

152 Report of Schimmel § Co. April/ October 1917. 



Phenolethers. 



Polymerides of anethole and of isosafrole. — E. Puxeddu ') has now continued an 

 investigation with L. Scaffidi 2 ) on the polymerides of anethole and isosafrole about 

 which he had already furnished some information at a former period. He describes 

 the polymerization of anethole according to 3 methods. On allowing concentrated 

 sulphuric acid to react with anethole he obtained anisoin, generally in an amorphous, 

 occasionally, however, in a crystalline state, melting from 205 to 210°; at the same 

 time a polymeric anethole (Ci Hi 2 O)x, a yollowish crystalline powder melting at about 

 250° was formed. When anethole is dissolved in acetone and submitted to the action 

 of iodine, anisoin, in the shape of a white amorphous powder melting at 185°, is the 

 result. The reaction of ferric chloride on an etheral solution of anethole leads to an 

 anisoin (Ci Hi 2 O)x, an amorphous powder melting at 210°, besides to a new polymeric 

 anethole (Ci Hi 2 O)x, which was insoluble in ether and consisted of a white powder 

 melting above 300°., The anisoin produced by means of sulphuric acid gave, when 

 treated with ethereal bromine, apparently a mixture of mono- and dibromine compounds, 

 whereas the anisoin prepared with the aid of ferric chloride absorbs much less bromine. 

 The product of the reaction of ferric chloride on an ethereal solution of isosafrole is a 

 white crystalline powder, a dimeric, melting at 92°. Its composition — from cryoscopical 

 data — was found to be C20H24O4. 



Years ago, we also obtained a polymeric isosafrole, melting at 90 to 91°, on heating 

 it with glacial acetic and sulphuric acid according to Bertram's and Walbaum's method. 

 This product boiled at 220° (3 mm.) 3 ). 



The reduction of azothymol and of azocarvacrol has been described on page 156. 



Acids and Esters. 



Campholenic acid. — The products of splitting-up of camphor, belonging to the cyclo- 

 pentane series, namely campholic acid, camphoric acid, and their further transformation 

 products are generated by the disrupture of the bicyclical system between the carbonyl 

 radicle and the neighbouring methylene group. On treating camphoroxime with dilute 

 acids, a scission takes place between the carbonyl group and the neighbouring quaternary 

 carbon atom whereby the oxime loses water and forms an unsaturated nitrile, which 

 can be saponified to optically active a-campholenic acid. The latter can be transformed 

 into the inactive /^-campholenic acid by molecular rearrangement. 



Recently, J. R. N. van Kregten 4 ) produced a-dihydrocampholenic acid (a-campholanic 

 acid) by hydrogenization from a-campholenic acid. He first produced «-campholenic 

 acid according to Tiemann's 5 ) method, namely by transforming camphoroxime into 

 a-campholenic nitrile and by saponification of the latter. . Instead of using sulphuric 

 acid for separating the acid from the potassium or ammonium salt he employed acetic 

 acid. He then reduced the campholenic acid according to the process of Sabatier 

 and Senderens by passing its vapour, mixed with pure hydrogen, over nickel heated 

 up to 200°. 



In order to purify it the product of the reaction was transformed into its sodium 

 salt by means of soda and the latter then oxidized by means of permanganate in a 



x ) Gazz. chim. ital. 43 (1913), I. 128; Report October 1913, 148. — 2 ) Gazz. chim. ital. 46 (1916), II. 169; 

 Chem. ZentralU. 1916, II. 1146. — 3 ) Report April 1905, 17. — *) Reeueil trav. chim. des P.-B. 36 (1916), 64; 

 Chem. ZentralU. 1916, II. 387. — Journ. chem. Soc. 110 (1916), I. 480. — B ) Berl. Berichte 29 (1896), 3007. 



