13124-15-7

Upstream product

• 95-76-1 m,p-dichloroaniline 
• 19763-90-7 3,4-dichlorophenylhydrazine hydrochloride 
• 541-41-3 chloroformic acid ethyl ester 
• 78521-69-4 N-(3-hydroxybutyl)-4-methylbenzenesulfonamide 
• 13124-18-0 3,4-dichlorophenylhydrazine 

Downstream Products

• 84282-70-2 N'-(3,4-Dichloro-phenyl)-N'-(piperidine-1-carbonyl)-hydrazinecarboxylic acid ethyl ester 
• 84282-69-9 C₁₄H₁₉Cl₂N₃O₃ 
• 84282-85-9 2-(3,4-dichlorophenyl)-2-<(methylthio)carbonyl>hydrazinecarboxylic acid ethyl ester 
• 84282-84-8 1-(3,4-dichlorophenyl)hydrazinecarboxylic acid methyl ester 
• 36012-23-4 2-(3,4-dichloro-phenyl)-4,4-dimethyl-semicarbazide 
• 84282-77-9 Piperidine-1-carboxylic acid N-(3,4-dichloro-phenyl)-hydrazide 
• 84282-76-8 4,4-diethyl-2-(3,4-dichlorophenyl)semicarbazide 
• 103722-67-4 C₁₂H₁₅Cl₂N₃O₃ 
• 84282-57-5 3-(3,4-Dichloro-phenyl)-5-ethoxy-3H-[1,3,4]oxadiazol-2-one 

Relevant academic research and scientific papers

Systematic Evaluation of 2-Arylazocarboxylates and 2-Arylazocarboxamides as Mitsunobu Reagents

2-Arylazocarboxylate and 2-arylazocarboxamide derivatives can serve as replacements of typical Mitsunobu reagents such as diethyl azodicarboxylate. A systematic investigation of the reactivity and physical properties of those azo compounds has revealed that they have an excellent ability as Mitsunobu reagents. These reagents show similar or superior reactivity as compared to the known azo reagents and are applicable to the broad scope of substrates. pKa and steric effects of substrates have been investigated, and the limitation of the Mitsunobu reaction can be overcome by choosing suitable reagents from the library of 2-arylazocarboxylate and 2-aryl azocarboxamide derivatives. Convenient recovery of azo reagents is available by one-pot iron-catalyzed aerobic oxidation, for example. SC-DSC analysis of representative 2-arylazocarboxylate and 2-arylazocarboxamide derivatives has shown high thermal stability, indicating that these azo reagents possess lower chemical hazard compared with typical azo reagents.

Aerobic Oxidation of Alkyl 2-Phenylhydrazinecarboxylates Catalyzed by CuCl and DMAP

Recently, various fruitful organic reactions such as a catalytic Mitsunobu reaction were reported by virtue of alkyl 2-phenylazocarboxylates, however, the synthesis of alkyl 2-phenylazocarboxylates largely depended on the stoichiometric use of toxic oxidants. In this manuscript, an environment-friendly aerobic oxidative transformation of alkyl 2-phenylhydrazinecarboxylates to alkyl 2-phenylazocarboxylates is disclosed. The use of CuCl and DMAP system efficiently catalyzed the aerobic oxidation of alkyl 2-phenylhydrazinecarboxylates under mild conditions. The reaction rate of the present Cu-catalysis was much faster than that of the previously reported Fe-catalysis, and a variety of azo products were synthesized within 3 h. The present protocol was effective on larger scale. It was observed that the produced azo compound could undergo various reactions without isolation through one-pot sequential protocols.

Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents

Ethyl 2-arylhydrazinecarboxylates can work as organocatalysts for Mitsunobu reactions because they provide ethyl 2-arylazocarboxylates through aerobic oxidation with a catalytic amount of iron phthalocyanine. First, ethyl 2-(3,4-dichlorophenyl)hydrazinecarboxylate has been identified as a potent catalyst, and the reactivity of the catalytic Mitsunobu reaction was improved through strict optimization of the reaction conditions. Investigation of the catalytic properties of ethyl 2-arylhydrazinecarboxylates and the corresponding azo forms led us to the discovery of a new catalyst, ethyl 2-(4-cyanophenyl)hydrazinecarboxylates, which expanded the scope of substrates. The mechanistic study of the Mitsunobu reaction with these new reagents strongly suggested the formation of betaine intermediates as in typical Mitsunobu reactions. The use of atmospheric oxygen as a sacrificial oxidative agent along with the iron catalyst is convenient and safe from the viewpoint of green chemistry. In addition, thermal analysis of the developed Mitsunobu reagents supports sufficient thermal stability compared with typical azo reagents such as diethyl azodicarboxylate (DEAD). The catalytic system realizes a substantial improvement of the Mitsunobu reaction and will be applicable to practical synthesis.

Recyclable mitsunobu reagents: Catalytic mitsunobu reactions with an iron catalyst and atmospheric oxygen

Aerobic recycling: A catalytic amount of a hydrazine reagent is sufficient to promote Mitsunobu reactions in the presence of triphenylphosphine, an iron catalyst, and air. The active form of the catalyst, an azo species, can be readily generated by iron-c

AN EFFICIENT METHOD FOR THE CONVERSION OF ARYLHYDRAZINES INTO 2-ARYL-4,4-DIALKYLSEMICARBAZIDES

Arylhydrazines are converted into 2-aryl-4,4-dialkylsemicarbazides by subsequent reaction with chloroformate, phosgene, dialkylamine, and alkaline hydrolysis.