552
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
Samet et al.
10ꢀ(4ꢀMethoxybenzyl)ꢀ3ꢀnitrodibenzo[b,f ][1,4]oxazepinꢀ
3ꢀ(2ꢀMethoxyphenoxy)dibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀ
one (7c) was obtained analogously from guaiacol. The yield was
46%, m.p. 181—182 °C. Found (%): C, 72.38; H, 4.29; N, 4.28.
C20H15NO4. Calculated (%): C, 72.06; H, 4.54; N, 4.20.
MS (EI, 70 eV), m/z (Irel (%)): 333 [M]+ (49), 127 (40), 77 (77),
63 (100), 52 (94). 1H NMR, δ: 3.72 (s, 3 H, Me); 6.71 (m, 2 H);
7.04 (t, 1 H, J = 7.9 Hz); 7.10 (m, 1 H); 7.16 (m, 3 H); 7.24 (d,
1 H, J = 8.5 Hz); 7.28 (m, 2 H); 7.73 (d, 1 H, J = 8.1 Hz); 10.29
(br.s, 1 H, NH).
11(10H )ꢀone (4c). The yield was 88%, m.p. 64—66 °C (benꢀ
zene). Found (%): C, 66.84; H, 4.40; N, 7.68. C21H16N2O5.
Calculated (%): C, 67.02; H, 4.28; N, 7.44. MS (EI, 70 eV),
m/z (Irel (%)): 376 [M]+ (16), 121 (100). 1H NMR, δ: 3.70
(s, 3 H); 5.32 (s, 2 H); 6.85 (d, 2 H, J = 8.2 Hz); 7.18—7.26
(m, 4 H); 7.48, 7.56 (both d, 1 H each, J = 8.1 Hz); 8.02, 8.13
(both d, 1 H each, J = 7.9 Hz); 8.22 (s, 1 H).
8ꢀChloroꢀ3ꢀnitrodibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀone
(4d). The yield was 85%, sublimed at 200 °C (benzene).
Found (%): C, 53.50; H, 2.40; N, 10.01; Cl, 11.96.
C13H7ClN2O4. Calculated (%): C, 53.72; H, 2.43; N, 9.64;
Cl, 12.20. MS (EI, 70 eV), m/z (Irel (%)): 292 [M]+ (26),
3ꢀ(4ꢀChlorophenoxy)dibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀ
one (7d) was obtained analogously from 4ꢀchlorophenol. The
yield was 38%, m.p. 227—230 °C. Found (%): C, 67.72; H, 3.68;
Cl, 10.57; N, 4.09. C19H12ClNO3. Calculated (%): C, 67.56;
H, 3.58; Cl, 10.50; N, 4.15. MS (EI, 70 eV), m/z (Irel (%)):
1
290 [M]+ (100), 255 (56), 75 (32). H NMR, δ: 7.23 (m, 2 H);
1
7.52 (d, 1 H, J = 8.1 Hz); 8.03 (d, 1 H, J = 8.2 Hz); 8.15 (dd,
1 H, J = 7.9 Hz, J = 2.0 Hz); 8.27 (d, 1 H, J = 2.0 Hz); 10.93
(br.s, 1 H, NH).
339 [M]+ (37), 337 [M]+ (100), 73 (30), 56 (44). H NMR, δ:
6.89 (d, 1 H, J = 8.2 Hz); 6.93 (s, 1 H); 7.12 (m, 1 H); 7.18
(m, 4 H); 7.31 (d, 1 H, J = 8.0 Hz); 7.50 (d, 2 H, J = 8.4 Hz);
7.78 (d, 1 H, J = 8.2 Hz); 10.39 (br.s, 1 H, NH).
10ꢀMethylꢀ3ꢀnitrodibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀone
(4e). Dimethyl sulfate (1.51 g, 11.7 mmol) was added to a stirred
suspension of 3ꢀnitrodibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀone
(4a) (1.54 g, 6 mmol) and NaOH (0.47 g, 11.7 mmol) in a
mixture of acetone (7 mL) and water (7 mL). The reaction
mixture was stirred at 60 °C for 1 h. The precipitate was filtered
off, washed with water (50 mL), and dried. The yield was 1.38 g
(85%), m.p. 138—141 °C (benzene). Found (%): C, 62.47;
H, 3.61; N, 10.29. C14H10N2O4. Calculated (%): C, 62.22;
H, 3.73; N, 10.37. MS (EI, 70 eV), m/z (Irel (%)): 270 [M]+
3ꢀ(4ꢀBromophenoxy)dibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀ
one (7e) was obtained analogously from 4ꢀbromophenol. The
yield was 32%, m.p. 240—243 °C. Found (%): C, 59.62; H, 3.04;
Br, 20.79; N, 3.66. C19H12BrNO3. Calculated (%): C, 59.71;
H, 3.16; Br, 20.91; N, 3.66. MS (EI, 70 eV), m/z (Irel (%)):
1
383 [M]+ (98), 381 [M]+ (100), 101 (11), 56 (41). H NMR, δ:
6.90 (d, 1 H, J = 8.2 Hz); 6.94 (s, 1 H); 7.12 (m, 3 H); 7.18
(m, 2 H); 7.31 (d, 1 H, J = 8.0 Hz); 7.63 (d, 2 H, J = 8.4 Hz);
7.78 (d, 1 H, J = 8.4 Hz); 10.39 (br.s, 1 H, NH).
10ꢀBenzylꢀ3ꢀphenoxydibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀ
one (7f) was obtained from compound 4b and phenol. The yield
was 91%, m.p. 72—75 °C. Found (%): C, 79.52; H, 4.94; N, 3.62.
1
(100), 253 (22), 226 (21), 196 (39), 167 (27). H NMR, δ: 3.53
(s, 3 H, Me); 7.30, 7.54 (both m, 2 H each); 8.01 (d, 1 H,
J = 8.1 Hz); 8.12 (dd, 1 H, J = 8.1 Hz, J = 2.1 Hz); 8.24 (d, 1 H,
J = 2.1 Hz).
C
26H19NO3. Calculated (%): C, 79.37; H, 4.87; N, 3.56.
3ꢀSubstituted dibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀones
(7a—m) (general procedure). A stirred suspension of 3ꢀnitroꢀ
dibenzooxazepinone 4a—e (6.0 mmol), an appropriate nucleoꢀ
phile R3XH (6.45 mmol) (see Table 1), and dry K2CO3 (1.24 g,
9.0 mmol) in dry DMF (10 mL) was heated on an oil bath. The
reaction temperatures and durations are specified in Table 1.
The reaction mixture was cooled, poured into water (100 mL),
and acidified to pH 6. The precipitate that formed was filtered
off, washed with hot water (5×50 mL), and dried. Products were
crystallized from benzene. In the synthesis of compound 7h,
MeONa was used instead of MeOH and K2CO3; the product
was purified by flash chromatography on silica gel with hexꢀ
ane—ethyl acetate (5 : 1) as an eluent.
3ꢀPhenoxydibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀone (7a) was
obtained from compound 4a and phenol. The yield was 83%,
m.p. 213—215 °C. Found (%): C, 75.46; H, 4.48; N, 4.57.
C19H13NO3. Calculated (%): C, 75.24; H, 4.32; N, 4.62.
MS (EI, 70 eV), m/z (Irel (%)): 303 [M]+ (100), 275 (14), 154
(13), 87 (20). 1H NMR, δ: 6.85 (m, 2 H); 7.10 (m, 1 H); 7.17
(m, 4 H); 7.27 (m, 2 H); 7.46 (t, 2 H, J = 7.9 Hz); 7.79 (d, 1 H,
J = 8.1 Hz); 10.35 (br.s, 1 H, NH).
3ꢀ(3ꢀMethylphenoxy)dibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀ
one (7b) was obtained analogously from mꢀcresol. The yield was
88%, m.p. 183—186 °C. Found (%): C, 75.53; H, 4.89; N, 4.32.
C20H15NO3. Calculated (%): C, 75.70; H, 4.76; N, 4.41.
MS (EI, 70 eV), m/z (Irel (%)): 317 [M]+ (100), 316 (32), 170 (26),
65 (87), 63 (70). 1H NMR, δ: 2.31 (s, 3 H, Me); 6.85 (m, 2 H);
6.92 (d, 1 H, J = 8.0 Hz); 6.96 (s, 1 H); 7.06—7.12 (m, 2 H); 7.17
(m, 2 H); 7.28 (d, 1 H, J = 8.2 Hz); 7.33 (t, 1 H, J = 8.0 Hz);
7.78 (d, 1 H, J = 8.0 Hz); 10.29 (br.s, 1 H, NH).
MS (EI, 70 eV), m/z (Irel (%)): 393 [M]+ (60), 302 (21), 91 (100).
1H NMR, δ: 5.34 (s, 2 H); 6.87 (d, 1 H, J = 8.2 Hz); 6.93 (d,
1 H, J = 2.5 Hz); 7.12—7.22 (m, 5 H); 7.24—7.35 (m, 6 H); 7.46
(m, 3 H); 7.77 (d, 1 H, J = 8.4 Hz).
10ꢀMethylꢀ3ꢀphenoxydibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀ
one (7g) was obtained from compound 4e and phenol. The yield
was 92%, m.p. 59—61 °C. Found (%): C, 75.51; H, 4.59; N, 4.52.
C20H15NO3. Calculated (%): C, 75.70; H, 4.76; N, 4.41.
1H NMR, δ: 3.46 (s, 3 H, Me); 6.84 (dd, 1 H, J = 8.0 Hz, J =
2.2 Hz); 6.92 (d, 1 H, J = 2.0 Hz); 7.15 (d, 2 H, J = 8.0 Hz); 7.22
(t, 1 H, J = 8.2 Hz); 7.29 (m, 2 H); 7.37 (d, 1 H, J = 8.0 Hz);
7.45 (m, 3 H); 7.75 (d, 1 H, J = 8.0 Hz).
3ꢀMethoxyꢀ10ꢀmethyldibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀ
one (7h) was obtained from compound 4e and MeONa. The
yield was 66%, a light yellow oil which slowly solidified.
Found (%): C, 70.32; H, 5.02; N, 5.56. C15H13NO3. Calcuꢀ
lated (%): C, 70.58; H, 5.13; N, 5.49. 1H NMR, δ: 3.47 (s, 3 H,
NMe); 3.84 (s, 3 H, OMe); 6.88 (d, 1 H, J = 8.2 Hz);
6.92 (s, 1 H); 7.26, 7.42 (both m, 2 H each); 7.69 (d, 1 H,
J = 8.0 Hz).
8ꢀChloroꢀ3ꢀphenoxydibenzo[b,f ][1,4]oxazepinꢀ11(10H )ꢀ
one (7i) was obtained from compound 4d and phenol. The yield
was 88%, sublimed at 163—165 °C. Found (%): C, 67.82;
H, 3.67; Cl, 10.59; N, 4.10. C19H12ClNO3. Calculated (%):
C, 67.56; H, 3.58; Cl, 10.50; N, 4.15. MS (EI, 70 eV),
m/z (Irel (%)): 339 [M]+ (34), 338 (29), 337 [M]+ (100), 302 (46).
1H NMR, δ: 6.87 (dd, 1 H, J = 8.4 Hz, J = 3.0 Hz); 6.92 (d, 1 H,
J = 3.0 Hz); 7.16—7.20 (m, 4 H); 7.27 (t, 1 H, J = 8.0 Hz); 7.36
(d, 1 H, J = 8.4 Hz); 7.47 (t, 2 H, J = 8.0 Hz); 7.78 (d, 1 H, J =
8.4 Hz); 10.52 (br.s, 1 H, NH).