198 



ALDEHYDES AND KETONES : FATTY GROUP [106 M-B. 



permanganate followed by potassium 

 dichromate and sulphuric acid (Crossley 

 and Le Sueur, Trans. Ch. Soc. 75, 164). 



[N.] From lactic acid [Vol. II] and 

 melhyl alcoJiol [13] through a-brompro- 

 pionic acid by heating lactic acid with 

 saturated bromhydric acid (Kekule, Ann. 

 130, 1 6), and then dimethylisopropyl 

 carbinol by the interaction of a-brom- 

 propionyl bromide and zinc methyl, &c., 

 as above under I and K. 



Or from lactic acid through pyrora- 

 cemic acid (see under benzyl alcohol 

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



Or from lactic acid through citra- 

 conic acid (see under benzyl alcohol 

 [54 ; M, notes]) and /3-chlorcitramalic 

 acid as under Q, below. 



[O.] From oxalic acid [Vol. II] and 

 methyl alcohol [13] through a-hydroxy- 

 isobutyric (2-methyl-2-propanolic) acid 

 by the interaction of zinc methyl and 

 dimethyl oxalate (Frankland arid Duppa, 

 Ann. 133, 80 ; 135, 25). The acid gives 

 acetone on oxidation with chromic acid 

 mixture, or on fusion with caustic alkali ; 

 also on electrolysis of the potassium salt 

 (v. Miller and Hofer, Ber. 27, 468), on 

 decomposition of the silver salt by 

 iodine (Herzog and Leiser, Monats. 22, 

 357), or on heating with phosphorus 

 pentoxide (Bischoff and Walden, Ann. 

 279, in). 



Or from oxalic and propionic acids 

 and alcohol through methyloxalacetic 

 ester, /3- methyl malic acid, and citra- 

 conic acid (see under benzyl alcohol [54 ; 

 M, note]), and then as under Q below. 



[P.] Tartar ic acid [Vol. II] gives 

 acetone among the products of dry dis- 

 tillation (Volckel, Ann. -89, 57), or of 

 oxidation by hydrogen peroxide (Cotton, 

 Journ. Pharm. 10, 195). 



Or from tartaric (or racemic) acid 

 through pyroracemic acid (see under 

 benzyl alcohol [54 ; U"]), the calcium 

 salt of which gives acetone on distilla- 

 tion (Hanriot, Bull. Soc. [2] 43, 417; 

 45, 81). A mixture of potassium pyro- 

 racemate and acetate yields acetone on 

 electrolysis (Hofer, Ber. 33, 654). 



Or from tartaric acid through pyro- 

 tartaric acid and allylene, as under 

 benzyl alcohol [54 ; N], and then as 

 under B above. 



[Q.] Citric acid [Vol. II] gives ace- 

 tone among other products when heated 

 with strong sulphuric acid (Wilde, Ann. 

 127, 170); on dry distillation witli 

 glycerol (Clermont and Chautard, Com p. 

 Rend. 105, 520), or on heating the 

 sodium salt with lime (Freydl, Monats. 

 4, 151). Citric acid yields acetone 

 among the products of dry distillation or 

 of oxidation by potassium permangan- 

 ate, by sulphuric acid and manganese 

 dioxide (Robiquet, Berz< Jahresber. 18, 

 502; P6an de St. Gilles, Ann. Chim. 

 [3] 55, 374), or by hydrogen peroxide 

 (Cotton, Journ. Pharm. 10, 195). 



Acetone isformed by adding potassium 

 permanganate solution drop by drop to 

 a boiling solution of citric acid, or by 

 exposure of citric acid to air in presence 

 of iron or ferric chloride; also from 

 Kammerer's iron citrate under similar 

 conditions (Sabbatani, Atti Accad. Sci. 

 Torino, 35, 678 ; Journ. Ch. Soc. 78, 

 Abst. I, 536). 



Or citric acid may be converted into 

 acetonedicarboxylic acid (see under or- 

 cinol [75 ; O]), and this gives acetone 

 on heating at 135 per se or by boiling 

 with water, acid, or alkaline solutions. 



Or from citric acid through citraconic 

 acid (see under benzyl alcohol [54 ; M]) 

 and /3-chlorcitramalic acid by the action 

 of hypochlorous acid or chlorine on the 

 latter (Gottlieb, Ann. 160, 101 ; Carius, 

 Ann. 128, 204 ; Melikoff and Feldmann, 

 Ann. 253, 87). The chloro-acid gives 

 acetone on heating with water at 110- 

 120. 



Mesaconic acid; the isomeride of 

 citraconic acid, also gives /3-chlorcitra- 

 malic acid when a solution of the sodium 

 salt is chlorinated (Morawski, Journ. 

 pr. Ch. [2] 18, 392). 



Or from citraconic acid through allyl- 

 ene as under benzyl alcohol [54 ; M], 

 and the'n as above under B. 



[B.] From malonic and propionic acids 

 [Vol. II] through propanetricarboxylic 

 ester, citraeonic, and mesaconic acid 

 (see under benzyl alcohol [54 ; M, note]), 

 and then as above under Q. 



Or from malonic acid and acetic alde- 

 hyde [92] through crotonic acid and 

 allylene (see under benzyl alcohol [54; 

 G]), and then as above under B. 



