A. Alizadeh et al. / Tetrahedron xxx (2015) 1e7
5
3
CH3), 2.67 (2H, ABsystem
,
2JHH¼15.6 Hz, CH2), 3.35 (1H, d,
7.61 (2H, d, JHH¼8.4 Hz, 2CH of Ph). 13C NMR (100.0 MHz, DMSO-
d6): dC 13.29 (CH3),13.71 (CH3), 20.88 (CH3), 20.97 (CH3), 39.75 (CH2),
39.99 (CH2), 47.50 (C5), 60.09 (OCH3), 61.48 (OCH3), 91.91 (C3),109.25
(C8), 115.57 (CN), 116.16 (CN), 116.97 (C4a), 128.06 (2CH of Ar), 128.31
(CH of Ar), 128.63 (CH of Ar), 128.68 (CH of Ar), 128.96 (CH of Ar),
129.08 (2CH of Ar), 132.34 (Cipso), 134.03 (Cipso), 138.44 (Cipso-Me),
140.69 (Cipso-Me), 151.42 (C7), 154.01 (C4), 158.45 (C8a), 159.03
(C2eNH2), 170.27 (C]O), 172.56 (C]O). MS (EI, 70 eV): 534 (Mþ, 3),
462 (10), 447 (100), 419 (12), 402 (95), 387 (99), 372 (54), 357 (15),
330 (8), 311 (5), 295 (4), 282 (4), 264 (4), 239 (3), 209 (4),186 (6),165
(1), 151 (2), 121 (1), 91 (6), 65 (3), 50 (1).
2JHH¼18.0 Hz, CH of CH2), 3.53 (1H, d, 2JHH¼18.0 Hz, CH of CH2), 3.66
2
3
2
(2H, dq, JHH¼10.4, JHH¼7.2 Hz, OCH2), 3.90 (2H, dq, JHH¼19.6,
3JHH¼7.2 Hz, OCH2), 7.16 (2H, s, NH2), 7.18e7.19 (1H, m, CH of Ph),
7.30e7.32 (1H, m, CH of Ph), 7.48e7.56 (6H, m, CH of Ph), 7.69e7.71
(2H, m, CH of Ph). 13C NMR (100.0 MHz, DMSO-d6): dC 13.33 (CH3),
13.71 (CH3), 39.38 (CH2), 39.98 (CH2), 47.55 (C5), 60.11 (OCH2), 61.44
(OCH2), 91.88 (C3), 109.96 (C8), 115.47 (CN), 115.96 (CN), 116.79 (C4a),
128.05 (2CHmeta of Ar), 128.11 (CHpara of Ar), 128.12 (CHpara of Ar),
128.43 (CHortho of Ar), 128.54 (2CHmeta of Ar), 129.09 (CHortho of Ar),
129.10 (CHortho of Ar), 130.54 (CHortho of Ar), 135.21 (Cipso), 136.96
(Cipso), 151.31 (C7), 153,92 (C4), 158.45 (C8a), 159.23 (C2eNH2), 170.30
(C]O), 172.45 (C]O). MS (EI, 70 eV): 506 (Mþ, 2), 433 (11), 419
(91), 405 (16), 391 (11), 373 (82), 359 (100), 345 (28), 330 (14), 315
(8), 301 (8), 282 (13), 264 (4), 239 (3), 215 (3), 179 (3), 164 (2), 139
(2), 91 (6), 77 (13), 60 (4), 51 (3). Crystal data for 3b C30H25N4O4
4.2.5. Methyl 2-[2-amino-3,8-dicyano-4-(3-methoxyphenyl)-7-(4-
methoxyphenyl)-5-methyloxycarbonyl-5,6-dihydro-5-quinolinyl]ace-
tate (3e). Yellow powder, mp¼222e225 ꢁC, 0.45 g, yield: 84%. IR
(KBr) (nmax, cmꢀ1): 3460 and 3349 (NH2), 2217 (CN), 1727 (C]O),
1613, 1551 and 1438 (Ar), 1196 (CeO). Anal. Calcd for C30H26N4O6
(538.56): C, 66.91; H, 4.87; N, 10.40%. Found: C, 66.83; H, 4.80; N,
ꢀ
(CCDC 1033426): MW¼505.6, orthorhombic, Pbca, a¼23.5560(4) A,
ꢀ
3
ꢀ
b¼17.6196(2) A, c¼11.9742(5) A,
a
¼90.0,
b
¼90.0,
g
¼90.0,
3
ꢀ
V¼4969.9(2) A , Z¼8, Dc¼1.3513 mg/m , F (000)¼2120, Cu Kya
10.34%. 1H NMR (400 MHz, DMSO-d6): dH 2.71 (2H, ABsystem
,
ꢀ
(l
¼1.54184 A), 3.75ꢃ2
with a Xcalibur, Atlas, Gemini ultra area-detector diffractometer,
and employing /2 scanning technique, and employing /2
q
ꢃ67, intensity data were collected at 120 K
2JHH¼15.6 Hz, CH of CH2), 3.20 (1H, d, 2JHH¼17.6 Hz, CH of CH2), 3.33
2
(3H, s, OCH3), 3.44 (3H, s, OCH3), 3.55 (1H, d, JHH¼17.6 Hz, CH of
u
q
u
q
CH2), 3.83 (3H, s, OCH3), 3.84 (3H, s, OCH3), 7.01e7.10 (5H, m, CH of
Ph), 7.11 (2H, s, NH2), 7.20 (1H, d, 3JHH¼8.0 Hz, CH of Ph), 7.71 (2H, d,
3JHH¼8.8 Hz, CH of Ph). 13C NMR (100.0 MHz, DMSO-d6): dC 39.70
(CH2), 39.94 (CH2), 47.62 (C5), 51.34 (OCH3), 52.55 (OCH3), 55.15
(OCH3), 55.42 (OCH3), 92.04 (C3), 108.09 (C8), 113.37 (CH of Ar),
113.72 (CH of Ar),113.99 (2CH of Ar),115.66 (CN),115.49 (CN),117.08
(C4a), 127.18 (Cipso), 128.84 (Cipso), 129.79 (CH of Ar), 130.04 (2CH of
Ar), 130.51 (CH of Ar), 151.56 (C7), 153.77 (C4), 158.40 (C8a), 158.46
(C2eNH2), 159.50 (Cipso-OMe), 161.18 (Cipso-OMe), 170.85 (C]O),
172.94 (C]O). MS (EI, 70 eV): 538 (Mþ, 1), 479 (5), 464 (29), 433
(34), 419 (100), 405 (10), 390 (12), 375 (29), 361 (18), 345 (22), 332
(21), 319 (58), 304 (30), 290 (41), 276 (36), 263 (42), 239 (52), 227
(35), 213 (39), 202 (37), 189 (40), 178 (36).
scanning technique, in the range of ꢀ27ꢃhꢃ27, ꢀ20ꢃkꢃ20,
ꢀ13ꢃlꢃ10; the structure was solved by a direct method, all non-
hydrogen atoms were positioned and anisotropic thermal param-
eters refined from 2406 observed reflections with R (int)¼0.0346
by a full-matrix least-squares technique converged to R¼0.0359
and wR2¼0.1166 [I>2sigma(I)].
4.2.3. Methyl 2-[2-amino-3,8-dicyano-5-methyloxycarbonyl-4,7-
di(4-methylphenyl)-5,6-dihydro-5-quinolinyl]acetate
(3c). Yellow
powder, mp¼247e249 ꢁC, 0.44 g, yield: 86%. IR (KBr) (nmax, cmꢀ1):
3465 and 3357 (NH2), 2220 (CN), 1736 (C]O), 1622, 1552 and 1439
(Ar), 1188 (CeO). Anal. Calcd for C30H26N4O4 (506.56): C, 71.13; H,
5.17; N, 11.06%. Found: C, 71.06; H, 5.09; N, 11.12%. 1H NMR
(400 MHz, DMSO-d6): dH 2.39 (6H, s, 2CH3), 2.69 (2H, ABsystem
,
4.2.6. Ethyl 2-[2-amino-3,8-dicyano-5-ethyloxycarbonyl-4-(3-
methoxyphenyl)-7-(4-methoxyphenyl)-5,6-dihydro-5-quinolinyl]ace-
tate (3f). Yellow powder, mp¼227e229 ꢁC, 0.43 g, yield: 76%. IR
(KBr) (nmax, cmꢀ1): 3452 and 3346 (NH2), 2219 (CN), 1714 (C]O),
1615, 1552 and 1454 (Ar), 1187 (CeO). Anal. Calcd for C32H30N4O6
(566.61): C, 67.83; H, 5.34; N, 9.89%. Found: C, 67.76; H, 5.27; N,
9.82%. 1H NMR (400 MHz, DMSO-d6): dH 1.03 (6H, t, 3JHH¼6.4 Hz, CH
2JHH¼15.6 Hz, CH of CH2), 3.30 (3H, s, OCH3), 3.31 (1H, d,
2JHH¼17.6 Hz, CH of CH2), 3.43 (3H, s, OCH3), 3.52 (1H, d,
2JHH¼17.6 Hz, CH of CH2), 7.04 (1H, dd, 3JHH¼7.8 Hz, 4JHH¼1.6 Hz, CH
of Ph), 7.12 (2H, s, NH2), 7.16 (1H, dd, 3JHH¼7.8 Hz, 4JHH¼1.6 Hz, CH of
Ph), 7.28 (1H, d, 3JHH¼8.0 Hz, CH of Ph), 7.32 (1H, d, 3JHH¼8.0 Hz, CH
of Ph), 7.35 (2H, d, 3JHH¼8.0 Hz, CH of Ph), 7.61 (2H, d, 3JHH¼8.0 Hz,
2CH of Ph). 13C NMR (100.0 MHz, DMSO-d6): dC 20.90 (CH3), 20.98
(CH3), 39.75 (CH2), 39.95 (CH2), 47.58 (C5), 51.36 (OCH3), 52.51
(OCH3), 91.97 (C3), 109.19 (C8), 115.54 (CN), 116.15 (CN), 116.77 (C4a),
128.00 (2CH of Ar), 128.24 (CH of Ar), 128.64 (CH of Ar), 128.77 (CH
of Ar), 128.95 (CH of Ar), 129.18 (2CH of Ar), 132.25 (Cipso), 134.03
(Cipso), 138.47 (Cipso-Me), 140.69 (Cipso-Me), 151.34 (C7), 154.34 (C4),
158.41 (C8a), 158.96 (C2eNH2), 170.80 (C]O), 172.89 (C]O). MS (EI,
70 eV): 506 (Mþ, 4), 448 (16), 433 (91), 402 (72), 387 (88), 372 (26),
348 (5), 324 (5), 293 (4), 271 (5), 234 (8), 205 (8), 182 (17), 155 (17),
140 (17), 117 (16), 99 (25), 84 (100), 57 (33).
of CH3), 2.66 (2H, ABsystem
,
2JHH¼16.4 Hz, CH of CH2), 3.28 (1H, d,
2JHH¼18.0 Hz, CH of CH2), 3.53 (1H, d, 2JHH¼18.0 Hz, CH of CH2), 3.69
3
(2H, q, JHH¼7.2 Hz, CH of CH2), 3.82 (3H, s, OCH3), 3.84 (3H, s,
OCH3), 3.87e3.98 (2H, m, CH of CH2), 7.02 (2H, t, 3JHH¼7.2 Hz, 2CH
of Ph), 7.07 (1H, d, 3JHH¼8.0 Hz, CH of Ph), 7.09 (2H, s, NH2), 7.10 (2H,
t, 3JHH¼8.4 Hz, 2CH of Ph), 7.22 (1H, d, 3JHH¼8.0 Hz, CH of Ph), 7.71
(2H, d, 3JHH¼8.8 Hz, CH of Ph). 13C NMR (100.0 MHz, DMSO-d6): dC
13.33 (CH3), 13.72 (CH3), 39.68 (CH2), 39.81 (CH2), 47.53 (C5), 55.16
(OCH3), 55.43 (OCH3), 60.09 (OCH2), 61.47 (OCH2), 92.03 (C3),108.16
(C8), 113.32 (CH of Ar), 113.68 (CH of Ar), 113.96 (2CH of Ar), 115.70
(CN), 116.49 (CN), 117.27 (C4a), 127.26 (Cipso), 128.85 (Cipso), 129.84
(CH of Ar), 130.09 (2CH of Ar), 130.52 (CH of Ar), 151.64 (C4), 153.78
4.2.4. Ethyl 2-[2-amino-3,8-dicyano-5-ethyloxycarbonyl-4-(3-
methylphenyl)-7-(4-methylphenyl)-5,6-dihydro-5-quinolinyl]acetate
(3d). Yellow powder, mp¼248e250 ꢁC, 0.43 g, yield: 80%. IR (KBr)
(C7), 158.46 (C8a),158.53 (C2eNH2), 159.51 (Cipso-OMe),161.19 (Cipso
-
OMe), 170.33 (C]O), 172.61 (C]O). MS (EI, 70 eV): 566 (Mþ, 1), 493
(1), 478 (42), 433 (47), 419 (54), 404 (7), 390 (16), 375 (9), 361 (14),
348 (11), 332 (14), 319 (16), 305 (7), 291 (14), 276 (26), 256 (33), 239
(16), 215 (16), 198 (100), 174 (66), 159 (28), 145 (71), 121 (92), 108
(97).
(
nmax, cmꢀ1): 3458 and 3351 (NH2), 2224 (CN), 1721 (C]O), 1633,
1553 and 1450 (Ar),1196 (CeO). Anal. Calcd for C32H30N4O4 (534.61):
C, 71.89; H, 5.66; N, 10.48%. Found: C, 71.81; H, 5.59; N, 10.43%. 1H
3
NMR (400 MHz, DMSO-d6): dH 1.02 (3H, t, JHH¼7.2 Hz, CH3), 1.03
3
(3H, t, JHH¼7.2 Hz, CH3), 2.38 (6H, s, 2CH3), 2.66 (2H, ABsystem
,
2JHH¼16.0 Hz, CH of CH2), 3.30 (1H, d, 2JHH¼18.0 Hz, CH of CH2), 3.51
(1H, d, 2JHH¼18.0 Hz, CH of CH2), 3.62e3.70 (2H, m, CH2), 3.83e3.96
4.3. General procedure for the preparation of compounds
5aed
3
4
(2H, m, CH2), 7.04 (1H, dd, JHH¼8 Hz, JHH¼1.6 Hz, CH of Ph), 7.12
3
4
(2H, s, NH2), 7.17 (1H, dd, JHH¼8.0 Hz, JHH¼1.6 Hz, CH of Ph), 7.30
To a mixture of 2-(3,4-dihydronaphthalen-1(2H)-ylidene)malo-
nonitrile 4 (2 mmol) and dialkyl acetylenedicarboxylate 2 (1 mmol)
(2H, t, 3JHH¼6.8 Hz, 2CH of Ph), 7.35 (2H, t, 3JHH¼8.0 Hz, 2CH of Ph),