Copper diethyl malonate

Diethyl N-[2,4-bis(dimethylamino)-1,3,5-triazin-6-yl]aminomethylene-malonate was prepared in the reaction of 2,4-bis(dimethylamino)-6-isocya-no-l,3,5-triazine and diethyl malonate in boiling benzene in the presence of copper(I) chloride for 4 hr in 83% yield (89JHC901). 

The coupling of aryl halides and classical carbon nucleophiles, such as malonates, is also feasible in the presence of a properly selected palladium or copper catalyst. Diethyl malonate and 3-iodopyridine, for example, gave diethyl 2-(3 -pyridyl)malonate in 73% yield (7.84.), The optimal catalyst in this process consisted of copper(I) iodide and 2-hydroxylbiphenyl.106... 

Asymmetric cyclopropanation. Three laboratories have reported that copper complexes of chiral bis(oxazolines) are effective catalysts for asymmetric cyclopropanation of alkenes with diazoacetates. Bis(oxazolines) such as 1 are readily available by condensation of a-amino alcohols with diethyl malonate followed by cyclization, effected with dichlorodimethyltin or thionyl chloride. Cyclopropanation of styrene with ethyl diazoacetate catalyzed by copper complexes of type 1 indicates... 

Potassium hydroxide Copper cyanide Hydrochloric acid Sulfuric acid Thionyl chloride Diethyl malonate Acetic anhydride Sodium fluoride Ethyl orthoformate Acetic acid... 

In a related reaction, ethyl cyanoacetate is the source of the cyano(ethoxycarbonyl)methylene unit which is transferred to alkenes by a radical mechanism, e.g. synthesis of 3. This transformation is mediated by copper(II) chloride or acetate, accompanied by lithium chloride. Synthesis of diethyl cyclopropane-1,1-dicarboxylates from diethyl malonate and alkenes is much less efficient. ... 

Preparation. The reagent is prepared by the reaction of paraformaldehyde and diethyl malonate in glacial acetic acid catalyzed by copper acetate and potassium acetate (yield 46%).1 It is obtained as an oil which polymerizes at room temperature to a wax. The monomer can be recovered by distillation in vacuum. 

Several reactions of the triazepine (7) have been examined. Heating (7) at 80°C in benzene results in isomerization to form quantitatively benzo[c]dnnoline iV-imide (8), which is also obtained directly from the diaminobiphenyl (5) by aprotic diazotization without isolation of the triazepine intermediate (7). The triazepine (7) reacts as a masked diazonium compound with hydrazine, hydriodic acid, hydrobromic acid and copper, or diethyl malonate to give the corresponding products (9)-(12), respectively (Scheme 2). 

Besides benzofurans, benzofuranones eould be prepared using 2-halo-phenols as substrates as well. In 1986, Setsune and eo-workers developed a copper-mediated coupling of 2-bromophenols with ethyl cyanoacetate and diethyl malonate. In the presence of an equal amount of CuBr, the desired benzofuranones were formed in satisfied yields. 

In 2004, Cristau et al. [114] found that chelating di-imine Chxn-Py-Al (Figure 8.8) generates a remarkable general copper catalyst for a-arylation in diethyl malonate and diethyl methylmalonate... 

Csp Csp C Bond Formation. Takeda et al. have reported that the stereospecific allylation of vinylstannanes with allylic halides proceeded in the presence of copper iodide (and in the absence of palladium) in dipolar aprotic solvents such as DMSO and THF at room temperature. The stereoselectivity of the reaction was dependent on the stractures of the vinylstannanes and allylic halides, and also on the leaving group of allylic halides employed. 0 -Aryl malonates can be synthesized by Cul-catalyzed C-C bond formation between aryl iodides (bearing a variety of functional groups) and diethyl malonate in the presence of CS2CO3 and 2-phenylphenol as the ligand (eq 25). ... 

A new asymmetric urea-copper complex catalyst that is capable of helical chirality inversion has been developed. The enantioselectivity of the asymmetric conjugate addition of diethyl malonate to trans- -nitrostyrene has been found to depend on the helicity of the catalyst. Either enantiomer of the product can be predetermined by selection of the oxidation state of the copper ion. Facile interconversion between the... 

Olefinic esters may be obtained directly by the Knoevenagel reaction. Alkyl hydrogen malonates are used in place of malonic acid. Decarboxylation then gives the ester directly as in the preparation of ethyl 2-heptenoate (78%) and methyl m-nitrocinnamate (87%). Alkyl hydrogen malonates are readily available by partial hydrolysis of dialkyl malonates. The use of malonic ester in the condensation leads to olefinic diesters, namely, alkylidenemalonates such as ethyl heptylidenemalonate (68%). A small amount of organic acid is added to the amine catalyst since the salts rather than the free amines have been shown to be the catalysts in condensations of this type. Various catalysts have been studied in the preparation of diethyl methylenemalonate. Increased yields are obtained in the presence of copper salts. Trimethylacetalde-hyde and malonic ester are condensed by acetic anhydride and zinc chloride. Acetic anhydride is also used for the condensation of furfural and malonic ester to furfurylidenemalonic ester (82%). ... 

Aryl-5,5-bis(oxazolin-2-yl)-l,3-dioxanes 169 have been easily prepared in three steps from diethyl bis(hydroxymethyl)malonate, amino alcohols, and aromatic aldehydes. They have been used for the copper-catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate in up to 99% ee for the trawx-cyclopropane (maximum transicis ratio = 77/23) <05TA1415>. The same reaction performed on 2,5-dimethyl-2,4-hexadiene with tert-butyl diazoacetate in the presence of copper catalysts bearing ligand 170, prepared from arylglycines, exhibited remarkable enhancement of the rrawx-selectivity (transicis ratio = 87/13), with 96% ee for the trans product <05JOC3292>. 

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... 

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