142 



AROMATIC ALCOHOLS AND PHENOLS [69 M-7O. 



soda sohition (Araki, Zeit. physiol. Ch. 

 19, 460). 



[N.] Benzene [6] when combined 

 with chlorine gives a hexachloride 

 which yields catechol, among other pro- 

 ducts, when heated with water at 200 

 (Meunier, Ann. Cbim. [6] 10, 366 ; 

 Comp. Rend. 100, 1591)- 



Or chlorbenzene on nitration gives 

 (with para-) orthochlornitrobenzene 

 ( Jungfleisch, Ann. Chim. [4] 15, 1 86 ; 

 Laubenheimer, Ber. 7, 1765; 8, 1621 ; 

 Sokoloff, Zeit. [2] 2, 621 ; Lesimple, 

 Ibid. [2] 4, 225), and this by the action 

 of sodium methylate in methyl alcohol 

 yields o-nitroanisole (Lobry de Bruyn, 

 Rec. Tr. Ch. 9, 200), from which o- 

 anisidine, guaiacol, and catechol can be 

 obtained as under A and F. 



Catechol is among the products of 

 the oxidation of benzene with hydrogen 

 peroxide in the presence of ferrous 

 sulphate (Young, Proc. Ch. Soc. 15, 

 131 ; Cross, Bevan, and Heiberg, Ber. 

 33, 2018). 



Nitrobenzene gives o-nitrophenol 

 when warmed with finely divided 

 potassium hydroxide. The transforma- 

 tion takes place slowly even at ordinary 

 temperatures (Wohl, Ber. 32, 3486). 

 Subsequent steps as above under A. 



Or nitrobenzene by mild reduction 

 gives phenylhydroxylamine, which oxi- 

 dises to nitrosobenzene (Bamberger and 

 Storch, Ber. 26, 472 ; Bamberger and 

 Landsteiner, Ibid. 482 ; Bamberger, 

 Ber. 27, 1182; 1273; 1347; 1548; 

 1555; Wohl, Ibid. 1432). The latter 

 gives o-aminophenol among the pro- 

 ducts of the action of hot aqueous alkali 

 (Bamberger, Ber. 33, 1939). 



Or aniline (by nitration of acetani- 

 lide) gives (with p-) o-nitraniline, which 

 reduces to o-phenylenediamine. The 

 latter yields catechol on heating with 

 10 per cent, hydrochloric acid to 180 

 (Meyer, Ber. 30, 2569). 



[O.] From furfural [126] through 

 pyromucic and mucobromic acids and 

 nitromalonic aldehyde (see under phloro- 

 glucinol [86 ; l]). The latter condenses 

 with acetoacetic ester [Vol. II] to form 

 3-nitrosalicylic acid (Hill, Soch, and 

 Oenslager, Am. Ch. Journ. 24, i). 

 Subsequent steps as above under B. 



[P.] Caff&ic acid [Vol. II] decom- 

 poses at 200 with the formation of 

 3 : 4-dihydroxystyrene = vinylcatechol 

 (Kunz-Krause, Ber. 30, 1618). The 

 latter gives catechol on distillation under 

 reduced pressure (Ibid. 1620). 



7O. Besorciiiol ; 



MetadiliycTroxybenzeiie ; 



1 : 3-Phenediol. 



HO 



NATURAL SOURCES. 



The compound itself has not yet been 

 found as a natural product, but the 

 complex apparently, with the catechol 

 complex, enters into the constitution 

 of fisetin (for sources of fisetin see iinder 

 catechol), and also into the constitution 

 of morin, the yellow colouring-matter 

 from old fustic, the wood of Moms 

 (Madura) tinctoria, and in the Indian 

 dyestuff from jack-fruit, Artocarpns 

 integrifolia (A. G. Perkin and Cope, 

 Trans. Ch. Soc. 67, 937 ; Bablich and 

 A. G. Perkin, Ibid. 69, 798; A. G. P. 

 and Horsfall, Proc. Ch. Soc. 16, 182). 



The complex exists in the glucoside, 

 lotusin, of the Egyptian vetch, Lotus 

 arabicus, through lotoflavin (Dunstan 

 and Henry, Proc. Roy. Soc. 68, 374). 



The resorcinol complex may be con- 

 sidered to exist also in paonol [133], 

 gentisin [137], pnrpiiroxanthin [146], 

 methylpurpuroxanilun [15O], umbelli- 

 ferone and met/iyliimbelliferone [Vol. 

 II], euxantJione [136], and possibly in 

 brazilin from Brazil wood (Cffsalpinia 

 crista, C. brasiliensis, &c.) and sapan 

 wood (C. sapan}. 



Compounds containing this complex 

 may also exist in many resins and gum- 

 resins, such as galbanum, gum-ammoniac, 

 asafcetida, acaroid, sagapenum, &c. (For 

 references to constitution of brazilin see 

 under catechol [69] ; also Herzig, Mo- 

 nats.16,906; 19,738; GilbodyandW.H. 

 Perkin, junr., Proc. Ch. Soc. 16, 105; 



