Diethyl sodio-malonate

Buchta and his coworkers have contributed to the problem we are discussing. The tetraester of the [3.3.1]propellane shown, 17, is formed uberraschenderweise from 1,1,2,2-tetrakis-hydroxymethylcyclopropane tetramesylate 16 and sodio-diethyl malonate, in 53 % yield 4f. ... 

When the cyclopropane homolog 24, with the same 1,1,2,2-tetrabromide array, was treated with zinc, the analogous fragmentation reaction occurred, leading in this case to an 84% yield of 2,4-dimethyl-penta-1,4-diene, 25 4g). This is in contradistinction to the reaction of the corresponding tetramesylate 16 with sodio-diethyl malonate 4f>, (vide supra). 

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

Sodio diethyl malonate Malonic acid, diethyl ester, ion(l-), sodium (8) Propanedioic acid, diethyl ester, ion(l-), sodium (9) (996-82-7) 3-Formylquinoline-2( l//)-thione 3-Quinolinecarboxaldehyde, 1,2-dihy-dro-2-thioxo- (9) (51925-41-8)... 

The ortho-substituted isothiocyanates are valuable intermediates for the preparation of a variety of heterocyclic compounds for example, o-isp-thiocyanato-( )-cinnamaldehyde with sodio diethyl malonate undergoes facile cyclization to 3-formylquinoline-2(l//)-thione,9 which in turn may be used for the preparation of tricyclic9,10 and large ring heterocyclic compounds."... 

Another unusual phosphate ester reported is that of the enol from malonic ester (17), formed by reaction of sodio diethyl malonate with diethyl phos-phorochloridate. 

Few examples of additions of stabilized carbanions to N-sulfonyl imines currently exist. Kresze et al. [6] have added sodio diethyl malonate to the benzalde-hyde/p-toluenesulfonamide N-sulfonyl inline to produce adduct 59 [Eq. (19)]. 

Treatment of the acetonide of (107) with one mole of methanesulfonyl chloride at low temperature gave the monomesylate (108) contaminated with some dimesylate. In glycosides such as (8), the acidity of the 2-hydr03Qfl group is enhanced by the inductive effect of the acetal (100). This effect is absent in the present case, but the observed selectivity could conceivably reflect less hindrance of the 2-hydroxyl group. Scission of the derived oxirane with sodio diethyl malonate was non-regioselective, but the... 

Since Trost and co-workers demonstrated that the C-C bond forming reaction between an allylic acetate and a soft nucleophile such as sodio diethyl malonate was catalysed by Pd ° complexes [39], many attempts have been made to develop a catalytic asymmetric synthesis based on this principle. A particular problem is that the catalytic reaction involves nucleophilic attack on the allyl from the side remote from Pd so that the influence of the chiral ligand is severely curtailed. The most successful early work was the reaction type exemplified in Figure 4.18(a) described by Bosnich and co-workers [40]. The essential features are the combination of a CHIRAPHOS Pd catalyst with an allylic acetate reactant carrying aryl substituents at both terminal positions. This combination gave rise to products of allylic alkylation with a typical e.e. of 80%. 

Ethyl cyanoacetate (Section 111,131) is sometimes preferable to diethyl malonate for the synthesis of acids. It forms a sodio derivative with sodium ethoxide ... 

Diethyl Ethylmalonate.—Sodium (4-6 g.) is dissolved, in a small flask fitted with an efficient reflux condenser, in 75 c.c. of absolute alcohol and to the cooled solution 33 g. of diethyl malonate are added (precipitation of diethyl sodio-malonate). To the mixture thus obtained, ethyl bromide (25 g.) or ethyl iodide (35 g.) is added in small portions with shaking and the flask is then heated on the water bath until, after one to two hours, the contents are no longer alkaline. The alcohol is removed by distillation in a vacuum from the water... 

Shah and Heeramaneck improved the yields (30-45%) of 318 when mixtures of imidoyl chlorides (317), diethyl malonate, and diethyl sodio-malonate in 1 1 1 molar ratio were reacted in toluene at reflux temperature for 2 hr (36JCS428). This modification was later applied by others too (46JA1272 49J1C171). Diethyl (naphthylamino)phenylmethylenemal-onates (319) were also prepared in 18% and 30% yields by starting from N-( 1- and 2-naphthyl)imidoyl chlorides (37JCS867). 

Perfluoro[AT-fluoro-Af-(4-pyridyl)acetamide], prepared via direct fluorination of the sodium salt of perfluoro[/V-(4-pyridyl)acetamide], readily fluorinates diethyl sodio(phenyl)malonate, 1-morpholinocyclohexene, phenol and anisole under mild conditions.129... 

Condensation of the sodio derivatives of diethyl malonate.,JW ethyl aoetoacetate,11 and ethyl cyanoacetate1814 hoe been found to take place exclusively at the terminal position of 1, 2-epoxy-3-buteine (Kr 880). It may be recalled that this substance gives significant proportions of other products on treatment with less bulky nucleophiles. 

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

When treated with one equivalent of sodium ethoxide, diethyl malonate is converted into the mono-sodio derivative, as a result of removal by base of one of the a-methylene protons to yield a mesomeric anion (12). This nucleophilic anion undergoes an S 2 reaction with an alkyl halide to give a C-substituted malonic ester. A second, different, alkyl group can be similarly introduced on to the a-carbon atom, or alternatively two identical alkyl groups may be introduced in a one-step operation by using appropriate proportions of reactants. 

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). 

In 450 cc of methanol is added 47 grams of sodium metal and the mixture allowed to completely react to form a methanol solution of sodium methoxide. The methanol solution of sodium methoxide is then cooled to 60°C and 68 grams of thiourea which has been thoroughly dried is added with stirring until a uniform solution is formed. Thereafter, 157 grams of diethyl allyl-(1-methylbutyl)malonate is added to the solution of the sodio derivative of thiourea at a temperature of 55°C and the condensation reaction mixture maintained at the said temperature for 24 hours. Methyl alcohol is removed under vacuum during the course of the reaction while maintaining a temperature of 55°C. 

In the reactions which are here discussed, ethyl sodio-acetoacetate, which may be chosen as an example for the following reactions, behaves exactly as diethyl sodio-malonate. 

Cyclohexane oxide (Eq. 889) and certain methyl-substituted derivatives have been condensed successfully with diethyl Sodio-malonate,321 107a-1SW-1241 ethyl eodioaoetoaoetate,M< and ethyl eodio-cyanoaoefcate Lactone rings aw generated in all cases, since transfused six-membered rings are stable. 

Diethyl sodio malonate Tetraethyl cthane-l,l,2,2-tetracarboxylate, hexaethyl (EtOH, DMSO, DMF) propane-1,1,2,2,3,3-hexacarboxylate (main product... 

Three methods for the conversion of 3-chlorocarbonyl-1,2,5-thiadiazole (81) to ketones were investigated by Gill. The Lund procedure for the malonic ester synthesis of ketones proved quite successful for the preparation of 3-acetyl-1,2,5-thiadiazole (83). Condensation of 81 with diethyl ethoxymagnesiomalonate provides the ketodiester (82) which undergoes acid hydrolysis and decarboxylation to 83 in 90 % yield. The same reaction sequence employing the sodio derivative of malonic ester was much less efficient. 

The eemit clic eposide 2treatment with diethyl sodio-malonate, thereby affording a apiroIactone Mi as shown in q. <6Sg),... 

Cyclobexeiie oxide ( q. 889) and oertain methyl-eubstituted dwivativea have been condensed eucceesfuUy with diethyl sodio-malonate. i ethyl eodioaoetoaoetate, and ethyl sodio-... 

In the case of 1,3-dicarbonyl compounds, the solvent frequently interferes with the coupling reaction. So with diethyl sodio malonate in ethanol [212b], methanol [212b], dimethylacetamide [212b], or HMPTA [216], besides the dimer and the trimer, the compounds LIXa-c are obtained. They are presumably formed by oxidation of the solvent to the aldehyde and its condensation with the active methylene compound. No dimer was detected in the oxidation of sodio acetoacetate in ethanol, with the major product being LX [217]. Anodic oxidation of cyclic 1,3-diketones in aqueous methanolic sodium hydroxide does not yield the dimer but product LXI, formed by condensation of the starting compound with formaldehyde [218]. 

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