78 



ALCOHOLS 



[21 D-I. 



Chim. [6] 12, 234) and the iodopentane 

 into the alcohol by the usual methods. 



[E.] From propionic acid [Vol. II] 

 through diethyl ketone (3-pentanone) by 

 distillation of the barium salt (Morley, 

 Ann. 78, 187), the dichloride by heat- 

 ing- with phosphorus pentachloride, 

 methylethylacetylene (3-pentine) by the 

 action of alcoholic potash on the di- 

 chloride (Faworsky, Journ. pr. Ch. [2] 

 37, 387), methylpropyl ketone by heat- 

 ing the acetylene derivative with water 

 and mercuric bromide (Kutscheroff, 

 Ber. 14, 1542), and reduction as under 

 A. 



Also from propionic acid through 

 diethyl ketone by the action of propionyl 

 chloride on zinc ethyl (Freund and 

 Pebal, Ann. 11 8, 9) and treatment as 

 above. 



[P.] From formic acid [Vol. II] and 

 ethyl alcohol [14] through diethyl car- 

 binol = 3-pentanol by the action of zinc 

 and ethyl iodide on formic ester and 

 decomposition of the product with water 

 (Wagner and Saytzeff, Ann. 175, 351), 

 diethyl ketone by oxidation of the 

 alcohol (Ibid. Ann. 179, 322), and then 

 as under E. 



Also by converting the diethyl car-" 

 binol into amylene = symmetrical 

 methylethylethylene = 3-pentene by the 

 action of alcoholic potash on the iodide 

 (Wagner and Saytzeff, Ann. 175, 373 ; 

 179, 302), combining the amylene with 

 hydrogen chloride to form 2-chlorpen- 

 tane (Ibid. Ann. 179, 321), and conversion 

 into the alcohol by the usual methods 

 (Schorlemmer, Ann. 161, 268). Hydro- 

 gen iodide combines with the amylene to 

 form 2-iodopentane (Wurtz, Ann. 148, 

 132), which can be converted into the 

 alcohol by the same methods. 



[G.] From oxalic acid [Vol. II] and 

 ethyl alcohol [14] through diethoxalic 

 = hydroxydiethacetic = 3-pentanol-3- 

 carboxylic acid by the action of zinc 

 ethyl on oxalic ester and decomposition 

 of the product with water (Frankland, 

 Proc. Roy. Soc. 12, 396; Frankland 

 and Duppa, Ibid. 13, 140 ; Ann. 135, 

 0,6 ; Geuther, Zeit. [2] 3, 705 ; Fittig, 

 Ann. 200, 21), diethyl ketone by the 

 oxidation of diethoxalic acid or by 

 heating its ester with hydrochloric acid 



(Chapman and Smith, Journ. Ch. Soc. 

 20, 173; Geuther and Wackenroder, 

 Zeit. [2] 3, 709), and then as under E. 



Or from diethoxalic ester through 

 a-ethylcrotonic ester by the action of 

 phosphorus trichloride (Frankland and 

 Duppa, Journ. Ch. Soc. 18, 133 ; Ann. 

 136, 2 ; Fittig and Howe, Ann. 200, 

 22 : see also Geuther, Bull. Soc. [2] 

 10, 34), the hydrobromide of ethylcro- 

 tonic = 2-pentene-3-carboxylic acid by 

 the direct addition of hydrogen bromide 

 to the acid (Fittig and Howe, loc. cit. 23), 

 3-pentene by the decomposition of the 

 hydrobromide by cold sodium carbonate 

 solution (Fittig, Ibid. 30), 2-chlor- or 

 2-iodo-pentane, &c., as under P (see 

 also under hexoic aldehyde [2-methyl- 

 pentanol; 96 ; L]). 



[H.] From citric acid [Vol. II] and 

 methyl alcohol [13] through acetone- 

 dicarboxylic acid (3-pentanonediacid) 

 by heating the former with sulphuric 

 acid (v. Pechmann, Ber. 17, 2543 ; 

 Ann. 261, 157; Peratoner and Straz- 

 zeri, Gazz. 21, 295 : see also under 

 orcinol [75 ; C]), the diethyl ester, 

 dimethylacetonedicarboxylic (2 : 4-di- 

 methylpentanonediacid) diethyl ester by 

 the action of sodium methylate and 

 methyl iodide on acetonedicarboxylic 

 ester (Diinschmann and v. Pechmann, 

 Ann. 261, 182), diethyl ketone by the 

 action of hot dilute sulphuric acid on 

 the dimethylacetonedicarboxylic ester 

 (lbid.} } and then as under E. Citric 

 acid gives acetonedicarboxylic acid by 

 oxidation with potassium permanganate 

 (Deniges, Comp. Rend. 130, 32). 



NOTE : Other generators of diethyl ketone 

 are : sodium ethyl and carbon monoxide (Wank- 

 lyn, Ann. 140, 211) ; acetyl or propionyl chloride 

 acted upon by dry ferric chloride (Hamonet, 

 Bull. Soc. [2] 50, 356 and 547) ; sine ethyl and 

 nitropropane (Bevad, Ch. Centr. 1900, 2, 944). 



[I.] From crude (fusel oil) amyl 

 alcohol [22] by conversion into amylene, 

 amylene bromide, and ' valerylene ' by 

 the action of alcoholic potash (Reboul, 

 Ann. 131, 238 ; Eltekoff, Journ. Russ. 

 Soc. 9, 378). This ' valerylene' pro- 

 bably contains methylethylacetylene (3- 

 pentine), and can be converted into 

 methylpropyl ketone, &c., as under E. 



Normal primary amyl alcohol [20] 



