274 



SCIENCE PROGRESS 



dioxide, otherwise oxidation occurs (Section I.) ; the action is 

 only partial, equilibrium being established when 10 per cent, 

 of the ketone has been transformed. 



Laevulinic acid is hydrolysed : by water (ten volumes) in a 

 highly characteristic manner, methylic alcohol, formic acid and 

 propionic acid being the products, instead of acetic acid and 

 propionic acid as might have been anticipated : 



CH,;CO:CHj.CH».CO.OH + 2H,0->CH 3 OH + 

 H.CO.OH + CH 3 .CH 2 .C0 2 H 



The behaviour of the cyclic ketones when exposed with 

 an excess of water (ten times the weight of the ketone) to the 

 action of sunlight is generally twofold in its character : usually 

 a fatty acid is formed, together with an unsaturated aldehyde. 

 In the case of cyc/ohexanone the changes that occur are : 2 



CH 2 

 H,C/-\CH 2 



H,C 



H 2 



CO 



-> CH 3 . CH 2 .CH 2 .CH 2 .CH 2 .CO.OH 



M-Hexoic acid. 



CH, 



CH 2 



ii. H.,C/^CH„ 



H 2 C 



CO 



CH 2 : CH . CH 2 . CH, . CH 2 . CHO 



Hexylene aldehyde. 



CH, 



o-Methylcyc/ohexanone under like conditions is changed as 



follows : 



CH, 

 i. H.,C/vCHMe 



+ H,0 -> CH 3 .CH 2 .CH 2 .CH 2 .CH 2 . CH 2 .C0 2 H 



H 2 C 



CO 



CH, 



CH 2 



H,C/\CHMe 



H,C 



CO 



M-Heptoic acid (15 %). 



CHMe: CH . CH 2 .CH,. CH, . CHO 



6-Heptenaldehyde (8 %). 



CH, 



In the latter case, the ring is split only in the manner 

 indicated; no methyl-w-butylacetic acid is formed, as would 

 be the case if splitting occurred between the CO and CH 2 , as 

 in the case of cyc/ohexanone. 



1 AM R. Accad. Lincei, 1907, 16, i. 835 ; Ber. 1907, 40, 2415. 

 3 AM X. Accad. Lincei, 1908, 17, i. 179 5 Ber. 1908, 41, 107 1. 



