Ethyl ethoxyacetate

The Step 3 product (14.2 mmol) and ethyl ethoxyacetate (17.75 mmol) were stirred in 80 ml toluene at 0—5°C, then slowly treated with potassium /-buloxidc (15.6 mmol), and then stirred 48 hours at 65°C. The mixture was further treated with 20 ml toluene and 2.4 ml ethyl ethoxy acetate and then stirred an additional 48 hours at 65°C. The solution was then concentrated and triturated with EtOAc to remove unreacted Step 3 reagent. The remaining solid was further triturated with CHC13 and 3.66 g product isolated with an HPLC purity of 80%. 

Ethyl dihydroxyuialonate, 10, S7 Ethylene chlorohydrin, 12,68 14, 28, SS Ethylene cyanohydrin, 16, 88 Ethylene dibromide, 10, 96 Ethyl ethoxyacetate, 13, 42 Ethyl ethyleketeteacarboxylate, 11, 36... 

A large number of symmetrical diaryl- or dialkyl-acetaldehydes, difficult to obtain by other means, have been prepared by the reaction of ethyl ethoxyacetate, or ethyl phenoxyacetate, with Grignard reagents followed by treatment of the resulting glycol monoalkyl ether with anhydrous oxalic acid or dilute sulfuric acid. The yield in the first step is 40-80%, and the yield in the subsequent transformation is 50-80%. 

Ethyl ethoxyacetate has been prepared by the action of ethyl iodide on sodium ethoxyacetate, of sodium ethylate on ethyl chloroacetate, of alcohol on crude diazoacetic ester, and by the alcoholysis of ethoxyacetonitrile using alcoholic hydrogen chloride. ... 

Ethyl iec.-butylmalonate, 11, 22, 76, 77 Ethyl -butyrate, 13, 24 purification of, IS, 25 Ethyl carbonate, 11, 98 Ethyl chloroformatc, 12, 38 Ethyl cinnamate, 12, 36 Ethyl a,j3-mBROM o-p-PHENYLFROPio-nate, 12, 36, 37, 60 Ethyl dihydroxymalonate, 10, S7 Ethylene chlorohydrin, 12, 68 Ethylene dibromide, 10, g6 Ethyl ethoxyacetate, 13, 42 Ethyl ethylenetetracarboxylate, 11, 36... 

B. Ethyl Ethoxyacetate The ethoxyacetic acid, which should amount to about 125 g. (1.2 moles), is placed in a 750-cc. Erlen-meyer flask containing 230 cc. (3.9 moles) of absolute ethyl alcohol. The flask is set in a pan filled with cold water (Note 3), and dry hydrogen chloride is passed into the mixture. After the mixture becomes saturated, (Note 4) it is allowed to stand twenty-four hours to insure the completion of the reaction at room temperature (Note 5). The solution is cooled, and a saturated solution of sodium carbonate is added cautiously and with stirring to avoid excessive foaming. The addition is continued until the mixture is faintly alkaline to litmus an excess of sodimn carbonate lowers the yield and should he avoided. The ester is extracted with four loo-cc. portions of ether the extract is dried with 25 g. of anhydrous potassium carbonate, and the ether is distilled from a steam bath. The residue is distilled at ordinary pressure. The yield of ester boiling at 153-155° is 110-115 g. (55-58 per cent of the theoretical amount based on the chloroacetic acid, or 69-72 per cent based on the ethoxyacetic add). 

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