I'm trying to find information on the synthesis of thiols via Grignard reagents. While looking at the synthesis routes on Wikipedia, it said that a Grignard reagent will react with sulphur to form thiolates which will hydrolyse easily to the thiol; however, I'm struggling to find any references for this. Has anyone ever heard of this before or maybe tried it themselves?

  • $\begingroup$ Yeah that's pretty much what I expected except i'll just use ether cause for some reason nobody sells THF to individuals. Thanks for the help. $\endgroup$ – Hamish Oct 16 '18 at 11:34

I've done this with aromatic Grignards, but I have no reference and no database access any longer.

I think when I did it, I was relying on an older colleague's instructions. It was pretty much generate your Grignard from ArBr + Mg in THF, cool in ice bath, stir vigorously and add elemental sulfur. You may need to introduce a reductive step as you can generate polysulfides.

Grignards will also add to disulfides so you could react with dibenzyl disulfide then reduce off the benzyl group.

This reference is the nearest that Google has managed to find Can. J. Chem. 70 (1992) 30

  • $\begingroup$ Thank you this is very helpful, definitely will be doing some tests soon. $\endgroup$ – Hamish Oct 16 '18 at 11:35
  • $\begingroup$ A borohydride work-up step should minimise polysulfide formation $\endgroup$ – Waylander Oct 16 '18 at 11:46

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy

Not the answer you're looking for? Browse other questions tagged or ask your own question.