Quinalizinꢀ2ꢀones, pyrido[1,2ꢀa]azepinꢀ2ꢀones
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 10, October, 2011
2029
1 H each, 2 CH); 7.43, 7.86 (both m, total 5 H, Ar); 9.76 (br.s, 1 H,
NH). 13C NMR (CDCl3), δ: 18.3, 21.0, 29.6, 42.4, 91.4, 94.0, 126.6,
128.3, 131.2, 133.9, 168.4 (C=O), 169.2 (C=O), 175.3. 11B NMR
(CHCl3), δ: 0.67. IR, ν/cm–1: 3316, 2960, 2876, 1552, 1448.
Difluoroboron chelate of 1ꢀ(4ꢀchlorophenyl)ꢀ4ꢀ(piperidinꢀ2ꢀ
ylidene)butaneꢀ1,3ꢀdione (4b) was obtained from difluoroboron
chelate of 4ꢀchlorobenzoylacetone (1b) and 6ꢀmethoxyꢀ2,3,4,5ꢀ
tetrahydropyridine (2). The yield was 41%, m.p. 215—216 °C.
Found (%): C, 55.09; H, 4.80; N, 4.19. C15H15BClF2NO2. Calꢀ
culated (%): C, 55.34; H, 4.64; N, 4.30. MS, m/z (Irel (%)): 325
[M]+ (4), 306 [M – F]+ (2), 259 (6). 1H NMR (CDCl3), δ: 1.83
(m, 4 H, 2 CH2); 2.55, 3.52 (both m, 2 H each, 2 CH2); 4.82,
5.91 (both s, 1 H each, 2 CH); 7.36, 7.80 (both d, 2 H each, Ar,
J = 8.8 Hz); 9.81 (br.s, 1 H, NH). 11B NMR (CHCl3), δ: 0.53.
IR, ν/cm–1: 3308, 2952, 2852, 1556, 1480.
4ꢀPhenylꢀ7,8,9,10ꢀtetrahydroꢀ6Hꢀpyrido[1,2ꢀa]azepinꢀ2ꢀ
one (8a). The yield was 77%, m.p. 153—154 °C (hexane—benzꢀ
ene, 1 : 1). Found (%): C, 80.18; H, 7.30; N, 5.65. C16H17NO.
Calculated (%): C, 80.30; H, 7.16; N, 5.85. MS, m/z (Irel (%)):
1
239 [M]+ (59), 211 (100), 182 (36). H NMR (CDCl3), δ: 1.64
(m, 6 H, 3 CH2); 2.76, 3.78 (both m, 2 H each, 2 CH2); 6.17,
6.28 (both m, 1 H each, 2 CH); 7.25, 7.40 (both m, total 5 H,
Ar). 13C NMR (CDCl3), δ: 26.2, 28.0, 28.1, 34.4, 50.0, 117.6,
118.4, 127.8, 128.3, 128.8, 134.9, 152.4, 154.3, 178.2. IR, ν/cm–1
:
3048, 2928, 1628, 1560.
4ꢀ(4ꢀChlorophenyl)ꢀ7,8,9,10ꢀtetrahydroꢀ6Hꢀpyrido[1,2ꢀa]ꢀ
azepinꢀ2ꢀone (8b). The yield was 81%, m.p. 207—208 °C (benzꢀ
ene). Found (%): C, 69.98; H, 6.00; N, 5.02. C16H16ClNO.
Calculated (%): C, 70.20; H, 5.89; N, 5.12. MS, m/z (Irel (%)):
1
273 [M]+ (100), 245 (87), 216 (20). H NMR (CDCl3), δ: 1.64
Difluoroboron chelate of 4ꢀ(azepanꢀ2ꢀylidene)ꢀ1ꢀphenylꢀ
butaneꢀ1,3ꢀdione (5a) was obtained from difluoroboron chelate of
benzoylacetone (1a) and 7ꢀmethoxyꢀ3,4,5,6ꢀtetrahydroꢀ2Hꢀ
azepine (3). The yield was 43%, m.p. 189—190 °C. Found (%):
C, 62.76; H, 6.10; N, 4.37. C16H18BF2NO2. Calculated (%): C, 62.95;
H, 5.90; N, 4.59. MS, m/z (Irel (%)): 305 [M]+ (66), 285 [M – F]+
(38), 239 (42). 1H NMR (CDCl3), δ: 1.70 (m, 6 H, 3 CH2); 2.53,
3.53 (both m, 2 H each, 2 CH2); 4.94, 6.00 (both s, 1 H each, 2 CH);
7.44, 7.88 (both m, total 5 H, Ar); 9.69 (br.s, 1 H, NH). 11B NMR
(CHCl3), δ: 0.61. IR, ν/cm–1: 3332, 2928, 2864, 1544, 1448.
Difluoroboron chelate of 4ꢀ(azepanꢀ2ꢀylidene)ꢀ1ꢀ(4ꢀchloroꢀ
phenyl)butaneꢀ1,3ꢀdione (5b) was obtained from difluoroboron
chelate of 4ꢀchlorobenzoylacetone (1b) and 6ꢀmethoxyꢀ3,4,5,6ꢀ
tetrahydroꢀ2Hꢀazepine (3). The yield was 46%, m.p. 213—214 °C.
Found (%): C, 56.42; H, 5.13; N, 4.04. C16H17BClF2NO2. Calꢀ
culated (%): C, 56.59; H, 5.05; N, 4.12. MS, m/z (Irel (%)):
339 [M]+ (65), 319 [M – F]+ (9), 273 (18). 1H NMR (CDCl3), δ:
1.70 (m, 6 H, 3 CH2); 2.50, 3.54 (both m, 2 H each, 2 CH2);
4.94, 5.96 (both s, 1 H each, 2 CH); 7.38, 7.82 (both d, 2 H each,
Ar, J = 8.8 Hz); 9.73 (br.s, 1 H, NH). 11B NMR (CHCl3),
δ: 0.55. IR, ν/cm–1: 3312, 2936, 2860, 1540, 1476.
Synthesis of 4ꢀarylꢀ6,7,8,9ꢀtetrahydroꢀ2Hꢀquinolizinꢀ2ꢀones
7a,b and 4ꢀarylꢀ7,8,9,10ꢀtetrahydroꢀ6Hꢀpyrido[1,2ꢀa]azepinꢀ2ꢀ
ones 8a,b (general procedure). Concentrated HCl (0.2 mL) was
added to a suspension of chelate 4a,b or 5a,b (1 mmol) in ethanol
(5 mL), and the reaction mixture was refluxed for 4 h, neutralꢀ
ized with 10% aqueous NaOH, and extracted with ethyl acetate.
The ethyl acetate extract was dried, the solvent was evaporated,
the residue was recrystallized from the corresponding solvent to
obtain bicyclic compounds 7a,b, 8a,b as white crystals.
(m, 6 H, 3 CH2); 2.76, 3.78 (both m, 2 H each, 2 CH2); 6.16,
6.30 (both m, 1 H each, 2 CH); 7.24, 7.40 (both m, total 4 H,
Ar). IR, ν/cm–1: 3056, 2924, 1628, 1560.
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4ꢀPhenylꢀ6,7,8,9ꢀtetrahydroꢀ2Hꢀquinolizinꢀ2ꢀone (7a). The
yield was 76%, m.p. 152—153 °C (hexane—benzene, 1 : 5).
Found (%): C, 79.76; H, 6.83; N, 6.09. C15H15NO. Calculatꢀ
ed (%): C, 79.97; H, 6.71; N, 6.22. MS, m/z (Irel (%)): 225 [M]+
1
(53), 198 (100), 169 (51). H NMR (CDCl3), δ: 1.83 (m, 4 H,
2 CH2); 2.78, 3.63 (both m, 2 H each, 2 CH2); 6.27, 6.29 (both m,
1 H each, 2 CH); 7.30, 7.50 (both m, total 5 H, Ar). IR, ν/cm–1
:
3044, 2924, 1624, 1536.
4ꢀ(4ꢀChlorophenyl)ꢀ6,7,8,9ꢀtetrahydroꢀ2Hꢀquinolizinꢀ2ꢀone
(7b). The yield was 79%, m.p. 183—184 °C (hexane—benzene,
1 : 5). Found (%): C, 69.25; H, 5.52; N, 5.25. C15H14ClNO.
Calculated (%): C, 69.37; H, 5.43; N, 5.39. MS, m/z (Irel (%)):
1
259 [M]+ (70), 232 (100), 203 (49). H NMR (CDCl3), δ: 1.85
(m, 4 H, 2 CH2); 2.80, 3.63 (both m, 2 H each, 2 CH2); 6.27,
6.31 (both m, 1 H each, 2 CH); 7.27, 7.44 (both m, total 4 H,
Ar). IR, ν/cm–1: 3036, 2948, 1636, 1540.
Received March 29, 2011;
in revised form, August 23 2011