Diethyl isocyanomethylphosphonate

Diethyl 2-chloro-2-cyclopropylethene-l,1-dicarboxylate, 66, 173, 174 Diethyl cyclopropylcarbonylmalonate (7394-16-3), 66, 175, 179 Diethyl cyclopropylmalonate, 66, 173 Diethyl dioxosuccinate (59743-08-7), 66, 144, 149 Diethyl isocyanomethylphosphonate Phosphonic acid, (isocyanomethyl)-, diethyl ester (41003-94-5), 65, 119 Diethyl malonate (105-53-3), 66, 175, 179... 

Phosphoryl substituted nitrile ylides have also been generated via the imidoyl chloride-base route using precursors 118 (R=Et, c-CeHn, f-Bu) prepared by the addition of an acid chloride to diethyl isocyanomethylphosphonate (120) (65). Treatment of the imidoyl chloride with triethylamine at —10 to 0 °C in the presence of dipolarophiles gave adducts in yields of up to 55% (e.g., 119 and 121) in ratios 1 4, 1 3 for R=Et and c = CgHn, respectively. 

Diethyl isocyanomethylphosphonate Phosphonic acid, (isocyanomethyl)-, diethyl ester (9) (41003-94-5)... 

Base-induced cycloaddition of diethyl isocyanomethylphosphonate 1326 to trifluoroacetimidoyl chlorides 1327 produces 1-substituted diethyl 5-trifluoromethylimidazole-4-phosphonates 1328 with high regioselectivity (Scheme 339) <19968511>. 

Michael addition has been applied to the formation of cyclopropanic systems. Thus, the addition of phosphonate carbanions generated by LDA in THF, by NaH in THF, by thallium(I) ethoxide in refluxing THF, or by electrochemical technique to oc,P-unsaturated esters provides a preparation of substituted 2-(alkoxycarbonyl)cyclopropylphosphonates in moderate to good yields via a tandem Michael addition-cyclization sequence (Scheme 8.47). The cyclopropanation has also been achieved via oxidation with iodine in the presence of KF-AI2O3. Nitrile ylides prepared from acyl chlorides and diethyl isocyanomethylphosphonate in the presence of Et3N react with methyl acrylates by a 1,3-dipolar cycloaddition to give phosphoryl pyrrolines or pyrroles. ... 

Huang, W.-S., Zhang, Y.-X.. and Yuan, C.. Studies on organophosphorus compounds. Part 96. Nucleophilicity of the isocyano carbon atom in diethyl isocyanomethylphosphonate. First generation of a phosphorylated nitrile ylide and new syntheses of pyiTolinephosphonates and pyrrolephosphonates, J. Chem. Soc., Perkin Trans. 1. 1893, 1996. 

J-HALOVINYL KETONES Triphenylphosphine-Carbon tetrachloride. HETEROCYCLES Carbon suboxide. Diethyl isocyanomethylphosphonate. Ethoxy-carbonyl isothiocyanate. Propargyltriphenylphosphonium bromide. Selenium. HOMOALLYLIC ALCOHOLS 7r-2-Methylallylnickel bromide. 2-Methyl-2-thia-zoline. 

The synthesis of A/-substituted 5-trifluoromethylimidazole-4-phosphonates was reported by Yuan (Scheme 61) [76]. Addition of lithiated species, derived from diethyl isocyanomethylphosphonate using n-BuLi, to A-substituted trifluoroaceti-midoyl chloride gave an imine intermediate which underwent intramolecular cycli-zation to furnish regioselectively the 5-(trifluoromelhyl)imidazole-4-phosphonate. The addition of an enamine to the isocyano carbon under these conditions, especially without any catalytic assistance, was driven by aromatization. However, replacement of n-BuLi with NaH was ineffective and produced an inseparable complex mixture. 

N butyllithium in pentane added dropwise with vigorous stirring at -70° during ca. 15 min. to a soln. of diethyl isocyanomethylphosphonate in tetrahydrofuran, the resulting suspension treated at -60° with a soln. of cyclohexanone in tetrahydrofuran, and allowed to warm to room temp. cyclohexylidenemethyliso-cyanide. Y 84%. F. e., also from aldehydes, s. U. Sdiollkopf, R. Schroder, and D. Stafforst, A. 1974, 44. 

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