Allocryptopine

Allocryptopine, C21H23O6N, like protopine occurs in two allotropic modifications, the a-form melting at 160° and the /3-form melting at 170°. The older names of and 7-homochelidonine were based upon an assumed relation to chelidonine and are no longer acceptable. It is readily separable from protopine, with which it is nearly always associated, by reason of the fact that its hydrochloride and nitrate are readily soluble in water. It may also be separated from many associated alkaloids by extracting an aqueous solution of their hydrochlorides with chloroform (34). The protopine alkaloids remain in the aqueous phase. 

The free alkaloid is sparingly soluble in methanol and readily soluble in chloroform and crystallizes in stout monoclinic prisms when its solution in chloroform is evaporated to a thin resin and dissolved in boiling methanol. The writer has not encountered the higher-melting /3-modification. 

Allocryptopine has been found in plants outside of the Papaveraceae first by Jowett and Pyman (78) in Zanthoxylum brachyacanthum and then in Z. coco (79), from the latter of which it was first recorded under the name of a-fagarine (80). 

Perkin having recognized certain characteristic reactions for cr3rptopine and protopine, it remained for Gadamer (81) to demonstrate that the same reactions were also characteristic of allocryptopine. Indeed the formation of dihydroberberine methochloride (VII) from allocr3rptopine (XXXIV) 

The synthesis of allocryptopine by Haworth and Perkin (82) was the first application of the process already outlined for cryptopine and protopine. This choice was made because the starting material, tetrahydro-berberine ((XXIX) with the methylenedioxy and the methoxy groups interchanged) was readily available. Furthermore, Pyman (18) had already made a full investigation of the decomposition of the methohydroxide to 

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Bentley and Murray (201) reported another method for synthesis of protopine alkaloids allocryptopine (392) and cryptopalmatine (395) from tetrahydroprotoberberine /V-oxides (35a and 400) through oxidative rearrangement with potassium chromate (Scheme 73). 

Scheme 75. One-step synthesis of allocryptopine (392) from tetrahydroberberine methiodide (1) by photooxygenation. Reagents a, h, 02, Rose Bengal, MeOH. 

Akuammicine 81, 82, 200 Akuammidine 16 Albertidine 103 Albine 34, 100 Alcuronium 38 Alginate 203 Alioline 16, 38 AUcaloid-C 150 Allocryptopine 22 Aloe-emodin 35, 45 Aloperine 103 Alstomacroline 16, 37 Alstomacrophyline 37 Alstonerine 16, 37 Alstophyline 37 Alstoumerine 16, 37 Amabiline 52... 

Alpha-allocryptopine Anti-arrhythmia, local anesthetic, antibacterial... 

Chelidonium album L. C. hybridum L. C. majus L. C. serotinum L. Bai Qu Cai (Celandine poppy) (whole plant) Chelidonine, chelidocystatin, protopine, stylopine, allocryptopine, chelerythrine, sparteine, coptisine.33-256-449-497 Anodyne, analgesic, diuretic, antitussive, detoxicant, anticancer. Treat abdominal pain, peptic ulcers, chronic bronchitis, and whooping cough. 

Macleaya cordata (Willd.) R. Br. Bo Lou Hui (whole plant including root, fruit) Sanguinarine, oxysanguinarine, ethoxysanguinarine, protopine, alpha-allocryptopine, bocconine, chelerythrine, coptisine, herberinecorysamine, bocconoline, ethoxychelerythrine, chelilutine, chelirubine.33 This herb is toxic. Antiplasmodial, treat vaginal trichomonas, antibacterial. 

N.A. Isoquinoline alkaloids, allocryptopine, berberine, chelidonine, sparteine." Analgesic, antispasmodic, lower blood pressure. A mild sedative. 

Corydalis yanhusuo W. T. Wang ex Z. Y. Su et C. Y. Wu China d-corydaline, corydalis, dl-tetrahydropalmatine, crybulbine, alpha-allocryptopine, tetrahydrocoptisine, corydalamine, tetrahydrocolumbamine, protopine, coptisine, dehydrocorydaline, columbamine, dehydrocorydalmine.33 Overdosage is toxic. Analgesic, sedative, hypnotic, synergistic, increase coronary flow. 

Certain berberine alkaloids can also be directly prepared from the appropriately substituted protopine alkaloid by photolysis in ethanol.387 Berberine itself (359) is obtained in this way from a-allocryptopine (360), and similar preparations of epiberberine and coptisine have been recorded. 

Protopine, cryptopine, and allocryptopine have been isolated from Papaver rupifragum,75 protopine and allocryptopine from Glaucium vitellinum,109 Corydalis ophiocarpa,71 and C. cava,70 and protopine from Nandina domestica110 and Thalictrum rugosum,12... 

Allocryptopine has been prepared111 by the photolytic oxidation of tetra-hydroberberine methiodide its antiarrhythmic effects have been studied.112... 

Thus far the pharmacologically investigated alkaloids of this group (protopine, cryptopine, and a-allocryptopine) affect the heart activity. They are active dilators of the coronary vessels (573). After i.v. administration to rabbits and guinea pigs, a slight increase in blood pressure and a greater tendency to the development of cardiac arrhythmia induced by epinephrine are observed. 

Berberine, protopine, allocryptopine, chelerythrine, sanguinarine, and three unidentified bases (12). 

The tested isoquinolines were observed to display a selective inhibition against PI-3 as seen in Table 4, except for (-t-)-isoboldine, (-)-stylopine, and ( )-corydalidzine, that were totally ineffective against both viruses. Protopine, b-allocryptopine, chelidimerine, fumarophycine, a-hydrastine, (-t-)-bulbocapnine, (+)-isoboldine, (-)-sinactine, palmatine, dehydrocoryda-... 

Protopine has been found in Argemone mexicana,110 and allocryptopine in Thalic-trum revolutum,44 Allocryptopine has been prepared by photo-oxidation of tetra-hydroberberine methiodide.101... 

Protopine has been isolated from Bocconia frutescens,110 Fumaria judaica,111 F. schleicheri,112 and Papaver bracteatum,146 cryptopine from F. schleicheri,112 and allocryptopine from B. frutescens110 and Zanthoxylum nitidum.141 The protopine ring-system has been prepared from tetrahydrobenzindenoazepines (75) by photo-oxidation to the amides (76) followed by reduction with lithium aluminium hydride and re-oxidation with manganese dioxide.148-150 The tetrahydrobenzindenoazepines have been prepared from A-chloroacetyl-/ -phenylethylamines (73) by cyclization to the lactam (74) followed by reaction with a benzyl bromide and phosphorus oxychloride. -Protopine (77 R R2 — CH2)148 and fagarine II (77 R1 = R2 = Me)149 have been synthesized in this way. 

Macleaya cordata (Papaveraceae) contains alkaloids in alkaloid cells filled with yellow to orange-red liquid (27). Alkaloid cells were observed as bluish yellow fluorescence in transverse and longitudinal sections of roots of M. cordata with a fluorescence microscope (48). Four main alkaoloids are known to be present in roots of M. cordata, namely, sanguinarine and chelerythrine, which are benzo[c]phenanthridine alkaloids red and yellow in color, respectively, and protopine and allocryptopine, which are colorless protopines. The liquid from colored cells in M. cordata roots was aspirated into the microtrap under a microaspiratoscope. The liquid remaining in the capillary and the connector tubes between the capillary and microtrap was washed into the microtrap with the solvent used for HPLC analysis. It was shown that the liquid of colored cells contained all four alkaloids, judging by comparison with authentic samples on HPLC. Therefore, HC proved the colored cells to be the alkaloid cells named by Neumann and Muller. 

The alkaloid contents in a single alkaloid cell from M. cordata roots of three different thicknesses (age 1-2 years) were determined as follows. The liquid from various numbers of alkaloid cells (Table II) was removed uniformly and collected in the microtrap. The liquid in the capillary and connection tubes was washed into the microtrap to make a certain definite volume for analysis. Quantitative analysis of each alkaloid was carried by preparing a calibration graph (4). Figure 3 shows the HPLC chromatogram of alkaloids from the alkaloid cells. The content of each alkaloid per single alkaloid cell in tissues from three different thickness of roots and its ratio are shown in Table II. The liquid in colorless cells contained only a minute amount of protopine and allocryptopine (Fig. 3). The thicker the roots, the more alkaloids were contained in a single alkaloid cell. In any thickness of root, the content of protopine-type alkaloids exceeded that of benzo[c]phenanthridine-type alkaloids. The ratio of the former to the latter was almost steady over 5 mm of root thickness (86-87%). The ratio of alkaloids in methanol extracts of the same fresh samples (thickness 5 mm) was determined by HPLC (Table III). The ratio of protopine-type alkaloids in the methanol extracts ( 80%) was less than that in the liquid from the alkaloid cells ( 87%). This was because the liquid in alkaloid cells near the cambium were picked up more than that in center cells (pith). Thus, intracellular components scattered in different places are analyzed qualitatively and quantitatively in situ by HC. 

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