Microfluidic electrosynthesis of thiuram disulfides

Abstract

An electrolytic approach of sodium dithiocarbamates based on microfluidic reactor is proposed for the green synthesis of thiuram disulfides, which are versatile free radical initiators. The electro-oxidation reactions avoid over-oxidation of sodium dithiocarbamates and the generation of waste salts, which have perplexed the industry for a long time. This microfluidic electrolysis method prevents solid deposition by introducing liquid-liquid Taylor flow into the microchannel, and promotes the synthesis efficiency of thiuram disulfides with the enlargement of electrode specific surface area. The highest yield of thiuram disulfide achieves 88% in the experiment without any oxidation by-products. Faraday efficiencies of most reactions are higher than 96%, showing the excellent electronic utilization. In addition to improving of the environmental friendliness of sodium dithiocarbamate oxidation, the electrosynthesis method helps to create a cyclic technology of thiuram disulfide synthesis via the combination of sodium dithiocarbamate generation in a packed bed reactor. The cyclic technology finally achieved >99% atom utilization thiuram disulfide synthesis from secondary amines and carbon disulfide.