( 139 ) 



tities of alljl formate may be prepared in a still more convenient 

 manner by heating- equal parts by weight of glycerol and formic 

 acid. The temperature is kept for some time at 125°, during which 

 dilute formic acid distills over. Gradually it is raised to 240° and, 

 with a quiet evolution of CO^ containing a little CO, a mixture 

 passes over consisting of allyl formate, allyl alcohol and a very 

 little formic acid. This is again submitted to distillation, the portion 

 boiling up to 100° being collected. After treatment with dry potas- 

 sium carbonate, the liquid is again distilled and the portion boiling 

 below 85°, which mainly consists of allyl formate, is collected 

 separately. 



This ester may also be procured by distilling allyl alcohol with 

 twice its weight of formic acid and collecting the portion passing 

 over below 85°. The product is then treated with dry potassium 

 carbonate and once more rectified. 



After it had been ascertained that ammonia acts so very readily 

 with allyl formate it was decided to try the action of amines also. 



The investigation showed that amines of the fatty series, primary 

 as well as secondary ones, readily react with the same. Benzylamine, 

 phen^dhydrazine and piperidine also seemed to react but no reaction 

 could be observed with aniline. 



If we mix one of these amines with allyl formate, in the majority of 

 cases a rise in temperature does not necessarily take place immediately. 



This rise rather varies in the different cases ; whilst its maximum 

 is sometimes reached fairly quickly, sometimes only after a lapse of 

 about 20 minutes. 



The reaction appears to be of such a nature that when working 

 at a constant temperature we can ascertain its progress by means 

 of a quantitative determination of the absorbed amine. 



I intend making a series of experiments with different amines. The 

 following contains a brief description of some qualitative experiments. 



If methyl- or ethylamine is passed into allyl formate these sub- 

 stances are absorbed with great evolution of heat and the amides 

 formed are left behind after distilling off the allyl alcohol. 



5 grams of ])ropylamine being mixed with 10 grams of allyl for- 

 mate the temperature rapidly rose from 19° to 60° and propylform- 

 amide (b.p. 219"— 220°) was formed. 



5 grams of isopropylamine being mixed Avith 10 grams of the 

 ester the temperature slowly rose to 50°, whilst a good yield of 

 isopropylformamide was obtained (b.p. 203° — 204°). 



10 



Proceedings Royal Acad. Amsterdam. Vol YIII, 



