﻿ACTION OF SODIUM ON ACETONE. 75 



of the isoacetone ester in the oil. Miss Taylor's supposition is that 

 this acetone comes from mesityloxide present in the mixture. If enough 

 mesityloxide occurred in the mixture to yield 30 per cent of acetone, 

 then the carbon dioxide found would be reduced by 11 per cent, to say 

 nothing of the change brought about in the analytical results. A mixture 

 which consists of ethyl isopropylcarbonate, diethylcarbonate and sufficient 

 mesityloxide to yield 30 per cent of acetone and which will also give 

 33.7 per cent of carbon dioxide, can not be calculated. Miss Taylor 

 allowed her reaction product to stand over phenylhydrazine for four days. 

 It is possible that, if isopropenylethylcarbonate was present at all, it 

 would by that time have reacted with phenylhydrazine ; it is also possible 

 that, owing to some variation in her work Miss Taylor never had the 

 body in the oil she prepared. Attention is further called to the fact 

 that Freer obtained enough 2-chlorpropene by the action of phosphorus 

 pentachloride to isolate this very low-boiling substance. The reaction 

 product also absorbs bromine in the cold, without yielding hydrobromic 

 acid. 



Miss Taylor did not use benzoyl chloride in studying the composition 

 of sodium acetone, substituting p-nitrobenzoyl chloride therefor. Again, 

 in her reaction she does not seem to have had a sodium derivative which 

 acted like the one described above, for she obtained none of the addition 

 products described by Freer as a result of the action of benzoyl chloride 

 on sodium acetone. That p-nitrobenzoyl chloride might not form an 

 isoacetone ester is conceivable, but in that event it should give addition 

 products. Freer, in studying the action of benzoyl chloride on sodium 

 acetone separated the reaction products into two parts, one soluble in 

 alkalies, the other insoluble. In this instance, the insoluble oil (12 

 grams) boiling at 120° (39 millimeters pressure) added bromine in 

 the cold, gave acetone in sufficient quantity to be isolated from the sodium- 

 bisulphite compound, isopropyl alcohol, and ethyl alcohol. The organic 

 liquid containing the acetone was twice as great in volume as the remainder. 

 The portion of the reaction proditct which was soluble in alkalies yielded 

 acetophenon, mono- and dibenzoyl acetone. Here we are not dealing with 

 a mixture of oils, but with crystalline solids which can be isolated in the 

 pure state. It is difficult to see how mono- and dibenzoyl acetone could 

 result from a mixture of condensation products of acetone, sodium 

 isopropylate and caustic soda. Sodium acetone must have taken part in 

 the reaction. 



It should also be remembered that Freer and Lachman 13 studied the 

 action of sodium on methyl propylketone, obtained 22.1 per cent of 

 sodium in the derivative (calculated 21.3 per cent), isolated dibenzoyl 

 methyl propylketone, and from 2 grams' of the alkali insoluble portion 



a Amer. Chem. Journ. (1897), 19, 878. 



