80438-75-1

Upstream product

• 4231-35-0 methyl(diethylamino)acetylene 
• 949-00-8 phenyl dithiobenzoate 

Relevant academic research and scientific papers

Organic Syntheses via Transition Metal Complexes, 41. - Thioenol Ethers by Insertion of Alkynes into M=C Bonds of Thiocarbene Complexes and Disengagement of Ligands on Silica Gel

A first example of reactions between alkynes and thiocarbene complexes is described.Et2N-CC-CH3 (2) adds to (alkylthio)phenylcarbene complexes LnM=C(SR)C6H5 (1) with insertion of the CC into the M=C bond to form stereoselectively aminocarbene complexes LnM = C(NEt2)-C(CH3)=C(SR)C6H5 .With tungsten, but not with chromium, small amounts of indanone derivatives 4 - 6 were also obtained.We describe a straightforward and efficient method for the disengagement of ligands from carbene chromium complexes 3 on silic gel.Metal residues remain attached to the solid phase, and products are isolated by elution.Depending on the reaction conditions, different thioenol ethers 7 - 9 were obtained.Thus (E)-3a - d on silica gel at ambient temperature under the influence of air give β-(alkylthio)propenamides O=C(NEt2)-C(CH3)=C(SR)C6H5 and β-(alkylthio)thiopropenals O=CH-C(CH3)=C(SR)C6H5 .Thermolysis of 3 on silica gel in the absence of oxygen leads to the formation of aldehydes 8 and 3-(alkylthio)-1-indanones 5.Thermolysis of 3 on silica gel in the presence of sulfur yields β-(alkylthio)propenethioamides 9 as the only products.

Addition of dithio esters and trithiocarbonates to 1-(diethylamino)propyne. Formation of α,β-unsaturated thioamides and vinylogous thioamides

α,β-Unsaturated thioamides and vinylogous thioamides have been prepared by thermal addition of trithiocarbonates RS-C(S)SR1 to 1-(diethylamino)propyne.Aromatic dithio esters Ar-C(S)SR only gave the α,β-unsaturated thioamides.The dithio ester Me2CH-C(S)SMe adds as acidic enethiol tautomer Me2C=C(SH)SMe to 1-(diethylamino)propyne.Reaction mechanisms and the stereochemistry of the adducts are discussed.