Quinolizinium , 1-, 2-, 3-hydroxy

Quinolizinium bromide, l-bromo-2-hydroxy-hydrogenolysis, 2, 546 synthesis, 2, 542... 

Quinolizinium hydroxide, 3-amino-l-hydroxy-synthesis, 2, 543 Quinolizinium iodide C-hydroxylation, 2, 531 reduction, 2, 535... 

Quinolizinium salts, 2-amino-l-hydroxy-diazotization, 2, 542 Quinolizinium salts, l-amino-3-methyl-diazotization, 2, 542 Quinolizinium salts, 2-bromo-synthesis, 2, 544 Quinolizinium salts, carboxy-anhydrides... 

Product was 10-hydroxy-9-methoxy-2,3-methylenedioxydibenzo[a,g]quinolizinium bromide. d Although evidence was offered in support of the structure shown, later evidence (70YZ82) has raised serious doubts about the structure of the product obtained in example 18. e Product isolated was the 2,3-methylenedioxy-9-amino-10-methoxy salt. 

Using the more versatile tool of aromatic cyclodehydration (Scheme 98), Sawa and Ikekawa have prepared a variety of dibenzo[a,g]quinolizinium derivatives for use in cancer chemotherapy. Their results are described in a large number of Kokai (e.g. 75JAP(K)75154295). From these, it is clear that the compounds of greatest interest bear a hydroxy group or hydroxy derivative at position 8. In a German patent (75GEP2520524) it was claimed that 8-hydroxy-9-methoxydibenzo[a,g]quinolizinium bromide (231) increased the survival time of mice infected with sarcoma 180 and leukemia 1210 by 100% and 240% respectively. 

Dihydro-3-hydroxy-2,9,10-trimethoxy-13-methyl-dibenzo-[a,g]-quinolizinium Dehydrocorybulbine... 

The conversion of 1-hydroxyquinolizinium bromide (187 R = R = H, X = Br) into three quinolizinium-l-olate derivatives (186) has been achieved as follows (i) Treatment with aqueous sodium carbonate gives the hydrated betaine (186 R = R = H) as a yellow solid (ii) brief reaction with hot dilute nitric acid gives red needles of the 4-bromo-2-nitro derivative (186 Ri = NO2, R = Br) and (iii) prolonged reaction with hot dilute nitric acid gives the dinitro derivative (186 R = R = NO2). 1-Hydroxyquinolizinium nitrate (187 R = R = H, X = NO2) and dilute nitric acid give the 2-nitro derivative(186 R = NO2, R = H). Betaine 186(R = Me, R = H) has been detected in aqueous solutions of l-hydroxy-2-methylquinolizinium bromide (187 R = Me. R = H). ° ... 

Hydroxyquinolizines have been reported only recently. In this connection the salts of 4-quinolizone may be considered as 4-hydroxy-quinolizinium derivatives. Boekelheide and Lodge18 hydrolyzed and decarboxylated I,3-dicarbethoxy-4-quinolizone (6) to the free quino-lizone (7) and found that the compound had the characteristics of the quinolizinium cation 8 as indicated by the identity of the ultraviolet spectra determined in neutral and acidic media. 

Quinolizinium picrate, 2-bromo-l-hydroxy-synthesis, 2, 543 Quinolizinium salts applications, 2, 569-570 deuteration, 2, 531 IR spectra, 2, 527 mass spectra, 2, 529 nucleophilic reactions, 2, 531 photodimerization, 2, 536 polymers, 1, 312 reactions... 

Table 7 Synthesis of 1-Hydroxy quinolizinium Bromides (174 Scheme 95)...

---