1-(3-(fluoromethyl and trifluoromethyl)phenyl)-5-oxopyrrolidine-3-carboxylate derivatives
1519
s-cis, CH), 4.02–4.24 (m, 0.7(1H), s-trans, CH ? 2H,
NCH2), 7.23–8.23 (m, 8H, Har ? 1H, N=CH), 11.62, 11.67
(2s, (0.7/0.3)(1H), s-cis/s-trans, NH) ppm; 13C NMR
(75.4 MHz, DMSO-d6): d = 32.79, 34.76 (s-cis/s-trans,
C-30), 35.02, 35.72 (s-cis/s-trans, C-40), 49.95, 50.43 (s-cis/
s, C-4), 122.65, 122.74 (s-cis/s-trans, C-6), 123.09, 123.35
1
(C-400), 124.04 (q, JC-F = 272.5 Hz, CF3), 128.78, 128.92
2
(C-200, C-600), 129.35 (q, JC-F = 31.8 Hz, C-3), 129.97
(C-5), 131.78 (C-300, C-500), 133.38 (C-100), 139.79 (C-1),
142.55, 145.84 (s-cis/s-trans, N=CH), 168.60 (s-cis,
CONH), 172.56, 172,75 (s-cis/s-trans, C-50), 173.46
(s-trans, CONH) ppm; MS (ESI, 20 eV): m/z (%) = 454
(M?, 97.5), 456 ([M ? H ? 1]?, 100).
3
s-trans, C-20), 115.67 (q, JC-F = 3.1 Hz, C-2), 115.87
(C-300, C-500), 120.29 (br s, C-4), 122.65, 122.74 (s-cis/s-
1
trans, C-6), 124.09 (q, JC-F = 272.4 Hz, CF3), 129.11 (d,
3
3JC-F = 8.9 Hz, s-cis, C-200, C-600), 129.28 (d, JC-F
=
N0-(4-(Dimethylamino)benzylidene)-5-oxo-1-(3-(trifluoro-
methyl)phenyl)pyrrolidine-3-carbohydrazide
(8b, C21H21F3N4O2)
9.1 Hz, s-trans, C-200, C-600), 130.77 (C-5), 129.81 (q, 2JC-F
=
29.0 Hz, C-3), 130.76 (br s, C-100), 139.80 (br s, C-1), 142.55,
1
145.84 (s-cis/s-trans, N=CH), 163.01 (d, JC-F = 247.3 Hz,
M.p.: 238–239 °C (from 1,4-dioxane); yield 91.0%; IR
1
s-cis, C-400), 163.16 (d, JC-F = 248.4 Hz, s-trans, C-400),
ꢀ
(KBr): m = 3,246 (NH), 2,931 (N=CH), 1,690 (C=O),
168.60 (s-cis, CONH), 172.56, 172.75 (s-cis/s-trans, C-50),
173.56 (s-trans, CONH) ppm; MS (ESI, 20 eV): m/z
(%) = 394 ([M ? H]?, 100).
1,657 (C=O), 1,603 (N(CH3)2) cm-1; 1H NMR (300 MHz,
DMSO-d6): d = 2.81–2.96 (m, 2H, CH2CO), 2.97, 2.98 (2s,
6H, N(CH3)2), 3.31–3.43 (m, 0.3(1H), s-cis, CH), 4.13–
4.25 (m, 0.7(1H), s-trans, CH ? 2H, NCH2), 6.72–8.31
(m, 8H, Har 1 1H, N=CH), 11.33, 11.37 (2s, (0.7/0.3)(1H),
s-cis/s-trans, NH) ppm; 13C NMR (75.4 MHz, DMSO-d6):
d = 32.78, 34.68 (s-cis/s-trans, C-30), 39.78 (N(CH3)2),
N0-(4-Chlorobenzylidene)-5-oxo-1-(3-(trifluoro-
methyl)phenyl)pyrrolidine-3-carbohydrazide
(6b, C19H15ClF3N3O2)
M.p.: 238–239 °C (from 1,4-dioxane); yield 95.7%; IR
(KBr): m = 3,132 (NH), 3,201 (N=CH), 1,688 (C=O),
35.02, 35.75 (s-cis/s-trans, C-40), 50.01, 50.52 (s-cis/s-
ꢀ
1,667 (C=O) cm-1
;
1H NMR (300 MHz, DMSO-d6):
trans, C-20), 111.75 (C-300, C-500), 115.56 (q, JC-F
=
3.7 Hz, s-cis, C-2), 115.59 (q, JC-F = 3.5 Hz, s-trans,
3
3
d = 2.74–2.95 (m, 2H, CH2CO), 3.32–3.23 (m, 0.3(1H),
s-cis, CH), 4.02–4.23 (m, 0.7(1H), s-trans, CH ? 2H,
NCH2), 7.40–8.22 (m, 8H, Har ? 1H, N=CH), 11.66, 11.73
(2s, (0.7/0.3)(1H), s-cis/s-trans, NH) ppm; 13C NMR
(75.4 MHz, DMSO-d6): d = 32.74, 34.73 (s-cis/s-trans,
C-30), 34.97, 35.63 (s-cis/s-trans, C-40), 49.88, 50.36 (s-cis/
C-2), 120.22 (br s, C-4), 121.30, 121.46 (C-100), 122.62,
1
122.69 (s-cis/s-trans, C-6), 124.05 (q, JC-F = 272.5 Hz,
2
CF3), 128.13, 128.39 (C-200, C-600), 129.35 (q, JC-F
=
31.9 Hz, C-3), 129.97 (C-5), 139.77, 139.84 (s-cis/s-trans,
C-1), 144.49, 147.88 (s-cis/s-trans, N=CH), 151.35, 151.51
(C-400), 167.83 (s-cis, CONH), 172.73, 172.89 (s-cis/
s-trans, C-50), 173.73 (s-trans, CONH) ppm; MS (ESI,
20 eV): m/z (%) = 419 ([M ? H]?, 100).
3
s-trans, C-20), 115.51 (q, JC-F = 4.2 Hz, s-cis, C-2),
3
115.61 (q, JC-F = 3.8 Hz, s-trans, C-2), 120.26 (br s,
C-4), 122.63, 122.73 (s-cis/s-trans, C-6), 124.01 (q, 1JC-F
=
272.4 Hz, CF3), 128.54, 128.69 (C-200, C-600), 129.36 (d,
2JC-F = 31.7 Hz, C-3), 129.95 (C-300, C-500), 133.05 (C-100),
134.32, 134.56 (C-400), 139.74, 139.79 (C-1), 142.46, 145.77
(s-cis/s-trans, N=CH), 168.59 (s-cis, CONH), 172.57, 172.75
(s-cis/s-trans, C-50), 173.45 (s-trans, CONH) ppm; MS
(ESI, 20 eV): m/z (%) = 410 ([M ? H]?, 100), 412 ([M ?
H ? 1]?, 33).
N0-(4-Methoxybenzylidene)-5-oxo-1-(3-(trifluoromethyl)-
phenyl)pyrrolidine-3-carbohydrazide
(9b, C20H18F3N3O3)
M.p.: 164–165 °C (from 2-propanol); yield 94.8%; IR
ꢀ
(KBr): m = 3,211 (NH), 2,961 (N=CH), 1,688 (C=O),
1
1,678 (C=O), 1,607 (OCH3) cm-1; H NMR (300 MHz,
DMSO-d6): d = 2.73–2.93 (m, 2H, CH2CO), 3.30–3.41 (m,
0.3(1H), s-cis, CH), 3.78, 3.79 (2s, 3H, s-cis/s-trans, OCH3),
4.01–4.23 (m, 0.7(1H), s-trans, CH ? 2H, NCH2), 6.96–
8.23 (m, 8H, Har ? 1H, N=CH), 11.50, 11.56 (2s, (0.7/
0.3)(1H), s-cis/s-trans, NH) ppm; 13C NMR (75.4 MHz,
DMSO-d6): d = 32.74, 34.68 (s-cis/s-trans, C-30), 34.97,
35.69 (s-cis/s-trans, C-40), 49.93, 50.43 (s-cis/s-trans, C-20),
55.21 (OCH3), 114.24 (C-300, C-500), 115.59 (br s, C-2),
120.18 (br s, C-4), 122.57 (C-5), 122.57 (C-6), 124.47 (q,
1JC-F = 272.6 Hz, CF3), 126.66 (C-100), 128.44 (C-200, C-
600), 128.44 (C-5), 129.94 (C-3), 139.79 (C-1), 143.55,
146.91 (s-cis/s-trans, N=CH), 160.62, 160.81 (C-400), 168.21
(s-cis, CONH), 172.64, 172.83 (s-cis/s-trans, C-50), 173.09
(s-trans, CONH) ppm; MS (ESI, 20 eV): m/z (%) = 406
([M ? H]?, 100).
N0-(4-Bromobenzylidene)-5-oxo-1-(3-(trifluoromethyl)-
phenyl)pyrrolidine-3-carbohydrazide
(7b, C19H15BrF3N3O2)
M.p.: 200–201 °C (from 2-propanol); yield 91.5%; IR
ꢀ
(KBr): m = 3,136 (NH), 2,978 (N=CH), 1,687 (C=O),
1,664 (C=O), 693 (C–Br) cm21
;
1H NMR (300 MHz,
DMSO-d6): d = 2.72–2.94 (m, 2H, CH2CO), 3.31–3.43
(m, 0.3(1H), s-cis, CH), 4.01–4.23 (m, 0.7(1H), s-trans,
CH ? 2H, CH2N), 7.47–8.21 (m, 8H, Har ? 1H, N=CH),
11.67, 11.73 (2s, (0.7/0.3)(1H), s-cis/s-trans, NH) ppm; 13
C
NMR (75.4 MHz, DMSO-d6): d = 32.74, 34.73 (s-cis/
s-trans, C-30), 34.97, 35.63 (s-cis/s-trans, C-40), 49.88,
50.35 (s-cis/s-trans, C-20), 115.51 (q, 3JC-F = 4.3 Hz, s-cis,
3
C-2), 115.61 (q, JC-F = 3.8 Hz, s-trans, C-2), 120.22 (br
123