128 



IMMUNO-CATALYSIS 



it was treated with 0.5 g. (0.001 5M) quinine or quinidine alkaloid as 

 catalysts. After 24 hours the reaction mixture was treated with 100 

 ml. of 4 N aqueous sulfuric acid and shaken for five minutes to remove 

 the catalyst alkaloid. A study of the chloroform solution showed that 

 the alkaloid had acted as a specific directive catalyst in the formation 

 of nitrile. Laevorotatory quinine caused the formation preponderantly 

 of a dextrorotatory nitrile, from which laevo- and ^dextrorotatory man- 

 delic acids were obtained on hydrolysis. In contrast, ^dextrorotatory 

 quinidine gave preponderantly kevorotatory nitrile: 



CgHsCHO-fHCN 



1 -quinine 



CeHgCHOHCN Cdextro:) 

 Mandelonitrile 



Hydrolysis 



CeHgCHOHCOOH, dextro- 

 Mandelic acid, laevo- 



d-quinidine 



CflHfiCHOHCN Claevo') 

 Mandelonitrile 



-48.5% 

 -51.5% 



Hydrolysis 



C0H5CHOHCOOH. dextro-54.3% 

 Mandelic acid, Zaevo— 45.7% 



Analogous results were obtained when cinnamic aldehyde, anis- 

 aldehyde, citral, piperonal and acetaldehyde were used in the place 

 of benzaldehyde. 



Bredig and Fiske believed that alkaloids and cyanhydrin form a 

 complex compound as a necessary condition for catalytic synthesis. 

 They found that the alkaloids disappeared from the aqueous solution 

 into the chloroform or toluene solution of cyanhydrin; only cyan- 

 hydrins appeared to participate in such a combination. McKenzie 

 (1936), commenting on the findings of Bredig and Fiske, cited Isobel 

 A. Smith's interpretation of the findings of Traube and Onodera 

 (1914) who found that alkaloids of high molecular weight, such as 

 atropine or quinine, formed colloidal solutions in water, while their 

 salts formed true solutions. Accordingly it appeared to Smith that 



