Protopine alkaloids derivatives

Other alkaloids are codamine, cryptopine, gnoscopine, hydrocotarnine, lanthopine, lauda-nine, laudanosine, meconidine, oxynarcotine, papaveramine, protopine, pseudomorphine, rhoeadine, and tritopine. Many of them occur only in traces, and some are regarded as probable derivatives of morphine. Porphyroxin is said to be a complex combination of several of the alkaloids, and not a proximate principle (Potter, 1910). 

The probability63 that (69) lies along the pathway to protoberberine and derived alkaloids, between scoulerine (65) and stylopine (70), has been supported by the observation that tritiated (69) is a precursor for protopine (73), and also for corynoline (78).64 Evidence previously obtained for the intermediacy of the metho-salt of stylopine [as (71)] in the biosynthesis of chelidonine (62)63 and protopine (73)63,65 has been affirmed, and it is apparently the a-form (71) and not the /3-form that is involved. [The authors are mistaken in assuming that ( —)-stylopine has the R-configuration at C-14 cf. ref. 63]. 

In 1890, Kauder (93b) worked up the mother liquors of protopine oxalate and isolated an alkaloid which he named tritopine. It was soluble in alkali, and its analysis and color reactions made likely its relation to the monophenolic laudanosine derivatives. Spath and Seka (97) obtained a sample of tritopine, probably from Kauder s original collection, and determined its correct formula, CjoH26N04. It melted at 184° (evac. tube) and exhibited [a] —85.7° (in chloroform). A comparison of tritopine and its salts with (—)-laudanidine and its corresponding salts established the identity of the two samples. 

Aliev KHU, Kamilov IK 1967 Pharmacology of the alkaloid protopine and its derivatives. Farmakol Alkaloidov Glikozidov pp. 176-178... 

At the subcellular level, the morphine biosynthetic pathway combines several cytochrome P-450 enzymes, bound to ER membranes (Chou and Kutchan, 1998) with soluble enzymes that reside in ER derived vesicles, e.g. norcoclaurine synthase, or in the cytosol, e.g. codeinone reductase (Zenk, 1994 Facchini and St-Pierre, 2005). The diverse localization of the biosynthetic enzymes requires several transport steps of the intermediates between cytosol, vesicles and vacuoles. Only one of them has been characterized by pioneering experiments (Deus-Neumann and Zenk, 1986) vacuolar vesicles prepared from Fumaria capreolata accumulate (S)-reticulin or (S)-scoulerin via highly specific transporters, that discriminate between (S)- and (R) stereoisomer and exclude other benzylisoquinolines (sanguinarine, protopine, morphine) and alkaloids of unrelated families (e.g. indoles or tropanes). Uptake is energized by the pH gradient across the tonoplast. Accumulated... 

Barton DHR, Cohen T (1957) In Festschrift Dr A Stoll, Birkhauser, Basel, p 117 Barton DHR, Kirby GW, Taylor JB, Thomas GM (1963) Phenol oxidation and biosynthesis, part VI. The biogenesis of amaryllidaceae alkaloids. J Chem Soc 4545—4558 Barton DHR, Hesse RH, Kirby GW (1965) Phenol oxidation and biosynthesis, part VIII. Investigations on the biosynthesis of berberine and protopine. J Chem Soc 6379-6389 Barton DHR, Bracho RD, Potter CJ, Widdowson DA (1974) Phenol oxidation and biosynthesis, part XXIV. Origin of chirality in the erythrinan system and derivation of the lactone rings of a- and ]3-erythroidine. J Chem Soc Perkin Trans 1 2278-2283 Basmadjian GP, Paul AG (1971) The isolation of an O-methyltransferase from peyote and its role in the biosynthesis of mescaline. Uoydia 34 91-93 Basmadjian GP, Hussain SF, Paul AG (1978) Biosynthetic relationships between phenethylamine and tetrahydroisoquinoline alkaloids in peyote. Lloydia 41 375-380 Battersby AR, Binks R, Francis RJ, McCaldin DJ, Ramuz H (1964) Alkaloid biosynthesis, part IV. 1-Benzylisoquinolines as precursors of thebaine, codeine and morphine. J Chem Soc 3600-3610... 

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