120 C-12L] 



ANISIC ALDEHYDE 



219 



354 ; Rossel, Ann. 151, 25 ; Labbe, 

 Bull. Soc. [3] 21, 1076; Otto and 

 Verley, Germ. Pat. 97620 of 1895; 

 Ch. Centr. 1898, 2, 693), or by the 

 action of boron fluoride (Landolph, Ber. 

 12, 286). 



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

 through anisole by distilling the methyl 

 ether with baryta (Cahours, Ann. 48, 

 65), and then as above under B. 



[E.] From p-hydroxybenzyl alcohol 

 [56] through p-methoxybenzyl = anisyl 

 alcohol by methylation (Biedermann, 

 Ber. 19, 2376) and the aldehyde by 

 oxidation (Cannizzaro and Bertagnini, 

 Ann. 98, 189). 



[P.] Anisic acid [Vol. II] gives the 

 aldehyde on distilling the calcium salt 

 with calcium formate [Vol. II] (Piria, 

 Ann. 100, 105). 



[G-.] From benzene [6 ; I, &c.] through 

 nitrobenzene and aniline. The latter, 

 on conversion into a diazonium salt and 

 treatment with methyl alcohol, gives 

 anisole (Beeson, Am. Ch. Journ. 16, 

 234 ; Cameron, Ibid. 20, 250 : see also 

 Hantzsch and Spear, Ber. 33, 2538 ; 

 Hantzsch and Jochem, Ber. 34, 3337). 

 Subsequent steps as above under B. 



Or benzenesulphonic acid gives ani- 

 sole directly on distilling its sodium 

 salt with sodium methylate (Moureu, 

 Bull. Soc. [3] 19, 403). 



121. Vanillin; Metliylproto- 



catechuic Aldehyde; 



3-Meth.oxy-4-hydroxyben.zoic 



Aldehyde. 



CHO 



OCH 3 



HO 



NATURAL SOURCES. 



In pods of the vanilla bean, from 

 Vanilla planifolia and its varieties, V. 

 saliva, V. sylvestris, and V. pompona, all 

 from Mexico. In V. guyauensis from 

 Guiana and Surinam ; in V. palmarum 

 from Bahia; in 7. aromalica from 

 Brazil and Peru; in V. planifolia var. 



from Reunion, and in V. ensifolia from 

 New Granada. The isolation of vanillin 

 from the pods of 7. aromatica is due to 

 Gobley (Jahresber. 1858, 534 : see also 

 Stokkebye, Ibid. 1864, 612). 



Vanillin occurs in Siam benzoin 

 (Jannasch and Rump, Ber. 11, 1635; 

 Liidy, Arch. Pharm. 231, 461), in assa- 

 fffitida (Schmidt, Arch. Pharm. [3] 24, 

 534; Tschirch and Polacek, Ibid. 235, 

 126), in small quantities in certain beet 

 sugars (Weger, Ding. poly. Journ. 237, 

 i46;Scheibler,Ber.l3,335;v.Lippmann, 

 Ibid. 662), in asparagus (v. Lippmann, 

 Ber. 18, 3335), in the seeds of Lupinus 

 albus (Campani and Grimaldi, Gazz. 17, 

 545), in flowers of the orchid, Nigritella 

 suaveolens (v. Lippmann, Ber. 27, 3409), 

 and in resins from pine and larch (Max 

 Bamberger and Landsiedl, Monats. 18, 

 481 ; 502). Vanillin is possibly present 

 in yellow acaroid or Botany Bay resin 

 from XanthorrJtcca hastilis (Tschirch and 

 Hildebrand, Arch. Pharm. 234; Ch. 

 Centr. 1897, 1, 422). 



Vanillin occurs in cinnamem from 

 Peru balsam, San Salvador (Thorns, 

 Ber. deutsch. pharm. Gesell. 8, 264; 

 Ch. Centr. 1898, 2, 1030; Tschirch 

 and Knitl, Arch. Pharm. 237, 271 ; Ch. 

 Centr. 1899, 2, 315), and in opoponax 

 from Opoponax c/dronium (Tschirch and 

 Knitl, loc. cit. 256; Ch. Centr. 1899, 



2, 3*5\- . 



Vanillin has been found in oriental 



storax from Liquidambar orientalis and 

 American storax from L. styracijlua 

 (Tschirch and Van Itallie, Arch. Pharm. 

 239,506; 532). 



A vanillin glucoside occurs in the 

 husk of oats (Rawton, Com p. Rend. 

 125,797). According to Singer (Monats. 



3, 409), vanillin is widely distributed 

 in traces in all woody portions of plants 

 (see also Czapek, Zeit. physiol. Ch. 27, 

 148). Vanillin occurs in cork (Kiigler, 

 Journ. Pharm. [5] 10, 123 ; Brautigam, 

 Ch. Centr. 1898, 2, 858; 889; Thorns, 

 Ibid. 1102), and in the volatile oil of 

 Spircea (Schneegans and Gerock, as 

 quoted by Gildemeister and Hoffmann, 

 p. 551). According to Brautigam, po- 

 tato peel contains a compound which 

 gives vanillin under the influence of 

 heat and atmospheric oxygen (Pharm. 



