932
SHCHEPIN et al.
δ, ppm: 1.85 s (3H, CH3), 2.06 s (3H, CH3), 3.80 s
(3H, COOCH3), 3.87 s (3H, COOCH3), 4.37 s (1H,
CH), 7.25–8.31 m (4H, 4-BrC6H4). Found, %: C 52.87;
H 4.00; N 2.73. C187H17O10. Calculated, %: C 53.08; H
4.21; N 3.44.
Dialkyl
2-{4-[2,2-bis(alkoxycarbonyl)-6,6-di-
methyl-4,8-dioxo-5,7-dioxaspiro[2.5]oct-1-yl]phenyl}-
6,6-dimethyl-4,8-dioxo-5,7-dioxaspiro[2.5]octane-
1,1-dicarboxylates (XIIa, XIIb). These compounds
were prepared analogously to compounds XIa, XIb.
Dialkyl
2-{4-[3,3-bis(alkoxycarbonyl)-1',3'-
Dimethyl 2-{4-[2,2-bis(methoxycarbonyl)-6,6-di-
methyl-4,8-dioxo-5,7-dioxaspiro[2,5]oct-1-yl]phe-
nyl}-6,6-dimethyl-4,8-dioxo-5,7-dioxaspiro[2.5]oc-
tane-1,1-dicarboxylate (XIIa). Yield 47%, mp 255–
257°C. IR spectrum (mineral oil), ν, cm–1: 1720, 1735.
1H NMR spectrum, δ, ppm: 1.75 s (6H, 2CH3), 1.92 s
(6H, 2CH3), 3.67 s (6H, 2COOCH3), 3.70 s (6H,
2COOCH3), 4.04 s (2H, 2CH), 7.262 s (4H, C6H4).
Found, %: C 54.80; H 3.94. C30H30O16. Calculated, %:
C 55.73; H 4.68.
dioxospiro[cyclopropane-2,2'-indan]-1-yl]phenyl}-
1',3'-dioxospiro[cyclopropane-2,2'-indan]-1,1-dicar-
boxylates (XIa, XIb). A mixture of 0.5 g of zinc
turnings and 20 ml of THF was treated with 0.0064
mol of dibromomalonic ester, and the resulting mixture
was heated until the beginning of the process. After
that the reaction proceeded spontaneously. After the
completion of the process the mixture obtained was
refluxed for 15 min, cooled, and the organic phase was
decanted into another flask, 0.0025 mol of 2-[4-(1,3-
dioxoindan-2-ylidenemethyl)phenyl]methyleneindan-
1,3-dione was added, and the resulting mixture was
refluxed for 40–50 min. The reaction mixture was
cooled, hydrolyzed with 5% acetic acid, and the
reaction product was extracted with benzene. The
extract was dried over Na2SO4, solvents were distilled
off, and the residue was crystallized from methanol.
Diethyl 2-{4-[2,2-bis(ethoxycarbonyl)-6,6-dime-
thyl-4,8-dioxo-5,7-dioxaspiro[2,5]oct-1-yl]phenyl}-
6,6-dimethyl-4,8-dioxo-5,7-dioxaspiro[2.5]octane-
1,1-dicarboxylate (XIIb). Yield 53%, mp 210–212°C.
1
IR spectrum (mineral oil), ν, cm–1: 1720, 1740. H
NMR spectrum, δ, ppm: 1.17 q (12H, CH3-ethyl, J
9.3 Hz), 1.76 s (6H, 2CH3), 1.94 s (6H, 2CH3), 4.025 s
(2H, 2CH), 4.09–4.266 m (8H, CH2OOC), 7.28 s (4H,
C6H4). Found, %: C 57.37; H 4.84. C34H38O16.
Calculated, %: C 58.12; H 5.45.
Dimethyl 2-{4-[3,3-bis(methoxycarbonyl)-1',3'-
dioxospiro[cyclopropane-2,2'-indan]-1-yl]phenyl}-
1',3'-dioxospiro[cyclopropane-2,2'-indan]-1,1-dicar-
boxylate (XIa). Yield 43%, mp 241–243°C. IR
ACKNOWLEDGMENTS
spectrum (mineral oil), ν, cm–1: 1700–1745. H NMR
1
spectrum, δ, ppm: 3.60 s (6H, 2COOCH3), 3.69 s (6H,
2COOCH3), 3.89 s (2H, 2CH), 7.10–7.27 m (4H,
C6H4), 7.80–7.90 m (8H, 2C6H4). Found, %: C 65.84;
H 3.72. C36H26O12. Calculated, %: C 66.46; H 4.03.
The work was carried out with a financial support
from the Russian Foundation for Basic Research (grant
no. 07-03-96035).
Diethyl
2-{4-[3,3-bis(ethoxycarbonyl)-1',3'-di-
REFERENCES
oxospiro[cyclopropane-2,2'-indan]-1-yl]phenyl}-
1',3'-dioxospiro[cyclopropane-2,2'-indan]-1,1-dicar-
boxylate (XIb). Yield 45%, mp 109–111°C. IR
1. Gaudemar-Bordone, F. and Gaudemar, M., Bull. Soc.
Chim. France, 1971, vol. 10, no. 12, p. 4188.
1
spectrum (mineral oil), ν, cm–1: 1700–1745. H NMR
2. Shchepin, V.V., Stepanyan, Yu.G., Silasichev, P.S., and
Kodess, M.I., Zh. Obshch. Khim., 2006, vol. 76, no. 12,
p. 2008.
spectrum, δ, ppm: 1.14 t, 1.21 t (6H, CH3-ethyl, J
7.4 Hz), 1.18 t, 1.28 t (6H, CH3-ethyl, J 7.4 Hz), 3.99 s
(2H, 2CH), 4.16–4.22 m (8H, 4COOCH2, J 7.4 Hz),
7.19–7.23 m (4H, C6H4), 7.88–7.95 m (8H, 2C6H4).
Found, %: C 67.03; H 3.95. C40H34O12. Calculated, %:
C 67.98; H 4.85.
3. Shchepin, V.V., Silaichev, P.S., Stepanyan, Yu.G., and
Vakhrin, M.I., Zh. Obshch. Khim., 2006, vol. 76, no. 6,
p. 981.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008