25-27 A.] 



ACTIVE HEXYL ALCOHOL 



83 



25. Active Hexyl Alcohol ; 



Methyletliylpropyl Alcohol ; 



3-Methyl-5-Pentanol. 



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



NATURAL SOURCE. 



As ester of angelic and tiglic acids 

 in Roman oil of chamomile from 

 Anthemis nobilu (Kobig, Ann. 195, 79 ; 

 8 1 ; 92 : see also Van Romburgh, Rec. 

 Tr. Ch. 5, 219; Q, 150). 



SYNTHETICAL PROCESSES. 



[A.] From isopropyl alcohol [16] 

 through diisopropyl (2, : 3-dimethyl- 

 butane) by the action of sodium (Schor- 

 lemmer, Ann. 144, 184), chlorination 

 (Silva, Bull. Soc. [2] 6, 36 ; 7, 953), 

 and conversion of the chlorhexane into 

 the alcohol by the usual methods (Ibid. 



Q, 147). 



[B.] From acetone [106] through 

 pinacone (2 : 3-dimethyl-2 : 3-butane- 

 diol) by the action of sodium (see under 

 tertiary butyl alcohol [19 ; D]), diiso- 

 propyl by heating with hydriodic acid 

 (Bouchardat, Comp. Rend. 74, 809), 

 and then as under A. 



NOTE : Generators of pinacone are summa- 

 rised under normal hexyl alcohol (23 ; L). 



[C.] Normal heptoic (cenanthic) acid 

 [Vol. II] when its barium salt is 

 heated to redness gives a hexane which 

 is said to be diisopropyl (Riche, Ann. 

 Chim. [3] 59,432). 



[D.] From glycerol [48] through 

 diallyl (see under normal butyl alcohol 

 [17; D]) and action of hydriodic acid 

 in excess on the latter at a high tempera- 

 ture (Berthelot, Bull. Soc. [2] 9, 268). 

 The hexane thus obtained is said to be 

 diisopropyl. 



[E.] From mannitol [5l] by heating 

 with excess of hydriodic acid (Bou- 

 chardat, Ann. Chim. [5], 6, 1 24 ; Le 

 Bel and Wassermann, Jahresber. 1885, 

 1211). This hexane is also said to be 

 diisopropyl. 



NOTE : The identity of Silva's alcohol with 

 the natural product requires confirmation ; it 

 is difficult to see how an alcohol having the 

 constitution 3-methyl-5-pentanol could be 

 derived from diisopropyl by chlorination and 

 hydroxylation. 



26. Normal Heptyl Alcohol ; 

 1-Heptanol. 



CH 3 .[CH 2 ] 5 .CH 2 .OH 



NATURAL SOURCE. 



The heptyl alcohol stated to have 

 been found in fusel oil from brandy 

 (see under isoheptyl alcohol [27]) may 

 be the normal alcohol, as it is said to 

 give n-heptoic (oenanthic) acid on 

 oxidation. 



SYNTHETICAL PROCESSES. 



[A.] From n-Jieptane [2] through 

 i-chlorheptane by chlorination and the 

 usual method (Schorlemmer, Ann. 127, 

 315; 161, 278). n-Heptane gives 

 i-nitroheptane on nitration (Worstall, 

 Am. Ch. Journ. 20, 2io; 21, 223). 

 The heptylamine obtained from this by 

 reduction might give n-heptyl alcohol 

 by the usual (nitrous acid) method. 



[B.] From cenanthol [97] by reduc- 

 tion (see under n-heptane [2 ; D]). 



27. Isoheptyl Alcohol ; 

 Isohexyl Carbiiiol ; 

 2-Meth.yl-G-Hexaiiol. 



CH 3 .CH(CH 3 ).[CH 2 ] 3 .CH 2 .OH 



NATURAL SOURCE. 



Heptyl alcohol is said to have been 

 obtained from fusel oil of brandy 

 (Faget, Bull. Soc. 1862, 59 ; Ann. 

 124, 355 ; Ordonneau, Comp. Rend. 

 1O2, 217). The constitution of this 

 fermentation heptyl alcohol has not 

 yet been satisfactorily established, and 

 it is only placed here provisionally (see 

 also above under n-heptyl alcohol [26]). 



SYNTHETICAL PROCESSES. 



[A.] From ethyl [14] and isoamyl 

 [22] alcohols through isoheptane (5- 

 methylhexane) by acting with sodium 

 on the iodides or bromides (Wurtz, 

 Ann. Chim. [3] 44, 275 ; Grimshaw, 

 Journ. Ch. Soc. 26, 309; Ann. 166, 



