Catalyst system for the aerobic dehydrogenation of alkyl 2-phenylhydrazinecarboxylate derivatives

Eco-friendly asymmetric azo compound synthesis system using CuCl-DMAP catalyst

This technology is a copper-based catalyst system that produces alkyl 2-phenylazocarboxylates via aerobic dehydrogenation by combining DMAP and copper(I) chloride or Cu(OAc)2 with alkyl 2-phenylhydrazinecarboxylate compounds under oxygen supply.

While alkyl 2-phenylazocarboxylates are gaining attention for their reactivity, which differs from symmetric azo compounds, existing synthesis methods have been limited by the use of toxic oxidants or slow reaction rates, as seen with iron catalysts. They also struggle to maintain efficiency at a large scale.

This technology produces various azo compounds with yields of over 70% in 0.5 to 3 hours at room temperature in a dichloromethane solvent, with water as the only byproduct. The copper catalyst is significantly faster than iron catalysts and maintains its effectiveness when scaled up. It can be applied to Mitsunobu reagent, dye/pigment, and pharmaceutical intermediate synthesis, reducing toxic waste disposal burdens and shortening production times.

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Key Features:

• Catalyst system for aerobic dehydrogenation comprising alkyl 2-phenylhydrazinecarboxylate compounds, DMAP, and copper(I) chloride or Cu(OAc)2
• Catalyst system where the reaction is performed in a dichloromethane solvent at room temperature for 0.5 to 3 hours under oxygen supply
• Catalyst system that produces alkyl 2-phenylazocarboxylates with a yield of 70% or more via aerobic dehydrogenation
• Method for preparing azo compounds using alkyl 2-phenylhydrazinecarboxylate derivatives as starting materials under a constant stirring speed of 900 rpm

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This invention was developed with support from the Ministry of Science and ICT for the development of eco-friendly and economical selective aerobic oxidation reactions.

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