-a]isoindoles 10d. Mp 273–274ЊC;
1H NMR (DMSO-d6, d, J Hz): 3.86 (3H, s, OCH3), 3.96
(3H, s, OCH3), 7.04 (2H, d, J8.4 Hz, Harom), 7.37 (2H, d,
J8.6 Hz, Harom), 7.62 (2H, d, J8.4 Hz, Harom), 7.95 (2H,
d, J8.6 Hz, Harom), 8.76 (1H, s, Harom), 8.80 (1H, s, Harom),
9.68 (1H, s, Harom); 13C NMR (DMSO, d): C, 182.4, 162.4,
160.4, 138.9, 138.0, 135.6, 133.5, 133.2, 123.4, 107.1,
106.7; CH, 129.5, 129.0, 125.2, 123.2, 120.9, 115.5,
114.3; CH3, 55.8, 55.5; m/z (%): 525 (MϩK, 30), 510
(MϩNa, 100), 488 (Mϩ1, 5), 295 (6ϩ8), 36 (61); IR
(KBr, cmϪ1): 3097, 1589, 1560, 1510, 1303, 1258, 1164,
1078, 1021, 911, 833; Anal. Calcd for C24H17N5O7: C,
59.12; H, 3.52; N, 14.37; found: C, 58.86; H, 3.34; N, 14.28.
1-(4-Methoxy-phenyl)-1H-[1,2,4]triazol-4-ium-4-meth-
oxybenzoyl-2,4,6-trinitrophenylmethylide 8d. Mp 99–
1
100ЊC; H NMR (CDCl3, d, J Hz): 3.80 (3H, s, OCH3),
3.89 (3H, s, OCH3), 6.72 (2H, d, J8.6 Hz, Harom), 7.04
(2H, d, J9.0 Hz, Harom), 7.24 (2H, d, J8.6 Hz, Harom),
7.65 (2H, d, J9.0 Hz, Harom), 8.30 (1H, s, Harom), 8.49
(2H, s, Harom), 9.95 (1H, s, Harom); m/z (%): 557 (MϩNa,
50), 535 (Mϩ1, 100), 489 (Mϩ1ϪNO2, 25), 295 (25), 175
(25); IR (KBr, cmϪ1): 2932, 1603, 1517, 1257, 1255, 1165,
1022, 833.
General procedure for the synthesis of 1H-[1,2,4]tria-
zolo[3,4-a]isoindoles. A solution of 8 (1.5 mmol) in
DMSO (20 mL) was stirred under Ar at room temperature
in the presence of piperidine (3 mmol) for 5 h without
light. Initially the solution had a deep purple colour and
progressively became red. The solution was acidified with
3N acetic acid solution and washed with water to afford a
red precipitate which was filtered and washed in boiling
EtOH.
References
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1-Benzyl-5-benzoyl-6,8-dinitro-1H-[1,2,4]triazolo[3,4-
a]isoindoles 10a. Mp 225–226ЊC; 1H NMR (DMSO-d6, d, J
Hz): 5.87 (2H, s, CH2Ar), 7.38–7.56 (10H, m, Harom), 8.45
(1H, s, Harom), 8.79 (1H, s, Harom), 9.41 (1H, s, Harom); 13C
NMR (DMSO, d): C, 183.3, 140.7, 140.3, 138.1, 136.4,
134.4, 124.1, 107.3, 107.0; CH, 132.9, 131.8, 128.9,
128.5, 128.0, 127.1, 125.1, 121.0; CH2, 54.1; m/z (%): 481
(MϩCH3CN, 30), 464 (MϩNa, 80), 442 (Mϩ1, 20), 295
(40), 91 (100), 63 (15), 36 (35); IR (KBr, cmϪ1): 2933, 1706,
1558, 1498, 1450, 1385, 1304, 1266, 1142, 1053, 732, 700;
Anal. Calcd for C23H15N5O5: C, 62.57; H, 3.43; N, 15.87;
found: C, 62.06; H, 3.38; N, 15.76.
¨
3. Krohnke, F.; Schmeiss, H. Chem. Ber. 1937, 70, 172.
¨
4. Reusching, D. B.; Krohnke, F. Chem. Ber. 1971, 104, 2103.
1-Benzyl-5-(4-methyl)benzoyl-6,8-dinitro-1H-[1,2,4]-
triazolo[3,4-a]isoindoles 10b. Mp 235–236ЊC; H NMR
5. Surpateanu, G.; Lablache-Combier, A. Heterocycles 1984, 22,
2079.
1
(DMSO-d6, d, J Hz): 2.51 (3H, s, CH3), 6.14 (2H, s,
CH2Ar), 7.26 (2H, d, J7.8 Hz, Harom), 7.37–7.50 (7H, m,
Harom), 8.69 (1H, s, Harom), 9.18 (1H, s, Harom), 9.53 (1H, s,
Harom); 13C NMR (DMSO, d): C, 183.1, 141.9, 138.1, 138.0,
136.2, 134.4, 132.8, 123.9, 107.4, 106.8; CH, 129.4, 128.9,
128.5, 128.0, 127.3, 125.1, 121.0; CH2, 54.1; CH3, 21.1; m/z
(%): 494 (MϩK, 10), 478 (MϩNa, 100), 456 (Mϩ1, 20),
295 (30), 36 (20); IR (KBr, cmϪ1): 2362, 1621, 1558, 1528,
1302, 1255, 1136, 1105; Anal. Calcd for C24H17N5O5: C,
63.28; H, 3.75; N, 15.38; found: C, 63.05; H, 3.56; N, 14.99.
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Heterocycles 1999, 4, 51.
¨
7. Krohnke, F. Ber. Dtsch. Chem. Ges. 1935, 68, 1177.
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1-(4-Methoxyphenyl)-5-benzoyl-6,8-dinitro-1H-[1,2,4]-