TROFIMOV et al.
1258
Likewise, from 16 g (276 mmol) of acetone, 16.4 g
REFERENCES
(45 mmol) of dibenzo-18-crown-6, and 0.86 g
(15 mmol) of calcined KOH in 100 ml of DMSO, after
appropriate treatment, we isolated a fraction boiling in
the temperature range from 50 to 140°C (720 mm),
18.61 g, which contained 52.3% (9.73 g, 168 mmol) of
acetone (conversion 39%), 6.9% (1.28 g, 15 mmol)
of 2-methyl-3-butyn-2-ol (yield 5%), and DMSO
(Table 2, run no. 6).
1. Kotlyarevskii, I.L., Shvartsberg, M.S., and Fisher, L.B.,
Reaktsii atsetilenovykh soedinenii (Reactions of Acetyl-
enic Compounds), Novosibirsk: Nauka, Sib. Otd., 1967.
2. Trofimov, B.A., Curr. Org. Chem., 2002, p. 1121.
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vol. 34, p. 435.
Ethynylation of acetone in the presence of di-
benzo-18-crown-6·KOH·MeOH in DMSO. a. A sus-
pension of 7.01 g (15 mmol) of the complex dibenzo-
18-crown-6·KOH·MeOH containing 11.98% of KOH
(according to the potentiometric titration data) in 50 ml
of DMSO was cooled to 11–13°C and saturated with
acetylene over a period of 7 h under vigorous stirring.
Acetone, 16 g (276 mmol), was added over a period of
7 h at that temperature, the mixture was stirred for 2 h
under continuous supply of acetylene, neutralized with
carbon dioxide, and filtered, and the filtrate was dis-
tilled under reduced pressure. A fraction (7.31 g) was
collected in a cooled trap (–60 to –70°C); it contained
95% (6.94 g, 120 mmol) of acetone and 2.4% (0.18 g,
2 mmol) of 2-methyl-3-butyn-2-ol. Another fraction
boiled in the temperature range from 50 to 90°C
(60 mm), 5.02 g; it contained 2% (0.11 g, 2 mmol) of
acetone, 24% (1.20 g, 14 mmol) of 2-methyl-3-butyn-
2-ol (overall yield 1.38 g, 16 mmol, 6%), and DMSO.
Conversion of acetone 56% (Table 2, run no. 7).
4. Vitkovskaya, N.M., Kobychev, V.B., Matveenko, N.Yu.,
Dubnikova, F.S., Dolgunicheva, O.Yu., and Trofi-
mov, B.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1990,
p. 1793.
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na, I.M., Zh. Org. Khim., 1967, vol. 3, p. 2075.
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Gusarova, N.K., and Vyalykh, E.P., Fundamental’nye
issledovaniya. Khimicheskie nauki (Fundamental Re-
search. Chemical Sciences), Novosibirsk: Nauka, Sib.
Otd., 1977, p. 174; Trofimov, B.A., Z. Chem., 1986,
vol. 26, p. 41; Trofimov, B.A., Zh. Org. Khim., 1986,
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1995, vol. 31, p. 1233.
7. Moskovskaya, T.E., Vitkovskaya, N.M., and Trofi-
mov, B.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1982,
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shtein, V.G., and Trofimov, B.A., Izv. Akad. Nauk SSSR,
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skaya, T.E., and Trofimov, B.A., Izv. Akad. Nauk SSSR,
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b. A suspension of 6.97 g (15 mmol) of dibenzo-18-
crown-6·KOH·MeOH (12.06% of KOH, potentio-
metric titration) in 50 ml of DMSO was vigorously
stirred and heated to 130°C over a period of 1 h until
a dark brown transparent solution was obtained. The
solution was slowly cooled to 20–22°C and saturated
with acetylene over a period of 1.5 h, 16 g (276 mmol)
of acetone was added over a period of 40 min, and the
mixture was stirred for 3 h under continuous supply of
acetylene. The mixture was neutralized with carbon
dioxide and filtered. The filtrate was distilled to isolate
a fraction boiling in the temperature range from 50
to 150°C (724 mm), 23.5 g, which contained 40.3%
(9.47 g, 163 mmol) of acetone (conversion 41%),
2.7% (0.63 g, 7.5 mmol) of 2-methyl-3-butyn-2-ol
(yield 3%), and DMSO (Table 2, run no. 8).
8. Gokel, G.W., DiBiase, S.A., and Lipusko, B.A., Tetra-
hedron Lett., 1976, vol. 39, p. 3495.
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This study was performed under financial support
by the President of the Russian Federation (program
for support of leading scientific schools, project
no. NSh-2241.2003.3).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005