Phenanthridine, hydroxy

Hydroxy-phenanthridin ist das Hauptprodukt der Reduktion von 2-Nitro-2 -carb-oxy(bzw. athoxycarbonyl)-biphenyl in waBrig athanolischer Losung an Quecksilber1 ... 

Pezzuto, J. M., Antosiak, S. K., Messmer, W. M., Slaytor, M. B. and Honig, G. R. 1983. Interaction of the antileukemic alkaloid, 2-hydroxy-3,8,9-trimethoxy-5-methylbenzo[c]phenanthridine (fagaronine) with nucleic acids. Chemistry and Biology Interaction, 43 323-339. 

Hydroxy-8,9-methylenedioxyphenanthridine, [10]. The method developed by Kessar et al. [11] for phenanthridines and related compounds was applied to the synthesis [10] of 3-hydroxy-8,9-methylenedioxyphenanthridine (22) (Scheme 5). Thus, the benzylidene aniline 23, prepared from 6-chloropiperonal and 3-benzyloxyaniline, was reduced to the secondary amine 24. Treatment of 24 with excess lithium diisopropylamide furnished, on work-up, the benzyl ethers 25 (22%) and 26 (6%) respectively. Catalytic debenzylation of the former generated 22. 

Takao and co-workers (60) have examined a number of hydro-benzo[c]phenanthridine alkaloids and their derivatives by a variety of physical methods in order to determine the conformation of the B/C rings (Fig. 18). The 13C chemical shifts (Table XVII) were particularly sensitive to the influence of substituents on the conformation of the B and C rings. Chelidonine (94) for example, with a cis ring junction, has both the B and C rings as half-chairs [see Fig. 1 in (60)]. Acetylation of the hydroxy l group to form 95 shielded C-6, C-12, and C-13 relative to 94. The interpretation of these observations was that ring C in 94 adopted a twist half-chair conformation which increased the number of gauche interactions for these carbons. 

Hydroxy-6-methyl-7,8,9,10-tetrahydrophenanthridine methio-dide is formed directly by the action of methyl iodide on the corresponding base.168 In an interesting reaction with acrylamide in methanolic hydrogen chloride, phenanthridine gives AT-(2-carbamoyl-ethyl)phenanthridinium chloride.288... 

The reaction between phenanthridine-5-oxide and ethyl acrylate takes an entirely different course leading to the isoxazolidine (217), and then to ethyl l-hydroxy-2-(6-phenanthridinyl)propionate.307... 

Phenanthridin 6-Hydroxy-1,2,3,4-tetrahydro- E19a, 1030 (Ar —Br + Enolat/+ Cyclo-kond.)... 

On the route to benzo[c]phenanthridine alkaloids [37], naphthol 51 (Scheme 20) was 0-alkylated with 2-bromo-2-methylpropionoamide under forcing conditions to give 52 in 93% yield. The rearrangement of 52 was executed with sodium hydride in DMF-DMPU and the hydroxy-amide 53 was hydrolyzed to give the aminonaphthyl derivative 54. 

From 7-hydroxy-5-methyl-10,10a-dihydro-SH,6aH-phenanthridine-6,9-dione. Abass and Othman (01SC3361) heated phenanthridine-6,9-dione 401 with hydrazine hydrate in 7S7,N-dimethylformamide to afford 3-(3-oxopyrazol-3-yl)quinolin-2-one 402, in 92% yield (Scheme 90). 

The U.V., i.r., and H n.m.r. absorptions of 1000 simple aromatic compounds substituted by hydroxy-, methoxy-, and methylenedioxy-groups have been collected as a possible aid to identification of alkaloid degradation products. Homobenzylic and homoallylic spin-spin coupling interactions in some octahydro- and hexahydro-phenanthridines have been discussed. 

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