CHEMISTRY OF DIOXACYCLOALKANES: VII.
139
at 18 20 C 30.4 g of 50% peroxyacetic acid over
a period of 60 min. The mixture was stirred for
an additional 1.5 h and treated with a 5% solution of
sodium carbonate. The organic phase was washed
with water, dried over MgSO4, and evaporated, and
the residue was distilled under reduced pressure to
and the residue was subjected to vacuum distillation
to isolate product XVI (see table).
2-(3,4-Dibromocyclohexyl)-4-methyl-1,3-dioxo-
lane (XVII). Bromine, 25.6 g (0.16 mol), was added
dropwise to a mixture of 25.2 g (0.15 mol) of com-
pound I and 50 ml of chloroform, stirred at 5 to
10 C. The mixture was stirred for an additional
1.5 2 h and washed with a 5% solution of sodium
hydroxide and water. The aqueous phase was ex-
tracted with chloroform, and the extract was combined
with the organic phase, washed with water, dried
over CaCl2, and evaporated. The residue was distilled
under reduced pressure to isolate 33.8 g (69%) of
product XVII (see table). Compound XVIII was
obtained in a similar way.
2-(7,7-Dichloro-4-methylbicyclo[4.1.0]hept-3-yl)-
4-methyl-1,3-dioxolane (XIX). Chloroform, 15 ml,
was added dropwise with stirring to a mixture of
25 ml of 50% aqueous sodium hydroxide, 10 ml of
benzene, 0.2 g of benzyltriethylammonium chloride,
and 9.2 g (0.05 mol) of compound II. The mixture
spontaneously warmed up to 30 C. It was stirred for
an additional 3 h, diluted with ether, washed with
a 1% aqueous solution of acetic acid and with water,
dried over MgSO4, and evaporated. Vacuum distilla-
tion of the residue gave 21.5 g (63%) of product XIX.
1H NMR spectrum (CCl4), , ppm: 0.9 1.20 d (3H,
CH3), 1.45 2.25 m (7H, cyclohexane), 4.46 d (1/2H,
OCHO-trans, J = 7 Hz), 4.59 d (1/2H, OCHO-cis,
J = 7 Hz).
1
isolate compound IX (see table). H NMR spectrum
(CCl4), , ppm: 1.25 2.25 m (7H, CH2CH2CHCH2),
2.95 d (2H, 2CH, oxirane), 3.25 4.30 m (3H, CH2O,
CHO), 4.55 d (1/2H, OCHO-trans), 4.65 d (1/2H,
OCHO-cis). Compounds X XIII were obtained in
a similar way (see table).
2-(3-Cyclohexenyl)-4-methoxymethyl-1,3-dioxo-
lane (XIV). A mixture of 9.6 g (0.3 mol) of methanol
and 4 g of powdered sodium hydroxide was stirred for
60 min at 65 70 C, 20.3 g (0.1 mol) of compound V
was added, and the mixture was heated to 75 80 C
and stirred for 4 h at that temperature. It was then
cooled, diluted with ether, neutralized with acetic
acid, washed with water, dried over MgSO4, and
evaporated. Vacuum distillation of the residue gave
product XIV (see table).
2-(3-Cyclohexenyl)-4-propylthiomethyl-1,3-di-
oxolane (XV). a. To 18.7 g (0.25 mol) of propane-
thiol we added dropwise 15 ml of a 40% solution of
sodium hydroxide, and the mixture was stirred for
60 min at 85 90 C. The mixture was cooled to room
temperature, 48.6 g (0.24 mol) of compound V was
added in one portion, and the mixture was stirred for
3 4 h at 125 C. The product was isolated as described
above for compound XIV and was purified by vacuum
distillation (see table).
4-Chloromethyl-2-(7,7-dibromobicyclo[4.1.0]-
hept-3-yl)-1,3-dioxolane (XX) was synthesized in
a similar way (see table).
b. A mixture of 55.1 g (0.5 mol) of 3-cyclohexene-
carbaldehyde, 76 g (0.5 mol) of 3-propylthio-1,2-
propanediol, 70 ml of toluene, and 0.16 g (0.3 wt %
with respect to the aldehyde) of KU-2 cation ex-
changer was stirred for 5 h at 130 C with azeotropic
distillation of water. The mixture was filtered, and
the solvent was distilled off. Vacuum distillation of
the residue gave 79.5 g (66%) of compound V with
2-[2(3)-Chloro-3(2)-hydroxybicyclo[2.2.1]hept-5-
yl]-4-methyl-1,3-dioxolane (XXI). Gaseous hydrogen
chloride was passed at 10 to 15 C through a mix-
ture of 11.8 g (0.06 mol) of compound XII and 50 ml
of diethyl ether until a required amount was absorbed
(by weight). The mixture was kept for 3 4 h, washed
with a 2% solution of sodium carbonate and with
water, dried over MgSO4, and evaporated. Vacuum
distillation of the residue gave 9.8 g (70%) of com-
pound XXI (see table).
bp 139 141 C (1 mm), d240 = 1.0486, nD20 = 1.5016.
2-(Bicyclo[2.2.1]hept-5-en-endo-2-yl)-4-diethyl-
aminomethyl-1,3-dioxolane (XVI). A mixture of
21.5 g (0.1 mol) of compound VII, 27.6 g of potas-
sium carbonate, and 36.5 g (0.5 mol) of diethylamine
was stirred for 3 h at 125 130 C. Excess diethylamine
was distilled off, and the mixture was cooled, diluted
with water, and stirred until dissolution of mineral
salts. The organic phase was separated, and the
aqueous phase was extracted with ether. The com-
bined extracts were dried over MgSO4 and evaporated,
The author is grateful to M.G. Babaev for his help
in determining the reaction rates and preparing the
manuscript.
REFERENCES
1. Kerimov, A.Kh., Babaev, M.G., Alieva, E.S., and
Mishiev, D.E., Zh. Obshch. Khim., 1991, vol. 61,
no. 10, pp. 2328 2332.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001