Berberines

Berberine, coptisine, and /3-stylopine methohydroxide have been isolated from Papaver rhoeas L., berberine, berberubine, isocorypalmine, and thalifendine from Thalictrum dioicum, berberine from T. sachalinense, corydaline from Corydalis marschalliana, scoulerine, ophiocarpine, isocorypalmine, and cheilanthifoline from C. vaginans, C. gigantea, and C marschalliana, and ophiocarpine, stylopine, cheilanthifoline, isocorypalmine, and the chlorides of berberine, coptisine, and dehydrocheilanthifoline from C. ophiocarpa. The alkaloids of C. ophiocarpa were separated by droplet counter-current chromatography.  

Four new alkaloids of the quaternary berberine type, but with the coreximine orientation of oxygen substituents, have been found in Isopyrum thalictroides. The structures of these pseudoberberines were determined as (61 R = = Me), 

A new alkaloid, solidaline, representing a modified protoberberine, has been isolated from Corydalis solida. It has been assigned the structure (63) on the basis of spectroscopic studies. The structures assigned to aequaline and scheflerine. 

Berberine chloride has been shown to be degraded, by heating with sodium acetate and acetic anhydride at 115 °C for 48 hours, to the acetyl ester of the dihydroquinolyl-jS-naphthol (69). The process has been formulated as involving initial nucleophilic attack of the isoquinolinium salt by the anhydride anion (64) to 

A patent that covers the oxidation of berberines to oxybisberberines with potassium ferricyanide, and the conversion of these into 13-methoxyoxyber-berines, e.g. (72), has been reported. Conditions for the conversion of the oxybisberberines into the 8-methoxyoxyberberine betaine (73) have previously been reported (Vol. 8, p. 105). 

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Two different mixtures of peptides and alkaloids (qv) have been analy2ed by ce/uv/ms using sims to determine whether this technique can detect trace impurities in mixtures (85). The first mixture consisted of two bioactive peptide analogues, which included Lys-bradykinin (kahidin) and Met-Lys-bradykinin. The presence of 0.1% Lys-bradykinin was detected by sim ce/ms but not by ce/uv at 0.1% level as it migrated from the capillary column prior to the main component, Met-Lys-bradykinin. The second mixture consisted of two antibacterial alkaloids, berberine and palmitine. The presence of 0.15% palmitine was detected by ce/uv and sim ce/ms at 0.15% level as it migrated from the capillary column, following the main component berberine. This technique can provide a complementary technique for trace components in such sample mixtures. 

Berberine hydrochloride (2H2O) [633-65-8] M 407.9, m 204-206 (dec), pK 2.47. Crystn from water gives the dihydrate. The anhydrous salt may be obtained by recrystn from EtOH/Et20, wash with Et20 and dry in a vacuum. The iodide has m 250°(dec) (from EtOH). [ J Chem Soc 113 503 1918 J Chem Soc 2036 7969.]... 

Dipping solution Dissolve 10 mg berberine chloride in 100 ml ethanol. Storage The dipping solution may be kept for several days. 

The mechanism of the reaction has not been elucidated. Berberine is probably enriched in the lipophilic chromatogram zones which then fluoresce more intensely than the environment. 

Argemone alba Lestib. Berberine base, picrate, m.p. 232-5°. ... 

Special Reactions of Papaverine. Papaverine undergoes a number of reactions, which are of interest as providing methods of synthesis for other alkaloids, of which examples will be found under laudanosine, laudanine, laudanidine, codamine (pp. 187-195), berberine (p. 331), corydaline (p. 284), and glaucine (p. 311). 

Dehydrocorydaline, C22H2304lSk (Items 8,14, 31 list, pp. 170-2.) This alkaloid is formed by the gentle oxidation of corydaline.It is a yellowish crystalline powder, m.p. 112-3° (dec.) the hydrochloride, B. HCl. 4H2O, forms yellow leaflets hydriodide, B. HI. 2H2O, small yellow needles aurichloride, B. HAUCI4, red-brown needles, m.p. 219°. Like berberine,... 

Other members of this sub-group, usually more closely associated with berberine in distribution, or in structure, or both, and therefore dealt with in the Berberis group, are canadine (p. 338), capaurine (p. 339), cheilanthifoline (p. 339), ophiocarpine (p. 338), sinactine (p. 338), tetra-hydroshobakunine (p. 340) and tetrahydroworenine (p. 344). 

The reverse change, viz., the conversion of berberine derivatives by iV-methylation into substances constituted similarly to corresponding derivatives of cryptopine, was achieved by the methylation of dihydroanhydroberberine, to the methochloride, which corresponds to tsocrypto-pine chloride and resembles it closely in character and reactions,... 

Maranon, and later Santos and Reyes, found artabotrine and suaveoline in Artabotyris suaveolens, Blume. In one species of the Anonaceas, Xylopia macrocarpa Oliv., berberine has been recorded (p. 329). Anolobine, Ci,H, OaN. This alkaloid has m.p. 262° (dec.) and... 

Berberine is probably the most widely distributed alkaloid. It and the allied alkaloids palmatine, jatrorrhizine, columbamine and coptisine occur somewhat frequently in the Rhcnadales (list, p. 169) as the tetrahydro-derivatives, but, in the botanical families referred to in the distribution list below, the tetrahydro-derivatives are exceptional and the unreduced alkaloids usual. The associated alkaloids include two members of the aporphine group, domesticine and t odomesticine (p. 315), one member of the cryptopine group, y-homochelidonine (p. 294) and two members of the double woquinoline type, viz., berbamine and oxyacanthine (p. 346). 

The following list is not exhaustive, but it records the reasonably authenticated occurrences of the berberine type of alkaloid and its associates. Brief descriptions are included in the list, of alkaloids not of Sufficient importance to be described fully in the later text. 

RANUNCULACEAil. (1) Coptis japonica Mak. Berberine, palmatine, columbamine, coptisine, worenine. 

Berberine, Coptine (an uncharacterised yellow alkaloid first mentioned by Gross for C. Teeta). 

The following Berberis spp. contain mixtures of alkaloids — B. heteropoda Schrenk. Berberine, palmatine, jatrorrhizine, columbamine, berbamine and oxyacanthine. ... 

B. laurina Billb. (Thunb.). Berberine and possibly hydrastine. (9) B. Thunhergii DC. var Maximowiczii. Berberine, oxyberberine,... 

B. vulgaris L. Berberine, berberrubine, palmatine, jatrorrhizine, columbamine, berbamine, oxyacanthine and a base C19H22ON2, hydrochloride, m.p. 256°. 

Mahonia aquifolium Nutt. Berberis aquifolium Pursh.) Berberine, berbamine, oxyacanthine, a phenolic base, m.p. 190-3°, and undetermined alkaloids. 

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