OPARINA et al.
666
The diols used in the study were distilled, NaOH was
REFERENCES
of chemically pure grade, CsF (Sigma-Aldrich) and
DMSO (Merck) were commercial reagents.
1. Oparina, L.A., Shaikhudinova, S.I., Parshina, L.N.,
Vysotskaya, O.V., Preiss, Th., Henkelmann, J., and Trofimov,
B.A., Zh. Org. Khim., 2005, vol. 41, p. 512.
2. Trofimov, B.A., Geteroatomnye proizvodnye atsetilena.
Novye monomery, reagenty i poluprodukty (Heteroatomic
Derivatives of Acetylene. New Monomers, Reagents, and
Intermediates), Moscow: Nauka, 1981, 319 p.
3. Trofimov, B.A., Usp. Khim., 1981, vol. 50, p. 248.
4. Trofimov, B.A., Z. Chem., 1986, vol. 26, p. 41.
5. Trofimov, B.A., Zh. Org. Khim., 1986, vol. 22, p. 1991.
6. Trofimov, B.A., Zh. Org. Khim., 1995, vol. 31, p. 1368.
7. Trofimov, B.A., Current, Org. Chem., 2002, vol. 6, p. 1121.
8. Shostakovskii, M.F., Prostye vinilovye efiry (Vinyl Ethers),
Moscow: Izd.Akad. Nauk SSSR, 1952, 280 p.
9. Reppe, W., Lieb. Ann., 1956, vol. 601, p. 81.
10. Steinborn, D., Mosinski, H., and Rosenstock, T.,
J. Organometal. Chem., 1991, vol. 414, p. 45.
11. Trofimov, B.A., Oparina, L.A., Parshina, L.N., Lavrov, V.I.,
Grigorenko, V.I., and Zhumabekov, M.K., Zh. Org. Khim.,
1986, vol. 22, p. 1583.
12. Trofimov, B.A., Oparina, L.A., Parshina, L.N., Vins, V.V.,
and Lavrov, V.I., Izv. Akad. Nauk SSSR, Ser. Khim., 1989,
p. 2873.
13. Trofimov, B.A., Parshina, L.N., Lavrov, V.I., and Opa-
rina, L.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1984, p. 1670.
14. Trofimov, B.A., Malysheva, S.F., Gusarova, N.K.,
Tatarinova,A.A., and Henkelmann, J., Zh. Org. Khim., 2003,
vol. 39, p. 1428.
15. Oparina, L.A., Parshina, L.N., Khilko, M.Ya., Gorelova, O.V.,
Preiss, Th., Henkelmann, J., and Trofimov, B.A., Zh. Org.
Khim., 2001, vol. 37, p. 1629.
16. Trofimov, B.A., Kudyakova, R.N., Oparina, L.A., Parshina,
L.N., and Vins, V.V., Zh. Prikl. Khim., 1991, vol. 64, p. 873.
17. Ustanovlenie struktury organicheskikh soedinenii fizi-
cheskimi i khimicheskimi metodami (Recognition of
Organic Compounds Structure with Physical and Chemical
Methods), Moscow: Khimiya, 1967.
General procedure for vinylation of diols at
enhanced acetylene pressure. Into a rotating steel
reactor of 1 liter capacity was charged 0.20.6 mols of
diol IaIg, NaOH and CsF in amounts indicated in
Tables 1 and 2 (0.0060.04 mol of each component), and
acetylene was supplied to the initial pressure of 10
14 at. The reaction was carried out at stirring and heating
to 135140°C for 15 h as indicated in Tables 1 and 2.
The reaction products were distilled at atmospheric or
reduced pressure depending on the boiling point of the
monovinyl and divinyl ethers and were analyzed by GLC.
Diol conversions and vinyl ethers yields are given in Tables
1 and 2, the physical constants and spectral characteristics
of compounds obtained are consistent with those
published in [2, 8, 9, 16].
General procedure for vinylation of diols at
atmospheric pressure of acetylene. Into a reaction
flask of 100 ml capacity, equipped with an efficient reflux
condenser, thermometer, magnetic stirrer, and a bubbler
for supplying acetylene was charged 0.05 mol of diol I,
NaOH and CsF in amounts indicated in Table 3 (0.005
0.02 mol of each component), and 50 ml of DMSO, the
content of the flask was heated to 100°C, and acetylene
was passed through the mixture at a rate of 2 liter per
hour. The process was monitored by GLC. The vinilation
reaction time is given in Table 3. From the mixture obtained
the reaction products were extracted with petroleum ether
(4´50 ml), the extract was washed with water (3´20
30 ml), and dried with calcined potassium carbonate. On
removing the petroleum ether the residue was distilled.
Diol conversions and vinyl ethers yields are given in
Table 3.
18. Strosacker, C.J. and Stephenson, W.T., US Patent 1866328,
1932; Chem. Abstr., 1932, vol. 26, p. 4345.
19. Strosacker, C.J., Kennedy, C.C., and Pelton, E.L., US Patent
The study was carried out by the financial support of
the President of the Russian Federation to the leading
scientific schools (grant RF no. NSh-2241.2003.3).
1866329, 1932; Chem. Abstr., 1932, vol. 26, p. 4345.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005