59871-40-8

Upstream product

• 5442-34-2 ethyl 2-phenylacetimidate hydrochloride 
• 4760-34-3 N-methyl-1,2-phenylenediamine 
• 4344-61-0 1-methyl-2-(methylthio)-1H-benzimidazole 
• 62673-31-8 benzyl(bromo)zinc 
• 536-74-3 phenylacetylene 
• 1632-83-3 1-Methylbenzimidazole 
• 64-04-0 phenethylamine 
• 2876-08-6 1,2-dimethyl-1H-benzimidazole 
• 108-86-1 bromobenzene 
• 103-82-2 phenylacetic acid 
• 621-72-7 2-benzylbenzimidazole 
• 77-78-1 dimethyl sulfate 
• 80504-61-6 benzylthiophenylacetimidate 
• 39496-45-2 methyl imini ester hydrochloride of phenylacetic acid 

Downstream Products

• 13745-35-2 (1-methyl-1H-benzo[d]imdiazol-2-yl)(phenyl)methanone 
• 1237776-30-5 1-methyl-2-(1-phenylethyl)-1H-benzo[d]imidazole 
• 1222-07-7 1-(1-methyl-1H-benzo[d]imidazol-2-yl)-1-phenylethanol 

Relevant academic research and scientific papers

Reactivity of TpMe2-supported yttrium alkyl complexes toward aromatic n-heterocycles: Ring-opening or C=C bond formation directed by C-H activation

Unusual chemical transformations such as three-component combination and ring-opening of N-heterocycles or formation of a carbon-carbon double bond through multiple C-H activation were observed in the reactions of Tp Me2-supported yttrium alkyl complexes with aromatic N-heterocycles. The scorpionate-anchored yttrium dialkyl complex [TpMe2Y(CH 2Ph)2(THF)] reacted with 1-methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24-membered rare-earth metallomacrocyclic compound [TpMe2Y(μ-N,C-Im)(η2-N,C-Im)]6 (1; Im=1-methylimidazolyl) through two kinds of C-H activations at the C2- and C5-positions of the imidazole ring. However, [TpMe2Y(CH 2Ph)2(THF)] reacted with two equivalents of 1-methylbenzimidazole to afford a C-C coupling/ring-opening/C-C coupling product [TpMe2Y{η3-(N,N,N)-N(CH3)C 6H4NHCH=C(Ph)CN(CH3)C6H 4NH}] (2). Further investigations indicated that [Tp Me2Y(CH2Ph)2(THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C-C coupling/ring-opening product {(TpMe2)Y[μ-η2:η1-SC 6H4N(CH=CHPh)](THF)}2 (3). Moreover, the mixed TpMe2/Cp yttrium monoalkyl complex [(TpMe2)CpYCH 2Ph(THF)] reacted with two equivalents of 1-methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [Tp Me2CpY(μ-N,C-Im)]3 (5), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [TpMe2Y(Im-TpMe2)] (7; Im-Tp Me2=1-methyl-imidazolyl-TpMe2) and [Cp3Y(HIm)] (8; HIm=1-methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a C=C bond through multiple C-H activations. Copyright

Preparation of 1,2-substituted benzimidazolesviaa copper-catalyzed three component coupling reaction

1,2-Substituted benzimidazoles were prepared by simply stirring a mixture of copper catalysts,N-substitutedo-phenylenediamines, sulfonyl azides and terminal alkynes. Particularly, the intermediateN-sulfonylketenimine occurred with two nucleophilic addition and the sulfonyl group was eliminatedviacyclization. In a way, sulfonyl azides and copper catalysts activated the terminal alkynes to synthesize benzimidazoles.

Reactions of 2-carbonyl- And 2-hydroxy(or methoxy)alkylsubstituted benzimidazoles with arenes in the superacid CF3SO3H. NMR and DFT studies of dicationic electrophilic species

Reactions of 2-carbonyl- and 2-hydroxy(or methoxy)alkylbenzimidazoles with arenes in the Br?nsted superacid TfOH resulted in the formation of the corresponding Friedel-Crafts reaction products, 2-diarylmethyl and 2-arylmethyl-substituted benzimidazoles, in yields up to 90%. The reaction intermediates, protonated species derived from starting benzimidazoles in TfOH, were thoroughly studied by means of NMR and DFT calculations and plausible reaction mechanisms are discussed.

A general approach to substituted benzimidazoles and benzoxazoles via heterogeneous palladium-catalyzed hydrogen-transfer with primary amines

The synthesis of benzimidazoles starting from o-phenylenediamines and amines in the presence of palladium on charcoal as catalyst is reported. Under microwave dielectric heating it is possible to use a tertiary, a secondary, and even a primary amine as the substrate for a palladium-mediated process to get 2-substituted or 1,2-disubstituted benzimidazoles, depending on the nature of the o-phenylenediamine employed. Primary amines are the most suitable reagents for the atom economy of the overall process that resulted to be general as several different substituted benzimidazoles were obtained in good yield. Benzoxazoles can be also prepared starting from primary amines and o-aminophenol. The reaction is also highly selective as no (poly)-alkylated phenylenediamines or cross-contaminated benzimidazoles are obtained starting from N-monoalkylphenylenediamines. This behavior was interpreted as a scarce aptitude to dehydrogenation of the methylene bonded to the aromatic NH of N-alkylarylamines. The experiments carried out consent to draw an almost complete picture of the reaction pathways occurring during the process. The catalyst can be recycled several times and, although far from optimal performances, catalyst TON=90 is encouraging for further large-scale optimization protocols. In addition, the palladium on charcoal-catalyzed microwave-assisted reaction of o-phenylenediamine gives de-alkylation of tertiary amines and transformation into the secondary ones. Copyright

A general approach to substituted benzimidazoles and benzoxazoles via heterogeneous palladium-catalyzed hydrogen-transfer with primary amines

The synthesis of benzimidazoles starting from o-phenylenediamines and amines in the presence of palladium on charcoal as catalyst is reported. Under microwave dielectric heating it is possible to use a tertiary, a secondary, and even a primary amine as the substrate for a palladium-mediated process to get 2-substituted or 1,2-disubstituted benzimidazoles, depending on the nature of the o-phenylenediamine employed. Primary amines are the most suitable reagents for the atom economy of the overall process that resulted to be general as several different substituted benzimidazoles were obtained in good yield. Benzoxazoles can be also prepared starting from primary amines and o-aminophenol. The reaction is also highly selective as no (poly)-alkylated phenylenediamines or cross-contaminated benzimidazoles are obtained starting from N-monoalkylphenylenediamines. This behavior was interpreted as a scarce aptitude to dehydrogenation of the methylene bonded to the aromatic NH of N-alkylarylamines. The experiments carried out consent to draw an almost complete picture of the reaction pathways occurring during the process. The catalyst can be recycled several times and, although far from optimal performances, catalyst TON=90 is encouraging for further large-scale optimization protocols. In addition, the palladium on charcoal-catalyzed microwave-assisted reaction of o-phenylenediamine gives de-alkylation of tertiary amines and transformation into the secondary ones. Copyright

Pd(0)-catalyzed diarylation of sp3 C-H bond in (2-azaaryl)methanes

A highly efficient and selective palladium-catalyzed diarylation of (2-azaaryl)methanes at the methyl group is described. Aryl chlorides proved reactive enough. A palladium η3-azaallyl intermediate has been identified on the basis of DFT studies.

Microwave-assisted one step high-throughput synthesis of benzimidazoles

One-pot synthesis of benzimidazoles from diamines and carboxylic acids was developed under microwave irradiation condition, which provided a practical and efficient method for high-throughput synthesis of this important class of heterocyclic compounds.

Smart cleavage reactions: The synthesis of benzimidazoles and benzothiazoles from polymer-bound esters

The preparation of an array of benzimidazoles and benzothiazoles from polymer-bound esters is described. Polymer-bound esters were treated with 2-aminothiophenols or 1,2-phenylenediamines in the presence of a Lewis acid to afford the corresponding benzothiazole or benzimidazole cleavage products. The reaction of 2-aminophenols with the polymer-bound esters failed to give the desired benzoxazole products using this procedure.

Palladium-catalyzed cross-coupling of benzylzinc reagents with methylthio N-heterocycles: A new coupling reaction with unusual selectivity

Benzylzinc reagents undergo palladium-catalyzed cross-coupling reactions with methylthio-substituted N-heterocycles in moderate to good yields. 2- (Methylthio)pyrimidines are particularly reactive substrates for this reaction. As a result, the regioselectivity of 2,4-bis(methylthio)pyrimidines is opposite to that of their 2,4-dichloropyrimidine analogues. This unusual cross-coupling reaction offers new flexibility in the regioselective synthesis of substituted pyrimidines and other heterocycles.

Diheteroarylmethanes. 5. E-Z isomerism of carbanions substituted by 1,3-Azoles: 13C and 15N π-charge/shift relationships as source for mapping charge and ranking the electron-withdrawing power of heterocycles

Previously proposed π-charge/shift relationships have been applied to 13C and 15N shifts of the carbanions of 2-benzylazoles (thiazole, oxazole, and imidazole), their corresponding benzo-fused analogs, and bis(2-azolyl)methanes (azol