Ryan and Dillon — On Higher Tertiary Alcohols. 237 



rapid and more satisfactory. This is probably due to the fact that the 

 reacting mixture is diluted too much by the addition of the ether sohition, 

 since there appears to be an optimum concentration, not only for the formation 

 of the Grignard compounds, but for their reaction with other bodies. 



The general equations for the reaction of a Grignard compound with an 

 ester are as follows : — 



OMgBr 

 (1). E-COOMe + Mg(.Br)Il' = R-C'OMe 



E,' 

 OMg. Br OMgBr 



(2). R-C-OMe + Mg(Br) R' = R-C-R' + Mg (Br) OMe 

 R' R' 



OMgBr qK 



(3). RCR' + H2O = R-C-R' + Mg (Br) OH. 

 R' R' 



In our experiments the esters used were those of palmitic and stearic acids, 

 and they were treated with magnesiunr halide compounds of the methyl, 

 ethyl, propyl, and phenyl radicles. Tertiary alcohols were, therefore, obtained 

 in which radicles containing fifteen and seventeen carbon atoms were attached, 

 together with various small groups, to the carbinol residue. The compounds 

 are oily liquids or solids with melting-points ranging from about 20'^ to 

 50° C, and crystallizing in plates or prisms of a white or slightly yellowish 

 colour. They are readily soluble in chloroform, ether, petroleum ether, and 

 hot alcohol. 



The melting-points of the tertiary alcohols show a curious variation, their 

 values depending less upon the number of carbon atoms in the molecule than 

 upon their method of arrangement. Thus tertiary butyl alcohol melts at 

 25° C.,' while dimethyl-ethyl-carbinol, prepared by Popow^ from zinc alkyl 

 and acid chloride, is a liquid at ordinary temperatures, its melting-point being 

 - 12° C. Of the compounds prepared by us, those containing the pentadecyl 

 group melt about 10° C. lower than the corresponding heptadecyl derivatives. 

 Amongst those in which the large radicle is the same, the diethyl and dimethyl 

 compounds have very nearly the same melting-point ; while the dipropyl 

 compound melts about 14° C. lower and the diphenyl compound about 1-4° C. 

 higher than the dimethyl and diethyl derivatives. 



The preparation of esters of these alcohols presented some difficulty. 

 Menschutkin^ has observed that ester -formation takes place much less 

 readily with tertiary alcohols than with primary, and that when the former 



' Butlerow, loc. cit. • Annalen, cxlv, p. 292. ^ Annalen, cxcyii, p. 193. 



