Diethyl malonate benzoylation

The interaction of 2-(acetylmercapto)benzoyl chloride with sodio diethyl malonate gives 3-carbethoxy-4-hydroxythiocoumarin (Eq. I) - ... 

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... 

I, Br 11 diethyl malonate, ethyl acetoacetate, ethyl benzoyl acetate Cul, CS2CO3 DMSO, 40-50°C [67]... 

CuI/L-proUne (LI) was proved to be a quite efficient catalytic system for this coupling. The reaction proceeded smoothly in DMSO at 40-50°C in the presence of CS2CO3 (Table 9.14, entry 1) [67]. Both aryl iodides and bromides were suitable substrates. A wide range of activated methylene compounds, including ethyl ace-toacetate, ethyl benzoyl acetate, and diethyl malonate were compatible with these reaction conditions. This catalytic system could also be used for the arylation of aryl iodides with acetylacetone and ethyl cyanoacetate (entry 2) [68]. Recently, it was found that 2-picoUnic acid (L4) could lead to the arylation of aryl iodides and diethyl malonate worked at room temperature (entry 3) [69]. For hindered substrates or aryl bromides, higher reaction temperatures were still required. Additionally, Chxn-Py-Al (L16) was revealed to accelerate the Cul-catalyzed coupling of iodobenzene with diethyl malonate, ethyl cyanoacetate and malononitrile (entry 4) [26],... 

Acylmalonic acid esters. Diethyl malonate added to NaH covered with tetra-hydrofuran, after ca. 1 hr. when H2-evolution has ceased and a soln. is formed, benzoyl chloride added all at once, stirring continued 5-10 min., then poured into water -> diethyl benzoylmalonate. Y 72%.—Tetrahydrofuran is an excellent medium for condensation reactions. In it, sodio compounds are soluble, and active halogen compounds, e.g. acyl chlorides, react instantly. F. e. s. S.-O. Lawesson and T. Busch, Acta Ghem. Scand. 13, 1717 (1959). 

Ethyl pentafluorobenzoylacetate (33), benzoyl(pentafluorobenzoyl)methane (34), and bis(pentafluorobenzoyl)methane (35) have been synthesized as shown in Scheme 11. The first of these is not a new compound, having been prepared in the early 1960 s by treatment of pentafluorobenzoyl chloride with diethyl malonate in the presence of magnesium ethoxide followed by hydrolysis of the diester CeF8 C0 CH(C02Et)a thus produced, and by condensation of ethyl pentafluorobenzoate with ethyl acetate in the presence... 

Benzoyl chloride, and sodio-ethyl malonate yield diethyl benzoyl-malonate. 

In a similar fashion, diethyl cyclopropane-1,1-dicarboxylate (4) reacted with lithium dialkyl-cuprate to give the corresponding malonates S in high yields. Byproducts could be formed by the attack of the organometallic reagent at the carbonyl function. With diethyl 2-vinyl-cyclopropane-1,1-dicarboxylate (6), a preference for the 1,7-addition of the dialkylcuprate was found. Similar observations were made with 1-acetyl- (9,R = Me) and 1-benzoyl-2-vinylcyclopropane (9, R = Ph) when reacted with various dialkyl- and diphenylcuprates and with a vinylcyclopropanedicarboxylate fragment incorporated into a polycyclic system to yield compound 11. ... 

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... 

Diethyl (benzoy]amlno)malonate 585 Benzoyl chloride (48.5 g) is dropped into a stirred mixture of diethyl aminomalonate (58 g), pyridine (50 ml), and water (250 ml), the temperature being kept below 50°. After cooling to room temperature the precipitate is filtered off, dried in a vacuum, dissolved in the minimum amount of benzene, and reprecipitated by gradual addition of six times the volume of light petroleum. The amido ester (92.4 g, 90%) has m.p. 73-74°. 

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... 

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