chemia - Studia

OANA MOLDOVAN, PEDRO LAMEIRAS, ERIC HENON, FLAVIA POPA, AGATHE MARTINEZ, ET ALL
SER-NH), 7.02 (1 H, bs D-NH), 7.65 (2 H, d, 3 J H,H =7.5 Hz, H-2, -6 p-NPh), 8.14
(2 H, bd, 3 J H,H =6.0 Hz, H-3, -5 p-NPh) ppm; 13 C NMR (125 MHz, [D 6 ]DMSO,
298 K): δ C 7.8, 7.9 (1 C, CH 3 ), 22.1, 22.5, 23.0, 23.1 (1 C, CH 2 -CH 3 ), 49.3,
49.37, 49.4, 49.9 (1 C, C-5 D-NH), 60.9 (1 C, C-2 SER-NH), 61.2, 61.3, 61.4,
61.5 (2 C, CH 2 OH), 70.07, 70.1, 70.2, 70.5 (1 C, C-6 D-NH), 78.2, 78.4,
78.5, 78.8 (1 C, C-4 D-NH), 93.89, 93.94 (1 C, C-2 D-NH), 123.2, 123.3,
123.4, 123.6, (2 C, C-2, -6 p-NPh), 127.6, 127.7, 127.9, 128.0 (2 C, C-3, -5
p-NPh), 146.7, 146.8, (1 C, C-1 p-NPh), 147.1, 147.17, 147.22 (1 C, C-4 p-NPh),
164.7, 164.99, 165.04, 165.3, 165.4, 165.7 (2 C, C-4, -6 s-triazine), 167.8
(1 C, C-2 s-triazine) ppm. MS (ESI+), m/z (rel. int. %) 493.1 [M+K + ] (9), 477.1
[M+Na + ] (18), 457.1 [M + +2] (35), 455.1 [M + +H] (100), 438.2 (11), 437.2 (54),
419.2 (41). [α] D 25 =-34 (0.5 % DMSO).
2-Chloro-6-{[1,3-dihydroxy-2-(hydroxymethyl)prop-2-yl]amino}-4-{[(4S,
5S)-4-(4-nitrophenyl)-1,3-dioxan-5-yl]amino}-s-triazine I-2c (84 %) yellowish
crystalline powder, mp 200-205 °C (flash column chromatography, eluent toluene :
isopropanol, 2:1 v/v). [Found: C 45.01, H 4.39, N 18.59; C 17 H 21 ClN 6 O 7 (456.12)
requires: C 44.69, H 4.63, N 18.40%]. R f 0.80 (66% toluene/i-PrOH). IR ν max.
(KBr) 3369 (s), 2950 (m), 2865 (m), 1586 (s), 1519 (s), 1418 (m), 1387 (m),
1347 (s), 1243 (m), 1175 (s), 1096 (s), 1026 (s), 967 (m), 852 (w), 804 (m),
743 (m), 711 (m), 593 (w) cm -1 . 1 H NMR (500 MHz, [D 6 ]DMSO, 353 K): δ H 3.66
(6 H, bs, CH 2 OH), 4.05 (1 H, bd, 2 J H,H =9.5 Hz, H-6-a D-NH), 4.14 (1 H, d,
2 J H,H =11.5 Hz, H-6-e D-NH), 4.36 (1 H, bs, H-5-e D-NH), 4.36, 4.53 (3 H, 2×bs,
OH), 5.00 (1 H, d, 2 J H,H =6.0 Hz, H-2-a D-NH), 5.23 (1 H, d, 2 J H,H =6.0 Hz,
H-2-e D-NH), 5.27 (1 H, bs, H-4-a, D-NH), 6.24, 6.30 (1 H, 2×bs SER-NH), 7.01
(1 H, bs D-NH), 7.65 (2 H, d, 3 J H,H =8.0 Hz, H-2, -6 p-NPh), 8.14 (2 H, bd,
3 J H,H =7.0 Hz, H-3, -5 p-NPh) ppm; 13 C NMR (75 MHz, [D 6 ]DMSO, 298 K): δ C
49.2, 49.3, 49.7 (1 C, C-5 D-NH), 59.4, 59.6, 60.1 (1 C, C-2 SER-NH), 62.1,
62.3, 62.4 (3 C, CH 2 OH), 69.9, 70.3 (1 C, C-6 D-NH), 78.0, 78.1, 78.6 (1 C,
C-4 D-NH), 93.8 (1 C, C-2 D-NH), 123.2, 123.4 (2 C, C-2, -6 p-NPh), 127.4,
127.6, 127.7 (2 C, C-3, -5 p-NPh), 146.6 (1 C, C-1 p-NPh), 147.1 (1 C, C-4
p-NPh), 164.9, 165.0, 165.2, 165.4 (2 C, C-4, -6 s-triazine), 167.6, 167.8 (1 C,
C-2 s-triazine) ppm. MS (CI, isobutane) m/z (rel. int. %) 513 [M + +HC(CH 3 ) 3 -2 H]
(20), 495 [M+K + ] (9), 457 [M + ] (100), 421 (10), 225 (11),140(10). [α] D 25 =-36 (0.5 %
DMSO).
2-Chloro-6-{[1,3-dihydroxy-2-(methyl)prop-2-yl]amino}-4-{[(2R,4S,5S)-
5-(dimethylamino)-4-(4-nitrophenyl)-1,3-dioxan-2-yl]methylamino}-s-triazine
II-3a (83 %) yellowish crystalline powder, mp 126-134 °C (flash column
chromatography, eluent toluene : ethanol, 1:5 v/v). [Found: C 47.95, H 5.51,
N 19.39; C 20 H 28 ClN 7 O 6 (497.18) requires: C 48.24, H 5.67, N 19.69%]. R f 0.80
(17% toluene/EtOH). IR ν max. (KBr) 3382 (s), 3276 (s), 2941 (m), 2878 (m),
1587 (s), 1521 (s), 1462 (m), 1412 (m), 1349 (s), 1153 (m), 1113 (m), 1057 (s),
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