Thiocarboxylation

The reaction of thioethers with ethyleneimine in the presence of acid yields sulfonium compounds. The reaction is reversible under alkaline conditions (125). Compounds in which double-bonded sulfur can exist in tautomerism with a form having a free SH group, such as thiourea (126,127), thiocarboxyhc acids (128), and thiophosphates (129), react to give aminoaLkylated products. The P-aminoethyl thiocarboxylate rearranges to give the amide. 

Mercapto Exist largely in the thione form Thiocarboxylic acid... 

Dewar and Turchi described the Comforth rearrangement of 5-alkoxyoxazole-4-thiocarboxylates as a potentially general method for the synthesis of 5-thiooxazole-4-carboxylic esters. Specifically, they found that thiol ester 13 underwent thermal isomerization to the corresponding 5-thiooxazole 14 in 94% yield. 

S-Alkylation of a thiocarboxylic acid with an a-halogenated carbonyl compound gives a thiol ester in which the two carbons to be connected... 

Liquid Crystals Containing Carboxylic or Thiocarboxylic Groups... 

Lewis TA, A Paszczynski, SW Gordon-Wylie, S Jeedigunta, C-H Lee, RL Crawford (2001) Carbon tetrachloride dechlorination by the bacterial transition metal chelator pyridine,2,6-bis(thiocarboxylic acid). Environ Sci Technol 35 552-559. 

Because of the higher reaction rate, 7V(3)-alkylimidazolium-A ( 1 )-carboxylates or thiocarboxylates have often been used for the synthesis of carbamates and thiocarbamates by the azolide method instead of imidazole-iV-carboxylates. 

With tetrazole-A-thiocarboxylate the amino group of an OH-protected deoxy-adenosine is converted into a thiocarbamate 189 ... 

Whereas CDI reacts with thiols to give thiocarboxylic imidazolide and the corresponding dithiocarbonate. The reaction with Nfl -sulfinyldiimidazole afforded, surprisingly, a mixture of dithio and trithio compounds in good yield [36]... 

O/S ligands, such as monothiocarbamates and thiocarboxylates, have been quite extensively characterized and some representative examples are discussed. 

The complexes were shown to be monomeric in the solid state and have monodentate S-thiocarboxylate ligands. The thiocarboxylic anhydride elimination was studied by 1H and 13C NMR in solution, varying the R group and solvent.858... 

---