A thorough study directed towards the synthesis of methyl thiolcarboxylates was made on the basis of the following steps: (i) conversion of alkyl halides into the corresponding trimethyl trithioorthocarboxylates by using tris(methylthio)methyllithium in THF at –78 °C; (ii) selective hydrolysis of the intermediates to methyl thiolcarboxylates by using 35% aq. HBF4 in DMSO or, in some cases, in THF. The overall yields of the two stages are, usually, between 70 and 88%. By this procedure it is also possible to incorporate 8O in the carbonyl group of thiol esters (98% isotopic purity). Furthermore, a new, convenient method for the preparation of tris(methylthio)methane as the precursor of tris(methylthio)methyllithium was developed.

Synthetic application of lithiated Tris(methylthio)methane: preparation of aliphatic methyl thiolcarboxylates from the corrisponding halides.A convenient synthesis of tris(methylthio)methane.

BARBERO, Margherita;CADAMURO, Silvano;DEGANI, Jacopo;DUGHERA, Stefano;FOCHI, Rita
1993-01-01

Abstract

A thorough study directed towards the synthesis of methyl thiolcarboxylates was made on the basis of the following steps: (i) conversion of alkyl halides into the corresponding trimethyl trithioorthocarboxylates by using tris(methylthio)methyllithium in THF at –78 °C; (ii) selective hydrolysis of the intermediates to methyl thiolcarboxylates by using 35% aq. HBF4 in DMSO or, in some cases, in THF. The overall yields of the two stages are, usually, between 70 and 88%. By this procedure it is also possible to incorporate 8O in the carbonyl group of thiol esters (98% isotopic purity). Furthermore, a new, convenient method for the preparation of tris(methylthio)methane as the precursor of tris(methylthio)methyllithium was developed.
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2075
2080
methyl thiolcarboxylates alkyl halides trimethyl trithioorthocarboxylates tris(methylthio)methyllithium
BARBERO M; CADAMURO S; DEGANI I; S. DUGHERA; FOCHI R
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/1745
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