28 OPTICAL ACTIVATION 



absolute alcohol and polarised in a 2 dcm. tube. This solution 



1 oo 



gave a rotation of --1.59 corresponding to [O-] D = 8. 2, 



18 



whereas from kinetic calculations it should have been [a] p 



-23. 2. The excess of active acid is therefore 0.180 

 gram or 0.00066 mole, whereas it should be 0.513 gram 

 or 0.00150 mole. In this experiment 0.00066 equivalent of 

 acid has been made active by the catalytic influence of 0.00060 

 equivalent or 0.00030 mole of quinidine. 



In order to make certain that the optical activi-ty obtained 

 was due to a specific catalytic action of the base and not to any 

 error in the method employed, a controll experiment was carried 

 out in the same manner as the activation experiment. In this 

 experiment the quantity of materials used were the same as in 

 the activation experiment, except that here no base was used. 

 It was found that neither the potassium hydroxide or aceto- 

 phenone solutions showed the slightest optical activity on being 

 polarised. 



We see then from these experiments that, by means of an 

 optically active base, it is possible to produce catalytically both 

 active bromcamphor and bromcamphor-carboxylic acid from the 

 inactive acid, for 4 equivalents or 4 moles of acid have been 

 made optically active by the help of 4 equivalents or 2 moles 

 of base. According to the kinetic curves 2 moles of base should 

 activate about 10 equivalents or moles, of acid. But for a lack 

 of a sufficient quantity of the inactive acid, further activation 

 experiments would have been carried out with the object of 

 obtaining a quantitative yield of the active bromcamphor and 

 bromcamphor-carboxylic acid. 



Is THE ACTION OF THE BASE CATALYTIC ? 



The question of whether the acceleration of the decomposi- 

 tion of bromcamphor-carboxylic acid by optically active bases 

 is due to a catalytic influence or not, is of interest, and has been 



