70 



ALCOHOLS 



[17-E. 



prised under Clostridium bufyricum of 

 Prazmowski ( = Bacillus amylobacter, 

 Van Tieghem) can produce butyl alcohol 

 from carbohydrates (Gruber ; quoted 

 by Jorgensen, ' Mikroorganismen/ &c. 

 p. 87). 



Butyl alcohol is formed during the 

 butyric fermentation of milk by Bacillus 

 butyricus of Bodkin (Ch. Centr. 1891, 

 1, 183 ; 1892, 1, 484). A butyl alcohol 

 (? normal) occurs in rancid butter, pro- 

 bably a bacterial product (Nagel, Am. 

 Ch. Journ. 23, 172). 



Bacillus orthobutylicvs from ferment- 

 ing calcium tartrate solution ferments 

 saccharose, lactose, maltose, glucose, 

 galactose, mannitol, glycerol, glycogen, 

 arabinose, inulin, and starch with the 

 production of butyl alcohol among 

 other products (Grimbert, Ann. Inst. 

 Past. 7, 353). Amylobacter butylicum 

 and A. (stkylicum of Duclaux produce 

 small quantities of butyl alcohol during 

 the fermentation of glycerol, glucose ; 

 saccharose, maltose, lactose, and starch 

 (Duclaux, Ann. Inst. Past. 9, 811). 



n- Butyl alcohol has been said to be 

 a constituent of the fusel oils of brandy 

 (Ordonneau, Comp. Rend. 1O2, 217; 

 Claudon and Morin, Ibid. 104, 1187) 

 and potato starch spirit (Rabuteau, 

 Ibid. 87, 501 : see also Allen, Journ. 

 Fed. Inst. 3, 33). According to Bannow 

 (Meyer and Jacobson's ' Lehrbuch 

 d. org. Ch.' I, 161, note) n- butyl 

 alcohol is not a normal constituent of 

 fusel oil. EmmerKng has found n- 

 butyl alcohol (2-5 grams from 10 kilos.) 

 in fusel oil from grain spirit (Ber. 35, 

 694). 



SYNTHETICAL PROCESSES. 



[A.] From ethyl alcohol [14], n-butyl 

 alcohol being among the products 

 formed by heating barium ethylate and 

 ethyl alcohol to 230-240 (Guerbet, 

 Comp. Rend. 133, 300; Bull. Soc. [3] 

 27, 578). 



Or from ethyl alcohol through butane 

 from ethyl iodide (Frankland, Ann. 71, 

 I 73> 77, 221; Schoyen, Ann. 130, 

 233; Lowig, Jahresber. I860, 397). 

 From butane through n-butyl chloride 

 by chlorination (Schoyen, loc. cit. 235). 



Butyl chloride can be converted into 

 the alcohol by the usual methods (see 

 under methyl alcohol [13 ; B] ; ethyl 

 alcohol [14; D]). 



Or from ethyl and methyl alcohols 

 [14; 13] and potassium cyanide [172]. 

 Methyl iodide is converted into methyl 

 cyanide (see under ethyl alcohol [14; 

 D]), and this by the action of sodium 

 and ethyl iodide gives n-propyl cyanide 

 (Holtzwart, Journ. pr. Ch. [2] 39, 233). 

 The latter reduces to n-butylamine 

 (Linnemann and Zotta, Ann. 162, 3), 

 which yields the alcohol on treatment 

 with nitrous acid (Ibid. ; also Victor 

 Meyer, Ber. 10, 130 : methylethyl 

 carbinol is the chief product by this 

 method). 



[B.] From normal propyl alcohol [15] 

 through n-propyl iodide and cyanide 

 (Schmidt, Zeit. [2] 6, 576). From the 

 latter through n-butylamine as above. 



Or from n-propyl and methyl alcohol 

 [13] through n-butane by combining 

 the alky Is by the method of Wurtz 

 (see under n-heptane [2 ; A]). From 

 butane through butyl chloride as above. 



From n-propyl alcohol and trioxy- 

 methylene (formic aldehyde [9l]) by the 

 interaction of magnesium propyl brom- 

 ide and trioxymethylene (Grignard and 

 Tissier, Comp. Rend. 134, 107). 



[C.] From isoamyl alcohol [22], iso- 

 amyl iodide giving butane when heated 

 with aluminium chloride to 140 

 (Lothar Meyer, Ber. 27, 2766). 



[D.] From glycerol [48] through 

 allyl iodide (see tinder isobutyl alcohol 

 [18; D]), diallyl (i : 5-hexadiene) by 

 the action of sodium, &c., on the iodide 

 (Berthelot and De Luca, Ann. 100, 

 361 ; Wurtz and Leclanche, Ann. 

 Chim. [4] 3,129; Linnemann, Bull. Soc. 

 [2] 7, 424; Ann. 140, 180; Oppen- 

 heim, Ber. 4, 672). Diallyl combines 

 with hydrogen iodide to form a dihy- 

 driodide, which by the action of sodium 

 gives /3-hexylene. The latter combines 

 with hydrogen iodide to form secondary 

 hexyl iodide (2-iodohexane) (Wurtz, 

 Ann. 132, 306), and this yields butane on 

 heating to 128 with aluminium chlor- 

 ide (Lothar Meyer, Ber. 26, 2070 ; 27, 

 2766). 



[E.] From mannitol [5l] through 



