HETEROCYCLES, Vol. 80, No. 2, 2010
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diisopropylether). IR (KBr): 3366m (NH), 2955w, 2204m (CꢀN), 1747s (C=O), 1709s (C=O), 1618m,
1567vs (C=C), 1460m, 1438m, 1327vs, 1287s (C–F), 1261s (C–F), 1194m, 1134br.s, 1067s, 1015br.w,
930w, 830m, 763m, 701m. 1H-NMR (CDCl3): 7.60–7.15 (m, 5 arom. H); 7.35, 6.35 (AB, 3JH,H = 9.0 Hz, 4
arom. H); 4.85 (br.s, NH); 4.95 (br.s, CH2); 4.45 (br.s, CH2); 3.90, 3.70 (2s, 2 MeO). 13C-NMR (CDCl3):
164.8, 161.6, 158.5 (3s, 2 C=O, =C(2)); 164.5, 139.8 (2s, 2 arom. C); 124.5 (q,1JC,F = 270 Hz, CF3); 120.4
2
3
(q, JC,F = 32.8 Hz, 1 arom. C); 129.3, 128.4, 125.0, 113.6 (4d, 7 arom. CH); 126.7 (q, JC,F = 3.7 Hz, 2
arom. CH); 116.6 (s, CN); 71.3 (s, =C(3)); 67.6, 65.6 (2t, 2 CH2); 56.0 (s, Cq); 53.9, 52.3 (2q, 2 MeO).
ESI-MS (MeOH): 483 (37), 482 (100, [M+Na]+), 460 (5, [M+1]+), 459 (3, M+). Anal. Calcd for
C23H20F3N3O4: C, 60.13; H 4.39; N 9.15. Found: C, 59.68; H, 4.16; N, 8.92.
Dimethyl (E)-3-cyano-2-{3-phenyl-3-[3-(4-trifluoromethylphenyl)amino-3-phenylazetidin-1-yl]
azetidin-1-yl}butanedioate (9c). Isolated as the third, most polar fraction. Yield: 32 mg (6%). Colorless
crystals, mp 97–100 °C (dec.) (MeOH). IR (KBr): 3393m (NH), 2955w, 2207m (CꢀN), 1748vs (C=O),
1707s (C=O), 1617s, 1568vs (C=C), 1456br.m, 1325s, 1262br.s, 1191w, 1168w, 1114s, 1066m, 830m,
1
3
763m, 701m. H-NMR (CDCl3): 7.60–7.15 (m, 10 arom. H); 7.40, 6.40 (AB, JH,H = 9.0 Hz, 4 arom. H);
5.55 (br.s, NH); 5.95 (br.s, CH2); 4.70, 4.40 (AB, 2JH,H = 9.8 Hz, CH2); 3.90, 3.70 (2s, 2 MeO); 3.70, 3.50
2
13
(AB, JH,H = 7.5 Hz, 2 CH2). C-NMR (CDCl3): 165.0, 161.8, 158.3 (3s, 2 C=O, =C(2)); 147.4.5, 141.9,
137.5 (3s, 3 arom. C); 124.9 (q,1JC,F = 270 Hz, CF3); 126.4 (q, 3JC,F = 3.7 Hz, 2 arom. CH); 127.4 (q, 2JC,F
= 31.0 Hz, 1 arom. C); 129.4, 128.9, 128.8, 127.4, 126.5, 126.0, 125.4, 113.5 (7d, 12 arom. CH); 114.9 (s,
CN); 71.4 (s, =C(3)); 68.6, 67.6 (2t, 2 CH2); 66.2 (t, 2 CH2); 60.9, 60.5 (2s, 2 Cq); 53.7, 52.2 (2q, 2 MeO).
ESI-MS (MeOH): 629 (22, [M+K]+), 614 (34), 613 (100, [M+Na]+), 592 (31), 591 (87, [M+1]+), 509 (28),
488 (11), 482 (13), 449 (27), 430 (28). HR-ESI-MS: 613.2026 (calcd. 613.2033 for C32H29F3N4NaO4,
[M+Na]+), 591.2208 (calcd. 591.22214 for C32H30F3N4O4, [(M+1]+).
Reaction with N-methylaniline (8f). Separation of the crude material was achieved on PLC plates (SiO2)
using a mixture of CH2Cl2 and MeOH (99:1) as an eluent and gave 6e as the sole product. The experiment
was carried out using 1a, 8f and DCFM in the molar ratio 1:1:1 (procedure A).
Dimethyl (E)-3-cyano-2-{3-[(methyl)(phenyl)amino]-3-phenylazetidin-1-yl}butanedioate (6e). Yield:
387 mg (96%). Colorless crystals, mp 98–100 ºC (dec.) IR (KBr): 2952w, 2206m (CꢀN), 1750m (C=O),
1
1708m (C=O), 1568vs (C=C), 1503m, 1456m, 1436m, 1267br.s, 1135s, 753m, 701m. H-NMR (CDCl3):
7.43–7.20 (m, 5 arom. H); 7.17 (t-like, 2 arom. H); 6.78 (t-like, 1 arom. H); 6.37 (d-like, 2 arom. H); 5.10,
4.88 and 4.58, 4.38 (2 AB, J = 11 and 10 Hz, resp., 2 CH2); 3.93, 3.76 (2s, 2 MeO); 3.12 (s, MeN).
13C-NMR (CDCl3): 165.0, 161.7, 158.0 (3s, 2 C=O, =C(2)); 146.4, 140.7 (2s, 2 arom. C); 129.23, 129.17,