BY MEANS OF CATALYSTS. CREIGHTON. 5 



the presence of optically active bases, such as certain alkaloids. 

 It was found that not only was the rate of decomposition of the 

 acid greatly accelerated by the different alkaloids, but that the 

 d- and 1- acids decomposed at different rates. By acting 

 011 the racemic acid with quinine, and quinidine, and bj 

 stopping the reaction at the point where the excess of one 

 component over the other was greatest, Fajans was able to 

 prepare optically active solutions of the isomeric camphors and 

 the camphor carl> oxylic acids. This result is similar to that 

 obtained by DaJciri 1 through the catalytic enzyme action of 

 lipase (a catalyst of unknown structure) on mandelic acid 

 ester, and constitutes the first example of an asymmetric 

 division by means of a catalyst of definite structure. 



Recently, in the physical chemical institute of this place, 

 Bredig and Fiske 2 have further brought about an asymmetric 

 synthesis of a nitrile by the use of optically active catalysts. 

 The reaction 



C 6 H 5 CHO + HCN - C 6 H 5 CH OH CN 



is catalysed by bases, and when alkaloids (in this case quinine 

 and quinidine) are used as catalysts the resulting nitrile is 

 optically active (that is the d- and 1- nitrile are formed in 

 unequal amount), and the mandelic acid produced by the 

 saponification of the nitrile is also active. This asymmetric 

 synthesis is analogous to that of L. Rosen-thaler's? with the help 

 of emulsin. 



When solutions of bromcamphor-carboxylic acid are heated 

 it is found that the acid decomposes much more rapidly than 

 similar solutions of camphor-carboxylic acid. The decomposi- 

 tion takes place according to the equation : 



CBrCOOH OBH 



C 8 H 14 <| =C a H u <] +C0 2 



CO CO 



It was suggested by Professor Bredig that I should study 

 the catalytic influence of alkaloids on the above reaction, and 



~T Dakin, H. D.: loc. cit. 



2 Bredig- G.: Chem. Zeitung-, xxxv, 36, 324, (1911). 

 3. Rosenthaler, L.: Biochem. Zeit., 14, 238, (1908). 



