chemia - Studia

OANA MOLDOVAN, PEDRO LAMEIRAS, ERIC HENON, FLAVIA POPA, AGATHE MARTINEZ, ET ALL
45.45, 45.55, 45.64, 45.7 (2 C, C-2, -6 Piperazine), 48.8, 48,9 (1 C, C-5 D-NH),
60.2 (1 C, C-2 SER-NH), 62.5, 62.9 (2 C, CH 2 OH), 70.5, 70,6 70.8, 70.9 (1 C,
C-6 D-NH), 78.5, 78.95, 79.04 (1 C, C-4 D-NH), 93.9, 94.0 94.1 (1 C, C-2 D-NH),
123.2, 123.5 (2 C, C-2, -6 p-NPh), 127.3, 127.6 (2 C, C-3, -5 p-NPh), 147.0,
147.1 (2 C, C-1, -4 p-NPh), 164.5 (1 C, C-2 s-triazine), 165.4, 165.6 (2 C, C-4,
-6 s-triazine) ppm. MS (ESI+), m/z (rel. int. %) 505.3 [M + +H] (100), 403.2 (25),
224.0 (12), 208.0 (37). [α] D 25 =+42 (0.5 % DMSO).
1-{6-{[1,3-Dihydroxy-2-(hydroxymethyl)prop-2-yl]amino}-4-[(4S,5S)-4-
(4-nitrophenyl)-1,3-dioxan-5-yl]amino}-s-triazin-2-yl}-iperazine I-4c (86 %)
yellowish crystalline powder, mp 146-157 °C (flash column chromatography,
eluent ethanol : aq. NH 3 25% 9:1 v/v). [Found: C 50.11, H 5.88, N 21.90;
C 21 H 30 N 8 O 7 (506.22) requires: C 49.80, H 5.97, N 22.12%]. R f 0.71 (90%
ethanol/aq. NH 3 25%). IR ν max (KBr) 3392 (m), 2943 (m), 2856 (m), 1549 (s),
1504 (s), 1446 (m), 1346 (s), 1273 (m), 1174 (m), 1105 (m), 1025 (m), 872 (w),
852 (w), 809 (m), 744 (w), 711 (w), 584 (w) cm -1 . 1 H NMR (500 MHz, [D 6 ]DMSO,
353 K): δ H 2.65 (3 H, t, 3 J H,H =4.8 Hz, H-3, -5 Piperazine), 2.68 (3 H, s, OH), 3.46
(4 H, t, 3 J H,H =5.0 Hz, H-2, -6 Piperazine), 3.62 (6 H, s, CH 2 OH), 4.02 (1 H, d,
2 J H,H =11.0 Hz, H-6-a D-NH), 4.11 (1 H, 2 J H,H =11.0 Hz, H-6-e D-NH), 4.40 (1 H,
bd, 3 J H,H = 7.5 Hz, H-5-e D-NH), 5.00 (1 H, d, 2 J H,H =6.5 Hz, H-2-a D-NH),
5.22 (1 H, s, H-4-a D-NH), 5.23 (1 H, d, 2 J H,H =5.5 Hz, H-2-e D-NH), 5.43 (1 H,
s SER-NH), 5.61 (1 H, d, 3 J H,H =9.5 Hz D-NH), 7.63 (2 H, d, 3 J H,H =9.0 Hz, H-2, -
6 p-NPh), 8.12 (2 H, d, 3 J H,H =8.0 Hz, H-3, -5 p-NPh) ppm; 13 QC NMR (75 MHz,
[D 6 ]DMSO, 298 K): δ C 43.9 (2 C, C-3, -5 Piperazine), 45.4 (3 C, C-2, -6
Piperazine), 48.8 (1 C, C-5 D-NH), 61.0, 61.3 (4 C, C-2, CH 2 OH, SER-NH),
70.5, 70.7 (1 C, C-6 D-NH), 78.4, 78,8 (1 C, C-4 D-NH), 93.9 (1 C, C-2 D-NH),
123,1, 123,3 (2 C, C-2, -6 p-NPh), 127.1, 127.4 (2 C, C-3, -5 p-NPh), 146.9
(2 C, C-1, -4 p-NPh), 164.2 (1 C, C-2 s-triazine), 165.0, 165.2, 165.4, 165.5
(2 C, C-4, -6 s-triazine) ppm. MS (DCI positive, 200 eV, isobutane), m/z (rel.
int. %) 563 [M + +HC(CH 3 ) 3 -2 H] (9), 507 [M + +H] (100), 489 (10), 477 (10), 404
(10),282 (5), 225 (10), 115 (8), 104 (20), 87 (75). [α] D 25 =+24 (0.5 % DMSO).
1-{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-triazin-
2-yl}-piperazine II-5a (71 %) yellowish crystalline powder, mp 118-123 °C (flash
column chromatography, eluent ethanol : aq. NH 3 25% 9:1 v/v). [Found: C 52.88,
H 7.07, N 22.85; C 24 H 37 N 9 O 6 (547.29) requires: C 52.64, H 6.81, N 23.02%]. R f
0.57 (90% ethanol/aq. NH 3 25%). IR ν max (KBr) 3295 (s), 2932 (s), 2860 (s),
1670 (m), 1548 (s), 1516 (s), 1444 (s), 1348 (s), 1296 (m), 1151 (m), 1113 (m),
1055 (m), 1016 (m), 852 (m), 809 (m), 710 (m), 668 (w), 572 (w) cm -1 . 1 H NMR
(500 MHz, [D 6 ]DMSO, 353 K): δ H 1.27 (3 H, s, CH 3 ), 2.23 [6 H, s, N(CH 3 ) 2 ],
2.69 (4 H, t, 3 J H,H =4.8 Hz, H-3, -5 Piperazine), 2.86 (1 H, dd as t, 3 J H,H =2.8 Hz,
H-5-e D-NH), 3.496 (2 H, dd as t, 3 J H,H =4.5 Hz, CH 2 NH), 3.504 (2 H, d,
2 J H,H =10.0 Hz, CH 2 OH), 3.58 (4 H, t, 3 J H,H =5.3 Hz, H-2, -6 Piperazine), 3.60
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