276 



APPENDIX 



[180-181 A. 



180. Quercetiii ; 

 1:3:3': 4 1 -Tetrahydroxyflavonol. 



OH 



HO 



NATURAL SOURCES. 



The sources of quercetin are given 

 under catechol [69, pp. 138, 139]. To 

 these must be added Primus spinosa, 

 Viola odorata, and Trifolium repens, 

 white clover, in which the colouring- 

 matter has been found (A. G. Perkin 

 and Phipps, Trans. Ch. Soc. 85, 56). 

 Globulariacitrin, a glucoso-rhamnoside 

 of quercetin, is contained in Globularia 

 alypum (Tiemann, Arch. Pharm. 241, 

 289). 



SYNTHETICAL PROCESS. 



[A.] From phloroglucinol \QQ\,vanillin 

 [121], acetic acid [Vol. II], and methyl 

 alcohol [13]. Phloroglucinol dimethyl 

 ether (see under hydrocotoin [134; A, 

 p. 231]) is condensed with acetyl 

 chloride so as to form phloroaceto- 

 phenone dimethyl ether (see under 

 chrysin [138; A, p. 233]), and the 

 latter by condensation with vanillin 

 methyl ether (veratric aldehyde) con- 

 verted into 2 1 -hydroxy-4 1 : 6 1 : 3 : 4- 

 tetramethoxychalkone : 



H.C.O, 



OH 



into quercetin by heating with strong 

 hydriodic acid (Kostanecki, Lampe, and 

 Tambor, Ber. 37, 1402). 



181. Kamplierol ; 

 1:3: 4 T -Trihydroxyflavonol. 



HO 



O.CH:CH[i].C 8 H 3 (OCH3) 2 [3:4] 

 O . CH 3 



The latter on heating with alcoholic 

 hydrochloric acid is converted into i : 

 3 : 3 1 : 4 1 -tetramethoxyflavanone, from 

 which the isonitroso-derivative is ob- 

 tained by the action of amyl nitrite. 

 On heating with dilute sulphuric acid 

 in acetic acid the isonitroso-derivative 

 forms i : 3 : 3 1 : 4 1 -tetramethoxyflavonol, 

 which is demethylated and converted 



HO 



NATURAL SOURCES. 



Natural sources of kampherol are 

 given under phloroglucinol [86, p. 161, 

 and this appendix, p. 287]. 



SYNTHETICAL PROCESS. 



[A.] From phloroglucinol [86], anisic 

 aldehyde [120], acetic acid [Vol. II], 

 and methyl alcohol [13]. Phloraceto- 

 phenone dimethyl ether (see under 

 chrysin [138; A, p. 233]) and anisic 

 aldehyde condense in alcoholic solution 

 in presence of sodium hydroxide to form 

 2 1 -hydroxy-4 1 : 6 1 : 4 -trimethoxy chalk- 

 one : 



CO . CH : CH[i] . C 6 H 4 (OCH 3 )[4] 

 O.CH 3 



(Kostanecki and Tambor, Ber. 37, 792). 

 The latter, on boiling its alcoholic solu- 

 tion with dilute sulphuric acid, is con- 

 verted into 1:3: 4 1 -trimethoxyflavanone, 

 which by the action of nitrous acid 

 (amyl nitrite) yields isonitroso-i : 3 : 4 1 - 

 trimethoxyflavanone. On heating with 

 dilute mineral acids the isonitroso- 

 derivative gives 1:3: 4 1 -trimethoxy- 

 flavonol, and this, on demethylation by 

 heating with strong hydriodic acid, 

 yields kampherol (Kostanecki, Lampe, 

 and Tambor, Ber. 37, 2096). 



NOTE : Fisetin, quercetin, and kampherol 

 belong to the same group as chrysin [138, 

 p. 233], tectochrysin [139, p. 234], apigenin 

 [140, p. 234], and luteolin [141, p. 234]. 



