106 E-P.] 



ACETONE 



195 



dimethylallylene (3-methyl-i : 2-buta- 

 diene), which also yields acetone among 

 the products of its oxidation (Paworsky, 

 Journ. pr. Ch. [2] 37, 392). 



Trimethylethylene bromide on heat- 

 ing- with water and lead oxide at 150, 

 or with water alone, gives methyliso- 

 propyl ketone (Eltekoff, Journ. Russ. 

 Soc. 10, 215; Niederist, Ann. 196, 360; 

 NagelvBer. 16, 2983), and this yields 

 acetone among the products of its oxida^ 

 tion by chromic acid. 



Trimethylethylene glycol also gives 

 a-hydroxyisobutyric = 2 -methyl- 2-pro- 

 panolic acid on oxidation with nitric 

 acid (Wurtz, Ann. 107, 197), and this 

 yields acetone as under O. 



Or fusel oil amyl alcohol by conver- 

 sion into the iodide, isopropylethylene 

 (Wischnegradsky, Ann. 10Q, 358), 

 isopropylethylene bromide, and the 

 action of alcoholic potash on the latter 

 gives isopropylacetylene, which also 

 yields acetone among the products of 

 its oxidation (Eltekoff, loc. cit. 9, 222 ; 

 224; Flawitzky and Kryloff, Ibid. 1Q, 

 342). Isopropylethylene gives acetone, 

 among other products, on oxidation by 

 potassium permanganate (Wagner, Ber. 



21, I233)- 



Amyl alcohol gives allylene on pass- 

 ing the vapour over hot magnesium and 

 decomposing the product with water 

 (see above under C). Subsequent steps 

 as under B. 



[F.] From glycerol [48], acetone being 

 among the products formed by distilling 

 glycerol with lime (Tawilderoff, Ber. 12, 

 1487), or by oxidation with hydrogen 

 peroxide (Cotton, Journ. Pharm. 1O, 

 194). 



Or from glycerol through allyl iodide 

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

 propylene by the action of zinc and sul- 

 phuric acid or mercury and hydrochloric 

 acid (Berthelot and De Luca, Ann. 92, 

 306). or of acetic acid and zinc (Linne- 

 mann, Ann. 161, 54; Gladstone and 

 Tribe, Ber. 6, 1550 ; Niederist, Ann. 

 196, 358), and then as above under B. 

 Allyl iodide also gives propylene by 

 treatment with hydriodic acid (Butleroff, 

 Ann. 145, 271; Malbot, Comp. Rend. 

 1O7, 114; Bull. Soc. [2] 50, 449). 



Or glycerol can be converted into 



allyl alcohol (see under ethyl alcohol 

 [14; G]), and this gives propylene 

 (with ethylene) by heating with phos- 

 phorus pentoxide (Behal, Ann. Chim. 

 [6] 16, 360). Or allyl chloride from 

 allyl alcohol gives a chlorhydrin by the 

 action of sulphuric acid (Oppenheim, 

 Ann. Suppl. 6, 367), and this yields 

 acetone (with propaldehyde) on heating 

 with water (Krassusky, Journ. Russ. 

 Soc. 34, 287). 



Glycerol gives propylene (with allyl 

 iodide) by the action of iodine and 

 phosphorus (Berthelot and De Luca, 

 loo. cit. ; Oppenhejm, Ann. Suppl. 6, 



354)- 



Or from glycerol through allylene as 

 under benzyl alcohol [5, 4 ; F], and then 

 as above under B. 



Or glycerol can be converted into 

 allyl bromide (Tollens, Ann. 156, 152 ; 

 Henry, Zeit. [2] 6, 575 ; Grosheintz, 

 Bull. Soc. [2] 30, 98), the latter into 

 tribromhydrin = i : 2 : g-tribrompropane 

 (Tollens, Ann. 156, 168 : see also under 

 glycerol [48 ; .4]), the latter into i : 2- 

 dibrompropylene by the action of solid 

 potash or sodium in ethereal solution 

 (Henry, Ann. 154, 371; Tollens, loc. 

 cif.), and the dibrompropylene into 

 'allene' (CH 2 :C:CH 2 ) by reduction 

 in alcoholic solution with zinc (Gustav- 

 son and Demjanoff, Journ. pr. Ch. 38, 

 $01 : compare Behal, Bull. Soc. [2] 48, 

 788). Allene dissolves in sulphuric aci.l, 

 and the product gives acetone on dis- 

 tillation with water (G. and D., loc. cit.}. 



Allyl bromide also gives propylene 

 by the action of zinc dust in alcoholic 

 solution (Wolkoff and Menschutkin, 

 Ber. 31, 3072), and this yields acetone 

 as above. 



Glycerol gives propylene glycol 

 directly when the monosodium com- 

 pound is distilled (Belohoubek, Ber. 

 12, 1873; Morley and Green, Trans. 

 Ch. Soc. 47, 132), and this yields acetone 

 as under B. 



Propylene glycol may also be obtained 

 from glycerol by the action of sodium 

 amalgam on the monochlorhydrin (Lou- 

 reno, Ann. 120, 91), or by the action 

 of acetyl bromide on glycerol, and 

 reduction of the product (glycerol-aceto- 

 bromhydrin) with coppered zinc and 



2 



