H Y D R O L Y S I S OF B I S ( C H L O R O M E T H Y L ) T H I O P H O S P H O N I C ACID

N. V. I v a s y u k and I. M. S h e r m e r g o r n UDC542.938+661.718.1

In contrast to the basic hydrolysis of bis(chloromethyl}phosphonic acid, which occurs very slowly upon boiling a basic solution with its sodium salt, the basic hydrolysis of bis(chloromethyi)thiophosphonic acid proceeds sufficiently easily even at room temperature, during which two moles of sodium hydroxide are consumed for one mole of the sodium salt of bis(chloromethyl)thiophosphonic acid. The product isolated as the result of the hydrolysis (~80%) is 3-oxo-3-hydroxy-l,3-thiophosphetane (i); mp 142 ~ Found: C 19.31; H 4.21; P 24.70%. C2H5OgPS. Calculated: C 19.35; H 4.03; P 24.96%. Treatment of this compound with t r i - ethyl phosphite yielded 3-oxo-3-ethoxy-l,3-thiophosphetane (II); bp 60* (1.7.10 -2 mm); nD2~ 1.5078; d42~ 1.2551. Found: C 31.50; H 6.04; P 20.08%. C4HgO2PS. Calculated: C 31.57; H 5.92; P 20.39%, and t reat - ment with thionyl chloride yielded 3-oxo-3-chloro-l ,3-thiophosphetane (HI), mp 101-103 ~ Found: C 16.90; H 3.04; P 22.25%. C2H4C1OPS. Calculated: C 16~84; H 2.80; P 21.75%. Thus, migration of sulfur from phosphorus to the carbon atom of the methyl group and subsequent closure to the four-membered thiophos- phetane ring are observed upon hydrolysis of bis(chloromethyl)thiophosphonic acid. The scheme of this reaction can be represented in the following way:

CICH2 S- N/ P

C1Cg~ / %0 CH2 O-

___~S / "~p/

-~ NCHS %0

CH~ S --S--CH~ O- \ p / +~OH-.~ \p/

-o~- / % CICP~ 0 C1CHs / ~0

CH~ 0 CHs 0 +H+ S/ \V/ (EtO),p S / \pJ

SOO1, \CH~ / \0H 'kCg2/ \OEt

\CH~ / \ e l . (m)

A. E. Arbuzov Institute of Organic and Physical Chemistry, Academy of Sciences of the USSR. Trans- lated from Izvestiya Academy Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 481-482, February, 1969. Original article submitted November 14, 1968.

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