ALCOHOLS 



[23 G-24 B. 



of hydroxylamine, the action of phos- 

 phorus pentachloride on the ethereal 

 solution followed by that of water, 

 and the action of potash on the n- 

 hexylacetamide thus formed (Hantzsch, 

 Ber. 24, 4021). 



Also from heptoyl chloride through 

 methylhexyl ketone by the action of 

 zinc methyl (Behal, Bull. Soc. [3] 6, 

 132) and then as above. 



Or from heptoic acid through the 

 a-bromo-acid by bromination (Cahours, 

 Ann. Suppl. 2, 83 ; Hell and Schiile, 

 Ber. 18, 625), nitrohexane by the inter- 

 action of sodium nitrite and the sodium 

 salt (Auger, Bull. Soc. [3] 23, 333), 

 and then through hexylamine as above. 



[H.] From normal butyl alcohol [17] 

 through n-octane by the action of 

 sodium on the iodide (Schorlemmer, 

 Ann. 161, 280). On chlorination n- 

 octane yields (among other products) 

 secondary octyl chloride (2-chloroctane), 

 which is convertible into methylhexyl 

 carbinol (2-octanol) by the usual method 

 (Schorlemmer, Ann. 152, 152; Pelouze 

 and Cahours, Jahresber. 1863, 528). 

 The secondary alcohol gives methylhexyl 

 ketone on oxidation (Behal, loc. cit.), 

 and this can be converted into n-hexyl- 

 amine, &c., as under G-. 



NOTE : Among other generators of n-octane 

 are : sebacic acid (see above under E) by dis- 

 tillation with baryta (Riche, Ann. 117, 265) ; 

 ethyl alcohol [14] through the product of the action 

 ipf zinc ethyl on titanium chloride and decom- 

 position with water (Paternb and Peratoner, 

 Ber. 22, 467). 



[I.] From aldehyde [92] through 

 a-methylpyridine (a-picoline) by the 

 action of aldehyde on aldehyde ammonia 

 (Diirkopf and Schlaugk, Ber. 21, 297), 

 a-pipecoline by reduction (Ladenburg 

 and Roth, Ber. 18, 47 ; Ann. 247, 62 ; 

 Comp. Rend. 103, 747 ; Bunzel, Ber. 

 22, 1053). The latter base can be con- 

 verted into the methiodide and the 

 ammonium hydroxide base in the usual 

 way, the latter on heating to 140 

 giving ' pentallylcarbindimethylamine/ 

 CH 2 : CH(CH 2 ) 4 . N(CH 3 ) 2 , which can 

 again be converted into its methio- 

 dide and ammonium hydroxide base; 

 the latter on heating to 160 gives 

 (among other products) diallyl (Merling, 

 Ann. 264, 315 : see also Ladenburg, 



Mugdan, and Brzostovicz, Ann. 270, 

 344, &c.), which can be treated as 

 under C. 



[J.J From pyridine [Vol. II] through 

 a-picoline by heating the methiodide 

 to 300 in a sealed tube (Ladenburg and 

 Lange, Ann. 247, 7), and then through 

 pipecoline, &c., as under J. 



[K.] Normal butyric acid [Vol. II] 

 gives n-hexane among the products ot 

 electrolysis of the potassium salt (Peter- 

 sen, Ch. Centr. 1897, ^> 5 Z 9); an( ^ this 

 can be converted into n-hexyl alcohol 

 as under A. 



[L.] From acetone [106] through 

 pinacone (see under tertiary butyl alco- 

 hol [19 ; D]). The latter gives hexane 

 on heating with strong hydriodic acid 

 at 270 (Bouchardat, Zeit. [2] 7, 699). 



NOTE : The generators of pinacone referred 

 to under tertiary butyl alcohol [19 ; E ; F ; &c.] 

 thus become generators of hexane. These are : 

 isobutyric acid and methyl alcohol ; amyl and 

 methyl alcohols ; lactic acid and methyl alcohol ; 

 acetic acid and methyl alcohol ; ethyl and methyl 

 alcohols ; propionic acid and methyl alcohol ; diacetyl 

 and methyl alcohol. 



24. Isohexyl Alcohol ; 

 2-Methyl-5-Pentanol. 



CH 3 . CH(CH 3 ) . CH 2 . CH 2 . CH 2 . OH 



NATURAL SOURCE. 



A hexyl alcohol is said to have been 

 found in fusel oil from brandy (Faget, 

 Ann. 88, 325 ; Ordonneau, Comp. 

 Rend. 102, 217). The constitution of 

 this alcohol has not been determined, 

 but it is probably as above. 



SYNTHETICAL PROCESSES. 



[A.] From isoamyl alcohol [22] and 

 trioxymethylene [formic aldehyde : 91] 

 by the interaction of isoamyl magnesium 

 bromide and trioxymethylene in ethereal 

 solution (G-rignard and Tissier, Comp. 

 Rend. 134, 107). 



[B.] From isobutylacetic (^.-methyl- 

 pentanoic) acid [Vol. II] through the 

 aldehyde (4-methylpentanal) by dis- 

 tilling the calcium salt with calcium 

 formate (Rossi, Ann. 133, 178) and 

 reduction with sodium amalgam (Ibid. 

 1 80). 



