194 



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



glycerol [48] ; malonic add [Vol. II] and alde- 

 hyde [92] ; acetoacetic ester [Vol. II] ; allyl iso- 

 thiocyanate [166] ; P-hydroxybutyric acid ; normal 

 butyric acid ; citric acid ; lactic acid ; isovaleric 

 acid ; malonic and propionic acids ; tartaric and 

 racemic acids; isobutyl and amyl alcohols [18 ; 22]. 



[C.] Isobutyl alcohol [18] gives ace- 

 tone among 1 other products on oxidation 

 with chromic acid (Kramer, Ber. 7, 252; 

 Schmidt, Ibid. 1361). Or from isobutyl 

 alcohol through isobutylene (see under 

 tertiary butyl alcohol [19 ; B]). The 

 latter gives acetone among other pro- 

 ducts on oxidation with chromic acid or 

 potassium permanganate (F. and O. 

 Zeidler, Ann. 107, 251 ; Wagner, Ber. 

 21, 1232). 



Or indirectly from isobutyl iodide 

 and potassium cyanide [172] through 

 the nitrile of isobutylformic acid and 

 the acid by hydrolysis (Erlenmeyer 

 and Hell, Ann. 166, 266 ; Schmidt 

 and Sachtleben, Ann. 193, 92). The 

 acid on oxidation with dilute alkaline 

 permanganate gives /3-hydroxyiso valeric 

 (2-methyl-2-butanolic-3)acid (v. Miller, 

 Ann. 200, 273), and this yields acetone 

 on oxidation with chromic acid mixture. 



Isobutyl alcohol gives allylene when 

 the vapour is passed over hot magnesium 

 and the product decomposed by water 

 (Keiser and Breed, Ch. News. 71, 118 ; 

 Am. Ch. Journ. 18, 328). From allyl- 

 ene to acetone as under B. 



[D.] From tertiary butyl alcohol [19] 

 through isobutylene (see under isobutyl 

 alcohol [18 ; A]). Acetone is among 

 the products formed by passing the 

 vapour of this alcohol over a heated 

 platinum spiral (Trillat, Comp. Rend. 

 132, 1495). 



Or from tertiary butyl alcohol and 

 hydrogen cyanide [172] through tertiary 

 amyl alcohol (see under formic aldehyde 

 [91 ; X]), and then as under E below. 



Acetone is among the products of 

 oxidation of tertiary butyl alcohol by 

 chromic acid mixture (Butleroff, Zeit. 



[2] 7, 485). 



[E.] From amyl alcohol from fusel 

 oil [22]. Isobutylene is among the 

 products of decomposition by passing 

 through a hot tube (Wurtz, Ann. 104, 

 249 ; Butleroff, Ann. 145, 277 ; Ipatieff, 

 Ber. 35, 1053). 



Or the amyl alcohol can be converted 



into amylene by the usual methods 

 (Balard, Ann. Chim. [3] 12, 320; 

 Frankland, Ann. 74, 41 ; Wurtz, Ann. 

 128, 225; 3 I( 5 ; Bauer, Journ. pr. Ch. 

 84, 257 ; Etard, Comp. Rend. 86, 488 ; 

 Eltekoff, Ber. 10, 1904; Wischne- 

 gradsky, Ann. 190, 332 : fusel oil 

 amylene prepared by the action of zinc 

 chloride contains, in addition to tri- 

 methylethylene, some isopropylethylene 

 and a trace of the symmetrical methyl- 

 ethylethylene, Kondakoff, Journ. Russ. 

 Soc. 24, 1 13). By the action of strong 

 sulphuric acid and subsequent hydro- 

 lysis this amylene is converted into 

 tertiary amyl alcohol = dimethylethyl 

 carbinol (Osipoff, Ber. 8, 1 240 ; 

 Wischnegradsky, loc. cit. 336 ; Konda- 

 koff, loc. cit. 25, 354), and the latter, 

 when chlorinated in the presence of 

 water, yields acetone among other pro- 

 ducts (Brochet, Ann. Chim. [7] 10, 



3i). 



Amyl alcohol also gives acetone 

 among the products of its oxidation, or 

 by passing the vapour over a heated 

 platinum spiral (Trillat, Comp. Rend. 

 132, 1495). . 



Or fusel oil amylene (trimethylethyl- 

 ene) may be converted into the bromide 

 and trimethylethylene glycol (Wurtz, 

 Ann. Chim. [3] 55, 458 ; Wagner, 

 Ber. 21, 1235). The latter gives 

 acetone among the products of its 

 oxidation by chromic acid mixture 

 (Flawitzky, Ber. 1O, 2240). 



Trimethylethylene yields acetone by 

 oxidation with potassium permanganate, 

 the glycol being formed as an inter- 

 mediate product (Wagner, loc. cit.}. 

 Trimethylethylene chlorhydrin from the 

 hydrocarbon and hypochlorous acid 

 gives methylisopropyl ketone on heat- 

 ing with water, or by passing over 

 heated zinc oxide (Krassusky, Journ. 

 Russ. Soc. 34, 287). Or the chlor- 

 hydrin, on treatment with potash, yields 

 trimethylethylene oxide (Eltekoff, Ibid. 

 14, 361). This oxide on heating with 

 lead chloride to 200 gives methyl- 

 isopropyl ketone (Krassusky, loc. cit. 

 537). The ketone yields acetone as 

 below. 



Or trimethylethylene bromide on 

 heating with alcoholic potash gives 



