1090
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 5, May, 2004
Voznyi et al.
Bruker DPXꢀ300 instrument (300 MHz for 1H and 75 MHz
for 13C). The mass spectra were obtained on an HPꢀ59970C
instrument (EI, 70 eV). Elemental analysis was carried out on
an HPꢀ185B C,H,Nꢀanalyzer. The melting points were deterꢀ
mined on a Boetius hotꢀstage apparatus and are uncorrected.
The course of the reactions was monitored by TLC on Silufolꢀ254
plates. The reaction mixtures were separated by column chroꢀ
matography on LS 5/40 silica gel (Chemapol).
OꢀAcylsalicylaldehydes were synthesized by acylation of saliꢀ
cylaldehyde with the corresponding acid chlorides in dry DMF
in the presence of anhydrous K2CO3. Imines were prepared by
condensation of aldehydes with amines in ethanol.10 Sodium
trichloroacetate was dried over P2O5 for one week. The reacꢀ
tions were carried out with the use of chloroform, which was
purified from the stabilizer and distilled over P2O5.
Reactions of imines with dichlorocarbene (general procedure).
A. Powdered KOH (1.1—1.7 g, 20—30 mmol) was added
portionwise with vigorous stirring to the reaction mixture conꢀ
taining imine (1.4 mmol) and benzyltriethylammonium chloꢀ
ride (0.16 g, 0.7 mmol) in dry CHCl3 (40 mL) at 20 °C for
1—2 h, the composition of the reaction mixture being moniꢀ
tored by TLC. Then hexane (10 mL) was added to the reaction
mixture, the mixture was filtered through a layer of silica gel
(5 mm), the solvent was removed in vacuo, and the residue was
recrystallized.
B. Sodium trichloroacetate (3.5 g, 20 mmol) was added
portionwise with stirring and refluxing to the reaction mixture
containing imine (1.4 mmol) and benzyltriethylammonium chloꢀ
ride (0.16 g, 0.7 mmol) in dry CHCl3 (40 mL) for 1 h. The
reaction mixture was refluxed for ~1 h, the composition of the
reaction mixture being monitored by TLC. Then the mixture
was cooled and filtered. The solvent was distilled off in vacuo
and the residue was purified by column chromatography (a hexꢀ
ane—ethyl acetate mixture as the eluent) followed by recrystalꢀ
lization of the product.
128.8, 130.6, 130.8, 132.3, 132.4, 132.8, 148.4 (Ar, Cvinyl);
161.6 (C=O).
2ꢀ(2,4ꢀDichlorophenyl)ꢀ2,5ꢀepoxyꢀ4ꢀphenylꢀ2,3,4,5ꢀtetraꢀ
hydroꢀ1,4ꢀbenzoxazepinꢀ3ꢀone (6d). M.p. 220—222 °C (from
hexane—AcOEt). Found (%): C, 63.34; H, 3.36; N, 3.44.
C21H13Cl2NO3. Calculated (%): C, 63.34; H, 3.29; N, 3.52. IR,
ν/cm–1: 1750 (C=O). 1H NMR (CDCl3), δ: 6.48 (s, 1 H, H(5));
6.98—8.18 (m, 12 H, Ar). 13C NMR (CDCl3), δ: 83.8 (C(5));
98.0 (C(2)), 114.7, 117.0, 119.4, 120.4, 122.9, 123.6, 125.4,
126.9, 127.4, 128.3, 128.7, 129.1, 131.5, 132.7, 134.4, 148.0
(Ar); 161.2 (C=O).
4ꢀ(4ꢀBromophenyl)ꢀ2,5ꢀepoxyꢀ2ꢀphenylꢀ2,3,4,5ꢀtetrahydroꢀ
1,4ꢀbenzoxazepinꢀ3ꢀone (6e). M.p. 186—188 °C (from hexꢀ
ane—AcOEt). Found (%): C, 61.83; H, 3.45; N, 3.34.
C21H14BrNO3. Calculated (%): C, 61.78; H, 3.46; N, 3.43. IR,
ν/cm–1: 1745 (C=O). 1H NMR (CDCl3), δ: 6.45 (s, 1 H, H(5));
6.94—7.93 (m, 13 H, Ar). 13C NMR (CDCl3), δ: 86.3 (C(5));
100.8 (C(2)); 117.1, 118.7, 120.7, 121.0, 121.4, 123.9, 126.1,
128.1, 130.0, 130.9, 132.1, 132.2, 133.9, 151.1 (Ar); 164.4 (C=O).
4ꢀ(4ꢀBromophenyl)ꢀ2ꢀ(4ꢀcyanophenyl)ꢀ2,5ꢀepoxyꢀ2,3,4,5ꢀ
tetrahydroꢀ1,4ꢀbenzoxazepinꢀ3ꢀone (6f). M.p. 227—228 °C (from
hexane—AcOEt). Found (%): C, 61.16; H, 3.09; N, 6.56.
C22H13BrN2O3. Calculated (%): C, 60.99; H, 3.02; N, 6.47. IR,
1
ν/cm–1: 1745 (C=O); 2240 (C≡N). H NMR (CDCl3), δ: 6.49
(s, 1 H, H(5)); 6.97—8.03 (m, 12 H, Ar). 13C NMR (CDCl3), δ:
86.6 (C(5)); 100.0 (C(2)); 113.9, 117.1, 117.9, 119.1, 121.15,
121.17, 124.1, 127.1, 131.2, 131.9, 132.3, 133.5, 136.9, 150.7
(Ar, C=N); 163.7 (C=O).
2,5ꢀEpoxyꢀ2ꢀ(2ꢀfuryl)ꢀ4ꢀphenylꢀ2,3,4,5ꢀtetrahydroꢀ1,4ꢀ
benzoxazepinꢀ3ꢀone (6g). M.p. 179—181 °C (from EtOH).
Found (%): C, 71.42; H, 4.12; N, 4.21. C19H13NO4. Calcuꢀ
lated (%): C, 71.47; H, 4.10; N, 4.39. IR, ν/cm–1: 1745 (C=O).
1H NMR (CDCl3), δ: 6.43 (s, 1 H, H(5)); 6.55—6.57 (m, 1 H,
Hfuryl); 6.94—7.09 (m, 3 H, Ar); 7.23—7.27 (m, 1 H, Hfuryl);
7.32—7.63 (m, 6 H, Ar). 13C NMR (CDCl3), δ: 86.6 (C(5));
97.6 (C(2)); 110.3, 112.1 (Ar); 117.0 (C(3)furyl); 119.8 (C(4)furyl);
120.8, 121.7, 124.1, 125.8, 129.1, 130.8, 134.6 (Ar); 144.3
(C(5)furyl); 144.9 (Ar); 150.9 (C(2)furyl); 162.8 (C=O).
2,5ꢀEpoxyꢀ2ꢀ(4ꢀmethoxyphenyl)ꢀ4ꢀphenylꢀ2,3,4,5ꢀtetraꢀ
hydroꢀ1,4ꢀbenzoxazepinꢀ3ꢀone (6a). M.p. 164—165 °C (from
hexane—AcOEt). Found (%): C, 73.64; H, 4.72; N, 3.86.
C22H17NO4. Calculated (%): C, 73.53; H, 4.77; N, 3.90. IR,
ν/cm–1: 1740 (C=O). 1H NMR (CDCl3), δ: 3.88 (s, 3 H, OMe);
6.46 (s, 1 H, H(5)); 6.93—7.87 (m, 13 H, Ar). 13C NMR
(CDCl3), δ: 55.0 (OMe); 86.4 (C(5)); 101.0 (C(2)); 113.5, 117.0,
119.6, 120.4, 121.7, 124.0, 124.7, 125.5, 127.7, 129.1, 130.7,
134.9, 151.3, 160.7 (Ar); 164.6 (C=O).
Amino alcohols 11a—c (general procedure). Lithium alumiꢀ
num hydride (0.038 g, 1 mmol) was added to a solution of
compound 6a—c (0.3 mmol) in anhydrous Et2O (30 mL). The
reaction mixture was refluxed for 2 h and cooled. Water
(0.04 mL), a 15% NaOH solution (0.04 mL), and water
(0.12 mL) were successively added to the reaction mixture. The
precipitate that formed was filtered off. The filtrate was dried
with MgSO4, Et2O was removed in vacuo, and the residue was
recrystallized from a hexane—diethyl ether mixture.
2ꢀ{Nꢀ[2ꢀHydroxyꢀ2ꢀ(4ꢀmethoxyphenyl)ethyl]anilinoꢀ
methyl}phenol (11a). M.p. 133—135 °C (from hexane—diethyl
ether). Found (%): C, 75.99; H, 6.61; N, 3.86. C22H23NO3.
Calculated (%): C, 75.62; H, 6.63; N, 4.01. IR, ν/cm–1: 3300 br
(OH); 3590 (OH). 1H NMR (CDCl3), δ: 3.39, 3.47, and
4ꢀ(4ꢀBromophenyl)ꢀ2,5ꢀepoxyꢀ2ꢀ(4ꢀmethoxyphenyl)ꢀ
2,3,4,5ꢀtetrahydroꢀ1,4ꢀbenzoxazepinꢀ3ꢀone
(6b).
M.p.
171—172 °C (from hexane—AcOEt). Found (%): C, 60.24;
H, 3.78; N, 3.08. C22H16BrNO4. Calculated (%): C, 60.29;
H, 3.68; N, 3.20. IR, ν/cm–1: 1745 (C=O). 1H NMR (CDCl3),
δ: 3.88 (s, 3 H, OMe); 6.42 (s, 1 H, H(5)); 6.93—7.84 (m, 12 H,
Ar). 13C NMR (CDCl3), δ: 55.0 (OMe); 86.2 (C(5)); 100.8
(C(2)); 113.5, 117.1, 118.6, 120.46, 121.0, 121.3, 123.9, 124.4,
127.6, 130.9, 132.1, 133.9, 151.2, 160.8 (Ar); 164.6 (C=O).
(E)ꢀ2ꢀ(1,2ꢀDiphenylvinyl)ꢀ2,5ꢀepoxyꢀ4ꢀphenylꢀ2,3,4,5ꢀ
tetrahydroꢀ1,4ꢀbenzoxazepinꢀ3ꢀone (6c). M.p. 204—205 °C
(from hexane—AcOEt). Found (%): C, 80.78; H, 5.00; N, 3.27.
C29H21NO3. Calculated (%): C, 80.72; H, 4.91; N, 3.25. IR,
ν/cm–1: 1740 (C=O). 1H NMR (CDCl3), δ: 6.31 (s, 1 H, H(5));
6.91—7.52 (m, 20 H, Ar); 7.67 (s, 1 H, PhCH=). 13C NMR
(DMSOꢀd6), δ: 82.9 (C(5)); 99.0 (C(2)); 114.4, 116.7, 118.8,
120.0, 122.9, 123.3, 125.8, 125.9, 126.4, 127.1, 127.3, 127.8,
4.94 (ABX system, 3 H, CH2, CHOH, JAB = 14.5 Hz, JAX
=
10.7 Hz, JBX = 4.9 Hz); 3.82 (s, 3 H, OMe); 4.47 and 4.56
(both m, AB system, 2 H, CH2, J = 14.5 Hz); 6.78—7.33 (m,
13 H, Ar); 8.79 (br.s, 1 H, OH). 13C NMR (CDCl3), δ: 55.0
(OMe); 55.6 and 61.6 (both CH2); 71.4 (CHOH); 113.7, 116.1,
119.1, 119.6, 121.6, 122.3, 126.9, 128.5, 128.8, 128.9, 133.8,
148.9, 156.1, 159.1 (Ar). MS, m/z (Irel (%)): 349 [M]+ (2),
243 (9), 212 (40), 137 (11), 107 [HOC6H4CH2]+ (44), 106 (100),
77 [Ph]+ (17).