106-B.] 



ACETONE 



193 



Occurs among the products of fer- 

 mentation (putrefaction) of fish (Morner, 

 Zeit. physiol. Ch. 22, 514), and among 

 the products of fermentation of milk 

 sugar by Bacterium lactis aerogenes of 

 Escherich = Bact. aceticum of Baginsky 

 (Zeit. physiol. Ch. 12, 461), and of 

 dextrose by Dunbar's and other Vibrios 

 (Gosio : quoted by Emmerling in ' Die 

 Zersetzung, &c./ pp. 47 and 56). 



SYNTHETICAL PIIOCESSES. 



[A.] From acetic acid [Vol. II] by 

 dry distillation of the calcium or barium 

 salt (Liebig, Ann. 1, 223 ; Dumas, Ann. 

 Chim. [2] 49, 208), or by passing the 

 vapour over heated pumice and barium 

 carbonate (Squibb, Journ. Soc, Ch. Ind. 

 14, 506; 15, 612; Conroy, Ibid. 21, 



39) 



Or from acetic acid and methyl alcohol 

 [13] by the interaction of zinc methyl 

 and acetyl chloride (Chiozza, Ann. 85, 

 232 ; Freund, Ann. 118, i) ; or by the 

 action of nascent zinc methyl on acetic 

 anhydride, or of zinc-sodium alloy on 

 methyl iodide and acetic anhydride (Sayt- 

 zeff, Zeit. [2] 7, 104). 



Or zinc methyl and dichloracetyl 

 chloride give dimethylisopropyl carbinol 

 (see under tertiary butyl alcohol [19 ; 

 A]), which yields acetone on oxidation 

 as under K below. 



[B.] From normal or isopropyl alcohol 

 [15 ; 16] through propylene (see under 

 glycerol [48 ; A]), the chloride or brom- 

 ide, chlor- or brompropylene by the 

 action of alcoholic potash, and the action 

 of hypochlorous acid and mercuric oxide 

 on the halo-propylene. The chlor- 

 acetone thus formed gives acetone on 

 reduction. 



Or from brompropylene by heating 

 with mercuric oxide and acetic acid at 

 1 00 or with water at 190. Also from 

 propylene bromide by heating with 

 water at 180 (Linnemann, Ann. 138, 

 125; 161, 58; Bull. Soc. [2] 6, 216), 

 or with water and silver oxide (Michael, 

 Journ. pr. Ch. [2] 60, 418). 



Also by dissolving 2-chlorpropylene 

 in strong sulphuric acid and distilling 

 the product with water (Oppenheim, 

 Ann. Suppl. 6, 365). 2-(/3)-Chlorpropyl- 



ene is formed (with 3-(a)-chlorpropylene) 

 by the action of alcoholic potash on 

 propylene chloride (see under isopropyl 

 alcohol [16 ; B]). 



Or from propylene bromide or chloride 

 through propylene glycol (Wurtz, Ann. 

 Chim. [3] 55, 438 ; Eltekoff, Journ. 

 Russ. Soc. 1O, 210 ; Niederist, Ann. 

 196, 359), a^id the action of water at 

 180-190 on the latter, acetone and 

 propanal being simultaneously formed 

 (Eltekoff, loc. cit. 11, 409 : see also 

 Lieben, Monats. 23, 60), 



Propylene gives acetone also by direct 

 oxidation with chromic acid (Berthelot, 

 Ann. 150, 373). 



Or from propylene through acrole'in 

 [lOl] and pyroracemic or pyrotartaric 

 acid (see under benzyl alcohol [54 ; Ej), 

 and then as under P below, 



NOTE : Qenerators of propylene (see under 

 glycerol [48 ; B to I] and under isopropyl 

 alcohol [16]) thus become generators of acetone. 



Isopropyl alcohol gives acetone di- 

 rectly by oxidation with chromic acil 

 {Linnemann, Ann. 140, 178 ; Berthelot, 

 Comp. Rend. 68, 334). Also by electro- 

 lysis in sulphuric acid solution (Elbs 

 and Brunner, Zeit. Elektroch. 6, 604), 

 by passing over a heated platinum spiral 

 (Trillat, Comp. Rend. 132, 1495), or by 

 pyrogenic contact decomposition by 

 heated brass (Ipatieff, Ber. 35, 1057). 



Propylene bromide may also be con- 

 verted into allylene (see under benzyl 

 alcohol [54 ; E]), the latter giving ace- 

 tone on treatment with a solution of 

 mercuric bromide or chloride (Kut- 

 scheroff, Ber. 14, 1541 ; 17, 15). Or 

 allylene, when dissolved in strong sul- 

 phuric acid and the product distilled 

 with water, gives (with mesitylene) 

 acetone (Schrohe, Ber. 8, 367). At o 

 sulphuric acid with allylene yields only 

 acetone (Michael and Leighton, Journ. 

 pr. Ch. [2] 60, 442). 



Allylene is formed when the vapour 

 of propyl alcohol is passed over hot 

 magnesium and the product decomposed 

 by water (Keiser and Breed, Ch. News, 

 71, ii8; Am. Ch. Journ. 18, 328). 



NOTE : The generators of allylene referred 

 to under benzyl alcohol [54 ; P ; Q ; H ; I, 

 &c.] thus become generators of acetone : 



