POZDNYAKOV, MOISEEV
274
1-Adamantylacetyl chloride (I) was prepared by
procedure from [11], nD201.5185.
14.5 ml (127.4 mmol) of dimethyl malonate, and 6.37 g
(159.25 mmol of NaOH along the procedure described
for compound II. On distilling off the toluene the
residue was distilled in a vacuum, bp 130–131°C (7
mm Hg), nD20 1.4565. IR spectrum, n, cm–1: 2900
(CH3), 1740 br (COO and CO), 1650 (C=C).1H NMR
spectrum, d, ppm: 2.17 s (3H, COCH3), 2.22 s (3H,
OCOCH3), 3.68 s (3H, OCH3), 3.73 s (3H, COOCH3).
Methyl
[2-(1-adamantylacetyl)-3-(1-adamantyl-
methylcarbonyloxy)-3-methoxy]-2-propenoate (II).
A mixture of 21.5 ml (0.188 mol) of dimethyl
malonate, 9.4 g (0.235 mol) of NaOH, and 100 ml of
toluene was stirred at 25°C for 40 min. Then to the
reaction mixture was added dropwise a solution of 20
g (94 mmol) of acyl chloride I in 100 ml of toluene.
The reaction mixture was stirred at room temperature
for 1 h and then it was poured into 400 ml of 10%
aqueous sulfuric acid. The toluene layer was separated,
washed in succession with water, water solution of
sodium carbonate, and again with water. Toluene was
distilled off, and the residue was crystallized from
hexane. Yield 18.5 g (81%), mp 134–135°C. IR
spectrum, n, cm–1: 1780 (COO), 1750 (CO), 1660
(C=C). 1H NMR spectrum, d, ppm: 1.55–1.65 m (24H,
12CH2 in Àd), 1.95 s (6H, 6CH in Àd), 2.2 s (2H,
CH2), 2.45 s (2H, CH2), 3.68 s (3H, OCH3), 3.73 s
(3H, COOCH3). Mass spectrum, m/z (Irel, %): 484 (9.5)
[ Ì]+, 352 (2.5), 335 (6.4), 324 (8.7), 277 (8.1), 244
(8.2), 177 (43.5), 148 (39.3), 136 (43.5), 135 (100),
119 (51.1), 107 (33.1), 105 (31.9), 93 (47.8), 79 (52.3),
67 (41.3), 59 (45.7), 55 (47.8), 43 (90.5).
IR spectra were recorded on spectrometer IKS-22.
1H NMR spectra were registered on spectrometers
Bruker ÀC-200 and Bruker ÀÌ -300 at operating
frequencies 200 and 300 MHz respectively, solvent
DMSO-d6, internal reference HMDS. Mass spectrum
was measured on Finnigan MAN JNCOS50
instrument, ionizing electrons energy 70 eV.
REFERENCES
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Dimethyl benzoylmalonate (V) was prepared from
5 g (35.7 mmol) of benzoyl chloride, 8.2 ml (71.4
mmol) of dimethyl malonate, and 3.57 g (89.25 mmol)
of NaOH along the procedure described for compound
II. On distilling off the toluene the residue was
distilled in a vacuum, bp 168–171°C (2 mm Hg),
nD201.5270. IR spectrum, n, cm–1: 2860 (CH3), 1730
8. Kol’tsov, A.I., Izv. Akad. Nauk SSSR, Ser. Khim., 1979,
p. 1365.
(COO), 1650 (CO), 1600 (C=C).1H NMR spectrum, d, 9. Bankowska, Z., Zadrozna, I., and Bochenska, J., Pol. J.
Chem., 1980, vol. 54, p. 461.
ppm: 3.73 s (6H, 2COOCH3), 6.1 s (1H, CH), 7.59 t,
7.7 t, 7.97 d (2H, 1H, 2H, C6H5).
10. Zhang, Shizhong and Bordweel, F.G., J. Org. Chem.
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11. Stepanov, F.N., Isaev, S.D., and Vasil'eva, Z.P., Zh. Org.
Khim., 1970, vol. 6, p. 53.
Methyl (2-acetyl-3-methoxy)-2-propenoate (VI)
was prepared from 5 g (63.7 mmol) of acetyl chloride,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2003