18C 



The addition reactious of cuminoiii with cuminalacetoue, piperouylen- 

 acetoue and anisylideuacetone are being studied at present, and I liope to 

 he able soon to publisli tlie results obtained. 



V. ADDITION" OF AXISOIX TO EEXZALACETOXE. 



.)-4-fliiiiiixi/l~'j-jiIn'iii/!-4-().ri/- _ ,-J:i't(t-Ji-he.ieue. 



CH . Cllr. 



CHaO.Cilli.C. (OH) 



CH3O . C,;H4 . C 



CH, 



A.nisoin adds itself to tlie ethylene grouping much more readily than 

 either cuminoin or benzoin to j-ield the expected 1.5 diketone, but the 

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

 ing A o-keto-R-hexeiif derivative is markedly less. In fact the 1.5 dike- 

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

 prepare the 1.5 diketone pure, /. i-., free from the /^^-keto-R-hexene de- 

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

 has been obtained, nam^ely, 168-174^. When boiled with the ordinary sol- 

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

 A2~li6to-R-hexene derivative, wliich melts at 207°. 



The mixture of the 1.5 diketone and the ^j-keto-R-hexene derivarive 

 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 off and washed well witli absolute alcohol. 

 A trial determination of the melting point shows that tlie product is a 

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

 tals upon treatment with more sodium etliylate 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 



