Acylation of phosphoryl- and thiophosphorylacetonitriles under phase transfer catalysis conditions and the keto-enol tautomerism of phosphorus-substituted acylacetonitriles

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.     

Metabolism and Interaction with Esterases of O-Ethyl-S-(Methoxycarsonalmethylmercaptomethyl)Methylphospho-Nodithioate

Abstract

Metabolism of an effective insecticide and acaricide Me(EtO)P(S)SCH₂ SCH₂ COOMe (I) (I) in rat and American cockroacii was investigated. For this purpose the metabolites of oxidative activation and hydrolytic detoxication of (I) -Me(EtO)P(0)SCB₂SCH₂COOMe (II), Me(EtO)P(0)SCH₂S (0) CH₂COOMe (III), Me(EtO)P(S)SCH₂S(0)CH₂COOMe (IV) and Me(EtO)-P(S)SCH₂SCH₂COOH (V) were synthesized.     

Reactions of 2-alkoxy-3-alkyl-1,3,2-oxazaphosphinanes with alkyl chloroformates

2-Alkoxy-3-alkyl-1,3,2-oxazaphosphinanes containing a sterically hindered N atom react with alkyl chloroformates according to the Arbuzov mechanism only. The ratio of the open and cyclic reaction products depends on the nature of the alkoxy group in the starting phosphinane. With a less hindered N atom, acylation at the N atom gives acyclic chloridophosphites, in addition to the Arbuzov-type products. The structures of the chloridophosphites were confirmed by their chemical transformations into stable thiophosphates. Oxazaphosphinane analogs of phosphorylformamides and phosphorylformohydrazide were obtained.     

New 3-Cyano-1,2λ 3 -Thiaphosphacyclanes and Their Complexing Properties

Reduction of both individual diastereomers of 2-oxo-1,2-thiaphosphacyclanes by HSiCl 3 proceeds with retention of cyclic structure, cyano-group, and stereochemical configuration.     

Phosphorus-substituted carbothioamides

A facile procedure was developed for the synthesis of phosphorus-substituted carbothioamides by the reaction of the corresponding nitriles with O,O-diisopropyl dithiophosphate in the presence of methanol. The structural features and hydrogen bonding in crystals of structurally different P-thioamides are discussed.     

REACTIONS OF PHOSPHORUS MONOTHIO ACIDS WITH ALIPHATIC DIAZO COMPOUNDS

Abstract

Reactions of phosphorus monothio acids with diazomethane, diazoacetone, diphenyldiazomethane, and diazofluorene have been studied. The ratio of the yields of the S- and O-derivatives Q_S/Q_O has been found to be dependent on three factors: i) the nature of substituents at phosphorus - with electron-donor substituents raising the O-derivative yield and the quantity log (Q_S/Q_O) varying as εσ of the substituents; (ii) stability of alkyldiazonium and carbocation - with Q_O increasing with the carbocation stability; and (iii) polarity of the medium - the O-derivative yield rises with dielectric permeability of the medium and Q_S/Q_O has been found to be a linear function of 1/D. The most probable mechanism has been established as proton transfer from the acid to the diazocompound followed be formation of the S-derivative and the O-derivative. The former results from an S_N2 reaction of the alkyldiazonium cation with the thiol-thione anion within the ion pair. The O-derivative arises from the thiol-thion anion and the carbocation; the latter resulting from decomposition of the alkyldiazonium cation within the ion pair.     

Novel 3-Cyanosubstituted 1,2-Thiaphosphacyclanes: Synthesis and Stereochemistry

The facile synthetic route to 5- and 6-membered 3-cyano-2-oxo-1,2-thiaphosphacyclanes and 6-cyano-2-oxa-10-oxa(thia)-phosphabicyclo [4.4.0]-decane-1-oxides was elaborated via intramolecular S-alkylation in a series of y -haloalkylsubstituted thiophosphorylacetonitriles. The compounds were used to prepare novel P(III)-containing bidentate ligands with definite stereochemistry. Diastereomeric transformations among 2-oxo-1,2-thiaphosphinanes were found and the mechanism of such transformations is suggested.     

Synthesis and Tautomerism of 1,3,2-Azathiaphosphacyclanes

1,3,2-Azathiaphosphacyclanes were prepared by intramolecular alkylation of N-( y -haloalkyl)amidophosphates and phosphonates.     

Synthesis of 1,2-Azaphosphacyclanes; Generality of the Mechanism of P=N Alkylation and Arbuzov Reaction

A novel convenient "one-pot" synthesis of 2-oxo-1,2 u 5 -azaphosphacyclanes 1 and 1,2 u 4 -azaphosphacyclanium salts 2 via intramolecular N-alkylation of y -halogenalkyl-substituted iminophosphoryl compounds 3 has been developed. The common nature of the reaction of intramolecular cyclization of iminophosphoryl compounds having an alkoxy group at the phosphorus atom and the Arbuzov reaction has been established.