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Reactions of tert-butyl tetraethylphosphorodiamidite with acetic and trifluoroacetic acids involve substitution of the amido group. This process was described by a scheme beginning with protonation of phosphorus and proved by modeling separate reaction stages. A probable scheme of the proposed reactions is described. [ABSTRACT FROM AUTHOR]

The reaction of aryl(dichloro)phosphines with (2-chloroethoxy)trimethylsilane in the presence of haloacetic acid esters was studied with the goal of developing a new method for the synthesis of ethyl [(2-chloroethoxy)(4-dimethylaminophenyl)phosphoryl]acetate. The effect of various factors, such as substituent in the para position of the aromatic ring in the initial aryl(dichloro)phosphine, halogen nature in haloacetic acid ester, and chloro(trimethyl)silane, on the reaction course was analyzed. [ABSTRACT FROM AUTHOR]

Primary intermediates of P(III) chlorides reaction with aldehydes have been converted into the corresponding phosphates by treating with oxidants: dimethylsulfoxide and tert-butyl hypochlorite. In reactions of the intermediates with chlorinating agents (PCl and Cl) the oxidation products are formed (due to the ligand exchange at quasiphosphonium center) along with the expected P(IV) acid chlorides. [ABSTRACT FROM AUTHOR]

An approach to investigation of reactions of electrophilic P(III) chlorides with aliphatic aldehydes is developed. Its essence is the removal of HCl impurity from chloride and catalytic blocking of electrophilic center of the carbonyl group. For these purposes nitrogen-containing organic bases and alkyl vinyl ethers are used. Three types of primary intermediates with the nearest P(III) environment POCl, OPCl, and OP are synthesized. It is established that the stability of intermediates increases with the growing acceptor properties of substituents at P(III) and donor properties of the aldehyde fragment. [ABSTRACT FROM AUTHOR]

The peculiarities of the reactions of 2-R-benzo[d]-1,3,2-dioxaphosphorin-4-ones, 2-R-naphtho[d]-1,3,2-dioxaphosphorin-4-ones, 2-R-8-azabenzo[e]-1,3,2-dioxaphosphorin-4-ones, and 2-R-1,3,2-dioxaphospholan-4-ones with unsaturated compounds are summarized in the review. The reactions proceed in the mild conditions and lead to the formation of the seven- and six-membered heterocycles 1,3,2-dioxa-, 1,3,2-oxaza-, 1,4,2-dioxa-, and 1,4,2-oxazaphosphepines and 1,3,2- and 1,4,2-dioxaphosphorinanes with a high regio- and stereoselectivity. The hydrolysis and thermolysis of the some benzophosphepine derivatives leads to the substituted fluorinated ketones and various nonphosphorus heterocycles. [ABSTRACT FROM AUTHOR]

The facile synthetic approaches to a wide range of potentially biologically active compounds bearing the cyclic 1,3,2-oxazaphosphinane moiety as a 'cell transport' and the residues of formic, acetic, and amino acids or 3,5-bis(benzylidene)piperidone framework have been developed. The methods are based on the Arbuzov reaction of preformed cyclic P(III) esters with chloroacetic or chloroformic acid esters, where the nature of the reactants influences the ratio of cyclic and linear products, cyclizations of susbstituted dichlorophosphoryl compounds with aminopropanols, or amination of P-isothiocyanates. [ABSTRACT FROM AUTHOR]

The Reactions of 1-hydroxyphosphonates on the alumina-supported CrO3 are accelerated by microwave irradiation under solvent-free conditions to afford a high yielding synthesis of α-keto phosphonates. [ABSTRACT FROM AUTHOR]

A letter to the editor about the reactions of spiro[2.3]hexane-5-carbonyl chloride with phosphporus(III) acids esters is presented.