— i3 2 — 



phenyl acetone (boiling point 214 — 215 , melting point of the semi- 

 carbazone 198 ); in an analogous manner from anethol oxide, the 

 anethol ketone (Tardy' s anise ketone) obtained also by Hoering 1 ). 



The asymmetrically disubstituted oxides, as- will be seen from 

 the above report, are converted into substituted hydratropic alde- 

 hydes, which had already been produced by Bougault 2 ) in an 

 entirely different manner. 



In all these conversions, there occur no molecular migrations 

 (transposition of carbon linkings). 



In our Report of October 1904, 11, we communicated the results 

 of a work by Hoering, according to which, in the treatment of 

 monobromo anethol bromide C H 3 O • C 6 H 3 Br • C H Br • C H Br . C H 3 

 with nitric acid, the bromine atom of the side-chain in the a-position 

 enters the benzene ring, with formation of a ketone CH 3 0«C 6 H 2 

 Br 2 • CO • CHBr • CH 3 . This peculiar atomic transposition was re- 

 cently also observed by Hoering in the anethol dibromide itself, 

 when even with moderate oxidation with nitric, chromic, or glacial 

 acetic acid, a ketone CH 3 • C 6 H 3 Br • CO • CHBr • CH 3 is formed 

 in a good yield. An examination of the secondary products formed 

 shows that there also occur secondary products non-brominated in 

 the nucleus; on the other hand, when the latter are oxidised, higher 

 brominated products are formed, e. g., dibromo anisic acid. In order 

 to solve the problem whether this entrance of bromine in the nucleus 

 must not be attributed to the occurrence of free bromine, numerous 

 oxidation experiments were made, especially with dilute solution of 

 potassium permanganate. But as, in spite of every precaution, this 

 examination did not lead to any definite result, Hoering endeav- 

 oured to come to a decision in an indirect way, by oxidising a- 

 methoxy-/?-bromo-dihydrobromo anethol C H 3 O • C 6 H 3 Br • C H (O C H 3 ) 

 CHBr-CH 3 . He found that with moderate oxidation of this body, 

 no further bromine atom enters the benzene ring, as almost exclusively 

 the ketone C H 3 O - C 6 H 3 Br • C O • C H Br . C H 3 was formed. 



On oxidising isosafrol dibromide, the author did not succeed in 

 arriving at a separation of the secondary products; on the other 

 hand, when the dibromide was treated with a mixture of nitric and 

 glacial acetic acids, it was converted into an acetyl derivative C H 2 2 • 

 C 6 H 2 (N0 2 ).CH(OCOCH 3 )CHBr.CH 3 , nitrated in the nucleus, 



*) Berl. Berichte 38 (1905), 2296. Report October 1905, 117; compare also 

 the following abstracts. 



*) Annal. de Chim. et Phys. VII. 25 (1902), 515, 549, 560. Report 

 April 1903, 11. 



