TBAI/TBHP‐Promoted Generation of Malonyl Radicals: Oxidative Coupling with Styrenes Leads to γ‐Keto Diesters

A metal‐free protocol for oxidative coupling of malonic esters with styrenes to form γ‐keto diesters has been developed. Key to the success of this process is the generation of malonyl radicals from unfunctionalized malonic esters under organo‐catalysis conditions with TBAI and TBHP. This process tolerates both terminal and internal olefins with diverse malonic esters. It provides a new green metal‐free alternative to traditional metal mediated process for generation of malonyl radicals and there by γ‐keto diesters.     

Electrochemical selective trimerization of malonic esters into esters of propane-1,1,2,2,3,3-hexacarboxylic acid in the presence of hydrobromic acid salts

Conclusions The electrochemical oxidation of malonic esters in methanol, ethanol, or acetonitrile in the presence of alkali metal bromides as catalyst-carriers, with the use of 1.8–2 F of electricity per mole of the starting malonic ester leads to esters of propane-1,1,2,2,3,3-hexacarboxylic acid in a yield of up to 90%.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 352–355, February, 1989.     

A ‘one-pot’ synthesis of α-1,2,4-oxadiazolo esters from malonic diesters and amidoximes under solvent-free conditions

A ‘one-pot’ procedure for synthesis of α-1,2,4-oxadiazolo esters from malonic diesters and amidoximes under solvent-free conditions is described. It is likely that this reaction goes through a ketene intermediate generated from the malonic diester by elimination of a molecule of alcohol.     

A Novel Olefination of Carbonyl Compounds with Dibromomalonate Promoted by Dibutyl Telluride

α,β-Unstaturated malonic esters are conveniently synthesized from the reaction of dibromomalonate with carbonyl compounds promoted by dibutyl telluride in exellent yields. A possible mechanism involving twice halophilic attacks of dibutyl telluride is proposed. This methodology provides a facile route to α,β-unsaturated malonic esters and represents an alternative to the Knoevenagel reaction.     

Interaction of 2-bromo-7-methyl-5-oxo-5H-1,3,4-thiadiazolo[3,2-α]pyrimidine with methylene-active compounds and acid hydrolysis of its products

Reactions of 2-bromo-7-methyl-5-oxo-5H-1,3,4-thiadiazolo[3,2-a]pyrimidine with sodium derivatives of pentane-2,4-dione, malonodinitrile, Meldrum acid, acetoacetic, cyanoacetic and malonic esters have been shown to give the respective substituted derivatives. Azinyl-ylidene tautomerism has been found to be characteristic of these compounds, the latter existing mainly in the ylidene form. The acid hydrolysis of pentane-2, 5-dione and cyanoacetic and malonic esters derivatives has been investigated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1957–1961, November, 1993     

Phosphonomethylation of malonic and cyanoagetic esters

Conclusions Condensation was studied in the ternary system made up of a trialkyl phosphite, an aldehyde, and malonic or cyanoacetic ester. A number of [(dialkoxyphosphinyl)methyl]malonic and 2-cyano-2- (dialkoxyphosphinyl)propionic esters were prepared.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 889–893, April, 1969.     

Transesteeification of malonic esters

Conclusions Hither esters of malonic acid have been prepared in good yield by transesterification of lower esters with appropriate primary or secondary alcohols in the presence of alkaline or acid catalysts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 892–895 (1968).     

Nouvelle methode de decarbomethoxylation

Heterocycles substituted by two carbomethoxy groups on the same carbon lose one of these groups when reacted with piperidine. This reaction has been extended to substituted malonic and cyanacetic esters. The mechanism of this reaction is discussed. Piperidine also causes the decarboxylation of substituted malonic and cyanacetic acids.     

A mild,rapid and convenient esterification of half esters of malonic acid

A new method for the esterification of half esters of malonic acid with chloroformates is described. The reaction proceeds $\text{via}$ the mixed anhydride followed by spontaneous decarboxylation.     

Formation of oxaphospholane derivatives in the phosphonomethylation of compounds containing a labile hydrogen atom

Conclusions The condensation of trialkyl phosphites with malonic, cyanoacetic, and acetoacetic esters and excess paraform proceeds with the formation of 5-membered cyclic esters of phosphonic acids. The structure of the obtained products was proved by the PMR, NMR, and IR spectra.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 96–100, January, 1970.     

Malonic to Acetic Ester Transformation by Boric Acid

One of our synthetic projects involves a step of removing a carbalkoxy group from a substituted malonic ester. For accomplishing that goal, Krapcho's method¹ was deemed unsuitable, because the malonic ester contains an allylic halogen which is liable to attack by dimethyl sulfoxide (Kornblum reaction). Our recent work on using iodotrimethylsilane² to achieve decarbal-koxylation of such esters was partly impelled by that need; however, the prohibitive economics associated with even a medium-scale preparation forced us to develop a less expensive alternative.     

α-Amidoalkylation of CH-Acids by Means of N-(1,2,2,2-Tetrachloroethyl)-amides

The reaction of α-amidoalkylation of malonic and acetoacetic esters as well as tert. butylacetate, arylacetic acids and benzylcyanide with different N-(1,2,2,2-tetrachloroethyl)-amides was investigated and 2-substituted 3-acylamino-3-trichloromethyl propionic acids and esters were synthezised.     

An efficient synthesis of β-amino esters via Zn(OTf)2-catalyzed Mannich-type reaction

A Zn(OTf)₂-catalyzed Mannich-type reaction of the electron-deficient aromatic amines with the electron-deficient aromatic aldehydes and diethyl malonic ester was described. This three-component reaction afforded the corresponding β-amino esters in good yields.     

One-pot carbon-carbon bond formation at the β-position of cyclic ketones: oxidative Michael addition with alkyl malonates

A carbon-carbon bond was formed at the β-position of cyclic ketones in a one-pot manner by oxidation with N-tert-butylbenzenesulfinimidoyl chloride, followed by the reaction of malonic acid esters or potassium cyanide.     

Homogeneous catalytic hydrogenation of dicarboxylic acid esters

Esters of dicarboxylic acids are hydrogenated in the homogeneous phase in the presence of H₄Ru₄(CO)₈(PBu₃)₄. The corresponding hydroxy esters are the main products from oxalic and malonic esters. Dimethyl succinate gives γ-butyrolactone, while glutaric esters do not react.Only the ortho isomer of the phthalic esters reacts, giving phthalide and methyl benzoate.Both electronic and steric factors affect the course of this reaction.     

Some alkyldimethyldecadienoic acids

Conclusions Eight previously unknown 2-alkyl-5,9-dimethyldeca-4,8-dienoic acids and the eight corresponding disubstituted malonic esters have been synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1456–1457, August, 1966.     

Electrophilic substitution reactions of esters of 4,5-substituted 1,3-dithiol-2-ylideneacetic and 1,3-dithiol-2-ylidenemalonic acids

The electrophilic substitution reactions (with halogens, POCl₃ + DMF, diazonium salts, iodoso compounds) of both esters of 4,5-substituted 1,3-dithiol-2-ylideneacetic acids and sodium salts of monoethyl esters of the corresponding malonic acids can be used for the synthesis of 2-methylene-1,3-dithiole derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 898–900, July, 1989.     

Porphyrins. 20. Interaction of 2-formyl-5,10,15,20-tetraphenylporphyrin with ch acids

The reactions of 2-formyl-5,10,15-20-tetraphenylporphyrin (Ia) with nitromethane and of its Cu complex (Ib) with nitromethane, malonic acid, and its esters have been investigated. On interacting porphyrins (Ia,b) with nitromethane in AcOH/BuNH₂ the 2-(2-nitrovinyl)porphyrins (IIa,b) were formed, in liquid NH₃ the nitroalcohols (IIIa,b) were formed, and in DMF/BuNH₂ the dinitro derivatives (IVa,b) were formed. The interaction of porphyrin (Ib) with malonic acid and its esters led to the corresponding condensation products in high yield.For Communication 19 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 936–940, July, 1985.     

Synthesis and characterization of new thermotropic liquid crystalline polymers with paired mesogens containing azobenzene unit: Poly(malonic ester)s

New thermotropic liquid crystalline poly(malonic ester)s with two symmetrical mesogenic units (paired mesogens) were prepared by the polycondensation of 1,6-dibromohexane and novel malonic ester compounds with different flexible ethyleneoxy spacer lengths linked to azobenzene group. All the prepared malonic esters and the resulting polymers exhibited monotropic liquid crystallinity with a nematic texture. The length of the spacer had influence on the temperature of phase transition of them. A possibility of application of the prepared polymers to reversible optical information storage media was also identified through a trans–cis isomerization of azobenzene by UV irradiation.     

Solid-phase synthesis of 4(1H)-quinolone and pyrimidine derivatives based on a new scaffold-polymer-bound cyclic malonic acid ester

An efficient method for the preparation of polymer-bound cyclic malonic acid ester starting from Merrifield resin has been developed. Reaction of the resin-bound cyclic malonic acid ester with triethyl orthoformate and subsequent double substitution with nucleophilic reagents, such as arylamine, urea, thiourea, 2-aminobenzothiazoles, or isothiosemicarbazones, afforded the corresponding polymer-bound substituted aminomethylene cyclic malonic acid esters, which upon thermal treament led to 4(1H)-quinolones, 3-substituted uracils and thiouracils, 4H-pyrimido[2,1-b]benzothiazol-4-ones, and 1-(N-alkylidene or benzylideneamino)-1,6-dihydro-2-methylthio-6-oxo-pyrimidines, depending on the structures of the nucleophilic reagents.