145 B-146 B.] 



ALIZARIN 



239 



quinone. The halo-quinone gives 

 alizarin on fusion with alkali (Graebe 

 and Liebermann, Ann. Suppl. 7, 300 ; 

 Ber. 3, 359 ; Bull. Soc. [2] 11, 516). 



Or ant/tr a quinone is sulphonated, and 

 the monosulphonic acid (see under m- 

 hydroxyanthraquinone [144 ; C]) fused 

 with alkali and potassium chlorate 

 (G. and L. loc. cit. ; Perkin, Journ. Ch. 

 Soc. 23, 133 ; Ber. 9, 281). The latter 

 is the technical process. 



a-Nitroanthraquinone, a-dmitro-, and 

 diaminoanthraquinone give alizarin on 

 fusion with alkali (Bottger and Peter- 

 sen, Ber. 4, 227 ; Ann. 160, 145; 166, 

 147 ; Meister, Lucius, and Briining, 

 Jahresber. 1873, H22; Glaus, Ber. 15, 



Or anthraquinonesulphonic acid gives 

 on nitration a mixture of two nitro- 

 sulphonic acids (Glaus, loc. cit.} ; the 

 a-acid yields alizarin on fusion with 

 alkali. Or the nitrosulphonic acid can 

 be reduced to the corresponding amino- 

 acid (Glaus, loc. cit. 1519), and this 

 converted into i -hydroxyanthraquinone- 

 2-sulphonic acid by the diazo-method 

 (Lifschiitz, Ber. 17, 900). The latter 

 gives alizarin on alkaline fusion (Ibid. 

 901). 



[C.] m-Hydroxyanthraqumone [144] 

 (and the isomeric i-hydroxy quinone 

 simultaneously formed from phenol and 

 phthalic anhydride) gives alizarin on 

 alkaline fusion. 



[D.] Gallic acid [Vol. II] on heating 

 with strong sulphuric acid gives rufi- 

 gallic acid =1:2:3:5:6: 7-hexahydr- 

 oxyanthraquinone (Robiquet, Ann. 19, 

 204; Wagner, Ch. Centr. 1861, 47; 

 Lowe, Journ. pr. Ch. 107, 296 ; Jaffe, 

 Ber. 3,694; Klobukowski and Noelting, 

 Ber. 8, 819; 9, 1256; 10, 880 ; Wid- 

 mann, Ber. 9, 856). The latter yields 

 alizarin on reduction with sodium amal- 

 gam (Widmann, loc. cit. ; Bull. Soc. 

 [2] 24, 359). 



[E.] From vanillin [l2l] and benzene 

 [6 ; 1, &c.] through the following pro- 

 cesses : Acet vanillin (Tiemann and 

 Nagai, Ber. 11, 647 ; Pschorr and 

 Sumuleanu, Ber. 32, 3405) on nitra- 

 tion and hydrolysis of the product gives 

 o-nitrovanillin, and this on methylation 

 yields the methyl ether. The latter on 



oxidation by alkaline permanganate 

 gives o-nitroveratric acid, the nitro-acid 

 o-aminoveratric acid by reduction, and 

 hemipic acid (through the -nitrile) by 

 the diazo-method, followed by hydro- 

 lysis of the nitrile (Pschorr and Sumu- 

 leanu, loc. cit. 3411). Hemipic acid in 

 benzene solution under the influence of 

 aluminium chloride gives hydroxy- 

 methoxybenzoylbenzoic acid, and this, 

 by the action of strong sulphuric acid, 

 yields alizarin methyl ether, which gives 

 alizarin by demethylation on heating 

 with strong hydriodic acid at 127 

 (Lagodzinski, Ber. 28, 1427). 



[F.] From kystazarin [147] by heat- 

 ing with strong sulphuric acid to 200- 

 205 (Liebermann and Hohenemser, 

 Ber. 35, 1778). 



146. Fttrpuroxanthin ; 



Xaiitliopurpuriii ; 

 1 : 3-Dihydroxyanthraqninone. 



HO 



NATUKAL SOURCE. 



Occurs with alizarin and purpurin 

 in madder root (Schiitzenberger and 

 Schiffert, Bull. Soc. [2] 4, 12). The 

 carboxylic acid also is present in madder 

 (Schunck and Romer, Ber. 10, 172). 



SYNTHETICAL PROCESSES. 



[A.] From benzoic acid [Vol. II] 

 through the 3 : 5-disulphonic acid (Barth 

 and Senhofer, Ann. 159, 217), the 3 : 5- 

 dihydroxy-acid (Ibid. 222), and the 

 action of strong sulphuric acid on 

 a mixture of the latter with benzoic 

 acid at 105-110 (Noah, Ber. 19, 332 ; 

 Ann. 241, 266 : anthrachrysone = 

 1:3:5: 7-tetrahydroxyanthraquinone 

 is simultaneously formed in this pro- 

 cess). 



[B.] From pnrpurin [149] by reduc- 

 tion with phosphorus iodide and water, 



