17 E-L.] 



NORMAL BUTYL ALCOHOL 



71 



secondary hexyl iodide (see under n-pro- 

 pyl alcohol [15 ; G-]) ; from the latter 

 as above under D. 



Or secondary hexyl iodide can be con- 

 verted into n-hexane (see under n-hexyl 

 alcohol [23 ; B]). The latter on heating 

 with aluminium chloride breaks down 

 into pentane and the latter into butane 

 (Friedel and Gorgeu, Comp. Rend. 127, 



590). 



NOTE : Generators of pentane (see under n- 

 amyl alcohol [20 ; B ; C ; D]) and of hexane 

 (see under n-hexyl alcohol [23 ; A ; B ; C ; &c.]) 

 thus become generators of n-butyl alcohol 

 through butane. 



[F.] From formic aldehyde [Ol] and 

 n-propyl alcohol [13]. Trioxymethylene 

 (polymerisation product of the aldehyde) 

 and zinc propyl form a compound which 

 is decomposed by water with the forma- 

 tion of n-butyl alcohol (Tischtschenko, 

 Journ. Russ. Soc. 19, 484: see B, above). 



[G.] From acetic aldehyde [92] 

 through crotonic aldehyde [102] by 

 condensation (Lieben, Ann. Suppl. 1, 

 117; Bauer, Ann. 117, 141; Kekule, 

 Ann. 162, 92 ; Zeit. [2] 5, 572 ; Lieben 

 and Zeisel, Monats. 1, 820 ; Newbury 

 and Calkin, Am. Ch. Journ. 12, 523 ; 

 Orndorff and Newbury, Monats. 

 13, 513; Lieben, Ibid. 519; Miiller, 

 Bull. Soc. [3] 6, 796 ; Claisen, Ann. 

 306, 322 ; Charon, Ann. Chim. [7] 

 17, 197; Delepine, Comp. Rend. 133, 

 876). The aldehyde is reduced by iron 

 and acetic acid to n-butyl alcohol (with 

 butyric aldehyde and crotonyl = butenyl 

 alcohol) (Lieben and Zeisel, loc. cit. 825 ; 

 842). ' 



Or from aldehyde through /3-hydr- 

 oxybutyric aldehyde (aldol) by conden- 

 sation with acid or alkaline condensing 

 agents (Wurtz, Comp. Rend. 74, 1361 ; 

 76, 1165; 92, 1438; Jahresber. 1872, 

 449 > 1881, 599 ; Michael and Kopp, 

 Am. Ch. Journ. 5, 185; Orndorff and 

 Newbury, Monats. 13, 516; Claisen, 

 Ann. 306, 323). Aldol gives /3-butylene- 

 glycol on reduction with sodium amal- 

 gam (Wurtz, Comp. Rend. 97, 473 ; 

 Demjanoff, Ber. 28, 22). From the 

 glycol through i : 3-dibrombutane and 

 methylcyclopropane as below under P. 



NOTE : Aldol gives crotonic aldehyde on 

 dry distillation (Wurtz, Comp. Rend. 87, 45 ; 

 Orndorff and Newbury, loc. cit.}. 



[H.] From butyric aldehyde [94] by 

 reduction with sodium amalgam (Lieben 

 and Rossi, Ann. 158, 137 ; 165, 145). 



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

 erythritol [60], which give crotonic 

 aldehyde [102] on distillation (Hennin- 

 ger, Ann. Chim. [6] 7, 217), and then 

 as above under G. 



NOTE : Other generators of crotonic alde- 

 hyde are : aldol (from aldehyde ; Wurtz, 

 Jahresber. 1878, 61 2 ; Newbury, Am. Ch. Journ. 

 5, 112 ; Comp. Rend. 92, 196) : acetylene by the 

 successive action of sulphuric acid and water 

 (Lagermarck and Eltekoff, Ber. 10, 637 ; Ber- 

 thelot, Comp. Rend. 128, 336) : vinyl bromide 

 from ethylene bromide by the same treatment 

 (Zeisel, Ann. 191, 371) : the lactic acids [Vol. II] 

 by electrolysis of strong solutions of the sodium 

 salts (v. Miller and Hofer, Ber. 27, 468) : - 

 hydroxybutyric acid [Vol. IIJ by electrolysis of 

 the sodium salt (Ibid. 469). 



[J.] From acetic acid [Vol. II] and 

 ethyl alcohol [14]. Ammonium acetate 

 is converted into acetamide and aceto- 

 nitrile = methyl cyanide (Dumas, Comp. 

 Rend. 35, 383 ; Buckton and Hofmann, 

 Journ. Ch. Soc. 9, 242; Henry, Ann. 

 152, 149; Wallach, Ann. 184, 21 ; 

 Demar^ay, Bull. Soc. [2] 33, 456). 

 From methyl cyanide and ethyl iodide 

 through n-propyl cyanide, n-butylam- 

 ine, &c., as above under A. 



Or from acetic and formic ethyl esters 

 [Vol. II ; and 14], which condense under 

 the influence of sodium ethoxide to 

 form f ormylacetic = oxymethyleneacetic 

 ester (Wislicenus, Ber. 20, 2930 : see also 

 v. Pechmann, Ann. 264, 269), which 

 undergoes further condensation when 

 liberated from its sodium derivative 

 to form formylglutaconic ester (Wis- 

 licenus and Bindemann, Ann. 316, 18). 

 Formylglutaconic acid gives the lactone, 

 coumalic acid, and this on heating with 

 sulphuric acid yields crotonic aldehyde 

 [102], which can be reduced as above 

 under G. 



[K.] Propionic acid [Vol. II] gives 

 butane among the products of electro- 

 lysis of the potassium salt (Bunge, 

 Journ. Russ. Soc. 21, 551 ; Petersen, 

 Ch. Centr. 1897, 2,518). 



[L.] From butyric acid [Vol. II] 

 through butyryl chloride, which gives 

 the alcohol on reduction with sodium 

 amalgam (Saytzeff, Zeit. [2] 6, 108; 

 Linnemann, Ann. 161, 178) or with 



