Phosphorochloridate dimethyl

Poly(methyl 3-(l-oxypyridinyl)siloxane) was synthesized and shown to have catalytic activity in transacylation reactions of carboxylic and phosphoric acid derivatives. 3-(Methyldichlorosilyl)pyridine (1) was made by metallation of 3-bromopyridine with n-BuLi followed by reaction with excess MeSiCl3. 1 was hydrolyzed in aqueous ammonia to give hydroxyl terminated poly(methyl 3-pyridinylsiloxane) (2) which was end-blocked to polymer 3 with (Me3Si)2NH and Me3SiCl. Polymer 3 was N-oxidized with m-ClC6H4C03H to give 4. Species 1-4 were characterized by IR and H NMR spectra. MS of 1 and thermal analysis (DSC and TGA) of 2-4 are discussed. 3-(Trimethylsilyl)-pyridine 1-oxide (6), l,3-dimethyl-l,3-bis-3-(l-oxypyridinyl) disiloxane (7) and 4 were effective catalysts for conversion of benzoyl chloride to benzoic anhydride in CH2Cl2/aqueous NaHCC>3 suspensions and for hydrolysis of diphenyl phosphorochloridate in aqueous NaHCC>3. The latter had a ti/2 of less than 10 min at 23°C. 

Dimethyl and diethyl phosphorofluoridate were hydrolysed much more quickly, the order being Me>Et>Pr complete hydrolysis of the ethyl ester took about 4 hr. Small quantities of the di-isopropyl, but not the diethyl ester, could be steam-distilled. Bi-isopropyl phosphorochloridate can be readily identified by allowing it to react with aniline to give the crystalline phenylphosphoramidate ... 

Diethyl chlorophosphate, see Diethyl phosphorochloridate, 1675 Diethyl diazomalonate, 2824 Diethyl-3-diethylaminopropylaluminium, 3408 Diethyl l,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate, 3609 3,6-Diethyl-3,6-dimethyl-1,2,4,5-tetraoxane, 3047... 

The sequence can also be applied to the enolate anion formed by conjugate addition of organometallic reagents to a,/8-unsaturated ketones. Thus addition of diethyl phosphorochloridate to a mixture of A4-cholestene-3-one (4) and dimethyl-copperlithium gives the diethyl enol phosphate (5) in 55% yield. Reduction of the ester gives the olefin (6) in high yield. 

OLEFINS f-Butyl hydroperoxide. Diethyl phosphorochloridate. Di-methylcopper lithium. N,N-Dimethyl-thiocarbamoyl chloride. Trimethyl phosphite. Triphenylphosphine. 

At 600 °C in the vapour phase the aryl phosphorodichloridate (39) cyclizes to (40). The reaction of dimethyl phosphorochloridate with aniline in nitrobenzene appears to be catalysed by both the reactants and the products. When the phosphorimidic chloride (41) was treated with... 

Acylation of 3,5-diamino-1,2,4-thiadiazole by ethyl chloroformate yields the 3,5-bis(ethoxycarbonylamino) derivative.67 Phosphorochloridic esters [(RO)2POCl] attack the 3-position preferentially, producing the phosphor-amidic esters (509).390 The action of diphenylphosphinothioic chloride (Ph2PSCl) (see Section IV,C) on Hector s base in pyridine yields a monoacyl derivative, substitution occurring probably at the exocyclic imino group.391 Methylation of 3,5-bisanilino-l,2,4-thiadiazole with sodium hydride-methyl iodide in dimethylformamide produces the mono and dimethyl derivatives, of structures 510 and 511, as shown by 15N and 13C NMR spectroscopy.31... 

The parent phenylphosphoramidic acid, PO(NHPh)(OH)2, was obtained by a method which consisted in the ready hydro-genolysis of dibenzyl phenylphosphoramidate. An attempt to prepare dibenzyl p-dimethylaminophenylphosphoramidate by the action of iViV -dimethyl-p-phenylenediamine on dibenzyl phosphorochloridate gave only an oil. When, however, a mixture of the amine, dibenzyl hydrogen phosphite, and trichloro-bromomethane was used, a good yield of the dibenzylp-dimethyl-aminophenylphosphoramidate was obtained. It is a crystalline solid which causes severe dermatitis the irritation develops slowly and with some individuals persists for weeks. 

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