122
MUSLINKIN et al.
2. Gould H., Rouge D., and Gordon E., Compt. Rend., 1960,
β-Hydroxy-β′-methacryloyloxyisopropyl α-fluoro-
vol. 250, pp. 1073–1074.
acrylate (XV). а. From 23.5 g (0.185 mol) of α-fluoro-β-
chloropropanoic acid and 26.5 g (0.185 mol) of glycidyl
methacrylate by stirring at 60–80°С for 3 h in the
presence of 0.01 of TiCl4 and 0.1 g of copper(I) chloride
followed by heating for 3 h at 100°С, after fractionation
in a vacuum we obtained 22 g (52%) of β-hydroxy-β′-
methacrylyloxyisopropyl α-fluoro-β-chloropropanoate
(VII) as a viscous colorless liquid, soluble in benzene,
acetone, dichloroethane, and other organic solvents.
3. Japan Patent 2005112850 , GO2F1/1337; CO7C69/75,
Alpha-Fluoracrylate Compound and Composition, and
Polymer Thereof.
4. CN Patent 132 4877, C08F293/00; C08F293/00,
Fluoroacrylic Ester block Polymer and Its Prpen.
5. US Patent. 6369179, C07C69/653; C08F20/22, 2-
Fluoroacrylate ester Polymers and Use Thereof as Optical
Materials.
6. WO Patent 9518785, G02B6/00; C07C69/653, 2-
Fluoroacrylate ester Polymers and Use Thereof as Optical
Materials.
7. Japan Patent 8053402, C07C255/14; C08F20/34;
C07C255/00, Cyanoethyl fluoroacrylate.
b. From 21.5 g (0.08 mol) of compound VIII and
8.01 g (0.08 mol) of triethylamine in 150 ml of anhydrous
benzene we obtained after double vacuum distillation
14.65 g (80%) of β-hydroxy-β′-methacryloyloxyisopropyl
α-fluoroacrylate XV as a colorless labile liquid.
8. Japan Patent 5201921, C07B61/00; C07C67/343,
Production of alpha-Fluoroacrylate.
9. WO Patent 9219663, C08F220/22. Fuoroacrylate
Monomers and Polymers, Processes for Preparing the Same
and Their Use.
β-Chloro-β′-methacryloyloxyisopropyl α-fluoro-
acrylate (XVI). а. From 10.5 g (0.0725 mol) of α-
fluoro-β-chloropropanoyl chloride and 10.3 g (0.0725
mol) of glycidyl methacrylate in the presence of 0.005
g of TiCl4 and 0.1 g of copper(I) chloride by stirring at
30–50°С followed by heating for 2 h at 100°С, after
fractionation we obtained 10.8 g (71%) of β-chloro-β′-
methacryloyloxyisopropyl α-fluoro-β-chloropropanoate
(VIII) as a viscous colorless liquid, soluble in benzene,
tetrahydrofuran and other organic solvents.
10. Japan Patent 3103409, C08F4/50; C08F4/42. Preparation
of Poly(alpha-fluoroacrylate ester).
11. UK Patent 949904, C07C69/653; C07C69/00, Method of
Preparing alpha-Fluoroacrylic Acid Esters.
12. Boguslavskaya, L.S., Yarovykh, K.V., and Bulovyato-
va, A.B., Zh. Org. Khim., 1969, vol. 5, no. 11,
pp. 1932–1937.
13. USSR Inventor’s Certificate 380637 (SSSR Byull. Izobr.
MKI S 07 s 67/00), Method of Preparation of Ethylene
Glycol Mono- or Di-α-fluoroacrylates.
14. Arbuzov, B.A., Muslinkin, A.A., Vizel’ A.O., et al.., Izv.
Akad. Nauk SSSR, Ser. Khim., 1973, no. 8, pp. 1828–
1832.
15. USSR Inventor’s Certificate 351836 (SSSR Byull.
Izobr. MKI S 07 s 69/62), Method of Producing
Glycidyl α-fluoroacrylate.
16. Boguslavskaya, L.S. and Morozova, T.V., Zh. Prikl. Khim.,
1992, vol. 6, no. 4, pp. 881–886.
17. USSR Inventor’s Certificate 377017 (SSSR Byull. Izobr.
MKI S 07 s 69/62), Method of Producing α-Fluoroacrylic
Acid Esters.
18. USSR Inventor’s Certificate 370200 (SSSR Byull. Izobr.
MKI S 07 s 67/00, S07 s 69/92), Method of producing
fluorine-containing methacrylic esters.
b. From 10.7 g (0.037 mol) of β-chloro-β′-meth-
acryloyloxyisopropyl α-fluoro-β-chloropropanoate
(VIII) and 3.8 g (0.35 mol) of triethylamine in 75 ml
of anhydrous benzene we obtained after double vacuum
distillation 6.7 g (71%) of colorless labile liquid, β-chloro-
β′-methacyloyloxyisopropyl α-fluoroacrylate (XVI).
CONCLUSIONS
1. At the esterification of ethylene glycol
with α-fluoro-β-chloropropanoic acid are formed both
mono- and di-α-fluoro-β-chloropropanoates that by the
reaction with triethylamine are readily transformed to the
respective α-fluoroacrylates.
2. α-Fluoro-β-chloropropanoic acid and related acyl
chloride in the presence of Lewis acid react readily with
epoxy compounds to form the products of epoxide ring
cleavage that after dehydrochlorination with triethylamine
are converted into corresponding α-fluoroacrylates.
19. Rizpolozhenskii, N.I. and Muslinkin,A.A., Izv. Akad. Nauk
SSSR, Otd. Khim. Nauk, 1961. no. 9, pp. 1600–1606.
20. USSR Inventor’s Certificate 390107 (SSSR Byull. Izobr.
MKI S 08 f 3/62). Method of Producing Fluorine-
Containing Polymers.
REFERENCES
1. Boguslavskaya, L.S., Panteleeva, I.Yu., Morozova, T.V.,
et al., Usp. Khim., 1990, vol. 59, pp. 1555–1575.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 82 No. 1 2009