106 K-M.J 



ACETONE 



197 



holic potash yields isopropylacetylene 

 (Ibid. 286), which gives acetone on 

 oxidation (see under E). 



NOTE : Methyl isopropyl ketone is obtained 

 also from acetoacetic ester and isobutyryl 

 chloride through isobutyrylacetoacetic ester, 

 and the action of hydrochloric acid on the latter 

 at 140-150 (Bouveault, Comp. Rend. 131, 45). 



Ethylisopropyl ketone from isobutyryl 

 chloride and zinc ethyl (Butleroff, Ann. 

 189, 44 ; Pawloff, Journ. Russ. Soc. 8, 

 242 ; Wagner, Ibid. 16, 697) gives 

 acetone among the products of its oxida- 

 tion by chromic acid. 



Dimethylisopropyl carbinol from iso- 

 butyryl chloride and zinc methyl 

 (Prianischnikoff, Zeit. [2] 7, 275) gives 

 acetone among the products of its 

 oxidation by potassium permanganate 

 (Wagner, Journ. pr. Ch. [2] 44, 310). 

 Or dimethylisopropyl carbinol yields 

 tetramethylethylene and pinacone (see 

 under tertiary butyl alcohol [19 ; E]). 

 The latter gives acetone on oxidation 

 with chromic acid mixture. 



A mixture of calcium isobutyrate and 

 heptoate [Vol. II] gives isopropylhexyl 

 ketone on dry distillation, and this 

 yields acetone among the products of 

 its oxidation by chromic acid (Fuchs, 

 Journ. Russ. Soc. 7, 334). 



Isobutyric acid also gives the a- 

 bromo-acid on bromination (Markowni- 

 koff, Ann. 153, 229; Hell and Wal- 

 dauer, Ber. 10, 448 ; Michael and 

 Graves, Ber. 34, 4043), and the latter, 

 on heating with water or barium 

 hydroxide or sodium carbonate solution, 

 yields the a-hydroxy-acid (Markowni- 

 koff, loc. cit. ; Fittig, Ann. 20O, 70), 

 from which acetone can be produced as 

 below under O. 



Or a-bromisobutyric ester and alde- 

 hyde [92] condense under the influence 

 of zinc to form trimethylethylenelactic 

 = 2 : 2-dimethyl - 3 - butanolic - 1 - acid 

 (ester) (Ephrussi and Reformatsky, 

 Journ. Russ. Soc. 28, 600). The acid 

 gives tertiary amyl alcohol (with tri- 

 methylacrylic acid) on distillation with 

 dilute sulphuric acid (Giljaroff, Ibid. 

 508). The amyl alcohol yields acetone 

 as above under E. 



[L.] From normal butyric acid [Vol. 

 II] and methyl alcohol [13] through the 



tertiary heptyl alcohol produced by the 

 interaction of a-brom-n-butyryl bromide 

 and zinc methyl and decomposition of 

 the product with water (Kaschirsky, 

 Journ. Russ. Soc. 13, 89). This heptyl 

 alcohol gives acetone among the pro- 

 ducts of its oxidation. Or n- butyric 

 acid may be converted into crotonic 

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

 and allylene [Ibid. G-], and then into 

 acetone as above under B. 



NOTE : Crotonic acid gives a- (with some j8-) 

 brombutyric acid on combination with hydro- 

 gen bromide (Hemilian, Ann. 174, 325). The 

 generators of crotonic acid referred to under 

 benzyl alcohol [54 ; G; H, &c.] thus become, 

 with methyl alcohol, generators of acetone. 



[M.] From isovaleric acid [Vol. II] 

 and ethyl alcohol [14] through ethyl - 

 isobutyl ketone (2-methyl-4-hexanone), 

 which is obtained by passing carbon 

 monoxide over a mixture of sodium 

 isovalerate and ethylate at 160 (Loos, 

 Ann. 202, 327). The ketone gives 

 acetone among the products of its oxi- 

 dation by chromic acid mixture. 



Ethylisobutyl ketone is also obtained 

 from the same materials by the inter- 

 action of isovaleryl chloride and zinc 

 ethyl (Wagner, Journ. pr. Ch. [2] 44, 



274). . 



Or isovaleric acid, by the action of 

 nitric acid, gives 2 : 2-( = /3) dinitropro- 

 pane, which on reduction by tin and 

 hydrochloric acid yields acetone (Bredt, 

 Ber. 15, 2322; Meyer and Locher, Ann. 

 180, 147). 



Also from isovaleric acid and normal 

 propyl alcohol [15] through propyliso- 

 butyl ketone (2-methyl-4-heptanone) by 

 the interaction of isovaleryl chloride and 

 zinc propyl (Wagner, Journ. Russ. Soc. 

 16, 668). This ketone also gives ace- 

 tone among the products of its oxida- 

 tion by chromic acid mixture. 



Or from isovaleric acid through hy- 

 droxypyrotartaric acid and citraconic 

 acid (see under benzyl alcohol [54 ; M, 

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



Or from isovaleric acid and ethyl 

 alcohol through a-bromisovaleric ester, 

 /3-dimethylacrylic acid by heating the 

 latter with quinoline or diethylaniline 

 (see under isobutyl alcohol [18 ; C]), 

 and oxidation of the acid with potassium 



