Sodium cyanoacetate

The first part of this preparation (as far as the solidification of the sodium cyanoacetate) must be carried out in the fume-cupboard. Add 30 g. of monochloroacetic acid to 60 ml. of water contained in a wide evaporating-basin (about 12-15 diameter)... 

Ethyl malonate can be conveniently prepared by neutralising a solution of monochloroacetic acid with sodium bicarbonate, then heating with potassium cyanide to form sodium cyanoacetate ... 

CHjClCOONa + KCN —> CHj(CN)COONa + KCl Upon warming the crude sodium cyanoacetate with ethyl alcohol and sulphuric acid, ethyl malonate is produced. Two mechanisms of the reaction have been proposed —... 

A solution of sodium cyanide [143-33-9] (ca 25%) in water is heated to 65—70°C in a stainless steel reaction vessel. An aqueous solution of sodium chloroacetate [3926-62-3] is then added slowly with stirring. The temperature must not exceed 90°C. Stirring is maintained at this temperature for one hour. Particular care must be taken to ensure that the hydrogen cyanide, which is formed continuously in small amounts, is trapped and neutrali2ed. The solution of sodium cyanoacetate [1071 -36-9] is concentrated by evaporation under vacuum and then transferred to a glass-lined reaction vessel for hydrolysis of the cyano group and esterification. The alcohol and mineral acid (weight ratio 1 2 to 1 3) are introduced in such a manner that the temperature does not rise above 60—80°C. For each mole of ester, ca 1.2 moles of alcohol are added. 

Manufacture. Cyanoacetic acid and cyanoacetates are iadustrially produced by the same route as the malonates starting from a sodium chloroacetate solution via a sodium cyanoacetate solution. Cyanoacetic acid is obtained by acidification of the sodium cyanoacetate solution followed by organic solvent extraction and evaporation. Cyanoacetates are obtained by acidification of the sodium cyanoacetate solution and subsequent esterification with the water formed being distilled off. Other processes reported ia the Hterature iavolve the oxidation of partially oxidized propionittile [107-12-0] (59). Higher esters of cyanoacetic acid are usually made through transesterification of methyl cyanoacetate ia the presence of alumiaiumisopropoxide [555-31-7] as a catalyst (60). 

Pimelic acid has been prepared as a by-product of the reaction between trimethylene bromide and sodium cyanoacetic ester 1 by the action of carbon dioxide upon pcntamethylene-... 

Bromoacetic acid Sodium cyanoacetate Cyanoacetic acid... 

The reaction of aliphatic, alicyclic, and aromatic aldehydes and ketones with cyanoacetic ester, NCCHjCOjCjH, is general. The products are 0L,/3-olefinic cyanoacetates. The aldehydes are condensed with the ester in the presence of amines or with sodium cyanoacetate in the presence of sodium hydroxide, Similarly, cyanoacetic ester is condensed with ketones by catalysts such as acetamide or the acetates... 

Reactions of silver(i) or sodium cyanoacetates with Cp2TiCl2 afford the bis(cyanoacetato) complex Cp2Ti(02CCH2CN)2. The molecular structure shows O-unidentate carboxylate groups the cyano-nitrogen atom is not bonded to the metal. This compound can alternatively be prepared from Cp2TiMe2 and cyanoacetic acid.1581... 

While oxiranes afford with sodium ethylcyanoacetate only oc-cyano-y-butyrolactone, i.e., the insertion of the hydroxyethyl moiety into ethyl cyanoacetate,6 thiiranes give with sodium cyanoacetate, in a one-step... 

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