196 



ALDEHYDES AND KETONES : FATTY GROUP [106 F-K. 



hydrochloric acid (Hanriot, Ann. Chim. 



[5] 17, 84). 



Or from glycerol through crotonic 

 acid and tertiary heptyl alcohol (see 

 below under L). 



Or from glycerol through glyceric 

 and pyroracemic acids (see under benzyl 

 alcohol [54; F]), and then as under 

 P below. 



[&.] Acetic aldehyde [92] gives acetone 

 when the vapour is passed over red-hot 

 lime (Schloemilch, Zeit. [2] 5, 336). 

 Or indirectly from aldehyde through 

 crotonic acid and tertiary heptyl alcohol 

 (see below under L). Or from aldehyde 

 through butyrochloral and allylene (see 

 under benzyl alcohol [54; H]), and then 

 as above under B. 



[H.] Isovaleric aldehyde [95] on treat- 

 ment with phosphorus pentachloride and 

 decomposition of the product with alco- 

 holic potash gives isopropylacetylene = 

 3-methyl-i-butine, and this yields ace- 

 tone among the products of its oxidation 

 by chromic acid mixture (Bruylants, 

 Ber. 8, 407 ; 413). 



[I.] From propionic acid [Vol. II] 

 through tertiary amyl alcohol by the 

 interaction of propionyl chloride and 

 zinc methyl and decomposition of the 

 product with water (Popoff, Ann. 145, 

 292; Jermolajeff, Zeit. [2] 7, 275; 

 Wischnegradsky, Ann. 190, 336), and 

 then as above under E. 



Or propionic acid may be brominated 

 (see under aldehyde [92 ; E]), and the 

 a-brompropionic aci I converted into 

 a-brompropionyl bromide, which, by 

 interaction with zinc methyl and de- 

 composition of the product with water, 

 gives dimethylisopropyl earbinol (Kas- 

 chirsky, Journ. Russ. Soc. 13, 82). The 

 latter yields acetone among other pro- 

 ducts on oxidation by potassium per- 

 manganate (see below under K). 



Or from propionic acid through pyro- 

 racemic acid (see under benzyl alcohol 

 [54 ; O]), and then as under P below. 



Or from propionic and acetic acids, 

 alcohol [14] and potassium cyanide [172] 

 through a-methyl-3-cyanosuccinic ester 

 and citraconic acid (see under benzyl 

 alcohol [54; M]), and then as under 

 Q below. 



Or from propionic acid through pro- 



pionamide and propionitrile (Dumas, 

 Malaguti, and Leblanc, Ann. 64, 334), 

 and then as below under S. 



[J.] Acetoacetic acid [Vol. II] splits 

 up readily into acetone and carbon 

 dioxide on heating (Ceresole, Ber. 15, 

 1328). 



Or indirectly from acetoacetic ester 

 through acetonedicarboxylic acid (see 

 under orcinol [75 ; D]), and then as 

 under Q below. 



Or from acetoacetic ester and hydrogen 

 cyanide [172] through hydroxypyrotar- 

 taric acid and citraconic acid (see under 

 benzyl alcohol [54; M, note]), and then 

 as under Q below. 



Or from acetoacetic ester through 

 methylacetoacetic ester and mesaconic 

 acid (see under benzyl alcohol [54; I]), 

 and then as under Q below. 



Or from acetoacetic ester through 

 isonitrosoacetone and pyroracemic acid 

 [54 ; I], and then as under P below. 



Or from acetoacetic ester and a-brom- 

 propionic ester through /3-methylaceto- 

 succinic ester and pyrotartaric acid as 

 under benzyl alcohol [54; I], and from 

 the latter through allylene \lbid. P ; M ; 

 and NJ, and as above under B. 



Or from acetoacetic ester, chloracetic 

 ester, and methyl alcohol through aceto- 

 succinic ester, the a-methyl-derivative, 

 pyrotartaric acid, and allylene [54; I]. 



Or from acetoacetic ester through 

 the /3-chlorcrotonic acids, tetrolic acid 

 and allylene {Ibid.}. 



[K.] Isobutyric acid [Vol. II] gives 

 acetone when heated with chromic acid 

 solution at 140 (Popoff, Zeit. [2] 7, 4). 



Or on oxidation with alkaline per- 

 manganate isobutyric acid gives a- 

 hydroxyisobutyric (2-methyl-2-propan- 

 olic) acid, which yields acetone as below 

 under O. 



NOTE : Ketones which yield isobutyric acid 

 on oxidation are thus likely to give acetone, 

 e.g. diisopropyl ketone from calcium isobutyrate 

 or the corresponding diisopropyl earbinol 

 (Popoff, Ber. 6, 1255 ; Munch, Ann. 180, 327 ; 

 333)- 



Methylisopropyl ketone from iso- 

 butyryl chloride and zinc methyl 

 (Behal, Ann. Chim. [6] 15, 284) gives 

 j8-dichlorisopentane on treatment with 

 phosphorus pentoxide, and this by alco- 



