[ 235 ] 



VIII. 



ON HIGHEE TEETIAEY ALCOHOLS DEEIVED FEOM PALMITIC 

 AND STEAEIC ESTEES. 



By HUGH EYAN and THOMAS DILLON, University College, Dublin. 



Eead January 22. Published Ferruaiiy 23, 1912. 



Some discrepancies between theory and experiment with regard to the com- 

 position of beeswax, which have been indicated in a previous communication, 

 and the difficulty of accounting satisfactorily for these as well as for the 

 nature of the unsaponifiable portion of montan wax^ in any way other than 

 by assuming the existence of secondary or tertiary alcohols in beeswax and 

 montan wax, have made an investigation of the properties of the higher 

 tertiary alcohols very desirable. 



Since, however, with the single exception of the dimethyl-pentadecyl 

 carbiuol obtained by Ipatieff and Grawe^ by the action of zinc methyl on 

 palmityl chloride, higher tertiary alcohols were unknown, we were obliged to 

 prepare them by synthetical methods before a study of their properties could 

 be accomplished. 



The original method devised by Butlerow* for the synthesis of tertiary 

 alcohols, which was that followed by Ipatieff and Grawe in the preparation of 

 the alcohol mentioned above, is, owing to the spontaneous inflammability of 

 zinc methyl in air, too troublesome for extensive use in the laboratory. 



The fact that the alkyl-magnesium halides of Grignard* react with esters 

 to form tertiary alcohols led us to believe that, even in the case of an acid, 

 like stearic, of high molecular weight, the Grignard reagent might interact 

 with the ester to form a tertiary alcohol. We found that from palmitic and 

 stearic esters, by interaction with alkyl-magnesiimi halides, satisfactory yields 

 of tertiary alcohols were in all eases obtained with the single exception of 

 a-naphthyl-magnesium bromide whose product of interaction with methyl- 

 stearate was a ketone. 



1 Ryan, Sci. Proc.R.D.S., xii (1909), p. 210. 



'- Ryan and Dillon, Sci. Proc. R.D.S., xii (1909), p. 202. 



3 Journ. Euss. Phys-Chem. Soc, 1900, p. 33. 



* Annalen, cxliv, p. 1. ' Comptes Rendus, cxxviii (1899), p. 110. 



R.I. A. PROC, VOL. X.^X., SECT. B. [2 L^ 



