Formaldehyde reaction with diethyl malonate

Fluorenylamine, 40,5 Formaldehyde, reaction with diethyl malonate to form diethyl bis-(hydroxymethyl)malonate, 40,27 Formamide, condensation with 4,4-dimethoxy-2-butanone to give 4-methylpyrimidine, 43, 77 Formic acid, and hydrogen peroxide, with indcne, 41, 53... 

When the 3,7-diaza-l,9-nonanediamine-Cu(II) complex (n = 1) was treated with formaldehyde and nitroethane, the nitro-substituted macrocycle was the only product. Reduction of the nitro group by zinc in aqueous acid gave the amine-substituted macrocycle as shown above. Other peraza-crowns were obtained starting with other tetraamines (Comba et al., 1988a, 1988b Law-rance and O Leary, 1987). A similar reaction with diethyl malonate gave only a 2% yield of the corresponding macrocycle (Lawrance and O Leary, 1987). 

Reaction of selected metal ion complexes of multidentate amines with formaldehyde and a variety of activated carbon compounds (such as nitro-methane or diethyl malonate) have led to ring closure to yield polyaza macrocycles (Comba et al., 1986 Lawrance and O Leary, 1987). Reaction with the malonate ester gave less than a 2% yield. Another approach for the... 

Diethyl malonate, reaction with formaldehyde to form diethyl bis-(hydroxy methyl) malonate, 40, 27... 

In the case of 1,3-dicarbonyl compounds, the solvent frequently interferes with the coupling reaction. So with diethyl sodio malonate in ethanol [212b], methanol [212b], dimethylacetamide [212b], or HMPTA [216], besides the dimer and the trimer, the compounds LIXa-c are obtained. They are presumably formed by oxidation of the solvent to the aldehyde and its condensation with the active methylene compound. No dimer was detected in the oxidation of sodio acetoacetate in ethanol, with the major product being LX [217]. Anodic oxidation of cyclic 1,3-diketones in aqueous methanolic sodium hydroxide does not yield the dimer but product LXI, formed by condensation of the starting compound with formaldehyde [218]. 

Diethyl methylenemalonate was first prepared by Perkin 4 from formaldehyde and malonic ester. An alternative procedure involving the reaction of methylene chloride or iodide with... 

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