SYNTHESIS AND USE OF PARTIALLY FLUORINATED DIALKYL ETHERS
Hydrolysis of partially fluorinated dialkyl eth- ACKNOWLEDGMENTS
101
ers. (1) A 20-ml flask equipped with a magnetic stir-
rer and a reflux condenser was charged with 15 g of I
(with II, the procedure was similar), and 15 g of
concentrated sulfuric acid was added. The mixture
slightly warmed up. Then the mixture was heated with
stirring for 1 h at 40 C and poured onto 50 g of ice;
the organic layer was separated, washed with water,
The study was financially supported by grant no. 47
(2002) for innovation projects of the Siberian Divi-
sion, Russian Academy of Sciences.
REFERENCES
1. Orlov, A.P., Shchavelev, V.B., and Korol’kov, D.N.,
Abstracts of Papers, 3-ya Mezhdunarodnaya konferen-
tsiya Khimiya, tekhnologiya i primenenie ftorsoedi-
nenii (3rd Int. Conf. Chemistry, Technology, and
Use of Fluoro Compounds ), St. Petersburg (Russia),
June 6 9, 2001, report R 1-34, p. 170.
and dried over CaCl .
2
By this procedure, we prepared 10 g of compound
VIII to be used in the subsequent studies as inter-
mediate.
(2) A similar flask was charged with 27 g of SbF ,
5
2. Orlov, A.P., Shchavelev, V.B., Barabanov, V.G., and
Korol’kov, D.N., Abstracts of Papers, 3-ya Mezhduna-
rodnaya konferentsiya Khimiya, tekhnologiya i pri-
menenie ftorsoedinenii (3rd Int. Conf. Chemistry,
Technology, and Use of Fluoro Compounds ), St.
Petersburg (Russia), June 6 9, 2001, report R 1-36,
p. 172.
and 15 g of II was added in portions with stirring, so
as to avoid warming up above room temperature. The
mixture was stirred at room temperature for 1 h and
poured into 50 g of ice; the organic layer was sep-
arated, washed with cold water, and dried over CaCl .
2
The product was distilled, with collection of the frac-
tion boiling at 95 96 C; yield 8 g.
3. FR Patent Appl. 2771408.
4. US Patent 6187954.
Reaction of KOH with partially fluorinated
dialkyl ethers. A 100-ml flask equipped with a mag-
netic stirrer, a thermometer, and a reflux condenser
was charged with 40 g of I (with II, the procedure
was similar) and 50 ml of dry dioxane, after which
finely divided KOH was added in portions with stir-
ring at room temperature. The mixture warmed up.
Then the mixture was heated with stirring for 2 h at
40 C, and the reaction products were distilled off.
5. RF Patent Appl. 97102618/04.
6. Knunyants, I.L., Shchekotikhin, A.I., and Fokin, A.V.,
Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 1953, no. 2,
pp. 282 289.
7. US Patent 2862024.
8. Bargamova, M.D., Cheburkov, Yu.A., Dyatkin, B.L.,
et al., Izv. Akad. Nauk SSSR, Ser. Khim., 1967, no. 3,
pp. 611 614.
20
Compound V: yield 82%, bp 51 52 C, n 1.3208,
D
20
9. Dyatkin, B.L., Konstantinov, Yu.S., Lantseva, L.T.,
et al., Zh. Org. Khim., 1967, vol. 3, no. 6, pp. 1006
1011.
d
1.3601 (published data [8]: bp 51.5 C/743 mm
4
20
20
Hg, n 1.2970, d 1.3595); VI: yield 78%, bp 71
72 C, n 1.3210, d 1.2930 (published data [8]: bp
71 72 C/743 mm Hg, n 1.3103, d 1.2884).
D
4
20
20
D
4
20
20
10. England, D.C., Solomon, L., and Krespan, C.G.,
D
4
J. Fluorine Chem., 1973, vol. 3, no. 1, pp. 63 89.
11. Popova, L.M., Vinogradova, V.N., Prytkova, O.A.,
et al., Abstracts of Papers, 2-ya Mezhdunarodnaya
konferentsiya Khimiya, tekhnologiya i primenenie
ftorsoedinenii (2nd Int. Conf. Chemistry, Technol-
ogy, and Use of Fluoro Compounds ), St. Petersburg
(Russia), September 23 26, 1997, report Z 3-9, p. 123.
CONCLUSIONS
(1) The possibility of preparing partially fluori-
nated dialkyl ethers by reaction of hexafluoropropyl-
ene with alcohols (methanol, ethanol, isopropanol,
2,3,3,3-tetrafluoropropanol) in the presence of KOH
was examined. These ethers are formed by addition
of an alcohol across the double bond in hexafluoro-
propylene.
12. US Patent 5474657.
13. US Patent 5516946.
14. Novikova, M., Zakharov, V., Denisov, A., and Juko-
va, V., J. Fluorine Chem., 1992, vol. 58, nos. 2 3,
p. 169.
(2) Partially fluorinated dialkyl ethers are con-
verted to alkyl 2,3,3,3-tetrafluoropropionates by treat-
ment with concentrated H SO and to alkyl pentaflu-
15. Gubanov, V.A., Tumanova, A.V., and Dolgopol’-
skii, I.M., Zh. Obshch. Khim., 1965, vol. 35, no. 2,
pp. 398 399.
2
4
oropropenyl ethers by treatment with KOH.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 77 No. 1 2004