103 



AROMATIC ALCOHOLS AND PHENOLS 



[54 B. 



laurocerasus (Tilden, Pharm. Journ. [3] 

 5, 761). 



Benzyl acetate is the chief constituent 

 of the ethereal oil of jasmine from 

 Jasmimim grandiflorum (Hesse and 

 Miiller, Ber. 32, 565 ; 765 ; Hesse, 

 Ibid. 2611 ; 33, 1585 ; 34, 291 ; 2916 : 

 see also E. Erdmann, Ber. 34, 2281). 

 The free alcohol occurs also in this oil 

 (Hesse and Miiller, loc. cit., 765 ; Hesse, 

 Ibid. 2619; Ch. Ind. 25, i). 



The lower boiling fraction of the oil 

 of cassia flowers from Acacia farnesiana 

 probably contains benzyl alcohol (Schim- 

 meFs Ber. April, 1901). The alcohol 

 has been found in considerable quantity 

 in the distillation water from ylang- 

 yla.ng essence (v. Soden and Rojahn, 

 Ber. 34, 2809). It is contained in this 

 last oil probably as benzyl salicylate and 

 benzoate (Schimmel's Ber. Oct. 1901). 

 The chief constituent of the oil of 

 Gardenia is benzyl acetate (Parone, 

 Boll. Chim. Farm. 41, 489; Ch. Centr. 

 1902, 2, 703). 



SYNTHETICAL PROCESSES. 



[A.] From acetylene through benzene 

 (see under cymene [6; A]). Benzene 

 can be converted into toluene by treat- 

 ing- brombenzene and methyl iodide with 

 sodium (Fittig and Tollens, Ann. 131, 

 303), or by passing methyl chloride 

 into benzene containing aluminium 

 chloride (Friedel and Crafts, Ann. 

 Chim. [6] 1, 460; 11, 264). Toluene 

 gives benzyl alcohol among the pro- 

 ducts of its oxidation by manganese 

 dioxide and sulphuric acid (Weiler, Ber. 

 33, 464), and benzyl acetate by oxida- 

 tion with chromic acid or potassium 

 permanganate in acetic acid solution 

 (Boedtker, Bull. Soc. [3] 25, 843). 



Toluene is converted into benzyl 

 chloride by passing chlorine into the 

 boiling liquid (Cannizzaro, Ann. Chim. 

 [3] 45, 468 ; Beilstein and Geitner, 

 Ann. 139, 337 : see also Lauth and 

 Grimaux, Bull. Soc. [2] 7, 105), or at 

 ordinary temperatures by chlorinating 

 in sunlight (Schramm, Ber. 18, 608). 

 Benzyl chloride can be converted into 

 benzyl alcohol by treatment with 

 potassium acetate and subsequent hydro- 



lysis (Cannizzaro, Ann. 96, 246 ; Seelig, 

 Journ. pr. Ch. [2] 39, 167), by heating 

 with a solution of potassium carbonate 

 (Meunier, Bull. Soc. [a] 38, 159), with 

 water and lead hydroxide (Lauth and 

 Grimaux, Ann. 143, 81), or with water 

 only (Niederist, Ann. 196, 353). Ben- 

 zyl acetate is formed by the interaction 

 of benzyl chloride and lead acetate 

 (Bodroux, Bull. Soc. [3] 21, 288). 



Also from acetylene through ethylene 

 (see under ethyl alcohol [14; A]), ethy- 

 lene chloride, vinyl chloride by alcoholic 

 potash (Regnault, Ann. 14, 28), and 

 chloracetaldehyde by the action of 

 mercuric oxide on vinyl chloride (Glin- 

 sky, Zeit. [2] 3, 678 ; 4, 617 ; 6, 647). 

 The aldehyde by treatment with hydro- 

 gen cyanide [172] and hydrochloric acid 

 gives /3-chlorlactic acid (Ibid. [2] 6, 

 515; Frank, Ann. 206, 344), which is 

 converted by silver oxide into glyceric 

 acid (Frank, loc. cit. 348). The latter 

 gives pyrotartaric acid as under P, 

 citrabrompyrotartaric acid and allylene 

 as under N, mesitylene, uvitic acid, and 

 toluene as under D. 



NOTE : All generators of ethylene thus be- 

 come generators of toluene and of benzyl 

 alcohol. 



[B.] Benzoic aldehyde [114] on treat- 

 ment with caustic alkali gives benzyl 

 alcohol and benzoic acid (Cannizzaro, 

 Ann. 88, 129; Meyer, Ber. 14, 2394; 

 Kohn and Trantom, Trans. Ch. Soc. 

 75, H55; Raikoff and Raschtanoff, 

 Ch. Centr. 1902, 1, 1212), or benzyl 

 alcohol by reduction with sodium amal- 

 gam (Friedel, Jahresber. 1862, 263; 

 Bull. Soc. 1862, 1 8). Also from benzoic 

 aldehyde through toluene by heating 

 with hydriodic acid (Berthelot, Jahres- 

 ber. 1867, 346), and then as under A. 



Or benzaldoxime or hydrazone gives 

 benzylamine on reduction with sodium 

 amalgam and acetic acid, or by electro- 

 lysis (Goldschmidt, Ber. 19, 3232; 

 Tafel, Ibid. 1928; Tafel and Pfeffer- 

 mann, Ber. 35, 1510). Benzylamine 

 may be converted into benzyl alcohol 

 by the action of nitrous acid (see Curtius, 

 Ber. 17, 958). 



NOTE : For generators of benzylamine see 

 also under benzyl mustard oil [169]. 



