Thione-thiol rearrangement

Zonta C, De Lucchi O, Volpicelli R, Cotarca L (2007) Thione-Thiol Rearrangement Miyazaki-Newman-Kwart Rearrangement and Others. 275 131-161... 

Under conditions of electron transfer, thione-thiol rearrangement of the type P(S)OR —> P(0)SR takes place (Kajdas et al. 1986). The rearrangement changes the bond polarizability of a metal dialkyldithioposphates and enhances the forces driving all the chemical processes described earlier. 

This review is divided into three parts. The first part concerns the aromatic thione-thiol rearrangement, i.e. the typical MNK rearrangement, which since... 

Scheme 4 Example of [3.3] sigmatropic reaction giving thione-thiol rearrangement...

Scheme 5 Four-member intermediate present in the thione-thiols rearrangements...

During alkylation by alkyl halides in the presence of bases, -(2-oxoalkyl) phosphorodithioic esters have been found to undergo rearrangements of the general types (72) -> (73). The overall outcome is influenced both by experimental conditions as well as by the nature of other alkoxy groups attached to phosphorus. Thus, Q,Q-dimethyl -(2-oxo-2-phenylethyl) phosphorodithioate undergoes thione-thiol isomerization (72) -> (73a) in addition to dithiophosphate to thiophosphate rearrangement, (72) -> (73b),... 

Chloroalkyl-substituted thiophosphinates and thiophosphonates are thermally stable and represent easily distilled liquids (b.p. = 105-165 °C/2-3 Hg). 3-Chloropropyl(phenyl)thiophosphinate (R = Ph, n = 3), which undergoes the intramolecular thione-thiol rearrangement into 2-oxo-2-phenyl-1,2-thiaphospholane under distillation in vacuo, is the only exception. 

The thione thiol rearrangement of 0-alkyl phosphinothioic esters is catalysed by acids. In an investigation of the catalysis of isomerization of the esters Me2P(S)OPr and Ph2P(S)OMe by trifluoroacetic acid by means of P NMR spectroscopy, Bruzik and Stec assigned transient signals to the species 112. ... 

X 10 6 x 10. The formation of (153) shows that the allylic 1 -3 rearrangement accompanies thione-thiol rearrangement to (152), and it would thus appear probable that... 

The mechanism of the thione-to-thiol rearrangement of 0,5 -dialkylxanthates, catalysed by pyridine-A-oxide, has been analysed by MO methods. 

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