D-tetrahydropalmatine

Corydalis decumbens (Thunb.) Pers. Xia Tian Wu (aerial part) Protopine, bulbocapnine, d-tetrahydropalmatine.33-240 Toxic if overdosage. Relieve pain after bone fractures, antihypertensive, antirheumatic. 

C. decumhena Fers. Bulbocapnine (38) Dehydrocorydaline (88) d-Tetrahydropalmatine (38) Protopine (38, 39)... 

C. poAlida (Thunb.) Pere. Corypalline (44) Capauridine (45) Capaurimine (45) Capaurine (45) Scoulerine (45) d-Tetrahydropalmatine (45) di-Tetrabydropalmatine (45) FSl, CttHwOgN, m.p. 171" (45), yields dl-tetrahydro-palmatine on methyls-tion Protopine (45)... 

Constitution. d-Scoulerine, C19H21O4N, contains two methoxyl groups, two phenolic hydroxyls, and on methylation yields d-tetrahydropalmatine... 

Columbamine. (Items 1, 6, 9, 11, 18, 22 list, p. 328.) This base probably occurs among the phenolic alkaloids of calumba root, but it has only been isolated in the form of dl-tetmhydrocolutnbamine, Ci,H] gN(OH)(OMe)g, m.p. 223-4° (p. 291), which on methylation furnishes d tetrahydropalmatine. 

According to Huang-Minlon, Makoshi s base (I) is coptisine, while Chou s base, B, is dl-tetrahydropalmatine and D and E are I- and dl-tetrahydrocoptisine respectively. 

Jatrorrhizine (Jateorhizine). (Items 6, 9, 11, 14, 18, 19, 21, 22 list, p. 329.) The iodide, C20H20O4NI. H2O, crystallises in reddish-yellow needles, m.p. 210-2° the chloride C20H20O4NCI. H2O, forms copper-coloured needles, m.p. 206°, and the nitrate golden-yellow needles, m.p. 225° (dec.). On 0-methylation, jatrorrhizine iodide yields palmatine iodide, and on reduction it is converted into dZ-tetrahydrojatrorrhizine, m.p. 217-8°, the d-form of which is corypalmine and which on 0-methylation yields tetrahydropalmatine (p. 292). ... 

Vauquelin G, De Keyser J, Banyingela K, Vanhaelen M. ( )Tetrahydroanisocycline and ( )tetrahydropalmatine binding to D and D2 dopaminergic receptors in human putamen. Neurochem Int 1989 15 321-324. 

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. 

Descretamine, C19H21O4N (mp 221°-224° [ ]d —368° in pyridine), eontains two methoxyl groups and two phenolic hydroxyl functions. Methylation with diazomethane gave (— )-tetrahydropalmatine, which implies that descretamine is a bisdemethyl (— )-tetrahydropalmatine (see Section X) isomeric with (— )-scoulerine (XLVI). At the time of writing the location of the hydroxyl groups has not been determined. 

Tetrahydropalmatine yields a hydrochloride which is moderately soluble in boiling water and only sparingly soluble in cold water. This property, together with the fact that the hydrochloride is readily extractable from hydrochloric acid solutions of plant extracts by means of chloroform, renders its isolation and purification a simple procedure. The hydrochloride of the dZ-form is appreciably less soluble than that of the d- or Z-forms and separates in stout prisms even from hot aqueous solutions. The alkaloid is readily oxidized by air and slowly becomes yellow owing to the formation of palmatine. This oxidation can be readily completed by means of alcoholic iodine solutions when palmatine iodide is formed, or it may be brought about by heating in dilute acetic acid with mercuric acetate (224). 

Structure and Synthesis. In addition to the proof of the structure of tetrahydropalmatine by virtue of its preparation from palmatine and the reverse oxidation, the resolution of the dZ-base was accomplished by means of d- and Z-tartaric acids in succession, the d-base d-tartrate and the Z-base Z-tartrate being the forms of least solubility (225). The d- and Z-bases had [a]n +291° (ethanol) and —294° (ethanol), respectively, the natural d-base having [a] +292.5° (58). Spath and Mosettig (226) have also related tetrahydropalmatine directly to tetrahydroberberine, that is to canadine. The d-, Z-, and dZ-forms of canadine were demethylenated by means of phloroglucinol and sulfuric acid yielding the base XXX in its three possible forms, the d-form having +307° (ethanol). These when... 

At the time of its discovery there was not available enough d-isocory-palmine for the determination of its structure by degradative methods, but Spath and Mosettig (231) prepared it from d-canadine by, first, de-methylenation to XiXXVI (2,3-dihydroxy-9,10-dimethoxytetrahydro-protoberberine, m.p. 252-253°) by means of phloroglucinol and sulfuric acid and, then, by incomplete methylation with diazomethane. In addition to the non-phenolic tetrahydropalmatine, there was formed a separable mixture of d-corypalmine and d-isocorypalmine (XXXVTI),... 

C. solida (L.) Swartz. Protopine, allocryptopine, d stylopine, d- and dZ-tetrahydropalmatine, d-canadine, aurotensine, corydaline, 22, 23... 

An alkaloid, D, with virtually identical properties was isolated from Argemone munita and its identity with muramine seemed probable. A comparison of the two specimens confirmed this identity. In the meantime a repeat synthesis from tetrahydropalmatine has confirmed the... 

---