62 



ALCOHOLS 



[15 P-U. 



Or from a-brombutyric acid (ester) 

 through crotonic acid (see under benzyl 

 alcohol [54 ; K]), and then as above 

 under I through dicrotonic and pyro- 

 tartaric acid, &c. 



Or a-brombutyric acid (ester) by 

 interaction with potassium-mercuric 

 cyanide [172] gives a-cyanobutyric ester 

 (Markownikoff, Ann. 182,, 330), and 

 this on hydrolysis gives ethylmalonic 

 acid (Wislicenus and Urech, Ann. 165, 

 93 ; Tupoleff, Ann. 171, 243 ; Markow- 

 nikoff, loc. cit. 329). The latter gives 

 n-propyl alcohol as below under T. 



Or from butyric acid through butyr- 

 one (see under n-nonyl alcohol [29 ; 

 D]), which gives dinitropropane by the 

 action of nitric acid (Chancel, Comp. 

 Hend. 96, 1466; Bull. Soc. [2] 31, 

 503; Ann. 52, 296; 64, 331 ; Kurtz, 

 Ann. 161, 208 ; Fileti and Ponzio, 

 Journ. pr. Ch. [2] 55, 193). From 

 dinitropropane through propylamine 

 and propaldehyde as below under AA. 



NOTE : Mothylpropyl ketone from acetic and 

 butyric acids (see under n-secondary amyl 

 alcohol [21 ; A]) and ethylpropyl ketone from 

 propionic and butyric acids or from zinc ethyl 

 and butyryl chloride (Volker, Ber. 8, 1019; 

 Popoff, Ann. 161, 289) also give dinitropropane 

 on nitration (Chancel, Jahresber. 1884, 1048; 

 Fileti and Ponzio, loc. cit.~). Methylpropyl 

 ketone is also convertible into propylamine 

 through the oxime as below under AA. 



[Q.] Isobutyric acid [Vol. II] gives 

 propane among the products of photo- 

 chemical decomposition in presence of 

 uranium salts (Fay, Am. Ch. Journ. 

 18, 286). From propane as above 

 under A. 



[B.] From lactic acid [Vol. II], which 

 gives acrylic acid among the products 

 of the distillation of the calcium salt 

 (Claus, Ann. 136, 288). From acrylic 

 acid to pyrotartaric acid, &c., as above 

 under A. 



Or lactic acid by the action of phos- 

 phorus pentachloride gives a-chlorpro- 

 pionic acid (Wurtz, Ann. Chim. [3] 

 49, 58 ; Briihl, Ber. 9, 35). From 

 the latter through acrylic acid by heat- 

 ing with barium hydroxide solution 

 (Michael and Garner, Ber. 34, 4050). 



Or lactic acid gives pyroracemic 

 (pyruvic) acid on oxidising the calcium 

 salt with potassium permanganate (Beil- 



stein and Wiegand, Ber. 17, 840). 

 Pyroracemic acid gives pyrotartaric 

 acid on heating with hydrochloric acid 

 to 100 or per se to 170 (Clermont, 

 Ber. 6, 72; Bottinger, Ber. 9, 837; 

 1823 ; Ann. 188, 308 ; De Jong, Eec. 

 Tr. Ch. 20, 81; 21, 191; see also 

 Wolff, Ann. 317, 22). 



Or lactic acid gives citraconic acid 

 on distillation (Engelhardt, Ann. 7O, 

 243 ; 246). The latter can be con- 

 verted into pyrotartaric acid (see under 

 benzyl alcohol [54 ; M]). 



[S.] Hydracrylic acid [Vol. II] gives 

 acrylic acid on distillation of its salts 

 (Beilstein, Ann. 122, 372). Subse- 

 quent steps as above. 



[T.] From malonic acid [Vol. II] 

 and ethyl alcohol [14] through ethyl- 

 malonic acid (see under hexanal [2- 

 methylpentanal ; 96 ; G]). The latter 

 gives n- (with iso-) propyl alcohol on 

 electrolysis of a solution of the potas- 

 sium salt (Petersen, Zeit. physik. Ch. 

 33, 698; Ch. Centr. 1900, 2, 172). 



Or from malonic acid, aldehyde (par- 

 aldehyde) [92], and acetic acid through 

 crotonic acid (see under benzyl alcohol 

 [54 ; G]). From crotonic acid through 

 a-brombutyric acid and nitro-propane, 

 &c., as above under I. 



NOTE : Malonic acid (ester) on treatment 

 with chloroform and sodium ethylato gives 

 dicarboxyglutaconic ester (Conrad and Guth- 

 /eit, Ann. 222. 250), and this on boiling with 

 baryta water gives (with glutaconic acid) /3-oxy- 

 glutaric acid (Guthzeit and Bolam, Journ. pr. 

 Ch. [2] 54, 365), from which crotonic acid can 

 be obtained as below under W. 



Or from malonic ester, methyl iodide 

 [13], and chloracetic acid through pro- 

 pan etricarboxy lie acid = a-methyleth- 

 enyltricarboxylic acid (see under benzyl 

 alcohol [54 ; G]) and pyrotartaric acid 

 (Ibid.}. 



Malonic diethyl ester and aldehyde 

 [92] condense when heated with acetic 

 anhydride to form ethylidenemalonic 

 diethyl ester (Komnenos, Ann. 218, 157), 

 and the latter on heating with potas- 

 sium cyanide [172] in alcoholic solution 

 gives /3-cyanobutyric ester, which gives 

 pyrotartaric acid on treatment with 

 alkali (Bredt and Kallen, Ann. 293, 



35). 



[U.] From fi-hydroxybutyric acid 



