620
T. Guckꢀ, J. Slouka, M. Maloꢁ and I. Fryꢂová
Vol 43
Anal. Calcd. for C11H10N4O3: 53,66 C, 4,09 H, 22,75 N.
Found: 53,38 C, 4,43 H, 22,82 N.
Anal. Calcd. for C16H13N4O3Cl: 61.45 C, 4.19 H, 17.91 N.
Found: 61.58 C, 4.63 H, 17.84 N.
3-Phenyl-(2-aminobenzyl)-1H-[1,2,4]triazin-6-one (7b).
3-(3-Chlorophenyl)-5-(2-aminobenzyl)-1H-[1,2,4]triazin-6-one
(7h).
Yield: 57% (method A), 86% (method B), mp: 162-165°C
(ethanol), ir: 3325, 3310, 3279, 1640, 1613, 1521, 1485, 1421,
1403, 1322, 1129, 1090, 1033, 917, 755, 689, 1H nmr (DMSO):
3.15(d, 1H, CH2, J=16.5), 3.88(d, 1H, CH2, J=16.5), 6.38(d, 1H,
ArH, J=7.8), 6.59(t, 1H, ArH, J=7.2), 6.94(t, 1H, ArH, J=7.8),
7.05(d, 1H, ArH, J=7.2), 7.41-7.47(m, 4H, ArH, NH), 7.78(d,
2H, ArH, J=8.1), 8.28(s, 1H, NH), 10.81(s, 1H, NH), 13C NMR
(DMSO): 73.87, 107.65, 117.79, 124.06, 126.15, 126.69,
127.51, 128.64, 130.12, 133.03, 144.33, 148.94, 162.89. ms
(M++1) 279.
Yield: 92%, (method B), mp: 143-145°C, ir: 3196, 3068,
1669, 1632, 1601, 1519, 1488, 1379, 1299, 1249, 1076, 901,
749.
Anal. Calcd. for C16H13N4OCl: 61.45 C, 4.19 H, 17.91 N.
Found: 61.28 C, 4.36 H, 17.62 N.
3-Substituted-5,10-dihydro[1,2,4]triazino[6,5-b]quinolines (9) and
3-Substituted-1,5-dihydro[1,2,4]triazino[6,5-b]quinolines (10).
General Procedures.
Method A.
Anal. Calcd. for C16H14N4O: 69.05 C, 5.07 H, 20.13 N. Found:
69.06 C, 5.21 H, 19.98 N.
3-Substituted-5-(2-aminobenzyl)-1H-[1,2,4]triazin-6-one (7)
(1.00 mmol) was refluxed for 10 hours in acetic acid (5.0 ml).
After cooling to room temperature, the solvent was evaporated
in vacuo. The crude product was crystallized from an
appropriate solvent.
3-(4-Methoxyphenyl)-5-(2-aminobenzyl)-1H-[1,2,4]triazin-6-
one (7c).
Yield: 73% (method A), 95% (method B), mp: 223-225°C
(ethanol-toluene (1:1)), ir: 3201, 3004, 2841, 1659, 1606, 1571,
1522, 1462, 1346, 1254, 1176, 1132, 1027, 841, 789, H nmr
1
Method B.
(DMSO): 3.14(d, 1H, CH2, J=16.5), 3.79(s, 3H, OCH3), 3.87(d,
1H, CH2, J=16.5), 6.38(d, 1H, ArH, J=7.8), 6.59(t, 1H, ArH,
J=7.2), 6.91-6.99(m, 4H, ArH, NH), 7.04(d, 1H, ArH, J=7.8),
7.72(d, 2H, ArH, J=9.0), 8.17(s, 1H, NH), 10.72(s, 1H, NH), 13
nmr: 39.1, 55.7, 73.8, 107.6, 114.0, 17.8, 124.0, 125.4, 126.2,
127.5, 128.2, 144.2, 149.0, 160.9, 162.9. ms (M++1) 309.
Anal. Calcd. for C17H16N4O2: 66.22 C, 5.23 H, 18.17 N.
Found: 66.48 C, 5.34 H, 18.15 N.
3-Substituted-5-(2-aminobenzyl)-1H-[1,2,4]triazin-6-one
(7)
(1.00 mmol) and p-toluenesulphonic acid (100 mg) was refluxed
for 5 hours in anisole (5.0 ml). The solvent was evaporated in
vacuo. The residue was then dissolved in ethanol and evaporated
again in vacuo. The residue was suspended in water (10.0 ml), the
precipitate was collected by filtration and washed with water.
C
Method C.
3-(4-Acetylaminophenyl)-5-(2-aminobenzyl)-1H-[1,2,4]triazin-
6-one (7d).
3-Substituted-5-(2-aminobenzyl)-1H-[1,2,4]triazin-6-one (7)
(1.00 mmol) was heated at 110 °C for 1 hour in phosphorous
oxychloride (3.0 ml). The mixture was evaporated in vacuo. The
residue was dissolved in dioxane (5.0 ml) and poured over
crushed ice (30 g). The precipitate was collected by filtration
and washed with water. The crude product was crystallized from
an appropriate solvent.
Yield: 51% (method B), mp: 138-140°C, ir: 3285, 3110, 3050,
1684, 1644, 1609, 1528, 1508, 1418, 1377, 1323, 1255, 1188,
1036, 848, 748.
Anal. Calcd. for C18H17N5O2: 64.47 C, 5.11 H, 20.88 N.
Found: 64.31 C, 5.19 H, 20.33 N.
3-Methyl-5,10-dihydro[1,2,4]triazino[6,5-b]quinoline (9a).
3-(4-Styryl)-5-(2-aminobenzyl)-1H-[1,2,4]triazin-6-one (7e).
Yield: 73% (method A), 76% (method C), mp: 222-225°C
(toluene) [14], ir: 3053, 1618, 1553, 1521, 1386, 1209, 1027.
Anal. Calcd. for C11H10N4: 66.65 C, 5.08 H, 28.26 N. Found:
66.37 C, 5.38 H, 27.98 N.
Yield: 43% (method A), mp: 144-146°C, ir: 3244, 3210,
3154, 3059, 3029, 1666, 1580, 1524, 1449, 1346, 1303, 1183,
1130, 973, 860, 787, 748, 693.
Anal. Calcd. for C18H16N4O: 71.04 C, 5.30 H, 18.41 N. Found:
70.82 C, 5.02 H, 18.06 N.
3-Phenyl-5,10-dihydro-[1,2,4]triazino[6,5-b]quinoline (9b).
3-(2-Thienyl)-5-(2-aminobenzyl)-1H-[1,2,4]triazin-6-one (7f).
Yield: 88% (method A), 92% (method B), 90% (method C),
mp: 251-253°C (ethanol-toluene (1:1)) [14], ir: 3070, 1634,
1553, 1488, 1393, 1323, 1233, 1048, 1023. H nmr(DMSO):
3.75(s, 2H, CH2), 6.37(d, 1H, ArH, J=7.2), 6.51(t, 1H, ArH,
J=7.2), 6.70(t, 2H, ArH, J=7.5), 6.83-7.22(m, 3H, ArH), 7.70(d,
2H, ArH, J=7.5), 9.53(s, 1H, NH), 13C nmr (DMSO): 24.10,
83.16, 96.37, 108.40, 108.84, 112.75, 114.17, 115.60, 127.52,
127.90, 132.17, 145.68, 150.63, 174.27. ms (M++1) 261.
Anal. Calcd. for C16H12N4: 73.83 C, 4.65 H, 21.52 N. Found:
73.56 C, 4.88 H, 21.32 N.
Yield: 51% (method A), mp: 149-152°C (ethanol), ir: 3263,
3019, 1662, 1578, 1520, 1342, 1290, 1132, 853, 788, 726.
Anal. Calcd. for C14H12N4OS: 59.14 C, 4.25 H, 19.70 N, 11.28
S. Found:59.21 C, 4.45 H, 19.39 N, 11.59 S.
1
3-(4-Chlorophenyl)-5-(2-aminobenzyl)-1H-[1,2,4]triazin-6-one
(7g).
Yield: 45% (method A), 94% (method B), mp: 168-170°C, ir:
3242, 3088, 1667, 1595, 1520, 1485, 1406, 1341, 1299, 1090,
1013, 961, 845, 788, 1H nmr (DMSO): 3.16(d, 1H, CH2, J=16.8),
3.89(d, 1H, CH2, J=16.8), 6.38(d, 1H, ArH, J=8.1), 6.60(t, 1H,
ArH, J=7.2), 6.94(t, 1H, ArH, J=8.1), 7.00(s, 1H, NH), 7.05(d,
1H, ArH, J=7.2), 7.50(d, 2H, ArH, J=8.7), 7.80(d, 2H, ArH,
J=8.7), 8.35(s, 1H, NH), 10.87(s, 1H, NH). ms (M++1) 313, 314.
3-(4-Methoxyphenyl)-5,10-dihydro-[1,2,4]triazino[6,5-b]-
quinoline (9c).
Yield: 90% (method A), 92% (method C), mp: 198-200
(ethanol), ir: 3185, 3055, 2899, 1609, 1548, 1503, 1458, 1393,