Ethoxymethylenemalonate esters reaction with

Reaction with reactive-methylene compounds. Claisen" developed a method for the preparation of diethyl ethoxymethylenemalonate by heating a mixture of triethyl orthoformate, malonic ester, and acetic anhydride with a catalytic amount of zinc chloride. The yield cited is that obtained in a standardized procedure."... 

This closely related synthesis uses /3-ketoesters and leads to quinolones. Anilines and /9-ketoesters can react at lower temperatures to give the kinetic product, a / -aminoacrylate, cyclisation of which gives a 4-quinolone. At higher temperatures, / -ketoester anilides are formed and cyclisation of these affords 2-quinolones. / -Aminoacrylates, for cyclisation to 4-quinolones, are also available via the addition of anilines to acetylenic esters or by reaction with diethyl ethoxymethylenemalonate (Et0CH = C(C02Et)2 ArNHCH = C(C02Et)2). ... 

The lithium derivative of the 2-(methoxymethoxy)naphthalene (248) has been treated with diethyl ethoxymethylenemalonate to produce moderate yields of 6,7-benzocoumarin-3-carboxylate esters (249) in a one-pot reaction.The ort/io-lithiation of (methoxymethoxy)benzenes, followed by reaction with DMF... 

Reaction of diethyl ethoxymethylenemalonate or ethyl cyanoethoxy-methylene acetate with l-phenyl-4-aminopyrazole gave esters 187a, which cyclized in boiling Dowtherm to the corresponding pyridones 188a.158 The... 

Aminopyridazines can also be condensed with /6 -keto esters in the presence of polyphos-phoric acid to give 2ff-pyrimido[l,2-6]pyridazin-2-ones. 3-Ethoxycarbonylpyrimido-[1,2-6 ]pyridazin-4-ones (169) are obtained by the reaction of 3-aminopyridazines (168) with diethyl ethoxymethylenemalonate in the presence of polyphosphoric acid (71JOC2457). 

The ethyl 6-(trifluoromethyl)-2-pyrone-3-carboxylate (61) was prepared by condensation of trifluoroacetone with diethyl ethoxymethylenemalonate, followed by cyclization of intermediate diethyl p-acylethylidenemalonate. This pyrone was used for the preparation of cage derivatives to explore their usefulness as antiviral agents. Reaction of 61 with ethylene at high pressure afforded ester 62. Hydrogenation of 62 yielded the corresponding alkyl bicyclo[2.2.2]octane-l-carboxylate, which was hydrolyzed to 63. The latter was converted into bicyclo[2.2.2]octan-l-amine hydrochloride 64 via the Schmidt reaction [29] (Scheme 21). 

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