55-56.] 



SALIGENIN 



117 



also Van Rijn's ' Die Glycoside/ p. 143, 

 and Jowett and Potter, Pharm. Journ. 

 [4] 15, 157.) 



Salicin liberates saligenin under the 

 influence of certain moulds, such as 

 Aspergillus niger (Puriewitsch, Ber. 

 deutsch. bot. Gesell. 16, 368) and 

 A. oryzee (Brunstein, Abst. in Journ. 

 Fed. Inst. 7, 367 ; 8, 507). Populin 

 [158], which is benzoylsalicin, liberates 

 benzoylsaligenin under the influence of 

 an enzyme (? emulsin) contained in 

 Aspergillus niger. 



Salicin is said to occur also in cas- 

 toreum from glands of the beaver 

 (Wohler, Ann. 67, 360). 



SYNTHETICAL PROCESSES. 



[A.] From salicylic aldehyde [H7] by 

 reduction with sodium amalgam (Beil- 

 stein and Reineke, Ann. 128, 179). 



[B.] From salicylic acid [Vol. II] 

 through the amide (Limpricht, Ann. 

 98, 258), and reduction of the latter 

 with sodium amalgam in acid solution 

 (Hutchinson, Ber. 24, 175). 



[C.] From toluene (see under benzyl 

 alcohol [54; A, &c.]), o-nitrotoluene, 

 which is formed (with p-nitrotoluene) 

 by nitration, o-nitrobenzyl chloride by 

 chlorination at 120-130 in the presence 

 of sulphur (Haussermann and Beck, 

 Ber. 25, 2445), o-nitrobenzyl alcohol 

 by heating the chloride with potassium 

 carbonate solution or with chalk and 

 water (SoderbaumandWidman, Ber. 25, 

 3291 ; Haussermann and Beck, Journ. 

 pr. Ch. [2] 47, 400 : see also Paal and 

 Bodewig, Ber. 25, 2962 ; Fischer, Germ. 

 Pat. 48722 of 1888; Ber. 22, Ref. 788; 

 Kalle & Co., Germ. Pat. 10436 of 

 1897; Cn - Centr. 1899, 2, 950; Ch. 

 Fab. Griesheim-Elektron, Germ. Pat. 

 128046 of 1900; Ch. Centr. 1902, 1, 

 445; Germ. Pat. 128998 of 1900; Ch. 

 Centr. 1902, 1, 686). From o-nitro- to 

 o-aminobenzyl alcohol by reduction 

 (Friedlander and Henriques, Ber. 15, 

 3109) and diazo-reaction with latter 

 (Paal and Senninger, Ber. 27, 1084). 



NOTE : For references to processes for oxi- 

 dising o-nitrotoluene to o-nitrobenzaldehyde, 

 which gives the alcohol as below under D, see 

 under indigo [Vol. II], Orthonitrotoluene also 

 gives o-nitrobenzaldoxime by interaction with 

 amyl nitrite and dry sodium ethoxide (Lap- 



worth, Trans. Ch. Soc. 79, 1274). o-Nitrotol- 

 uene gives o-nitrobenzyl alcohol by electrolytic 

 oxidation (Pierron, Bull. Soc. [3] 25, 852). 



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

 through the o-nitro-acid which is formed 

 (with the p-nitro-acid) by nitration 

 (Beilstein and Kuhlberg, Ann. 163, 

 126), o-nitrobenzaldehyde by oxidising 

 the acid with potassium permanganate 

 (Einhorn, Ber. 17, I2i), and o-nitro- 

 benzyl alcohol, which is formed (with 

 o-nitrobenzoic acid) by the action of 

 cold aqueous caustic alkali on the alde- 

 hyde (Friedlander and Henriques, Ber. 

 14, 2804). Subsequent steps as above. 



NOTE : One of the products of nitration of 

 w-bromstyrene from cinnamic acid (see under p- 

 hydroxybenzaldehyde [119 ; B]), viz. a-o-nitro- 

 phenyl-/3-bromnitroethylene, gives o-nitrobenz- 

 aldehyde on boiling with water (Flurscheim, 

 Journ. pr. Ch. [2] 66, 16). 



[E.] From phenol [60] by the action 

 of methylene chloride in the presence of 

 alkali (Greene, Am. Ch. Journ. 2, 19). 

 Methylene chloride can be prepared 

 from chloroform [l ; D, &c.] by reduc- 

 ing the alcoholic solution with zinc and 

 hydrochloric acid (Greene, Ibid. 1, 522 ; 

 Ch. News, 50, 75; Comp. Rend. 89, 

 1077). 



Also from phenol and formic aldehyde 

 [91] by the action of caustic alkaline 

 solution on a mixture (Manasse, Ber. 

 27, 2411; Lederer, Journ. pr. Ch. [2] 

 5O, 225 : see also Farbenfab. vorm. 

 F. Bayer & Co., Germ. Pat. 85588 of 

 1894). Parahydroxybenzyl alcohol is 

 formed simultaneously in this process. 



56. Farahydroxybenzyl Alcohol ; 

 Fhenol-4-Methylol. 



CH 2 . OH 



HO 



NATURAL SOURCE. 



The p-hydroxy benzyl complex occurs 

 in sinalbin, a glucoside found in white 

 mustard seed (see under p-hydroxy- 

 benzyl mustard oil [171]). 



