Chelirubine

Figure 11.28 shows densitograms from the separation of Chelidonium majus quaternary alkaloids [114]. It is clearly apparent that multiple development results in better separation of the component bands. Threefold development results in separation or partial separation of eight alkaloid bands (Figure 11.28b), whereas after one run, only four zones — chelirubine, sanguinarine, chelilutine, and chelerithrine... 

Synthesis of 216, an analog of the amide alkaloids, starting with ketone 214 was performed by Ishii et al. (176) (Scheme 33). The initial step involved the formation of cis secondary amine 215, which on N-formylation and dehydrogenation led to 216. Under Bischler-Napieralski conditions 216 could be recyclized to chelirubine (217). 

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. 

Chelirubine. Although all of the 2,3,7,8,x-pentasubstituted alkaloids have been synthesized only recently, their synthetic routes had been hampered by the ambiguity of the structures of these alkaloids, particularly with respect to the positions of the substituents on the rings (90). The structure of cheliru-... 

The enamide 73 was prepared from 2,3-dimethoxy-5,6-methylenedioxy-benzoic acid and 6,7-methylenedioxy-l-tetralone, and was then irradiated to afford the lactam 74 in 38% yield. On acid treatment 74 was converted to the dehydrolactam 75 as a result of the elimination of the migrated meth-oxyl group. Dehydrogenation with 30% Pd/C, reduction with vitride, followed by treatment with DDQ, completed total synthesis of chelirubine (76) 91,92) (Scheme 43). 

In addition to the study of the bis-benzo[c]phenanthridines just discussed above, Marek and coworkers have also extensively studied other benzojcjphenanthridine alkaloids [111,121]. The structures of the alkaloids for which data have been reported and their respective chemical shifts are collected in Figure 14.12. These alkaloids include the methyl chloride salts, sanguinarine chloride (110), chelrythine chloride (111), sanguilutine chloride (112) and chelirubine chloride (113). 6-Substituted and... 

The alkaloids sanguinaiine and cbelerythrine are in most cases accompanied by the minor alkaloids chelirubine, chelilutine, sangudutine, sangui-rubine, and, in several plants, macarpine. These minor alkaloids have never been found in the Rutaceae frmily. In contrast, alkaloids of the nitidine type occur exclusively in the Rutaceae and are one of the chemotaxonomic features of some genera. 

The analogous structures and properties of the free bases of the related alkaloids chelerythrine, chelirubine, and chehlutine have been determined [123,124]. The H NMR spectrum of chelerythrine free base (37) is very useful in understanding the structure. 

Tetrahydrocoptisine (H- ) Tetrahydrocoptisine I ( + )-stylopine] Coptisine Chelidonine Chelerythrine Chelirubine Protopine Alloeryptopine Sanguinarine (+ )-Base II Dehydrobase-II (+ )-Corybulbine Dehydrocorybulbine (+ ) Corydaline Dehydrocorydaliiie ( )-Tetrahydropalmatine Palmatine... 

R =OMe, R R =CH2) respectively, followed by y-methylation. (Kessar et al.. Tetrahedron Letters, 1977, 1459 Takao et al.. Heterocycles, 1981, 1, 221). Dihydrochelirubine and cheli-rubine have also been prepared by photochemical cyclisation of the amide (386), which involves the loss of a methoxy group, followed by reduction and dehydrogenation of the resulting di-hydro-compound to chelirubine (Ishii et at., Chem.Pharm.Bul1., 1978, 864). 

Allocryptopine, berberine, chelerythrine, chelirubine, coptisine, protopine, sanguinarine... 

Allocryptopine, chelamidine, chelamine, chelidamine[( — )-stylopine], chelidonine, chelerythrine, chelilutine, chelirubine, coptisine, corysamine, oxysanguinarine, protopine, sanguinarine, sparteine Capaurme + sendaverine (Alkaloid F-28) = Corpaverine Columbamine, coptisine, dehydrocorydalline,... 

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