The invention relates to a new process for preparing known thiolcarbamate esters of the general formula (I) ##STR1## wherein R.sup.1 and R.sup.2 stand independently for hydrogen or a straight or branched chain alkyl group containing 1 to 6 carbon atoms or an alkenyl group containing 2 to 6 atoms, or an alkyl group containing 1 to 6 or an alkenyl group containing 2 to 6 carbon atoms and mono- or polysubstituted by halogen, oxygen, sulphur and/or nitrogen; orR.sup.1 and R.sup.2 together may represent an optionally substituted .alpha.,.omega.-alkylene group containing 4 to 6 carbon atoms;R.sup.3 and R.sup.4 stand independently for hydrogen or an alkyl group containing 1 to 4 carbon atoms and optionally substituted by halogen or by a group containing oxygen, sulphur and/or nitrogen; andR.sup.5 and R.sup.6 both stand for hydrogen; orR.sup.5 and R.sup.6 together may represent a chemical bond.The compounds of general formula (I) are prepared by reacting(a) thiolcarbamate salts of the general formula (II) ##STR2## wherein the meanings of R.sup.1 and R.sup.2 are as defined above, andY stands for a primary, secondary or tertiary ammonium ion or an alkaline metal ion; or(b) amines of the general formula (III) ##STR3## wherein the meanings of R.sup.1 and R.sup.2 are as defined above, together with sulphur and carbon monoxide; or(c) amine of the general formula (III) together with carbonyl sulphidewith alkynes of the general formula (IV)R.sup.3 --C.tbd.C--R.sup.4 (IV)wherein the meanings of R.sup.3 and R.sup.4 are as defined above and, if desired, hydrogenating the obtained product of general formula (I), wherein the meanings of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are as defined above and R.sup.5 together with R.sup.6 forms a chemical bond, to a compound of the general formula (I), wherein both R.sup.5 and R.sup.6 stand for hydrogen.