2268
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 12, December, 2017
Novokshonov et al.
THF (20 mL), the mixture was cooled to –70 °С and diisoproꢀ
pylamine (2.02 g, 0.02 mol) in anhydrous THF (5 mL) was
added over 2 min with stirring, which was accompanied by
spontaneous increase in temperature to –50 °С. Then, the temꢀ
perature of the mixture was raised to –10 °С over 10 min with
stirring. The resulting solution of LDA was cooled to –70 °С
and 3ꢀtrimethylsilyloxypropyne (1) (2.6 g, 0.02 mol) in anꢀ
hydrous THF (5 mL) was added over 5 min. The temperature
was gradually raised to 0 °С over 3 h and the mixture was poured
into a glass containing NH4Cl (7 g), followed by the addition of
saturated solution of NH4Cl (10 mL). The aqueous phase was
extracted with diethyl ether, the combined extracts were washed
with saturated aqueous NH4Cl (10 mL) and dried with MgSO4.
The evaporation of the solvent left a residue (1.9 g). GLC analꢀ
ysis showed that 1ꢀtrimethylsilylꢀ3ꢀtrimethylsilyloxypropyne (8)
(39%) and propargyl alcohol were isolated.
B. (with 2 equiv. of LDA). Ether 1 (2.6 g, 0.02 mol) in
anhydrous THF (5 mL) was added over 2 min to lithium diisoꢀ
propylamide obtained as described in method А from 1.6 М
solution of BunLi (26 mL, 0.042 mol) in anhydrous hexane and
diisopropylamine (4.05 g, 0.04 mol) at –70 °С. The reaction
was carried out according to the procedure described above.
The isolated residue (1.6 g) contained 1ꢀtrimethylsilylꢀ3ꢀtriꢀ
methylsilyloxypropyne (8) (33%) and propargyl alcohol
(GLC data).
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of the Siberian Branch of the Russian Academy of Sciꢀ
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Received June 26, 2017;
in revised form September 29, 2017