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Synlett 2023; 34(01): 57-62
DOI: 10.1055/a-1954-3155
DOI: 10.1055/a-1954-3155
letter
One-Step Simultaneous Synthesis of an Industrially Important Rubber Accelerator and a Lubricant Additive by Disulfide Bond Contraction
We thank Hebi Uhoo New Materials Co., Ltd. for financial support of this project. This work was also supported by the National Natural Science Foundation of China (grant no. 21872068) and the Technology Innovation Fund of Nanjing University.
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 monosulfideSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1954-3155.
- Supporting Information
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.