84 



ALCOHOLS 



[27 A-29 B. 



163), isoheptyl chloride by chlorina- 

 tion, conversion into the alcohol by the 

 usual method, and separation of the 

 primary from the secondary alcohol 

 (G-rimshaw, loc. cit. 313). 



[B.] From isobutyl alcohol [l8l, acetic 

 acid [Vol. II], and ethyl alcohol [14] by 

 combining isobutyl iodide with sodio- 

 acetoaceti 1 : ester, decomposing- the iso- 

 butylacetoacetic ester with potash, 

 reducing the ketone (2-methyl-6-hex> 

 anone) to the secondary alcohol, con- 

 verting the latter into the iodide, and 

 reducing to isoheptane with zinc and 

 hydrochloric acid (Purdie, Trans. Ch. 

 Soc. 39, 464 : see also Rohn, Ann. 

 190, 305). The isoheptane can then 

 be treated as under A. 



NOTE : A heptane (possibly identical with 

 the above) is said to be obtained from certain 

 cyclic compounds by heating to a high tem- 

 perature with strong aqueous hydriodlc acid 

 (Berthelot, Comp. Rend. 68, 606 ; Bull. Soc. 

 [2] 9, 455). The compounds are : toluene [54] 

 and the toluidines ; phthalic acid (see under benzyl 

 alcohol [54 ; B,]) and terephthalic acid. The latter 

 can be obtained by the oxidation of cymene [6] 

 and cumic aldehyde [116] (Hofmann, Ann. 97, 

 197; De la Rue and Miiller, Ann. 121, 87; 

 Schwanert, Ann. 132, 257 ; Homeyer, Arch. 

 Pharm. [3] 5, 326). 



28. Normal Primary Octyl Alcohol ; 

 1-Octaiiol. 



CH 3 .[CH: 2 ] 6 .CH 2 .OH 



NATURAL SOUECES. 



As ester of acetic acid in oil of 

 Heracleum giganteum (Franchimont and 

 Zincke, Ann. 163, 193) ; as ester of 

 acetic, hexoic, decoic, and lauric acids 

 in oil of Heracleum sphondylium (Zincke, 

 Ann. 152, I ; Moslinger, Ber. 9, 998 ; 

 Ann. 185, 26). As ester of n-butyric 

 acid in fruit of Pastinaca safiva, com- 

 mon parsnip (Renesse, Ann. 166, 84). 

 An octyl alcohol occurs as ester in the 

 ethereal oil from the root of Aspidium 

 filix mas (Ehrenberg, Arch. Pharm. 



231, 345)- 



A capryl (? n-octyl) alcohol occurs in 

 rancid fat, probably a bacterial product 

 (Nagel, Am. Ch. Journ. 23, 173). 



SYNTHETICAL PROCESSES. 



[A.] Normal octane (see under n-hexyl 

 alcohol [23; H]) by chlorination and 

 conversion into the primary and secon- 

 dary alcohols by the usual methods 

 gives a product which may contain an 

 alcohol identical with the natural pro- 

 duct, but this requires confirmation 

 (Schorlemmer, Ann. 152, 155). 



[B.] Sebacic acid [Vol. II] gives 

 octane on distillation with baryta 

 (Riche, Ann. 117, 265). 



NOTES: Certain aromatic compounds (which 

 can all be synthesised), such as xylene [62 ; A], 

 ethylbensene [64 ; A], styrene [7], naphthalene [12], 

 phthalic acid [54 ; B], &c., according to Berthe- 

 lot give octane among other products when 

 heated with strong aqueous hydriodic acid (for 

 references see under isoheptyl alcohol [27 ; B]). 

 The constitution of the octanes thus obtained 

 is unknown. 



A secondary octyl alcohol (methylhexyl 

 carbinol= 2-octanol) has been obtained by dis- 

 tilling the soap from the oil of Curcas purgans 

 (Silva, Zeit. [z], 5, 185). The alcohol has been 

 synthesised (see under n-hexyl alcohol [23 ; H]), 

 but it is doubtful whether it is at present to be 

 regarded as a biochemical product. 



29. Nonyl Alcohol ; Ennyl Alcohol ; 

 Nonanol. 



C 9 H 19 .OH 



NATUEAL SOUECE. 



Anonyl alcohol (394per cent.)has been 

 found in the oil of sweet orange (Schim- 

 mePs Ber. Oct. 1900; Ch. Centr. 1900, 

 2, 969 ; Stephan, Journ. pr. Ch. [2] 62, 

 523)- 



SYNTHETICAL PEOCESSES. 



The constitution of the natural pro- 

 duct is not known with certainty ; it is 

 probably the normal alcohol. The fol- 

 lowing nonyl alcohols are synthetical 

 products : 



[A.] Pelargonic and formic [Vol. II] 

 acids give the aldehyde (nonanal) on 

 distillation of the barium salts. The 

 aldehyde is reduced to normal nonyl 

 alcohol by zinc dust and acetic acid 

 (Krafft, Ber. 19, 2221). 



[B.] From isovaleric acid [Vol. II] and 

 isoamyl alcohol [22]. Isoamyl isova- 

 lerate on treatment with sodium gives 



