J = 5.6, CH2); 6.48 (1H, br. s, NH); 6.73 (1H, d, J = 8.6, H-4); 7.24 (1H, s, H-6); 7.26-7.35 (5H, m, C6H5); 7.39
(1H, d, J = 8.6, H-3); 12.21 (1H, s, OH). Found, %: C 64.88; H 4.75; Cl 13.39; N 5.21. C14H18ClNO2.
Calculated, %: C 64.75; H 4.62; Cl 13.55; N 5.35.
3-Benzyl-6-chloro-8'-formyl-7'-hydroxy-4-oxo-3,4-dihydro-2H-1,3-benzoxazine-2-spiro-2'-[2H]-
1
chromene(4c) was prepared similarly from compound 8 and 2,4-dihydroxyisophthalaldehyde. H NMR
spectrum, δ, ppm (J, Hz): 4.76 and 5.04 (2H, AB spectrum, J = 15.9, NCH2); 5.82 (1H, d, J = 9.9, H-3'); 6.58
(1H, d, J = 8.4, H-6'); 6.84 (1H, d, J = 8.6, H-8); 6.88 (1H, d, J = 10.7, H-4'); 7.15-7.24 (5H, m, C6H5); 7.32 (1H,
d, J = 8.6, H-5'); 7.45 (1H, t, J = 8.8, H-7); 8.08 (1H, d, J = 2.6, H-5); 9.7 (1H, s, CHO); 11.64 (1H, s, OH).
8'-Formyl-7'-hydroxy-1,3,3-trimethylspiroindoline-2,2'-[2H]chromene (6a). Piperidine (0.1 ml,
1.1 mmol) was added dropwise with heating to a solution of aldehyde 1 (166 mg, 1 mmol) and
1,2,3,3-tetramethylindolenium perchlorate 5 (274 mg, 1 mmol) in 2-propanol (5 ml). The reaction mixture was
refluxed for 10 min and cooled. The precipitate was filtered off and recrystallized. 1H NMR spectrum, δ, ppm (J,
Hz): 1.15, 1.25 (6H, 2s, gem (CH3)2); 2.72 (3H, s, NCH3); 5.68 (1H, d, J = 10.5, H-3'); 6.34 (1H, d, J = 8.7, H-
6'); 6.53 (1H, d, J = 7.8, H-5'); 6.85 (1H, t, J = 7.4, H-5); 7.08 (1H, d, J = 7.3, H-4); 7.19 (1H, t, J = 7.6, H-6);
7.25 (1H, d, J = 10.5, H-4'); 7.27 (1H, d, J = 8.4, H-7); 9.63 (1H, s, CHO); 11.78 (1H, s, OH).
5-Chloro-8'-formyl-7'-hydroxy-1,3,3-trimethylspiropindoline-2,2'-[2H]chromene(6b) was prepared
similarly to compound 6a from 1,2,3,3-tetramethylindolenium perchlorate and 2,4-dihydroxyisophthalaldehyde.
1H NMR spectrum, δ, ppm (J, Hz): 1.16, 1.26 (6H, 2s, gem (CH3)2); 2.68 (3H, s, NCH3); 5.66 (1H, d, J = 10.5,
H-3'); 6.53 (1H, d, J = 7.8, H-7'); 6.85 (2H, m, H-4,6); 7.08-7.25 (3H, m, H-8',4',7); 9.64 (1H, s, CHO); 11.64
(1H, s, OH).
3-Methyl-4-oxo-3,4-dihydro-2H-1,3-benzoxazine-2-spiro-2'-2H,8H-pyrano[2,3-f]chromene-8'-spiro-
2'',1'',3'',3''-trimethylindoline (7a). Piperidine (0.1 ml, 1.1 mmol) was added dropwise with stirring to a
solution of the spiropyran 4a (0.323 g, 1 mmol) and 1,2,3,3,-tetramethylindolenium perchlorate (0.274 g,
1 mmol) in 2-propanol (5 ml). The reaction mixture was refluxed for 10 min and cooled. The precipitate was
1
filtered off and recrystallized. H NMR spectrum, δ, ppm (J, Hz): 1.08 (3H, s, 3''-CH3); 1.21 (3H, s, 3''-CH3);
2.64 (3H, s, 1''-CH3); 3.18 (3H, s, 3-CH3); 5.50 (1H, d, J = 8.7, H-9'); 5.87 (1H, d, J = 9.7, H-3'); 6.30-7.60 (11H,
m, H-4',10', arom); 8.08 (1H, d, J = 7.8, H-8).
3-Methyl-4-oxo-3,4-dihydro-2H-1,3-benzoxazine-2-spiro-2'-2H,8H-pyrano[2,3-f]chromene-8'-spiro-
1
5''-chloro-2'',1'',3'',3''-trimethylindoline (7b) was synthesized similarly to compound 7a. H NMR spectrum,
δ, ppm (J, Hz): 1.08 (3H, s, 3''-CH3); 1.22 (3H, s, 3''-CH3); 2.62 (3H, s, 1''-CH3); 3.18 (3H, s, 3-CH3); 5.45 (1H,
d, J = 8.8, H-9'); 5.87 (1H, d, J = 9.7, H-3'); 6.30-7.60 (10H, m, H-4',10', arom.); 8.08 (1H, d, J = 7.8, H-8).
3-Benzyl-4-oxo-3,4-dihydro-2H-1,3-benzoxazine-2-spiro-2'-2H,8H-pyrano[2,3-f]chromene-8'-spiro-
1
2'',1'',3'',3''-trimethylindoline (7c) was synthesized similarly to compound 7a. H NMR spectrum, δ, ppm
(J, Hz): 1.08 (3H, s, 3''-CH3); 1.22 (3H, s, 3''-CH3); 2.65 (3H, s, 1''-CH3); 4.58 and 5.24 (2H, AB spectrum,
J = 16.0, NCH2); 5.48 (1H, d, J = 7.9, H-9'); 5.72 (1H, d, J = 9.7, H-3'); 6.30-7.60 (16H, m, H-4',10' arom); 8.08
(1H, d, J = 7.8, H-8).
3-Benzyl-4-oxo-3,4-dihydro-2H-1,3-benzoxazine-2-spiro-2'-2H,8H-pyrano[2,3-f]chromene-8'-spiro-
1
5''-chloro-2'',1'',3'',3''-trimethylindoline (7d) was prepared similarly to compound 7a. H NMR spectrum,
δ, ppm (J, Hz): 1.08 (3H, s, 3''-CH3); 1.22 (3H, s, 3''-CH3); 2.65 (3H, s, 1''-CH3); 4.56 and 5.25 (2H, AB
spectrum, J = 15.9, NCH2); 5.48 (1H, d, J = 7.9, H-9'); 5.72 (1H, d, J = 9.7, H-3'); 6.30-7.60 (15H, d, H-4',10',
arom); 8.08 (1H, d, J = 7.8, H-8);
X-ray Structural Investigation of Compounds 4a and 6a. Crystals of 4a and 6a for X-ray were
prepared by crystallization from isopropyl alcohol. The X-ray experiment was performed on a KYMA
automatic, four circle diffractometer (CuKα irradiation) at T = 293 K in the θ angle range from 4.14 to 79.76°
for compound 4a and from 4.26 to 80.0° for compound 6a.
The basic crystallographic data for 4a (C18H13NO5): a = 7.302(2), b = 19.115(2), c = 10.867(3) Å;
β = 101.08(5)°; V = 1154.3(9) Å3; P21/c; Z = 4 (monoclinic); d = 1.443 g/cm3; F(000) = 672; M = 323.29. The
structure of 4a was solved by a direct method using least squares analysis for F2 to R = 0.043 (Rw = 0.062 for
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