HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES ... XIII.
1513
Cl 11.05, 11.23; N 4.50, 4.79. C18H18ClNO2. Calcu-
lated, %: Cl 11.23; N 4.44.
CHMe2, J = 6.9 Hz), 2.71 br.s (3H, 4-Me), 3.60–
3.71 m (1H, 7-CH), 6.12 br.s (1H, OH), 7.51– 8.22 d.d
(4H, C6H4, J = 6.6 Hz). Found, %: Br+Cl 30.10,
30.38; N 3.55, 3.79. C17H15BrClNO2. Calculated, %:
Br+Cl 30.30; N 3.68.
5-Chloro-2-(4-chlorophenyl)-7-isopropyl-4-meth-
yl-1,3-benzoxazol-6-ol (XIIc). Yield 90%, mp 162–
1
164°C. H NMR spectrum, δ, ppm: 1.48 d (6H,
CHMe2, J = 7.8 Hz), 2.68 s (3H, 4-Me), 3.59–3.67 m
(1H, 7-CH), 5.98 br.s (1H, OH), 7.51–8.21 d.d (4H,
C6H4, J = 7.8 Hz). Found, %: Cl 21.10, 21.29; N 4.25,
4.39. C17H15Cl2NO2. Calculated, %: Cl 21.09; N 4.17.
5-Bromo-7-isopropyl-4-methyl-2-(4-nitro-
phenyl)-1,3-benzoxazol-6-ol (XIIId). Yield 85%,
1
mp 230–231°C. H NMR spectrum, δ, ppm: 1.49 d
(6H, CHMe2, J = 7.2 Hz), 2.69 s (3H, 4-Me), 3.62–
3.71 m (1H, 7-CH), 5.90 br.s (1H, OH), 8.37 s (4H,
C6H4). 13C NMR spectrum, δC, ppm: 17.71 (4-Me),
21.73 (Me2CH), 26.93 (CHMe2), 111.68 (C5), 116.41
(C7), 124.27 (C2′, C6′), 128.11 (C3′, C5′), 128.26 (C4),
132.90 (C1′), 135.71 (C3a), 148.06 (C6), 149.20 (C4′),
149.39 (C7a), 159.41 (C2). Found, %: Br 20.34, 20.51;
N 6.97, 7.33. C17H15BrN2O4. Calculated, %: Br 20.42;
N 7.16.
5-Chloro-7-isopropyl-4-methyl-2-(4-nitrophe-
nyl)-1,3-benzoxazol-6-ol (XIId). Yield 73%, mp 229–
1
230°C. H NMR spectrum, δ, ppm: 1.49 d (6H,
CHMe2, J = 6.9 Hz), 2.67 s (3H, 4-Me), 3.61–3.71 m
(1H, 7-CH), 6.08 br.s (1H, OH), 8.38 s (4H, C6H4).
Found, %: Cl 10. 06, 10. 34; N 7. 92, 8. 15.
C17H15ClN2O4. Calculated, %: Cl 10.22; N 8.08.
5-Chloro-7-isopropyl-4-methyl-2-(3-nitrophe-
5-Bromo-7-isopropyl-4-methyl-2-(3-nitro-
nyl)-1,3-benzoxazol-6-ol (XIIe). Yield 73%, mp 229–
230°C. H NMR spectrum, δ, ppm: 1.49 d (6H,
1
phenyl)-1,3-benzoxazol-6-ol (XIIIe). Yield 77%,
1
mp 192–194°C. H NMR spectrum, δ, ppm: 1.50 d
CHMe2, J = 7.5 Hz), 2.68 s (3H, 4-Me), 3.62–3.73 m
(1H, 7-CH), 5.98 br.s (1H, OH), 7.72 t (1H, 5′-H),
(6H, CHMe2, J = 7.5 Hz), 2.70 s (3H, 4-Me), 3.63–
3
3.72 m (1H, 7-CH), 6.15 br.s (1H, OH), 7.72 t (1H,
8.35–8.38 d.d (1H, 6′-H, J = 7.9 Hz), 8.57 d (1H,
3
3
4
5′-H), 8.35–8.38 d.d (1H, 6′-H, J = 9.0 Hz), 8.56 d
4′-H, J = 7.8 Hz), 9.03 q (1H, 2′-H, J = 3.3 Hz).
Found, %: Cl 10. 26, 10. 53; N 8. 24, 8. 57.
C17H15ClN2O4. Calculated, %: Cl 10.22; N 8.08.
(1H, 4′-H, 3J = 7.5 Hz), 9.03 q (1H, 2′-H, 4J = 3.6 Hz).
Found, %: Br 20. 15, 20. 39; N 6. 88, 7. 14.
C17H15BrN2O4. Calculated, %: Br 20.42; N 7.16.
5-Chloro-7-isopropyl-2,4-dimethyl-1,3-benzoxa-
zol-6-ol (XIIg). Yield 60%, mp 175.5–177°C. 1H NMR
spectrum, δ, ppm: 1.43 d (6H, CHMe2, J = 6.9 Hz),
2.83 s (3H, 2-Me), 3.22 s (3H, 4-Me), 3.57–3.69 m
(1H, 7-CH), 6.17 br.s (1H, OH). Found, %: Cl 14.65,
14.88; N 5.84, 6.03. C12H14ClNO2. Calculated, %:
Cl 14.79; N 5.84.
5-Bromo-7-isopropyl-2,4-dimethyl-1,3-benzoxa-
zol-6-ol (XIIIg). Yield 59%, mp 138.5–140°C.
1H NMR spectrum, δ, ppm: 1.43 d (6H, CHMe2, J =
7.2 Hz), 2.84 br.s (3H, 2-Me), 3.14 br.s (3H, 4-Me),
3.58–3.66 m (1H, 7-CH), 6.10 br.s (1H, OH). Found,
%: Br 28.19, 28.47; N 5.03, 5.26. C12H14BrNO2. Cal-
culated, %: Br 28.12; N 4.93.
5-Bromo-7-isopropyl-4-methyl-2-phenyl-1,3-
benzoxazol-6-ol (XIIIa). Yield 74%, mp 156–
157.5°C. H NMR spectrum, δ, ppm: 1.52 d (6H,
7-tert-Butyl-4,5-dichloro-2-phenyl-1,3-benzoxa-
zol-6-ol (XVa). Yield 68%, mp 189–190°C. H NMR
1
1
CHMe2, J = 6.6 Hz), 3.02 br.s (3H, 4-Me), 3.65–
3.75 m (1H, 7-CH), 6.12 br.s (1H, OH), 7.68–8.75 m
(5H, Ph). Found, %: Br 22.89, 23.17; N 4.15, 4.26.
C17H16BrNO2. Calculated, %: Br 23.08; N 4.05.
spectrum, δ, ppm: 1.67 s (9H, t-Bu), 6.12 br.s (1H,
OH), 7.52–8.23 m (5H, Ph). Found, %: Cl 21.19,
21.37; N 4.06, 4.58. C17H15Cl2NO2. Calculated, %:
Cl 21.09; N 4.17.
5-Bromo-7-isopropyl-4-methyl-2-(4-methyl-
7-tert-Butyl-4,5-dichloro-2-(4-methylphenyl)-1,3-
benzoxazol-6-ol (XVb). Yield 63%, mp 173–174°C.
1H NMR spectrum, δ, ppm: 1.66 s (9H, t-Bu), 2.45 s
(3H, MeC6H4), 6.11 br.s (1H, OH), 7.32–8.12 d.d (4H,
C6H4, J = 7.8 Hz). 13C NMR spectrum, δC, ppm: 21.58
(Me), 30.37 [C(CH3)3], 36.41 [C(CH3)3], 117.60 (C6),
119.53 (C4), 119.63 (C5), 123.77 (C7), 127.39 (C3′, C5′),
129.36 (C2′, C6′), 134.58 (C3a), 141.92 (C1′), 147.99
(C4′), 148.06 (C7a), 162.75 (C2). Found, %: Cl 20.37,
20.55; N 4.16, 4.39. C18H17Cl2NO2. Calculated, %:
Cl 20.24; N 4.00.
phenyl)-1,3-benzoxazol-6-ol (XIIIb). Yield 72%,
1
mp 163.5–165°C. H NMR spectrum, δ, ppm: 1.48 d
(6H, CHMe2, J = 6.6 Hz), 2.50 br.s (3H, MeC6H4),
2.91 br.s (3H, 4-Me), 3.64–3.73 m (1H, 7-CH),
6.17 br.s (1H, OH), 7.44–8.48 d.d (4H, C6H4, J =
7.8 Hz). Found, %: Br 22.19, 22.38; N 3.56, 3.74.
C18H18BrNO2. Calculated, %: Br 22.18; N 3.89.
5-Bromo-2-(4-chlorophenyl)-7-isopropyl-4-meth-
yl-1,3-benzoxazol-6-ol (XIIIc). Yield 81%, mp 168.5–
1
169.5°C. H NMR spectrum, δ, ppm: 1.47 d (6H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011