Formylacetone

Sodium formylacetone, 32, 32 Sodium hydrosulfite, 37, 16 Sodium hypobromite, solution of, 30, 3 Sodium hypochlorite, solution of, 31, 41 37, 2... 

To the solid residue of sodium formylacetone remaining in the flask are added a solution of 67 g. (0.8 mole) of cyanoaeetamide... 

Condensation, of paraldehyde with diethyl malonate, 32, 54 of a-phene thyl chloride with diphenylacetonitrile, 39, 74 of phenylacetylene with ethyl orthoformate, 39, 59 of 1-phenylbiguanide with ethyl chloroacetate, 38,1 of potassium diphenylacetonitrile with benzyl chloride, 39, 73 of potassium trithiocarbonate with potassium chloroacetate, 39, 77 of sodium acetylacetonate to tetraacetylethane, 39, 61 of sodium formylacetone with cyano-acetamide, 32, 32 of tetracyanoethylene with N,N-dimethylaniline, 39, 68 of thiophene, paraldehyde, and hydrogen chloride, 38, 86 of thiourea with furfuryl alcohol, 36,66... 

Although the methyl groups in acetylacetonate complexes retard some reactions by steric hindrance, they provide some electronic enhancement in reactions with electrophiles and furthermore protect the donor oxygen atoms from electrophilic attack. These properties have been discerned by a comparison of the numerous reactions of acetylacetone complexes with the relatively few successful reactions of complexes of formylacetone and malondialdehyde. 

Condensation, of 1-phenylbiguanide and ethyl chloroacetate, 38, 1 of sodium formylacetone with cyano-acetamide, 32, 32... 

Heterocycles. Dropwise addition of a mixture of 0.8 mole each of acetone and ethyl formate to a suspension of 0.86 mole of sodium methoxide in ether at 0° effected condensation to sodio formylacetone (1). Removal of the ether and treatment of the residual sodium enolate with 0.3 mole of cyanoacetamide in 400 ml. of... 

A procedure for the synthesis of 3-cyano-6-methyl-2(l)-pyridone (3) requires isolation of the sodio derivative of formylacetone, (1), and this was accomplished by stirring a suspension of sodium methoxide in ether with ice cooling, dropping in a mixture of acetone and ethyl formate, and removing the ether at a temperature below 70°. The solid residue was treated with an aqueous solution of cyanoacetamide (Eastman) and piperidine acetate and the solution was refluxed, for 2 hrs. After... 

The vinylogy principle was first formulated by Claisen in 1926, who observed for formylacetone acidic properties similar to that of acetic acid. The vinyl goup plays the role of an electron-conducting channel between the carbonyl and the hydroxyl group. The same effect explains the acidity of ascorbic acid (Figure 14.19). 

FIGURE 14.19 Formylacetone (enoUc form) and vitamin C are comparable in acidity to carboxylic acids. 

The de Mayo reaction is also observed for oxo-aldehydes these react exclusively from the enol form in which the aldehyde rather than the ketone is enolized. A representative example is the reaction of enolized formylacetone with 1,2-dimethylcyclohexene". 

By means of the above1 procedures, a variety of (3-dicarbonyl metal chelates have been halogenated. For example, the chromium chelates of formylacetone (52), l-phenyl-l,3-butanedione and dibenzoylmethane (67), ethylenediaminebis(2,4-pentanediono)copper(II) and the nickel(II) chelate of. TV-tt-butylsalicylaldimine (112) have been brominated in chloroform solution with Ar-bromosuccinimide. The chromium chelates of a number of... 

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