195 



fact that when boiled with aqueous alkali -carbonate it was readily 

 converted into an isomeric borneol carboxylic acid m. p. 17 6° which 

 differed likewise from the two original borneol carboxylic acids, and 

 when oxidised with nitric acid yielded no camphoric acid. 



C.E 



CH-COOH ,CBr. 



1 C 8 H / | 

 CHBr ^CH, 



COOH /CH-COOH 

 C 8 H 14 <( | 



X CH 2 



VII. VIII. 



XI. 



/CH.CH 2 OH 

 C 8 H 14 < | 



\CHOH 



y CH.CH 2 OH 

 C 8 H 14 < || 



X CH 



XIII. 



XIV. 



When the /? - brominated acid, m. p. 90 to 91 was treated with 

 alkali the result differed according to the quantity of alkali used. 

 Analogous to /?-hydrobromo cinnaminate of sodium, the sodium salt of 

 the acid, treated in a neutral aqueous solution, forms bornylene 

 and bornylene carboxylic acid, but the chief product of the conversion 

 is a lactone C u H 16 2 , m. p. 183 , b. p. 145 to 147 (12 mm.), of 

 peculiar constitution. The yield of this lactone is considerably raised 

 when the solution is made alkaline. This product has been re- 

 cognised as y-hydroxy-carbohydrocamphenic acid lactone IX 

 and, on the assumption that a rearrangement takes place, its formation 

 would be explained by the following formulae: — 



CH CH 



CH, C (CH 3 ) 



CH 



CH 



CH 



-CH- 



^c/ 



CH 



CH 



-CH 



0=C 



CH a -C.CH, 



CH 2 C(CH 3 )- 



-C0 9 



-c H 



CHg-CCHg 



CH, C(CH 3 )— CH 



XII. 



CH q .C-CH 3 / 



3 1 3 C=0 



CHg-C / 



CH 



•c 5 



CH- 



CH-CO 



r/^-^-3 PH 

 \CH 9 



-CH- 



V 



CH CH ■ 



-CH- 



\ 



O 



C /CH 3 

 X CH^ 



CH-CO v 



O 



C.CH 3 CH 2 CH- 



\ 



-C-COOH 



IX. 



X. 



Bredt argues from various indications that the rearrangement in 

 question, i. e. the displacement of the halogen from the /?- into the 

 7-position, occurs during the boiling of the aqueous solution of the 

 sodium />-hydrobromo or /?-hydrochloro bornylene carboxylate. The 

 constitution of the lactone was determined by its oxidation into 



13* 



