CHEMICAL PKOPEKTIES OF FATTY ACIDS AND RELATED COMPOUNDS 143 



the highest catalytic effect, followed in order by sulfuric, hydrobromic, and 

 nitric acids.^^*~^^^ Phosphoric acid in 100% concentration^^* is an ef- 

 fective hydrolyzing agent for the nitriles, but it has little effect in a 92.5% 

 solution. ^^^ The ethyl esters of the fatty acids are formed when the ni- 

 triles are heated under pressure at 130-140°C. with an excess of ethanol 

 (10 parts) and one part of concentrated sulfuric acid.^^'' 



Another reaction of interest which the nitriles undergo is the formation of 

 imino ethers (RCC1:NH) on treatment with hydrochloric acid in alcoholic 

 solution, ^^^ which, after reduction, and hydrolysis, are converted to the 

 corresponding aldehydes (RCHO).^^^ The Grignard reaction is one by 

 which higher ketones can be readily synthesized from the nitriles according 

 to the following reactions : 



RC:N+R'MgX * RR'C^NMgX — ^^^ 9. RR'CO+MgXCI+NH«CI 



Alkyl Dialkyl 



nitrite ketone 



By varying the R' component of the Grignard reagent and the nitrile one 

 can obtain any desired ketone. Amides can be formed if, instead of hy- 

 drolysis, oxidation with alkaline hydrogen peroxide is employed.**'^ The 

 corresponding hydroxylamines, RCH:NOH, are also readily synthe- 

 sized. ^^-^"^ Substituted aminopyridines result from the action of metallic 

 sodium on the nitriles^*^"^*^ while 2-alkenenitriles originate on treatment 

 of nitriles with bromine followed by removal of HBr.^**""" 



The higher nitriles have the property of imparting "oiliness" to petrol- 



"* B. S. Rabinovitch and C. A. Winkler, Can. J. Research, B20, 73-81 (1942). 



"5 B. S. Rabinovitch, C. A. Winkler, and A. R. P. Stewart, Can. J. Research, B20, 121- 

 132 (1942). 



"6 J. D. McLean, B. S. Rabinovitch, and C. A. Winkler, Can. J. Research, B20, 168- 

 173 (1942). 



"7 B. S. Rabinovitch and C. A. Winkler, Can. J. Research, B20, 221-230 (1942). 



"8 G. Berger and S. C. J. Olivier, Rec. trav. chim., 46, 600-604 (1927). 



"9 S. C. J. Olivier, Rec. trav. chim., 48, 568-570 (1929). 



"i^o L. Spiegel, Ber., 51, 296-298 (1918). 



5" A. Pinner, Ber., 23, 2917-2919 (1890). 



"2 P. Eitner and H. Wetz, Ber., 26, 2840-2847 (1893). 



"3 F. Tiemann, Ber., 17, 126-129 (1884). 



6" E. Nordmann, Ber., 17, 2746-2756 (1884). 



5« E. Frankland and H. Kolbe, Ann., 65, 269-287 (1848). 



6^« A. G. Bayer, Ber., 2, 319-324 (1869). 



«"E. von Meyer, /. prakt. Chem. [2], 22, 261-288 (1880); [2], 27, 152-156 (1883); 

 [2], 37, 396-407 (1888); [2], 39, 188-200 (1889). 



"8 R. van Caillie, Bull. soc. chim. Belg., 44, 438-440 (1935). 



"9 R. Merckx and P. Bruylants, Bull, classe sci. Acad. roy. Belg. [5], 19, 681-688 

 (1933). 



*5o A. Gavriloff, Bull, classe sci. Acad. roy. Belg. [5], 19, 815-820 (1933). 



