2 Proceeding ft ot the Roijal Irish Academy. 



by heating the corresponding acids with phosphorus pentoxide, and recentl}' 

 Easterfield and Taylor' prepared the ketones of higher saturated and 

 unsaturated fatty acids by heating the latter with iron turnings. 



Aliphatic-aromatic ketones, like phenylpentadecyl ketone and p-tolyl- 

 pentadecyl ketone have been obtained by Krafft^ and by Glaus and Hafelin' 

 by the condensation of the chlorides of aliphatic acids with aromatic hydro- 

 carbons. The lower . members of the ketone series have also been obtained 

 by the action of alkyl magnesium halides on nitriles* and amides.* We have 

 prepared some higher ketones by the action of alkj'l magnesium halides on 

 the amides of palmitic and stearic acids. With aliphatic Grignard reagents 

 poor results were obtained, but with aromatic compounds such as phenyl 

 magnesium bromide by using high concentrations and allowing the reaction 

 to proceed for about three days it was found possible to get a yield of the 

 desired ketone as high as sixty per cent. 



In this way we obtained methyl-, phenyl-, p-tolyl-, and o-naphthylpenta- 

 decyl ketones and ethyl-, phenyl-, and a-naphthylheptadecyl ketones. The 

 reactions, such as formation of oximes, phenyhydrazones, and semicarbazones, 

 which are characteristic of the lower ketones, were found quite similarly to 

 be characteristic of the higher members. 



By reduction of the ketones with sodium and alcohol, secondary alcohols 

 were . prepared from phenylpentadecyl, p-tolylpentadecyl, and phenylhepta- 

 decyl ketones. Eeactions, like the formation of esters with acetic anhydride 

 and sodium acetate and urethanes with phenyl isocyanate, characteristic of 

 the lower secondary alcohols were also obtained with the higher members. 



Experimental. 

 A. — Ketones. 



Methyl'pentadecyl Ketone CHaCOCisHai. — Methyl magnesium iodide was 

 prepared by acting on 3 grammes of magnesium with a solution of 20 grammes 

 of methyl iodide in 50 c.c. of anhydrous ether, and to the cold reaction- 

 product, which was contained in a flask fitted with an upright condenser, 

 10 grammes of dry powdered palmitamide were added. When the brisk 

 evolution of gas, which ensued on the addition of the amide, had subsided, 

 the mixture was heated by means of warm water for five hours, then cooled 



' Jour. Chem. Soc, xeix (1911), p. 2298. 



- Ber., xix (1886), p. 2982, xxi (1888), p. 2266. 



3 Journ.fur prakt. Chemie. (2) liv, p. 399. 



■■ Blaise, Comptes Eendus, cxxxii (1901), p. 38. 



'Beis, Comptes Eendus, cxxxvii (1903) p. 575. 



