Effective Electrochemical Synthesis of an Important Fungicide Tetramethylthiuram Disulfide and Its Bioactive Analogues

Abstract

Tetramethylthiuram disulfide (TMTD, thiram) is one of the most important fungicides and is widely used in agriculture for seed treatment and crop protection. TMTD is produced by a number of plants. Its annual sales are estimated at tens of millions of US dollars. Traditional chemical synthesis of thiram is accompanied by the formation of a significant amount of waste, including inorganic salts, thioacids, polysulfides, etc. Herein, we report an advanced method of TMTD and its structural analogues production, which is based on the usage of electric current as a key participant. Such an electrochemical approach avoids application of the chemical oxidant required for previous processes and can be efficiently scaled up. All of these characteristics make the developed synthetic method quite promising both economically and ecologically.

Challenges and opportunities on sustainable electrochemical transformations: application towards the synthesis of pharmaceuticals and precursors of drug-like molecules

“…In 2023, Terent'ev and co-workers utilised a combination of amines and carbon disulphide under constant current conditions in an undivided electrochemical cell for the synthesis of thiram and its analogues (Scheme 22a). 88 Potassium iodide played dual roles as a redox active catalyst and an electrolyte. As proposed, mechanistic studies suggested that a hydroxide anion formed at the cathode and assisted the formation of di-thiocarbamate via nucleophilic attack of 162 on CS 2 .…”