Triorgano Thallium Compounds. Thallium Triethyl and Thallium Diethyl Triphenylmethyl

Abstract

and eight-tenths grams of tetrakis(hydroxymethy1)phosphonium chloride dissolved in 100 cc. of water was boiled with 19 g. of barium hydroxide for several hours until the evolution of hydrogen ceased. The barium was then removed with a slight excess of sulfuric acid and the hydrochloric acid with silver carbonate. From the filtrate, dissolved silver was precipitated with hydrogen sulfide. The filtrate was then evaporated on the water-bath to a sirup and the heating continued for some time to drive off any formic acid which might have resulted from the action of barium hydroxide on formaldehyde. The acid was then converted into the barium salt by boiling with water and barium carbonate, the filtrate evaporated to small bulk and allowed to crystallize. The crystals were washed with a little water. The mother liquor seemed to contain caramel-like substances formed by the action of barium hydroxide on formaldehyde. The product consisted of well-developed crystals, moderately soluble in water, insoluble in alcohol. Anal.Calcd. for CaHlzOsPzBa: Ba, 35.4; P, 16.02. Found: Ba, 35.2; P, 15.68. SummaryThe action of alkali on tetrakis(hydroxymethy1)phosphonium chloride has been shown to take place in two stages, giving first tris(hydroxy-methy1)phosphonium oxide and finally bis(hydroxymethy1)phosphinic acid and liberating one molecule of hydrogen a t each stage. With a neutral carbonate the action stops a t the oxide stage.Tetrakis(chloromethy1)phosphonium chloride was prepared from the corresponding hydroxy derivative by treating with phosphorus pentachloride. This was converted into tris(chloromethy1)phosphine and the latter to tris(chloromethy1)phosphine oxide.A crystalline barium salt of bis(hydroxymethy1)phosphinic acid was obtained.The only organo thallium compounds known are of the type R2T1X,* i . e., salts of the bases RzTIOH first isolated by R. J. Meyer and A. Bertheim.2 Many alkyl and aryl compounds of this type have been prepared by attempted without success to prepare TIRI or ("1 (CzHd 2) 2.Hansen, Ber., 3, 3 (1870); Hartwig, ibid., 7, 298 (1874).