POLYFLUOROALLOXY PHOSPHONIC AND PHOSPHINIC ACID DERIVATIVES: I
433
was added dropwise with stirring, maintaining the
temperature of the reaction mixture within 20–25°C.
Simultaneously, hydrogen chloride was removed from
the reaction mixture by bubbling dry air through it.
After adding of phenyl dichlorophosphite the reaction
mixture was stirred for further 5 h with removal of
hydrogen chloride. The fractional distillation afforded
9.3 g (95%) of the target phosphonite. Other phenyl-
phosphonites were obtained analogously (Table 3).
off in a vacuum, and the residue that crystallized after
standing for 2 h, was washed with diethyl ether and
dried giving 11.5 g of Ia. Compounds Ib–If were
obtained in a similar way.
(1-Hydroxy-2,2,2-trichloroethyl)methylphosphonic
acid (IIa). To a solution of 2.5 g of chloral hydrate in
30 ml of anhydrous benzene 4.4 g of (1,1,5-trihydro-
octafluoropentyl)methylphosphonite was added
dropwise with stirring. The reaction mixture was kept
under stirring for 8 h at 40°C. The precipitate formed
during the reaction was filtered off, washed with
benzene, and dried, giving 3.1 g of the product that
was identified as (1-hydroxy-2,2,2-trichloroethyl)me-
thylphosphonic acid IIa (mp 159°C). Compounds IIb,
IIc were obtained similarly (mp, °C: IIb 160, IIc 148).
Synthesis of the other alkyl- and phenylphos-
phonites were described elsewhere [2, 7]. Dichlorides
of alkyl- and phenylphosphonic acids were prepared
accoding to the procedure from [11].
(1,1,5-Trihydrooctafluoropentyl)methylphos-
phonite (III). In a 4-neck flask equipped with a stirrer,
a reflux condenser, and a dropping funnel 32.5 g of
1,1,5-trihydrooctafluoropentanol was placed and
cooled to 0°C. Methylphosphonic acid dichloride,
8.2 g, was added dropwise at such a rate that the
temperature within the flask did not rise above 3°C.
Reaction mixture was kept at room temperature for
further 0.5 h, then hydrogen chloride was removed by
bubbling dry air through the reaction mixture for 5 h.
The residue was subjected to fractional distillation that
gave 13 g (63%) of III, bp 124°C (17 mm Hg).
REFERENCES
1. Cummings, J.L., Am. J. of Psychiatry, 2000, vol. 157,
no. 1, p. 4.
2. Palagina, T.V., Krutikov, V.I., Naidenov, A.V., and
Lavrent’ev, A.N., Zh. Obshch. Khim., 1986, vol. 56,
no. 12, p. 2696.
3. Krutikov, V.I., Naidenov, A.V., Palagina, T.V., and
Lavrent’ev, A.N., Zh. Obshch. Khim., 1989, vol. 59,
no. 2, p. 98.
4. Brestkin, A.P. and Godovikov, N.N., Usp. Khim., 1978,
(1,1,9-Trihydrohexadecafluorononyl)-(1-hydroxy-
2,2,2-trichloroethyl)methyl phosphinate (Ig). To a
solution of 4.14 g of chloral hydrate in 60 ml of
anhydrous benzene 22.7 g of di-(1,1,9-trihydro-
hexadecafluorononyl)methylphosphonite was added
dropwise with stirring under inert atmosphere. The
reaction mixture was stirred for 10 h at a temperature
not exceeding 40°C. The precipitate formed during the
reaction was filtered off, washed with benzene, and
dried. This product was identified as (1-hydroxy-2,2,2-
trichloroethyl)methylphosphonic acid IIa (mp 159°C).
Filtrates were combined, the solvent distilled off. The
fractional distillation afforded 14.6 g of the target ester
Ig. Compounds Ih, Ii were obtained in the same way.
vol. 47, no. 9, p. 1609.
5. Abramov, V.S. and Kashirskii, M.I., Zh. Obshch. Khim.,
1958, vol. 28, no. 11, p. 3059.
6. Barabanov, V.I. and Abramov, V.S., Zh. Obshch. Khim.,
1965, vol. 35, no. 12, p. 2225.
7. Krutikov, V.I., Semenova, E.S., Maslennikov, I.G., and
Lavrent’ev, A.N., Zh. Obshch. Khim., 1983, vol. 53,
no. 7, p. 1557.
8. Mikhailova, R.V., Lobanok, A.G., and Zakharenko, I.N.,
Prikl. Biokhim. i Mikrobiol., 1997, vol. 33, no. 5, p. 492.
9. Abduvakhabov, A.A., Mikhailov, S.S., and Shcher-
bak, I.G., Antifermentnoe deistvie i detoksikatsiya
fosfororganicheskikh ingibitorov esteraz (Antienzyme
Action and Detoxification of Organophosphorous
Esterase Inhibitors) Tashkent: Fan, 1989.
10. Musil, Ya., Novakova, O., and Kunts, K., Sovremennaya
biokhimiya v skhemakh (Modern Biochemistry in the
Schemes), Moscow: Mir, 1984.
(1,1,3-Trihydrotetrafluoropropyl)-(1-hydroxy-
2,2,2-trichloroethyl)phenyl phosphinate (Ia). To a
solution of 5 g of chloral hydrate in 70 ml of
anhydrous benzene 1.11 g of di-(1,1,3-trihydrotetra-
fluoropropyl)phenylphosphonite was added dropwise
with stirring under inert atmosphere. The mixture was
stirred for 12 h at 30–40°C. The solvent was distilled
11. Gefter, E.L., Fosfororganicheskie monomery i polimery
(Organophosphorus
Monomers
and
Polymers),
Moscow: Akad. Nauk SSSR, 1960.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 3 2010