Mechanism of sulfur transfer from 1,2,4-dithiazolidine-3,5-diones to triphenylphosphines

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F13%3A39896099" target="_blank" >RIV/00216275:25310/13:39896099 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1002/poc.3131" target="_blank" >http://dx.doi.org/10.1002/poc.3131</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/poc.3131" target="_blank" >10.1002/poc.3131</a>

Result language
angličtina
Original language name
Mechanism of sulfur transfer from 1,2,4-dithiazolidine-3,5-diones to triphenylphosphines
Original language description
The mechanism of sulfurization of substituted triphenylphosphines with 4-(3- and 4-substituted)-1,2,4-dithiazolidine-3,5-diones in acetonitrile, dichloromethane, tetrahydrofuran and toluene at 25 degrees C was studied. The reaction pathway involves rate-limiting initial nucleophilic attack of the phosphorus at sulfur followed by fast decomposition of the phosphonium intermediate to the corresponding phosphine sulfide, phenylisocyanate and carbonylsulfide. From the Hammett correlations and from the solvent dependency, it was concluded that the transition-state structure is very polar and resembles the zwitter-ionic intermediate. The extent of P-S bond formation and S-S bond cleavage is very similar in the solvents series, but the latter gradually decreases with the decreasing polarity of the solvent.
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CC - Organic chemistry
OECD FORD branch
—

Project
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Continuities
S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2013
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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