Chemistry of Heterocyclic Compounds 2015, 51(3), 223–228
into water (130 ml), neutralized with conc. aqueous ammonia
(1H, m, H-4" benzoxazole); 8.03 (1H, d, J = 2.6, H-7').
13C NMR spectrum, δ, ppm: 11.7; 19.7; 22.1; 25.0; 45.7;
52.4; 106.4; 108.3; 110.6; 110.7; 115.3; 119.6; 121.0;
121.4; 124.1; 124.3; 124.6; 125.0; 128.8; 129.2; 129.8;
130.0; 139.5; 141.0; 147.1; 150.8; 151.6; 160.9. Mass
spectrum, m/z (Irel, %): 536 [M]+ (100), 521 [M–CH3]+
(92). Found, %: C 62.53; H 4.42; N 5.10. C28H24BrClN2O2.
Calculated, %: C 62.76; H 4.51; N 5.23.
to рН 6–7, the precipitate was filtered off, washed with water,
dried, purified by chromatography on alumina column (eluent
chloroform), and recrystallized from 1:1 toluene–2-PrOH
mixture. Yield 2.02 g (76%), mp 188–190°C. 1H NMR
spectrum, δ, ppm (J, Hz): 7.45–7.54 (2H, m, H-5,6
benzoxazole); 7.65–7.73 (1H, m, H-7 benzoxazole); 7.78–7.86
(1H, m, H-4 benzoxazole); 7.92 (1H, d, J = 2.7, H-4); 8.21
(1H, d, J = 2.7, H-6); 10.60 (1H, s, 1-CHO); 12.06 (1H, s,
2-OH). Found, %: C 61.53; H 2.85; N 5.20. C14H8ClNO3.
Calculated, %: C 61.44; H 2.95; N 5.12.
8'-(1,3-Benzoxazol-2-yl)-5,6'-dichloro-1,3,3-trimethyl-
spiro[indoline-2,2'-chromene] (4d). Yield 59%, mp 187–
1
189°C (1:1 heptane–toluene). H NMR spectrum, δ, ppm
8'-(1,3-Benzoxazol-2-yl)-6'-chloro-3,3-dimethylspiro-
[indoline-2,2'-chromenes] 4a–d (General method). A mixture
of 3Н-indolinium salt 3a–d (1 mmol), triethylamine (0.14 ml,
(J, Hz): 1.22 (3H, s, 3-CH3); 1.32 (3H, s, 3-CH3); 2.68 (3H,
s, 1-CH3); 5.88 (1H, d, J = 10.3, H-3'); 6.44 (1H, d, J = 8.2,
H-7'); 6.88 (1H, d, J = 10.3, H-4'); 6.90–6.93 (1H, m, H-7"
benzoxazole); 7.17 (1H, d, J = 2.6, H-5'); 7.06 (1H, d,
J = 2.1, H-4); 7.16 (1H, dd, J = 8.2, J =2.1, H-6); 7.24–
7.27 (2H, m, H-5",6" benzoxazole); 7.62–7.65 (1H, m, H-4"
benzoxazole); 8.04 (1H, d, J = 2.6, H-7). Mass spectrum, m/z
(Irel, %): 463 [M]+ (53), 447 [M–CH3]+ (100). Found, %:
C 67.57; H 4.22; N 6.14. C26H20Cl2N2O2. Calculated, %:
C 67.39; H 4.35; N 6.05.
1
mmol), and aldehyde 2 (0.27 g, 1 mmol) in toluene
(10 ml) and 2-propanol (4 ml) was refluxed for 5 h, the
solvent was evaporated, the residue was separated by
chromatography on alumina column (eluent benzene) and
recrystallized.
8'-(1,3-Benzoxazol-2-yl)-1-benzyl-6'-chloro-3,3-di-
methylspiro[indoline-2,2'-chromene] (4a). Yield 60%,
1
mp 177–179°C (heptane). H NMR spectrum, δ, ppm (J,
Hz): 1.34 (3H, s, 3-CH3); 1.38 (3H, s, 3-CH3); 4.13 (1H, d,
J = 16.4) and 4.49 (1H, d, J = 16.4, 1-CH2Ph); 5.97 (1H, d,
J = 10.3, H-3'); 6.31 (1H, d, J = 7.7, H-7); 6.82 (1H, d,
J = 10.3, H-4'); 6.84–6.86 (1H, m, H-7" benzoxazolyl);
6.91 (1H, t, J = 7.4, H-5); 7.05–7.23 (6H, m, H-4,6,5',
Н Ph); 7.25–7.31 (4H, m, H-5'',6'' benzoxazolyl, Н Ph);
7.62–7.66 (1H, m, H-4" benzoxazolyl); 8.05 (1H, d,
J = 2.6, H-7'). 13C NMR spectrum, δ, ppm: 20.1; 25.5;
47.9; 52.4; 106.4; 108.1; 110.6; 115.2; 119.6; 121.3; 121.5;
124.3; 124.9; 125.0; 126.7; 126.9; 127.3; 128.4; 128.8;
129.2; 130.0; 137.0; 139.0; 141.1; 147.7; 150.9; 151.7;
161.0. Mass spectrum, m/z (Irel, %): 505 [M]+ (100), 489
[M–CH3]+ (36). Found, %: C 76.21; H 5.14; N 5.69.
C32H25ClN2O2. Calculated, %: C 76.11; H 4.99; N 5.55.
The work was performed with financial support from the
Russian Foundation for Basic Research (grant 13-03-
00901).
References
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methylspiro[indoline-2,2'-chromene] (4b). Yield 53%,
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1.22 (3H, s, 3-CH3); 1.32 (3H, s, 3-CH3); 2.67 (3H, s,
1-CH3); 5.88 (1H, d, J = 10.3, H-3'); 6.40 (1H, d, J = 8.2,
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(100). Found, %:
C
61.58;
H
3.83;
N
5.67.
C26H20BrClN2O2. Calculated, %: C 61.50; H 3.97; N 5.52.
8'-(1,3-Benzoxazol-2-yl)-5-bromo-6'-chloro-3,3-di-
methyl-1-propylspiro[indoline-2,2'-chromene]
(4c).
1
Yield 56%, mp 158–160°C (heptane). H NMR spectrum,
δ, ppm (J, Hz): 0.85 (3H, t, J = 7.4, 1-CH2CH2CH3); 1.21
(3H, s, 3-CH3); 1.30 (3H, s, 3-CH3); 1.46–1.66 (2H, m,
1 CH2CH2CH3); 2.94–3.14 (2H, m, 1-CH2CH2CH3); 5.87
(1H, d, J = 10.3, H-3'); 6.41 (1H, d, J = 8.2, H-7); 6.85
(1H, d, J = 10.3, H-4'); 6.92–6.96 (1H, m, H-7" benz-
oxazole); 7.16 (1H, d, J = 2.6, H-5'); 7.18 (1H, d, J = 2.0,
H-4); 7.25–7.31 (3H, m, H-6,5'',6'' benzoxazole); 7.62–7.65
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