Dimethylthiocarbamoyl chloride explained

Dimethylthiocarbamoyl chloride is an organosulfur compound with the formula (CH3)2NC(S)Cl. A yellow solid, it is often encountered as a yellow syrup. It is a key reagent in the synthesis of arylthiols via the Newman-Kwart rearrangement.[1]

Synthesis and reactions

Representative of other thiocarbamoyl chlorides, dimethylthiocarbamoyl chloride is electrophilic, serving as a source of R2NC(S)+.[2] It is analogous to dimethylcarbamoyl chloride (R2NC(O)Cl).

Dimethylthiocarbamoyl chloride is prepared by chlorination of the related tetramethylthiuram disulfide:

[Me<sub>2</sub>NC(S)]2S2 + 3 Cl2 → 2 Me2NC(S)Cl + 2 SCl2

Dimethylthiocarbamoyl chloride reacts with dithiocarbamates (R2NCS) to give thiuram sulfides [R<sub>2</sub>NC(S)]2S. With methanethiolate, it gives methyl dimethyldithiocarbamate (Me2NC(S)SMe).

References

  1. Thiophenols from Phenols: 2-Naphthalenethiol. Melvin S. Newman . Frederick W. Hetzel . Org. Synth.. 1971. 51. 139. 10.15227/orgsyn.051.0139.
  2. R. J. Cremlyn "An Introduction to Organosulfur Chemistry" John Wiley and Sons: Chichester (1996).