Acylation of phosphoryl- and thiophosphorylacetonitriles under phase transfer catalysis conditions and the keto-enol tautomerism of phosphorus-substituted acylacetonitriles |
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Authors: | T A Mastryukova I L Odinets O I Artyushin R M Kalyanova K A Lyssenko A G Matveeva P V Petrovskii M I Kabachnik |
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Institution: | (1) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813 Moscow, Russian Federation |
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Abstract: | A procedure was developed for acylation of phosphoryl- and thiophosphorylacetonitriles under phase transfer catalysis conditions.
The reaction in the solid KOH/MeCN system affordedC-acylation products in high yields. In the individual state and in aprotic solvents, these products exist in the enol form
(Z isomers) stabilizedvia a strong intramolecular hydrogen bond. In hydroxyl-containing media and in aprotic bipolar solvents, these compounds exist
as a mixture of two geometric isomers (E andZ) of the corresponding enols. In this case, theZ isomer exists in two forms, namely, in the cyclic form with an intramolecular hydrogen bond and in the open form stabilized
by intermolecular hydrogen bonds with the solvent. The results of X-ray diffraction analysis of both forms ofZ isomers of the compounds containing the phosphoryl and thiophosphoryl groups are discussed.
Deceased.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1687–1694, September, 1998. |
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Keywords: | phase transfer catalysis phosphorylacetonitriles thiophosphorylacetonitriles acylation Z andE isomers of enols hydrogen bond X-ray diffraction analysis NMR spectra |
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