﻿ACTION OF SODIUM ON ACETONE. '71 



excess of standard acid (found 30.9 per cent). This experiment gave 

 4.2 grams of iodoform, corresponding to somewhat less than one-half the 

 theoretical yield of acetone for pure sodium acetone. 



As -will be seen, even in the above two experiments, when air was not 

 rigidly excluded and where the sodium derivative was not handled with 

 particular care, no such high percentage of sodium as that obtained by 

 Miss Taylor, was found. Indeed, in a long series of experiments we 

 have never been able to obtain her results, which could only be accounted 

 for by a profound decomposition of her sodium derivative and the wash- 

 ing out of the acetone condensation products which would be formed. 

 If this decomposition were allowed to go far enough, then practically 

 nothing but sodium hydroxide mixed with the sodium derivatives of 

 alcoholic reduction products would remain. 



Experiment 4- — This was performed as was Experiment 1, with the 

 exception that petroleum ether was substituted as a solvent. The reaction 

 in this case is not so clean cut as with ether, the resulting compound is 

 somewhat pink and the sodium percentage higher. 



1.745 grams of the sodium derivative gave 0.6203 gram Xa and 3.4 

 grams iodoform, equivalent to 35.5 per cent sodium and 0.52 gram ace- 

 tone, 41 per cent, respectively. 



Experiment 5. — The apparatus was the same as in Experiment 1. 

 8.515 grams of the sodium compound was obtained, giving 2.567 grams 

 of sodium, equivalent to 30.14 per cent. After the sodium salt had 

 been decomposed, the acid solution was divided into four parts. One of 

 these was saturated with sodium acetate, then made very slightly alkaline 

 and the theoretical quantity of semicarbazid hydrochloride was added. 

 A precipitate of crystalline needles rapidly formed. After the mixture 

 had stood for 12 hours in the ice chest the precipitate was filtered and 

 it gave 1.2 grams of acetone semicarbazone, melting point 186°. This 

 was identical in all respects with a specimen of the same body prepared 

 for comparative purposes. One-eighth of the original acidified solution 

 gave 1.3 grams of iodoform... 



Experiment 6. — The conditions were the same as in Experiment 1. 

 8.25 grams of sodium derivative were obtained, from one-half of this, 

 acidified, etc., 2.9 grams acetone semicarbazone, melting at 186°, were 

 separated, and from one-quarter, 2.2 grams iodoform were precipitated. 

 One other sodium determination gave us 29.2 per cent of sodium. 



The above experiments render it practically certain that a sodium 

 derivative of acetone exists among the products of the action of sodium 

 on acetone, as acetone is obtained by their decomposition with acids. 

 However, it might possibly be true that the reaction product is sodium 

 isopropylate together with some caustic soda and that the acetone which 

 is found is held by the sodium isopropylate in a combination somewhat 

 similar to alcohol of crystallization. That this is unlikely is proved by 



