Phosphorus trichloride alkyl alcohols

Alkyl Phosphites. The Interaction of Phosphorus Trichloride and Alcohols. 

Reaction with phosphorus trihalides (Section 4 13) Phosphorus trichloride and phosphorus tribromide convert alcohols to alkyl halides... 

Alkyl chlorides have been obtained by the direct chlorination of hydrocarbons 1 and by the addition of hydrogen chloride to olefines.2 However, they have usually been prepared from the corresponding alcohol by the action of a number of reagents, such as dry hydrogen chloride,3 dry hydrogen chloride in the presence of zinc chloride,4 phosphorus trichloride,3 phosphorus oxychloride,6 phosphorus pentachloride,7 phosphorus trichloride... 

Several phosphorus halides are useful for converting alcohols to alkyl halides. Phosphorus tribromide, phosphorus trichloride, and phosphorus pentachloride work... 

Reactions with —OH Groups and Epoxides.—The formation of A -l,2-oxaphos-pholen derivatives from propargylic alcohols and phosphorus trichloride has been studied in detail. Intermediate phosphites (24) and allenic phosphonates (25) are described, and the A -l,2-oxaphosphoIen is produced in the final stage, as shown. Improved conditions have been outlined for the preparation of allylic bromides (26) from allylic alcohols and phosphorus tribromide. Related reactions of primary alcohols with the complex of phosphorus trichloride and DMF lead to the chloride (27) 22 addition of zinc bromide to the reaction results in the formation of alkyl bromides, but an attempt to extend this exchange to the preparation of cyanides was not successful. ... 

In the reaction of phosphorus trichloride with three moles of alcohol, dialkyl phosphonate ( dialkyl phosphite ) is formed, together with hydrochloric acid and alkyl chloride. 

Kosolapoff (182), who prepared tri- cr -butyl phosphite from phosphorus trichloride and er -butyl alcohol, claimed that This phosphite could not be made to undergo the Michaelis-Arbuzov reaction with alkyl halides at temperatures under 80-90°, while above that temperature it began to decompose with evolution of isobutylene. Further support for the concept that the tertiary ester group is unreactive was provided by the... 

The heat of reaction may decompose phosphorus acid to phosphine, which may ignite spontaneously or explode. It is decomposed by alcohols, producing alkyl halides. The reactions of phosphorus trichloride with acetic acid, nitric acid, nitrous acid, and chromyl chloride can produce explosions. It may ignite or react violently with dimethyl sulfoxide, lead dioxide, fluorine, hydroxyl amine, and iodine monochloride (Mellor 1946, Suppl. 1948 NFPA 1997). Its vapors bum to incandescence when heated with alkali metals. 

The most widespread method of producing complete esters of phosphorous acid, in which R = R2 = R3, is the treatment of alcohols or alkylated phenols, taken in small excesses (0.1-0.5 mole) with phosphorus trihalide (most often trichloride) at a temperature of 150-200°C [70, 158, 285, 294] ... 

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