140 



AROMATIC ALCOHOLS AND PHENOLS 



papaverine and narcotine, in pseud - 

 aconitine from the root of Aconilum 

 ferox, in berberine from Berberit vul- 

 garis, Xantlioxylon clava, Hydraslis cana- 

 densis, &c., in hydrastine from Hydra- 

 sfis canadensis, and in corydaline from 

 the roots of Corydalis(Aristolockia)cava. 



The colouring-matter of red grapes 

 appears to contain the catechol complex 

 (Sostegni, Gazz. 32, 17). 



The following synthesised natural 

 products contain the catechol, guaiacol, 

 or veratrole complex : Isoeugenol [79] ; 

 methylisoeugenol [80] ; methyleugenol 

 [81]; vanillin [l2l] ; luteolin [l4l] ; 

 alizarin [145] ; hystazarin [147] ; proto- 

 catechuic acid [Vol. II] ; verafvic acid 

 [Vol. II] ; piperonylic acid [Vol. II] ; 

 hydrocaffe'ic acid [Vol. II] ; caffeic acid 

 [Vol. II]; ferulatc acid [Vol. II]; 

 liesperetinic acid [Vol. II] ; piperic acid 

 [Vol. II]. 



Catechol has been found (as a salt of 

 catechol sulphate) in the urine of man 

 and herbivorous animals (Baumann, 

 Pfliiger's Arch. 12, 63 ; Baumann and 

 Herter, Zeit. physiol. Ch. 1, 244; Bau- 

 mann and Preusse, Ibid. 3, 157 ; Miiller, 

 Ber. 7, 1526 ; Nencki and Giacosa, 

 Zeit. physiol. Ch. 4, 335; Schmiede- 

 berg, Ibid. 6, 189). 



According to Halliburton (Journ. 

 Physiol. 10, 247), it is contained in the 

 cerebrospinal fluid. A phenolic sub- 

 stance extracted from the kidneys has 

 been considered to be catechol, but 

 according to O. v. Fiirth it is not this 

 compound (Zeit. physiol. Ch. 24, 143 ; 

 26, 15;. 29, 105). 



SYNTHETICAL PROCESSES. 

 [A.] Phenol [60] by various iodising 

 processes gives (with para-) ortho-iodo- 

 phenol (Schiitzenberger and Sengen- 

 wald, Comp. Rend. 54, 197; Kb'rner, 

 Ann. 137, 1 97 ; Hlasiwetz and Wesel- 

 sky, Sitzungsber. Wien. Akad. 60 [2] 

 290; Lobanoff, Ber. 6, 1251; Schall, 

 Ber. 16, 1897; Willgerodt, Journ. pr. 

 Ch. [2] 37, 446). The latter on fusion 

 with potash gives catechol (Korner, 

 Zeit. [2] 4, 322 ; Lautemann, Ann. 

 120, 315; Noelting and Strieker, Ber. 

 20, 3019). 



Or phenol when chlorinated or bromi- 

 nated at 150-180 gives orthochlor- or 

 bromphenol (Merck, Germ. Pat. 76597 

 of 1893). These derivatives give catechol 

 on heating with caustic soda-lye under 

 pressure (Ibid. Germ. Pat. 84828 of 



1893)- 



Or phenol may be nitrated, the ortho- 



(separated from the para-) nitrophenol 

 reduced, and the o-aminophenol con- 

 verted into o-iodophenol by the diazo- 

 method (Noelting and Wrzesinski, Ber. 

 8, 820 ; Noelting and Strieker, Ber. 

 20, 3018 ; Neumann, Ann. 241, 68). 



o-Aminophenol is also converted 

 (partially) into catechol by heating to 

 a high temperature with dilute mineral 

 acids (Meyer, Ber. 30, 2569). 



Or o-nitrophenol can be converted 

 into its methyl ether by methylation 

 (Brunck, Zeit. [2] 3, 204 ; Miihlhauser, 

 Ann. 2O7, 237; Willgerodt and Ferko, 

 Journ. pr. Ch. [2] 33, 153), into o- 

 anisidine by reduction (Miihlhauser, 

 loc. cit. 239), into guaiacol by the diazo- 

 method (Kalle, Eng. Pat. 7233 of 

 j 897 ; Journ. Soc. Ch. Ind. 17, 269), 

 and into catechol as below under P. 



Or o-aminophenol can be converted 

 into o-chlorphenol by the diazo-method 

 (Schmitt and Cook, Ber. 1, 67), and 

 the chlorphenol sulphonated (Kramers, 

 Ann. 173, 331)- The 2-chlorphenol- 

 4-sulphonic acid on heating at 250 

 with caustic soda solution gives cate- 

 cholsulphonic acid, from which catechol 

 can be obtained by hydrolysis (Soc. 

 Chim. d. Usines du Rhone, Germ. Pat. 

 97099 of 1896; Ch.Centr. 1898,2,521). 



Or a-phenoldisul phonic acid gives on 

 fusion with alkali catecholsulphonic 

 acid, from which catechol is obtained 

 by heating with 50 per cent, sulphuric 

 acid to 200 (Merck, Germ. Pat. 80817 

 of 1893). Or phenoltrisulphonic acid 

 (Senhofer, Ann. 17O, no; Arche and 

 Eisenmann, Germ. Pat. 51321 of 1889) 

 on fusion with alkali at 230-260 gives 

 catecholdisulphonic acid (Tobias, Germ. 

 Pat. 81210 of 1894), the sodium salt of 

 which yields catechol when the concen- 

 trated aqueous solution is heated to 2 1 o- 

 215 (Ibid. Germ. Pat. 81209 of 1894). 



Or phenol may be sulphonated (Ke- 

 kule, Zeit. [2] 3, 199), and the o-sul- 



