Benzimidazoles reactions

H-Pyrido[3,2-c]azepine, 7-methoxy-nucleophilic displacement reactions, 7, 514 Pyridoazepines synthesis, 7, 535, 540 Pyridoazepinones synthesis, 7, 531 Py rido[2,1-a]benzazepin-6-one physiological properties, 7, 546 Py rido[ 1,2-a]benzimidazoles reactions, 6, 1041... 

From these examples, the versatility of 1,3-cycloaddition reactions in the synthesis of 1,2,3-triazoles is apparent. Other strategies, however, are available. Greif and coworkers developed perfluoroalkyl-substituted p-chlorovinylaldehydes as new building blocks for a number of fluorinated heterocyclic systems such as thiazoles, pyridines, pyrazoles, and benzimidazoles. Reaction of the chlorovinylaldehydes with sodium azide leads to the formation of moderate to good yields of 4-perfluor-... 

Polybenzimidazole polymers can be formed in the melt or in solution. Mechanistic studies have proposed Schiff s base or aminoamide intermediates. Recent texts on high temperature polymers discuss benzimidazole reaction mechanisms with references to original works [1.2]. 

Phenylbenzimidazole is nitrated first at the 5-position with mixed acid, and subsequent reaction produces 5-nitro-2-(4-nitrophenyl)-and 5-nitro-2-(3-nitrophenyl)-benzimidazole. 2-Phenyl-, 2-(4-nitro-phenyl)- and 5-nitro-2-phenyl-benzimidazole are nitrated as their conjugate acids. ... 

Chemical Reactions of Dyes. Decolorization is important for cyanines used ia imaging materials. Understanding decolorization provides clues to dye reactions that may cause degradation of imaging materials duting preparation and storage. For many dyes, protonation of the methine chain occurs readily and reversibly (64). Highly basic carbocyanine dyes like those from benzimidazole (eg, 36) protonate so readily that this provides a practical decolorization method. 

The reactivity of these compounds is somewhat similar to that of the azolonium ions, particularly when the cationic species is involved. However, although the typical reaction is with nucleophiles, the intermediate (20) can lose the iV-oxide group to give the simple a-substituted azole (21). Benzimidazole 3-oxides are readily converted into 2-chloroben-... 

N-Unsubstituted pyrazoles and imidazoles add to unsaturated compounds in Michael reactions, for example acetylenecarboxylic esters and acrylonitrile readily form the expected addition products. Styrene oxide gives rise, for example, to 1-styrylimidazoles (76JCS(P1)545). Benzimidazole reacts with formaldehyde and secondary amines in the Mannich reaction to give 1-aminomethyl products. 

Imidazoles and benzimidazoles (155) react with acid chloride and alkali to give compounds of type (157), but these are reactions of the cation (156). 1,2,4-Triazoles and tetrazoles similarly undergo ring opening. 

Benzimidazole 3-oxides, e.g. (189), react with phosphorus oxychloride or sulfuryl chloride to form the corresponding 2-chlorobenzimidazoles. The reaction sequence involves first formation of a nucleophilic complex (190), then attack of chloride ions on the complex, followed by rearomatization involving loss of the fV-oxide oxygen (191 -> 192). 

Substituted imidazoles can be acylated at the 2-position by acid chlorides in the presence of triethylamine. This reaction proceeds by proton loss on the (V-acylated intermediate (241). An analogous reaction with phenyl isocyanate gives (242), probably via a similar mechanism. Benzimidazoles react similarly, but pyrazoles do not (80AHC(27)24l) cf. Section 4.02.1.4.6). 

The phototransposition reaction in the isoindazole series (187) to give benzimidazoles (188) has been carefully investigated when R = Me, Et, Pr , Bu, Bz and Ph (67HCA2244). The reaction is sensitive to steric effects thus for r = Bu and R = Me, the l-t-butyl-7-methylbenzimidazole is not formed. 

The photolysis of 1,2-benzisoxazole in the absence of air in acetonitrile gave salicylonitrile and benzoxazole (67AHC(8)277). When air-saturated acetonitrile was employed, 2,2 -dimeriz-ation to (38) occurred, accompanied by benzoxazole. Photolysis of the 2,2 -dimer (38) and benzoxazole did not alter the ratio, thus indicating that neither one arose from the other. Selective excitation also ruled out dimer formation from benzoxazole under the reaction conditions (Scheme 9). This dimerization is similar to that observed for benzimidazole, except that in that series no 2,2 -dimerization was observed (74TL375). 

Benzimidazo[2,1 -a]isoquinolines synthesis, 5, 161 Benzimidazole, 1-acetyl-reactions... 

Benzimidazole, 2-alkoxy-l-methyl-transalkylation, 5, 443 Benzimidazole, 1-alkyl-metal derivatives, 5, 448 reactions... 

Benzimidazole, 2-amino-5-bromo-l-methyl-diazo coupling, 5, 429 Benzimidazole, 2-amino-6-bromo-1 -methyl-diazo coupling, 5, 429 Benzimidazole, 2-amino-1-ethyl-alkylation, 5, 438 Benzimidazole, 2-amino-1-methyl-acylation, 5, 438 bromination, 5, 429 tautomerism, 5, 368 Benzimidazole, 4-amino-2-methyl-diazo coupling, 5, 429 Benzimidazole, 2-aroyl-mass spectra, 5, 360 Benzimidazole, 1-aryl-metallation, 5, 448 reactions... 

Benzimidazole, IV-aryl-reactions, 5, 448-449 Benzimidazole, 2-aryl-1-methyl-reactions,... 

Benzimidazole, 3-( o-hydroxyphenyl)-synthesis, 5, 158 Benzimidazole, 1-isopropyl-reactions... 

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