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O.G. Khudina et al. / Journal of Fluorine Chemistry 125 (2004) 1363–1370
(C¼O), 1535, 1500 (C¼N, C¼C), 1215–1115 (C–F) cmÀ1
.
12.32, 15.09 (2H, 2 br.s, 2NH) ppm. 13C NMR (DMSO-
d6/CCl4) d: 14.26 (C16), 20.49 (C1), 60.51 (C15), 112.77
(C7), 114.95 (C3), 116.56 (C10), 118.24 (C8), 122.14 (C9),
123.59 (C6), 129.82 (C4), 132.00 (C11), 132.66 (C2), 140.20,
140.63 (C12–13), 145.85 (C5), 164.49 (C14) ppm. IR: 3380,
1575 (NH), 1650 (CO2Et), 1605, 1535, 1500 (C¼N,
C¼C) cmÀ1. MS, m/z (Irel (%)): 324 (21.7) [M þ 1]þ,
323 (100) [M]þ, 250 (17.2) [M–CO2Et]þ, 249 (19.9), 159
(10.1), 147 (19.1), 144 (55.6), 119 (9.4) [N¼NC6H4Me]þ,
118 (9.8) [M–EtO2CC¼NNH–C6H4Me]þ, 106 (10.6)
[NHC6H4Me]þ, 105 (43.4), 91 (28.1) [C6H4Me]þ, 77 (10)
[C6H5]þ. Analysis: Calc. for C18H18N4O2: C, 67.1; H, 5.6;
N, 17.4%. Found: C, 66.6; H, 5.5; N, 17.2%.
Analysis: Calc. for C20H15F9N4O2: C, 46.7; H, 2.9; F, 33.2;
N, 10.9%. Found: C, 46.4; H, 2.9; F, 33.6; N, 10.9%.
4.2.3. 2-(p-Methylphenyl)hydrazono-3-oxo-4,4,5,5-
tetrafluoropentanoic acid 2-aminoanilide (3c)
1
Yield, 38%; m.p., 146–148 8C. H NMR (DMSO-d6) d:
2.33 (3H, s, Me), 5.16 (2H, br.s, NH2), 6.61–7.47 (8H, m,
2C6H4), 6.91 (1H, tt, H(CF2)2, 2JHÀF ¼ 52:0,
3JHÀF ¼ 5:5 Hz), 9.91, 14.50 (2H, 2 br.s, 2NH) ppm. 19F
NMR (DMSO-d6/CCl4) d: 24.1 (2F, dt, HCF2, 2JFÀH ¼ 52,
3JFÀF ¼ 10 Hz), 46.8 (2F, m, CF2) ppm. IR: 3410, 3350,
3240, 3200, 1600 (NH), 1660 (C¼O), 1640 sh, 1580, 1550,
1500 (C¼N, C¼C), 1230–1070 (C–F) cmÀ1. Analysis: Calc.
for C18H16F4N4O2: C, 54.6; H, 4.1; F, 19.2; N, 14.1%.
Found: C, 54.5; H, 4.1; F, 19.1; N, 14.0%.
4.2.7. 3-Ethoxycarbonyl-1-phenyl-5,6,7,8-tetrafluoro-1,
4-dihydrocinnolin-4-one (7)
Yield, 84% (a) and 82% (b); m.p., 174–176 8C; [8].
4.2.4. 2-(p-Methylphenyl)hydrazono-3-oxo-4,4-
difluorobytanoic acid 2-aminoanilide (3d)
4.3. Synthesis of benzodiazepin-2-ones 4b,d
1
Yield, 51%; m.p., 140–142 8C. H NMR (DMSO-d6) d:
2.33 (3H, s, Me), 4.90 (2H, br.s, NH2), 6.57–7.47 (8H, m,
A solution of o-aminoanilide 3b,d (1 mmol) in o-xylene
(10 ml) was refluxed for 40 h, then concentrated to dryness.
The residue was recrystallized from chloroform to give
compounds 4b,d as yellow powders.
2
2C6H4), 6.81 (1H, t, HCF2, JHÀF ¼ 51:6 Hz), 9.85, 14.20
(2H, 2 br.s, 2NH) ppm. 19F NMR (DMSO-d6/CCl4) d: 24.1
2
3
(2F, dt, HCF2, JFÀH ¼ 52, JFÀF ¼ 10 Hz), 46.8 (2F, m,
CF2) ppm. IR: 3410, 3340, 3250, 1590 (NH), 1650 (C¼O),
1620, 1580, 1500 (C¼N, C¼C), 1230–1120 (C–F) cmÀ1
.
4.3.1. 3-(p-Methylphenyl)hydrazono-4-nonafluorobutyl-
1H-2,3-dihydro-1,5-benzodiazepin-2-one (4b)
Analysis: Calc. for C17H16F2N4O2: C, 59.0; H, 4.7; F, 11.0;
N, 9.2%. Found: C, 58.7; H, 4.5; F, 11.1; N, 9.0%.
Yield, 85%; m.p., 203–205 8C. 1H NMR (DMSO-d6/
CCl4) d: 2.38 (3H, s, Me), 7.27–7.33, 7.53–7.79 (8H, 2m,
2C6H4), 14.24 (2H, br.s, 2NH) ppm. 19F NMR (DMSO-d6/
CCl4) d: 37.4 (2F, m, CF2), 41.8 (2F, m, CF2), 52.1 (2F, m,
CF2), 81.8 (3F, m, CF3) ppm. IR: 3375, 1580 (NH), 1640
(C¼O), 1605, 1535, 1500 (C¼N, C¼C), 1220–1115 (C–
F) cmÀ1. Analysis: Calc. for C20H13F9N4O: C, 48.4; H, 2.6;
F, 34.5; N, 11.3%. Found: C, 48.5; H, 2.4; F, 34.6; N, 11.3%.
4.2.5. N,N0-Phenylene-bis[2-(p-methylphenyl)hydrazono-
3-oxo-4,4,5,5-tetrafluoropentanamide] (5)
1
Yield, 25%; m.p., 144–146 8C. H NMR (DMSO-d6, a
mix of tautomers (5):(50) ꢀ 17:3) 5, d: 2.33 (6H, s, 2Me),
2
3
6.77 (2H, tt, 2H(CF2)2, JHÀF ¼ 52:2, JHÀF ¼ 5:5 Hz),
7.29–7.81 (12H, m, 3C6H4), 10.48, 14.48 (4H, 2s, 4NH);
50, d: 2.36 (6H, s, 2Me), 7.01 (2H, tt, 2H(CF2)2,
3
2JHÀF ¼ 52:6, JHÀF ¼ 5:5 Hz), 7.33–7.83 (12H, m,
4.3.2. 3-(p-Methylphenyl)hydrazono-4-difluoromethyl-1H-
2,3-dihydro-1,5-benzodiazepin-2-one (4d)
3C6H4), 10.48, 14.15 (4H, 2s, 2NH, 2OH) ppm. IR: 3350,
3265, 1560 (NH), 1680 sh, 1660 (C¼O), 1595, 1555, 1500
(C¼N, C¼C), 1235–1090 (C–F) cmÀ1. MS, m/z (Irel (%)):
685 (24.1) [M þ 1]þ, 684 (70) [M]þ, 396 (25.4), 289 (22.1)
[H(CF2)2CO(C¼NNHC6H4Me)CO]þ, 277 (11.6), 276
(82.9), 135 (14.2), 134 (33.5), 121 (19.5), 119 (19.5)
[N¼NC6H4Me]þ, 108 (66.1), 107 (100), 106 (78.3)
[NHC6H4Me]þ, 105 (22.1), 91 (66.1) [C6H4Me]þ, 79
(18.4), 77 (11) [C6H5]þ. Analysis: Calc. for C30H24F8N6O4:
C, 52.6; H, 3.5; F, 22.2; N, 12.3%. Found: C, 52.9; H, 3.6; F,
22.0; N, 12.4%.
Yield, 83%; m.p., 216–217 8C. 1H NMR (DMSO-d6/CCl4)
2
d: 2.30 (3H, s, Me), 6.71 (2H, t, HCF2, JHÀF ¼ 54:9 Hz),
7.09–7.32 (8H, m, 2C6H4), 10.41, 12.48 (2H, 2 br.s, 2NH)
ppm. 19F NMR (CDCl3) d: 42.7 (2F, d, HCF2,
2JFÀH ¼ 55 Hz) ppm. IR: 3290, 3180, 1575 (NH), 1630
(C¼O), 1555, 1500, 1490 (C¼N, C¼C), 1260–1125 (C–
F) cmÀ1. Analysis: Calc. for C17H14F2N4O: C, 62.2; H, 4.3; F,
11.6; N, 17.1%. Found: C, 61.9; H, 4.2; F, 11.4; N, 17.1%.
4.4. Reactions of 1,2,3-triketone 2-arylhydrazones 2a–h
with o-phenylenediamine
4.2.6. Ethyl-2-(benzimidazol-2-yl)-2-(p-
methylphenyl)hydrazonoethanoate (6)
A mixture of 1,2,3-triketone 2-arylhydrazone 2a–h
(1 mmol) and o-phenylenediamine (1 mmol) was dissolved
in o-xylene (8 ml) [or in toluene for 8d, in ethanol in the
presence of acetic (0.1 ml) and hydrochloric (0.1 ml) acids
for 8b]. The reaction mixture was refluxed for 30 h and then
concentrated to dryness. Column chromatography with
Yield after column chromatography (with CHCl3 as an
eluent) and washing with ethanol, 20% from 1d; 25% from
1
1e; m.p., 218–220 8C. H NMR (DMSO-d6/CCl4) d: 1.44
(3H, t, OCH2CH3, J ¼ 7.1 Hz), 2.35 (3H, s, Me), 4.41 (2H,
q, OCH2CH3, J ¼ 7.1 Hz), 7.19–7.72 (8H, m, 2C6H4),