Isomerization of Trimethyl alpha-Keto Trithioorthocarboxylates into alpha,alpha-Bis(methylthio) Thiolcarboxylates. A New Rearrangement of Synthetic Interest.
A study was made of the isomerization reaction of a great variety of trimethyl alpha-keto trithioorthocarboxylates to alpha,alpha-bis(methylthio) thiolcarboxylates, intermediates of high synthetic value for the synthesis of alpha-arylpropionic acids. The reaction was carried out in methylene chloride in the presence of catalytic amounts of trityl perchlorate or methanesulfonic acid and was complete in 2 h at rt. In most of the investigated cases the result was positive, the yields usually being greater than 90%. Also the reaction mechanism was subjected to an experimental study.
Degani
Iacopo
I
Dipartimento di Chimica Generale ed Organica Applicata dell'Università, C.so M. D'Azeglio 48, I-10125 Torino, Italy.
Dughera
Stefano
S
Fochi
Rita
R
Gazzetto
Sonia
S