— 170 — 



b. p. 153 to 1 54 (15 mm. pressure); diacetate of the glycol: 

 do 1,127, b. p. 187 to 189 (12 mm. pressure). 



When the acetic acid solution of anethol dibromide was boiled with 

 zinc acetate, there was unexpectedly formed, by means of re-arrangement, 

 p-methoxyhydratropic aldehyde, whose occurrence is provisionally ex- 

 plained by the authors by the following formulae: — (R = CH 3 •0 G H 4 .) 



— HBr 



R.CH(OCO.CH 3 ).CHBr.CH 3 - — > R . CH(OCO.CH 3 ) -C . CH 3 



t 



-fCH 3 COOH 

 R.C:CH(OCO.CH 3 ) — — > R . CH.CH(OCO • CH 3 ) 2 



CH 3 CH 3 



The anethoglycol of the m. p. 11 6° obtained from the glycol 

 diacetate, proved to be identical with the a-glycol of the m. p. 114 to 

 1 1 5 , produced from anethol directly (by oxidation with mercuric acetate) 

 in addition to a /Msomeride of the m.p. 62 to 63 . On distillation 

 in vacuo the glycol split off water, and was converted into a body melting 

 at 98 , and boiling between 240 and 250 (14 mm. pressure), to all 

 appearances a derivative of diethylene oxide. When treated with 

 20 per cent, sulphuric acid, the glycol yielded anise ketone CH 3 0« 

 C 6 H 4 - CH 2 • CO-CH 3 (m.p. of the oxime 74 , of the semicarbazone 

 175 ). It is a very remarkable fact that Varenne and Godefroy 1 ) 

 obtained an anethoglycol from anethol dibromide by treatment with 

 alcoholic potash, that is to say, under conditions, under which, accord- 

 ing to Wallach and Pond, the ketone CH 3 O.C 6 H 4 - CO- CH 2 .CH 3 

 should have been formed. 



New syntheses of anethol and isosafrol have been carried out 

 by Wallach and Evans 2 ). As crude material they employed anisic 

 aldehyde and piperonal respectively. Anisic aldehyde was condensed 

 in benzene solution with bromopropionic acid ester; from the hydroxy 

 ester formed 



7 OH 

 CH 3 O.C 6 H 4 . CH( 



\CH(CH 3 )C0 2 C 2 H 5 



(b. p. 235 to 245 at 35 mm. pressure) water was abstracted by means 

 of potassium bisulphate at 150 , and the unsaturated ester obtained 

 (b. p. 170 to 180 at 25 mm. pressure) was saponified. The acid 



*) Compt rend. 140 (1905), 591; Report October 1905, 119. 

 2 ) Nachr. K. Ges. Wiss. Gottingen 1907, Meeting of 20. July. 



