One-Step Simultaneous Synthesis of an Industrially Important Rubber Accelerator and a Lubricant Additive by Disulfide Bond Contraction

Abstract

A sustainable and atom-economic synthesis of the widely used rubber accelerator tetramethylthiuram monosulfide (TMTM) from tetramethylthiuram disulfide is reported. Triphenyl phosphite (TPPi) is employed as a green reductant to replace the usual sodium cyanide, which poses a severe safety risk due to its high toxicity. The new process proceeds smoothly under mild conditions with an excellent yield of TMTM. This single-step one-pot method also has the potential for producing the industrially important lubricant additive O,O,O-triphenyl thiophosphate as a high-added-value byproduct.

Key words

rubber accelerators - lubricant additives - disulfide contraction - green chemistry - reduction - tetramethylthiuram monosulfide

Publication History

Received: 29 August 2022

Accepted after revision: 30 September 2022

Accepted Manuscript online:
30 September 2022

Article published online:
28 October 2022

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• 33 Tetramethylthiuram Monosulfide (TMTM) and O,O,O-Triphenyl Thiophosphate (TPPT) A 25 mL round-bottomed flask was charged with TMTD (600 mg, 2.5 mmol), TPPi (786 μL, 3.0 mmol), and MeCN (10 mL), and the mixture was magnetically stirred at 80 °C for 10 h. When the reaction was complete (HPLC), the crude product was purified by column chromatography [silica gel, EtOAc–PE (1:100 to 1:4)] and the solvent was removed under vacuum to give TMTM as a yellow powder; yield: 386 mg (74%). ¹H NMR (400 MHz, CDCl₃): δ = 3.53 (s, 6 H), 3.43 (s, 6 H). ¹³C NMR (110 MHz, CDCl₃): δ = 187.36, 44.98, 44.03. MS (ESI): m/z [M + H]⁺ calcd for C₆H₁₃N₂S₃: 209; found: 209. Cold crystallization, filtration, washing with MeOH, and drying at 40 °C for 30 min gave TPPT as a white solid; yield: 380 mg (45%). ¹H NMR (400 MHz, CDCl₃): δ = 7.40–7.33 (m, 6 H), 7.25–7.21 (m, 9 H). ³¹P NMR (162 MHz, CDCl₃): δ = 53.04. ¹³C NMR (110 MHz, CDCl₃): δ = 150.74, 150.66, 129.74, 129.73, 125.75, 121.21, 121.16. MS (ESI): m/z [M + H]⁺ calcd for C₁₈H₁₆O₃PS: 343; found: 343.