306 REPORT — 1900, 



stitution o£ the latter oompounc] (C. 1. b.), the change can only l)e 

 written as follows ; — 



liOwry's observation that o-nitrocamphor yields the same camphoi'yloxime 

 as is obtained directly from camphoric anhydride by treatment with 

 hydroxylamine leads to the same conclusion (compare B. 1. b, i,), 



2. Formation of Camphenone. 



When a-aminocamphor is treated with nitrous acid it is converted 

 into diazocamphor, which loses nitrogen when heated and yields consider- 

 able quantities of camphenone, Ch,Hi40, which has all the properties of 

 an unsaturated ketone. ' 



CH.CH.NH, CH.C< II C=CH 



: 1 -» i : 1 ^N -> ^ : I 



C-CO C-CO C-CO 



c c c 



Aminocamphor. Diazocamphor. Camphenone. 



3. Formation op Dehydrohomocamphoric Acid. 



When homocamphoric acid is brominated it yields a monobromo- 

 derivative, a-bromohomocamphoric acid. When the diethyl-ester of 

 this monobromo acid is heated with quinoline and then with alcoholic 

 potash it loses hydrogen bromide, affording dehydrohomocamphoric acid, 

 which is certainly an a;8- unsaturated acid. Taking into consideration the 

 relationship subsisting between camphor and homocamphoric acid, this 

 fact is readily explained by the assumption comprised by C, and it may 

 be added that its behaviour on oxidation is only explicable by the aid of 

 that view (compare E. 3.). 



CH-CH,, CH.CHBr, COOH C : CH.COOH 



C - CO C.COOH C.COOH 



c c c 



Camphor. a-Bromohomocamphoric Acid. Dehydrohomocamphoric Acid. 



D.— CAMPHOR AND CAMPHORIC ACID CONTAIN TWO 

 NON-EQUIVALENT ASYMMETRIC CARBON ATOMS. 



Camphor and camphoric acid are optically active, and therefore 

 contain at least one asymmetric carbon atom. Whilst the former is only 

 known in two enantiomorphous forms and their externally compensated 

 inactive combinations, the latter is known to exist in six forms, of which 

 two pairs are enantiomorphously related, and the other two forms are 

 externally compensated mixtures of the other pairs. 



* Angeli, Gmzetta, 23 [2], 351. 



