Hunnemanine

Hunnemanine, C20H21O6N, has been isolated only from Hunnemannia fumariaefoUa (71) in which it is present to the extent of 0.18 %. It is readily separable from the associated bases because of its solubility in alkaline solution, from which it is precipitated quantitatively by carbon dioxide, but not well by ammonium chloride. 

Hunnemanine crystallizes from chloroform-methanol in stout colorless 

Hunnemanine contains a methylenedioxy group as well as one methoxyl and one phenolic hydroxyl. When methylated with diazomethane in methanolic suspension it gives rise to allocryptopine (XXXIV). It is therefore one of the two possible 0-desmethylallocryptopines. That it is XXXV in which the hydroxyl occupies the sterically hindered position 

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The main alkaloid in A. fruticosa is hunnemanine along with allo-cryptopine A, echinata contains mostly cryptopine and berberine (9). 

In hunnemanine (80), which differs from the other alkaloids in having a phenolic hydroxyl group, the carbonyl resonance was shielded by 15-20 ppm relative to the other alkaloids and was also broadened. It was considered... 

Berberrubine was converted to hunnemanine by the procedure used by Perkin to convert tetrahydroberberines into protopines. The free hydroxyl was protected as its benzyl derivative 108). 

That phenolic alkaloids are soluble in aqueous solutions of fixed alkalies need not be stressed but it is important to note that some free bases (notably corydine and ochotensine) are extracted from such solutions by ether while others (bulboeapnine and hunnemanine) are not. A convenient method for recovery of these phenolic bases is to saturate their aqueous alkaline solutions with carbon dioxide or ammonium chloride. The latter reagent, however, is not invariably satisfactory (e.g., hunnemanine). 

The only representative of the genus Hunnemannia A. Juss., which is closely related to the genera Eschscholtzia, Dendromecon, and Petromecon, is Hunnemannia fumariaefolia Sweet, native to Central America. In the aerial part of this plant, the major alkaloid is hunnemanine (312) (Tables XXXVIII and XXXIX) and in the roots, protopine (309), hunnemanine, and allocryptopine (310). Cyclanoline (245) represents the main component of the quaternary alkaloid fraction of the aerial part and the roots. 

Hunnemanine V 82 R2R3=0CH20, R7=Me, R9=OH, Dactylocapnos torulosa (Papaveraceae) no... 

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