76869-92-6

Usage

InChI:InChI=1/C9H11ClN2O2/c1-2-14-9(13)12-11-8-5-3-4-7(10)6-8/h3-6,11H,2H2,1H3,(H,12,13)

Upstream product

• 541-41-3 chloroformic acid ethyl ester 
• 14763-20-3 3-chlorophenyl hydrazine 
• 2312-23-4 m-chlorophenylhydrazine hydrochloride 
• 108-42-9 3-chloro-aniline 

Downstream Products

• 84282-56-4 3-(3-Chloro-phenyl)-5-ethoxy-3H-[1,3,4]oxadiazol-2-one 
• 76869-80-2 C₉H₉ClN₂O₃ 
• 84282-68-8 C₁₄H₂₀ClN₃O₃ 
• 84282-67-7 C₁₂H₁₆ClN₃O₃ 

Relevant academic research and scientific papers

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.

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.