REACTIONS OF 2-(α-HALOALKYL)THIIRANES WITH NUCLEOPHILIC REAGENTS: V.
1825
drochloric acid to pH 6. The organic phase was sepa-
rated, the aqueous phase was extracted with diethyl
ether (30 ml), the extracts were combined with the
organic phase, washed with a saturated aqueous solu-
tion of sodium chloride, and dried over sodium sulfate,
the solvent was distilled off, and the residue was dis-
tilled under atmospheric pressure. Yield 2.9 g (30%),
bp 91–92°C.
washed with a saturated solution of NaCl, dried over
Na2SO4, and evaporated. Volatile components were
distilled off under reduced pressure (1 mm) up to
a temperature of 100°C and were then distilled again.
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Reaction of thiiranes Ib–If with organolithium
reagents (general procedure). A solution of 0.1 mol of
thiirane Ib–If in 60 ml of anhydrous diethyl ether was
cooled to a required temperature, and 60 ml of a solu-
tion of an equivalent amount of the corresponding
organolithium compound in diethyl ether was added
dropwise with stirring under argon. The progress of the
reaction was monitored by GLC (until the conversion
of the initial thiirane exceeded 90%). The mixture was
then allowed to warm up to room temperature, water
was added to dissolve the precipitate (30–60 ml), the
mixture neutralized to pH 6 by adding 10% hydro-
chloric acid, the organic phase was separated, washed
with saturated aqueous solutions of Na2CO3 and NaCl,
and dried over Na2SO4, the solvent was distilled off,
and the residue was distilled under reduced pressure.
The yields of isolated individual compounds are given
in the corresponding schemes; mixtures of isomeric
products were not separated, and their yields were cal-
culated on the basis of the overall yield and isomer
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1
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Reaction of thiiranes Ia–If with organolithium
reagents in the presence of copper(I) iodide (general
procedure). A solution of 0.15 mol of organolithium
compound in 60 ml of anhydrous diethyl ether was
added dropwise with stirring under argon to a mixture
of 0.1 mol of thiirane Ia–If and 2.0 g (0.01 mol) of
CuI in 60 ml of anhydrous diethyl ether, cooled to
a required temperature. The mixture was stirred until
the conversion of the initial thiirane exceeded 90%
(GLC), allowed to warm up to room temperature,
treated with water (20 ml), and neutralized with
10% hydrochloric acid to pH 6. The red–black precip-
itate was filtered off, the organic phase was separated
from the filtrate and washed with saturated aqueous
solutions of Na2CO3 and NaCl. After 30 min, the bright
yellow precipitate was filtered off, and the filtrate was
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 12 2010