186 



The additiou reactions of cumiuoin with cuminalacetoue, piperouylen- 

 acetone and anisylidenacetoue are being studied at present, and I hope to 

 be able soon to publisli the results obtained. 



V. ADDITION" OF ANISOIX TO BEXZALACETOXE. 



;:?-4-r??Vn//x///-J-y<///';(///-;-(^j7/- \ 2-/.v'^y-/\-/(t'.iY'j/i'. 

 CH . C,,H, 



CH30.C,,H4.C. (OH) 



CH3O . CJI, . C 



cn, 



CO 



('II 



Anisoin adds itself to the ethylene grouping much more readily than 

 either cuminoin or benzoin to yield the expected 1.5 diketone, but the 

 readiness with which tliis 1.5 diketone loses water to form the correspond- 

 ing A2-keto-R-hexene derivative is markedly less. In fact the 1.5 dike- 

 tone constitutes the major portion of the reaction product. Attempts to 

 prepare the 1.5 diketone pure, /. c, free from the A z-^^^to-R-hexene de- 

 rivatives, have failed partially. However, its approximate melting point 

 has been obtained, namely, 168-174°. Wlien boiled with the ordinarj^ sol- 

 vents in which it is soluble, the 1.5 diketone loses water and forms the 

 A^-J^sto-R-hexene derivative, which melts at 207°. 



The mixture of the 1.5 diketone and the _^2-keto-R-hexene derivative 

 is prepared as follows : 



One molecule (4.4 gr. ) of anisoin and one molecule (2 38 gr. ) of ben- 

 zalacetone are dissolved in absolute ethyl alcohol (62cc. ) and to the mix- 

 ture sodium ethylate solution (4cc. ) is added. The solution becomes deep 

 red and upon standing for two hours deposits a large mass of crystals 

 (2.4 gr. ). The solid is filtered olf and washed well with absolute alcohol. 

 A trial determination of the melting ])oint shows that tlie product is a 

 mixture. It melts at 168-74° and 204°. The mother liquor from tlie crys- 

 tals upon treatment with more sodium ethylate solution yields more of the 

 same products (.4 gr. ) Upon recrystallization from either of three sol- 

 vents — benzene, alcohol or acetic acid — fine white needle-like crystals are 



