Ethoxymagnesium malonic ester

Mixed anhydride synthesis. For use of the reagent in peptide synthesis, see Butyl chloroformate. The principle involved is illustrated by a procedure for the preparation of diethyl benzoylmalonate (3). Benzoic acid is condensed with cathyl chloride in toluene in the presence of triethylamine to produce the mixed anhydride (I), and an ethereal solution of ethoxymagnesium malonic ester (2), prepared from mulunic ester, magnesium, ethanol, and a trace of carbon tetrachloride as catalyst, is added... 

Mixed anhydride synthesis. A method widfely used for the synthesis of peptides provides a general method of acylation, illustrated by the benzoylation of diethyl malonate. Benzoic acid is converted into the triethylamine salt in toluene, and the solution is treated at 0 with ethyl chloroformate to form the mixed benzoic-carbonic anhydride, with precipitation of triethylamine hydrochloride. The second component, ethoxymagnesium malonic ester, is prepared from diethyl malonate in ethanol-ether... 

Malonic ester, ethoxymagnesium derivative, solution of, 30, 70 Malonic ester synthesis, 30, 7... 

Esters, amides, and primary alcohols are obtained from benzo[6]-thiophene carboxylic acids by standard procedures.337 481,585 692 093,695 Acid chlorides undergo the Arndt-Eistert reaction,337,568,689 react with diethyl ethoxymagnesium malonate to give the corresponding methyl ketone,144 557 and are reduced to the aldehyde with 1 ithium tri-ferf-butoxy aluminohydride.33 7... 

A general convenient alkyl methyl ketone synthesis, which utilises the /7-keto ester system as an intermediate, involves the acylation of a malonate ester by way of the ethoxymagnesium derivative. Hydrolysis and decarboxylation to the ketone is accomplished by heating in acid solution the synthesis of cyclohexyl methyl ketone is the illustrative example (Expt 5.96). 

Syntheses sia ethoxymagnesiummalonic ester. Four Organic Syntheses procedures start with the reaction of absolute ethanol, malonic ester, and magnesium in the presence of a catalytic amount of carbon tetrachloride to produce ethoxymagnesium-... 

Diethyl benzoylmalonate has been prepared by treatment of the copper derivative of ethyl benzoylacetate with ethyl chlorocarbonate.9 It has also been obtained by the action of benzoyl chloride on a mixture of malonic ester and sodium ethoxide 1benzoyl chloride and the ethoxymagnesium derivative.14 The present method has been described in a previous communication and is of interest as an illustration of the use of mixed carbonic anhydrides as acylating agents.8... 

The ethoxymagnesium derivatives of malonic esters are excellent intermediates for selective introduction of different acyl groups into the esters 428 oxo esters can be acylated by boiling them with the acyl chloride and magnesium in benzene (46-52% yields) 429... 

ETHYL BUTYL ESTER, 37, 34 METHYLENE-, DIETHYL ESTER, 38, 22 Malonic ester, acylation by o-nitro-benzoyl chloride, 30, 70 ethoxymagnesium derivative, solution of, 30, 70 37, 20 Malonic ester syntheses, 30, 7 Malononitrile, 37, S3 Malonyl dichloride, 33, 20 Mandelic acid, 36, 3 -bromo-, 35, 11... 

A convenient method for preparing alicyclic or aromatic methyl ketones consists in the acylation of the ethoxymagnesium derivative of diethyl malonate with the appropriate acyl chloride, followed by acid hydrolysis and decarboxylation of the resulting /3-keto diester. The last step is Carried out like the ketonic cleavage of /3-keto esters. The over-all yields are 60-85%. 

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