8a 2-(Formyl-salicyl-methylidene)imidazolidine
(7a): Colorless crystalline solid, mp 265-266 °C
(acetone). UV (MeOH): 362.4, 263, 228.4 nm. IR (KBr): 3310 (s),
3118 (b), 1672 (HC=O), 1625 (C=O), 1602, 1533,
1452, 1434
cm-1. 1H
NMR (200 MHz, DMSO-d
6): δ = 9.18
(overlapping singlets, 2 H, NH, OH), 8.94 (s, 1 H, HC=O),
8.30 (s, 1 H, NH), 7.22 (dt, 1 H, J = 8.61, 2.35 Hz, C4′-H),
7.03 (dd, 1 H, J = 8.29 Hz, 1.69, C6′-H),
6.80-6.76 (m, 2 H, C3′-H and C5′-H),
3.63 (s, 4 H, N-CH2 × 2).
MS: m/z (%) = 230
(1) [M+ - 2], 214
(1.5), 213 (3), 205 (5), 204 (29), 203 (8), 84 (100), (Found: C,
62.28; H, 5.11; N, 12.34. C12H12N2O3 requires
C, 62.06; H, 5.21; N 12.06 %).
2-[(5-Chlorosalicyl)-formyl-methylidene]imidazolidine (7b): Colorless crystalline solid, mp 271-272 °C
(acetone). UV (MeOH): 262, 223 nm. IR (KBr): 3350 (b), 3100 (b), 1668
(HC=O), 1619 (C=O), 1595, 1556, 1532, 1541 cm-1. 1H
NMR (300 MHz, DMSO-d
6): δ = 9.75
(br s, 1 H, OH), 9.21 (br s, 2 H, NH × 2),
9.10 (s, 1 H, CHO), 7.15 (dd, 1 H, J = 8.61, 2.35 Hz, C4′-H),
7.08 (d, 1 H, J = 2.30 Hz, C6′-H), 6.85
(d, 1 H, J = 8.69
Hz, C3′-H), 3.77 (s, 4 H, N-CH2 × 2). 13C
NMR (75 MHz, DMSO-d
6): δ = 190.43
(C=O), 188.06 (CHO), 163.43 (C2), 152.69 (C2), 129.72 (C1′),
129.31 (CH), 127.67 (CH), 122.59 (C5′), 117.25 (CH), 99.65 (quat.),
42.43 (N-CH2). Mass (FAB+): m/z (%) = 269
(31) [(M + H)+ + 2
(37Cl)], 268 (22) [(M + H)+ + 1],
267 (100) [(M + H)+ for 35Cl],
266 (36), 249 (37), 155 (18), 154 (93), 140 (30), 139 (24), 138
(45), 137 (68), (Found: C, 53.87; H, 4.01; N, 10.81. C12H11N2O3Cl
requires C, 54.05; H, 4.16; N 10.50%].
2-[Formyl-(5-Methylsalicyl)-methylidene]imidazolidine (7c): Colorless crystalline solid, mp 267-269 °C
(acetone). UV (CHCl3): 324, 287, 267.5, 256 nm. IR (KBr):
3290 (b), 3060 (b), 1660 (HC=O), 1622 (C=O), 1580,
1520, 1500, 1428, 1392, 1378, 1331, 1288, 1261 cm-1. 1H
NMR (200 MHz, CDCl3-DMSO-d
6,
8:2): δ = 9.75 (br s, 1 H, -OH), 9.33 (s, 1 H,
CHO), 9.24 (br s, 2 H, NH × 2), 7.10-7.06 (m,
2 H, arom.-Hs), 6.80 (d, 1 H, J = 8.09 Hz, C3′-H),
3.82 (s, 4 H, N-CH2 × 2),
2.26 (s, 3 H, Ar-CH3). MS: m/z (%) = 245 (8) [M+ - 1],
243 (9), 188 (11), 169 (100), 111 (60), 94 (41), 83 (47), 71 (78),
(Found: C, 63.18; H, 5.51; N, 11.64. C13H14N2O3 requires
C, 63.40; H, 5.73; N 11.38%).
2-(Formyl-salicyl-methylidene)hexahydropyrimidine
(7d): Colorless crystalline solid (219
mg, 89%), mp 176-177 °C (acetone). UV
(MeOH): 332, 262.5, 219 nm. IR (KBr): 3400 (b), 3090 (b), 2755,
1656 (HC=O), 1642 (C=O), 1604, 1572, 1401, 1365,
1338, 1326, 1302, 1273, 1245, 1224, 1147 cm-1: 1H
NMR (200 MHz, DMSO-d
6): δ = 10.64
(br s, 2 H, NH and OH), 9.83 (br s, 1 H, NH), 9.13 (s, 1 H, CHO),
7.37 (dt, 1 H, J = 7.02, 1.51 Hz, C4′-H),
7.24 (br d, 1 H, J = 6.42 Hz, C6′-H),
7.07-6.99 (m, 2 H, C5′-H and C3′-H),
3.61 (b, 4 H, N-CH2 × 2),
2.13-2.08 (m, 2 H, -CH2). 13C
NMR (50 MHz, DMSO-d
6): δ = 194.25
(C=O), 189.70 (CHO), 158.82 (C2), 153.70 (C2′),
130.10 (CH), 128.98 (C1′), 128.80 (CH), 119.25 (CH), 115.80
(CH), 100.51 (quat.), 37.78 (N-CH2), 19.06 (CH2).
MS: m/z (%) = 246
(15) [M+], 228 (69) [M+ - 18],
172 (42), 108 (100), (Found: C, 63.26; H, 5.48; N, 11.11. C13H14N2O3 requires
C, 63.40; H, 5.73; N 11.38%).
2-[(5-Chlorosalicyl)-formyl-methylidene]hexahydro-pyrimidine
(7e): Colorless crystalline solid, mp 169-171 °C (acetone).
UV (CHCl3): 330, 269.5, 251 nm. IR (KBr): 3490 (b), 3100
(b), 1657 (HC=O), 1635 (C=O), 1611, 1535, 1468, 1430,
1418, 1358, 1322, 1282, 1260, 1240, 1215 cm-1. 1H NMR
(200 MHz, CDCl3-DMSO-d
6,
8:2): δ = 10.46 (br, 2 H, NHs), 9.02 (s, 1 H,
CHO), 7.28-7.01 (m, 2 H, arom.-Hs), 6.80 (d, 1 H, J = 8.58
Hz, C3′-H), 3.44-3.41 (m, 4 H, N-CH2 × 2),
2.00-1.93 (m, 2 H, -CH2). MS: m/z (%) = 282 [(M+ + 2
(37Cl)], 281 (1.9), 280 (10)[M+ (35Cl)],
279 (35), 264 (8), 262 (31), 254 (14), 252 (30), 247 (5), 246 (3),
245 (18), 152 (4), 150 (18), 172 (5), 171 (23), 169 (70), 99 (15),
98 (100), 97 (14), (Found: C, 55.84; H, 4.81; N, 9.63. C13H13N2O3Cl requires
C, 55.62; H, 4.67; N, 9.98%).
2-[Formyl-(5-methylsalicyl)-methylidene]hexahydro-pyrimidine
(7f): Creamy yellow crystalline solid,
mp 160-162 °C (acetone). UV (CHCl3):
332, 307, 271.5, 256.5 nm. IR (KBr): 3360 (b), 3040 (b), 1658 (HC=O),
1633 (C=O), 1606, 1571, 1470, 1451, 1390, 1361, 1280 cm-1. 1H
NMR (200 MHz, CDCl3): δ = 10.51 (br,
2 H, NHs), 9.35 (s, 1 H, CHO), 7.14-7.08 (m, 2 H, arom
-Hs), 6.84 (d, 1 H, J = 8.26 Hz, C3′-H),
3.48-3.41 (s, 4 H, N-CH2 × 2),
2.24 (s, 3 H, Ar-CH3), 2.05-1.97 (m, 2 H, CH2). 13C
NMR (50 MHz, CDCl3): δ = 196.66 (C=O),
189.78 (CHO), 159.99 (C2), 156.83 (C2′), 133.41 (CH), 131.71
(CH), 127.11 (C1′), 122.16 (C5′), 117.11 (CH),
100.06 (quat.), 37.81 (N-CH2), 20.41 (Ar-CH3),
19.20 (CH2). MS: m/z (%) = 260
(20) [M+], 259 (18), 169 (91),
111 (76), 83 (49), 71 (100), (Found: C, 64.28; H, 5.96; N, 10.99.
C14H16N2O3 requires
C, 64.60; H, 6.20; N 10.76%).