Hydrastines from berberines

The preparation of a- and /3-hydrastines from berberine has been described above.100 Photoracemization and epimerization of (—)-a-narcotine and of (—)-/3-hydrastine to mixtures of ( )-a- and ( )-/3-narcotines and of the corresponding hydrastines has been observed.114... 

The first conversion of protoberberines to phthalideisoquinoline alkaloids was achieved by Moniot and Shamma (88,89). 8-Methoxyberberinephenol-betaine (131), derived from berberine (15) (Section III,B,2), is an attractive compound having a carboxyl group masked as an imino ether in ring B. The masking was uncovered by hydration with water-saturated ether to furnish dehydronorhydrastine methyl ester (367) (Scheme 65). On N-methylation (68%) and subsequent sodium borohydride reduction (90%), 367 provided (+ )-/ -hydrastine (368) and ( )-a-hydrastine (369) in a 2 1 ratio. Compound 367 was converted to dehydrohydrastine (370), which also afforded 368 and 369 by catalytic hydrogenation. 

A recent stereospecific conversion of berberine to j8-hydrastine proceeds through the intermediacy of oxyberberine. Short photooxidation of this pyridone—readily derived from berberine—in the presence of oxygen provided a y-lactol. A -Methylation and reduction then supplied racemic j8-hydrastine, practically unadulterated with the diastereomeric a-hydrastine (see also Sec. 

Although there is not much experimental proof for the formation of the intermediates proposed, enzymes catalyzing the reactions which should lead from t3nrosine to dopamine (CLIII) and to the pyruvic acid (CLIV) are known. Another indirect evidence is the finding by Barton etal. (168) that under certain conditions 3,4-dihydroxyphenylalanine is a precursor of hydrastine and berberine. 

Gentry EJ, Jampani HB, Keshavarz-Shokri A, Morton MD, Velde DV, Telikepalli H, Mitscher LA, Shawar R, Humble D, Baker W. (1998) Antitubercular natural products Berberine from the roots of commercial Hydrastis canadensis powder. Isolation of inactive 8-oxotetrahydrothalifen-dine, canadine, beta-hydrastine, and two new quinic acid esters, hycandinic acid esters-1 and -2. J Nat Prod 61 1187-1193. 

Since it is reasonable that the two molecules derived from tyrosine which are involved in the formation of the benzylisoquinoline system should be different, an inequality of labeling at C-1 and C-3 in the derived alkaloids was anticipated. Whereas this was true for hydrastine, the ratio of activity at the two positions in berberine was approximately unity. 

Hydrastine, which occurs along with berberine and canadine in Hydrastis canadensis L. (golden-seal), is closely related to the minor opium alkaloit narcotine. At one time, it found hmited use as a bitter stomachic, and was employed in catarrhal conditions because of a rather obscure action on mucous membranes. It exerts a stimulant action on the uterus and has been advocated for the management of postpartum hemorrhage. It has been dropped, however, from the United States Pharmaco-... 

With this herb, more than any other, it is possible to find completely conflicting perspectives from clinicians of equal stature and length of practice. Some clinicians consider it to be a reliable immune stimulant, antibiotic, and antiviral. Many others do not. All can cite impressive clinical experience. In fact, very little research has been done on goldenseal, and almost no human clinical trials have been conducted. The science has generally focused on one constituent of goldenseal berberine. Here, too, the controversy continues. Goldenseal has another major constituent hydrastine. Some researchers consider this constituent to be... 

Cech, R., et al. "The Presence of Significant Quantities of Berberine and Hydrastine in the Leaf and Stem of Organically Cultivated Goldenseal (Hydrastis canadensis)." Publication data not available, from a copy of the analysis, 1996. 

Hydrastine, C21H21O6N, is conveniently separated from the mother liquors of plant extracts from which the associated berberine has first been removed as sulfate. It was first encountered in Hydrastis canadensis L. 

A stereospecific conversion of berberine into ( )-/3-hydrastine has been reported. Photolytic oxidation of oxyberberine yields the lactol (123), the N-methyl quaternary salt of which can be reduced with sodium borohydride to give racemic jS-hydrastine in 95% yield. Both phthalide-isoquinolines (e.g. adlumine) and spirobenzylisoquinolines e.g. corydaine) have been synthesized from /3-phenethylamines and methylenedioxyphthalide carboxylic acid (124). Several ethers of narcotoline have been prepared and converted into derivatives of nornarceine. The biotransformation of narcotine in rats has been examined and di-O-desmethylnarcotine, cotarnine, hydrocotarnine, oxocotarnine, and O-demethylmeconine have been isolated from urine. " Bicuculline, which has... 

From greater celandine (Chelidonium majus), widespread in Central Europe, such alkaloids as sanguinarine, cholidonine, hydrastine, berberine, and chelerythine have been isolated. Ph5rtochemical investigation of... 

Wi iewski W, Gorta T (1966) Separation of berberine, hydrastine and hydrastinine from rhizomes of Hydrastis Canadensis and from the liquid extract. Acta Pol Pharm 23 455... 

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