23 A G.] 



NORMAL HEXYL ALCOHOL 



81 



Ann. 187, 153 ; Kishner, Journ. Rass. Soc. 23, 

 20 ; 24, 451 ; Ann. 278, 88). The identity of 

 this hexane has not been fully established (see 

 under active hexyl alcohol [25 ; B ; C, &c.]). 



[B.] From mannitol [51] through 

 the secondary hexyl iodide (CH 3 [CH 2 ] 3 . 

 CHI . CH 3 ; 2-iodohexane) by heating 

 with hydriodic acid solution (Wanklyn 

 and Erlenmeyer, Zeit. 1861, 606 ; 1862, 

 641 j Ann. 135, 130; Domac, Monats. 

 2,310; Hecht, Ann. 165, 146; 209, 

 311; Schorlemmer, Phil. Trans. 171, 

 452), n-hexane by reduction with zinc 

 and hydrochloric acid (LeBel and Was- 

 sermann, Comp. Rend. 100, 1589; 

 Jahresber. 1885, 1211: also Schor- 

 lemmer, Phil. Trans. 162, 118; Erlen- 

 meyer and Wanklyn, Journ. Ch. Soc. 

 16, 227; Ann. 135, 136), and then as 

 under A. 



The secondary hexyl iodide is also 

 converted into hexane by heating- to 

 80-90 with aluminium chloride (Lo- 

 thar Meyer, Ber. 27, 2766). According 

 to Combes and LeBel (Bull. Soc. [3] 

 7, 551) the hexyl iodide obtained from 

 mannitol is 3-iodohexane. 



Mannitol gives hexane by heating 

 with strong aqueous hydriodic acid to 

 380 (Berthelot, as above under A). 



[C.] From glycerol [48] through 

 allyl iodide (see under isobutyl alcohol 

 [18 ; D]), diallyl (see under normal 

 butyl alcohol [17 ; DJ), diallyldihydrio- 

 dide (2 : 5-diiodohexane) by combination 

 with hydrogen iodide (Wurtz, Ann. 

 China. [4] 3, 129; Sorokin, Journ. pr. 

 Ch. [2] 23, 18), hexylene by the action 

 of sodium on the diiodohexane (Wurtz, 

 loc. cit.}, recombination with hydrogen 

 iodide to form secondary hexyl iodide 

 (Wurtz, Ann. 132, 306), and then 

 through n-hexane as under B and A. 



Also through diallyl by combining 

 with sulphuric acid and distilling with 

 water and heating the hexylene oxide 

 thus formed with hydriodic acid so as to 

 form secondary hexyl iodide (Jekyll, 

 Ch. News, 22, 221). 



[D.] From glutaric acid [Vol. II] 

 through suberic acid by the electrolysis 

 of potassium ethyl glutarate (Crum 

 Brown and Walker, Ann. 261, 120), 

 and hydrolysis, and then distillation of 

 the suberic acid with baryta (Riche, 



Ann. Chim. [3] 59, 432 ; Dale, Journ. 

 Ch. Soc. 17, 258; Ann. 132, 243). 

 Hexane is among the products (see 

 under A). 



NOTE : Myristic acid [Vol. II], stearic acid [Vol. 

 II], and cetyl alcohol [33] give suberic acid 

 among the products of their oxidation by nitric 

 acid (Noerdlinger, Ber. 19, 1896 ; Laurent, 

 Ann. Chim. [a] 66, 157 ; Bromeis, Ann. 35, 

 89). Aselaic acid [Vol. II] gives ketocyclo-octane 

 among the products of distillation of the cal- 

 cium salt (Mayer, Ann. 275, 364 ; Derlon, Ber. 

 31, 1960; Miiller and Tschitschkin, Ann. 307, 

 375), and this gives suberic acid by oxidation 

 (Derlon, loc. cit. 1962). 



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

 through sebacic acid by electrolysis or 

 potassium ethyl adipate and hydrolysis 

 of the ester (Crum Brown and Walker, 

 Ch. News, 66, 91 ; Ann. 261, 120), 

 bromsebacic and hydroxysebacic acid 

 by bromination and decomposition of 

 the sodium salt by boiling with water, 

 oxidation of the hydroxy-acid to suberic 

 acid by nitric acid (Weger, Ber. 27, 

 , and then as under D. 



Or sebacic acid is brominated in pre- 

 sence of phosphorus (Auwers and Bern- 

 hardi, Ber. 24, 2232), and the aa-di- 

 bromo-acid converted into the dihy- 

 droxy-acid by heating with barium 

 hydroxide solution. The dihydroxy- 

 acid on oxidation with lead peroxide 

 gives octanediol, and this on oxidation 

 with alkaline permanganate yields 

 suberic acid (v. Baeyer, Ber. 30, 1962). 



[F.] From normal hexolc (caproic) 

 acid [Vol. II] through the aldehyde by 

 distillation of the calcium salt with 

 calcium formate (Lieben and Janeeek, 

 Ann. 187, 130) and reduction of the 

 aldehyde by sodium amalgam (Lieben 

 and Rossi, Ann. 133, 178; Lieben and 

 Janecek, Ann. 187, 135). 



[G.] From normal heptoic (cenantk'ic) 

 acid [Vol. II] through n-hexylamine by 

 the action of bromine and potash on 

 the amide (Hofmann, Ber. 15, 771 ; 

 Frentzel, Ber. 16, 744) and distillation 

 of the nitrite with water (Frentzel, loc. 

 cit.}. 



n-Hexylamine can also be obtained 

 from n-heptoic acid and acetic acid 

 through methyl-n-hexyl ketone (Stade- 

 ler, Journ. pr. Ch. 72, 246 ; Jahresber. 

 1857, 359), the ketoxime by the action 



