94 



KETONE ALCOHOLS 



[43 A- 44. 



sunlight on the latter (Kling, Comp. 

 Rend. 129, 319). 



NOTE : Generators of propylene (see under 

 glycerol [48]) thus become generators of 

 acetol. 



[B.] From acetone [106] through 

 chloracetone (Riche, Ann. 112, 321 ; 

 Mulder, Ber. 5, 1010). The latter on 

 heating with potassium acetate in al- 

 coholic solution gives acetol acetate 

 (Henry, Ber. 5, 966), which can be 

 hydrol ysed by boiling with water and 

 barium carbonate (W. H. Perkin, junr., 

 Trans. Ch. Soc. 59, 791). 



Bromacetone (Sokolowsky, Journ. 

 Russ. Soc. 8, 330; Emmerling and 

 "Wagner, Ann. 204, 29) on boiling with 

 potassium carbonate solution gives acetol 

 (E. and W. loc. cit.^o : compare Simon- 

 cini, Gazz. 31, 496). 



Or acetone can be converted into 2 : 2- 

 dichlorpropane by phosphorus penta- 

 chloride (Friedel, Ann. 112, 236), and 

 this by alcoholic potash gives a-chlor- 

 propylene, which can be converted into 

 a/3-dichlorpropylene, &c., as above 

 under A. 



Or acetone by the action of sodium 

 and ethyl acetate gives acetylacetone 

 (Claisen and Ehrhardt, Ber. 22, ion), 

 which by the action of sulphuryl dichlor- 

 ide yields chloracetylacetone (Combes, 

 Comp. Rend. Ill, 292). The latter on 

 heating with potassium acetate in alco- 

 holic solution gives acetol acetate (Ibid.}. 



Or from acetone through mesityl 

 oxide (see under aldehyde [92 ; S]) and 

 trimethyltriose by oxidation of the 

 latter with potassium permanganate. 

 The triose decomposes readily into acetol 

 and acetone (Harries and Pappos, Ber. 

 34, 2979). 



Or from acetone and formic acid [Vol. 

 II] through formopyroracemic ester (H . 

 CO 2 . CH 2 . CO . CH 3 ) from chloracetone 

 and potassium formate. The ester on 

 heating with methyl alcohol gives me- 

 thyl formate and acetol (Henry, Bull. 

 Acad. Roy. Belg. 1902, p. 445; Ch. 

 Centr. 1902, 2, 928). 



NOTE : Allylene by the action of fuming 

 hydrochloric acid gives 2 : z-dichlorpropane 

 (Eeboul, Ann. Chim. [5] 14, 453), which can 

 be treated as above. The generators of allylene 

 referred to under benzyl alcohol [54] thus 

 become generators of acetol. 



[C.] Glycerol [48] by the action of 

 dry hydrogen chloride gives dichlor- 

 hydrin = dichlorisopropyl alcohol (see 

 under isopropyl alcohol [16 ; Gr]), and 

 this by the action of phosphorus penta- 

 chloride yields I : 2 : 3-trichlorpropane 

 (Berthelot and De Luca, Ann. Chim. 

 [3] 48, 304; 62, 433; Fittig and 

 Pfeffer, Ann. 135, 359), which can be 

 treated as above under A. 



Or from glycerol through allyl iodide, 

 which gives I : 2 : 3-trichlorpropane by 

 chlorination (Oppenheim, Bull. Soc. [2] 



2, 97)- 



NOTE : Propane gives 1:2: 3-trichlorpropane 

 by direct chlorination, so that generators of 

 propane thus become generators of acetol (see 

 under glycerol [48 ; A]). 



[D.] From acetic acid [Vol. II] 

 through the compound formed from 

 acetyl chloride and aluminium chloride, 

 which compound on decomposition with 

 water gives acetylacetone (Combes, 

 Ann. Chim. [6] 12, 207). The latter 

 can be treated as above under B. 



Or from acetic acid and isobutyl or 

 tertiary butyl alcohol [18; 19] through 

 mesityl oxide by the condensation of 

 isobutylene with acetyl chloride or acetic 

 anhydride (see under acetic aldehyde 

 [92 ; FP]), and then as above under B. 



[B.] From dextrose [154], acetol being 

 among the products formed by fusion 

 with caustic potash (Emmerling and 

 Loges, Ber. 16, 837). 



[F.] From acetoacetic ester [Vol. II] 

 through mesityl oxide (see under alde- 

 hyde [92; L]), and then as above 

 under B. 



44. Methylacetyl Carbinol ; 

 Dimethylketol ; 3-Butanol-2-one. 



CH 3 .CH(OH).CO.CH 3 



NATURAL SOURCE. 



A product of the action of Bacillus 

 tartricus (Grimbert and Ficquet, Comp. 

 Rend. Soc. Biol. 1897, p. 962) on the 

 ammonium or calcium salt of tartaric 

 acid (Grimbert, Comp. Rend. 132, 

 706). 



