Diethyl allyl- malonate

Preparation of Diethyl Allyl (1-Methyl-2-Pentynyl) Malonate A solution of 12.1 g of sodium in 182 ml of absolute ethanol was prepared, and thereto were added 126.6 g of diethyl (1-methyl-2-pentynyl) malonate. Most of the ethanol was then distilled off under reduced pressure, and the residue was cooled and 63.5 g of allyl bromide were slowly added thereto. After completion of the addition, the mixture was refluxed for about 1 hour. 

The reaction mixture was cooled, treated with about 100 ml of water, and the oily organic layer which formed was removed, washed with water and dried over anhydrous magnesium sulfate. The dried oily organic material was fractionally distilled in vacuo, and diethyl allyl (1-methyl-2-pentynyl) malonate boiling at 105° to 107°C at the pressure of 1 mm of mercury was recovered. 

Preparation of 1-Methyl-5-Allyl-5-( 1-Methyl-2-Pentynyl) Barbituric Acid A solution of 23.8 g of sodium in 360 ml of absolute alcohol was prepared and thereto were added 38.3 g of methyl urea and 96.8 g of diethyl allyl (1-methyl-2-pentynyl) malonate. The mixture was refluxed for about 20 hours, cooled, and the ethanol was removed by distillation in vacuo. The residue was dissolved in about 300 ml of water and the aqueous solution was washed with ether, and the washings were discarded. The aqueous solution was then acidified with acetic acid, and extracted with three 150 ml of portions of ether. 

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. 

C, H, 04 141-28-6) see Loxoprofen diethyl allyl(2-cyclopentenyl)malonate (C15H22O4 93981-13-6) see Cyclopentobarbital diethyl allyl(l-methylbutyl)malonate... 

Preparation of the intermediate for Allobarbitone (diethyl diallyl malonate). Diethyl malonate is dissolved in anhydrous alcohol and treated with one mole of clean sodium meted per every one mole of the ester. To this solution add one mole of allyl chloride and reflux for about 4 hours. Another equimolar ratio (1 mole of sodium per mole of ester) of sodium is added, followed by the same ratio of allyl chloride (1 mole per 1 mole), and this mixture is boiled for 2 hours. The alcohol is removed by distillation and the ester is extracted with benzene and distilled or evaporated in vacuo, recrystallized with a suitable "dry" solvent, and filtered. Evaporate again to remove traces of solvent. Keep this product, and any other substances that require dry reagents or solvents, stored away from contact with the atmosphere. When evaporating, filter the air coming into the evaporating vessel with a suitable drying agent. Use a little common sense. 

Evans used a single catalyst for an allylation-PKR sequence that only required changing the reaction temperature for each step. Thus, they synthesized cyclopentenone 101 from allylic acetate 99 and diethyl propargyl-malonate salt in the presence of [RhClCO(dppp)]2 with high yield. When formation of intermediate 100 was complete they just heated the reaction to 80 °C to get 101 (Scheme 29) [126]. 

Sodium hydrosulfide was found to afford a thiirane 67 upon reaction with 2-iodomethylcyclopropane-l,l-dicarboxylic acid diethyl ester <2005TL469>. In addition, 2-allyl malonic ester 68 was obtained. Scheme 12 shows the reasonable mechanisms proposed by the authors. 

This is a general procedure for a domino Heck/Diels-Alder reaction [69] (Scheme 3-58). To a solution of diethyl allyl(2-bromoallyl)malonate (261) [257] (640 mg, 2.01 mmol) in acetonitrile (16 mL) in a screw-capped Pyrex bottle were added Pd(OAc)2 (14 mg, 3 mol%), PPh3 (42 mg, 8mol%), silver carbonate (665 mg, 2.41 mmol), and methyl 2-chloro-2-... 

Ionic liquids ([BMIM][PF6]) are suitable media for the Co2(CO)8-catalyzed intramolecular and intermolecular Pauson-Khand aimulation, provided that the reaction is carried out under a CO pressure of 10 bar [299]. Two diethyl allyl propargyl malonates were quantitatively converted into the relevant cydopentenones, whereas heteroatom tethered enynes gave lower yields in their cydocarbonjiation products. An example is shown in Scheme 5.2-138. The reaction also works with the direct addition of ethyldiazoacetate to imines in [BMIM][BF4] and [BMIMjfPFe] [300]. 

Recently, Maulide el al. have presented another deracemization process in which the product has more than one stereogenic element and therefore allows the existence of different diastereomers. Each and every one of the four different stereoisomeric products (for diethyl(butyl)malonate enolate as the nucleophile) could be prepared from the racemic ds-cyclobutene lactone 61 with high selectivity by employing the Hgands LI, en Ll, 12, and mt-L2 (Scheme 12.30). The observed overall inversion in the presence of ligand L2 (and mt-L2) is thought to be a result of stereoretentive it-allyl generation caused by internal coordination of the carboxylate, followed by classical nucleophilic attack on the opposite side of palladium [51]. 

Scheme 14.30 Conversion of diethyl allyl (2-methylallyl) malonate in dichloromethane at 30°C in the presence of 1 mol% of complex 56 (a), 6 ( ), and 57a( ).

Pfaltz and coworkers [56] applied the ESI-MS technique for parallel screening of Pd-catalyzed enantioselective allylation reaction of diethyl ethyl malonate with allylic esters. Enantiodiscrimination of a palladium catalyst with different chiral ligands was... 

The first example of an allylic alkylation catalyzed by iron compounds was reported in 1979. Allylic halides and carboxylates are treated with a diethyl malonate anion in the presence of sodium tricarbonyl(nitrosyl)ferrate to give the allylated malonates with good regioselectivity in favor of the ipso product (Scheme 4-195). This transformation can be carried out in a carbon monoxide atmosphere catalyzed by the Hieber-type complex [Bu4N][Fe(CO)3NO] (TBAFe) that is easier to handle. The... 

C10H16O4 2-allyl-malonic acid diethyl ester 2049-80-1... 

The synthesis of the right-wing sector, compound 4, commences with the prochiral diol 26 (see Scheme 4). The latter substance is known and can be conveniently prepared in two steps from diethyl malonate via C-allylation, followed by reduction of the two ethoxy-carbonyl functions. Exposure of 26 to benzaldehyde and a catalytic amount of camphorsulfonic acid (CSA) under dehydrating conditions accomplishes the simultaneous protection of both hydroxyl groups in the form of a benzylidene acetal (see intermediate 32, Scheme 4). Interestingly, when benzylidene acetal 32 is treated with lithium aluminum hydride and aluminum trichloride (1 4) in ether at 25 °C, a Lewis acid induced reduction takes place to give... 

Stable enolates such as diethyl malonate anions react with allyl sulfones (or acetates) in the presence of nickel complexes to give a mixture of the a- and /-product83. The regioselectivity is generally poor in the nickel-catalyzed reaction, but the molybdenum-catalyzed reaction is selective for alkylation at the more substituted allylic site, thereby creating a quaternary carbon center84. 

C3H5S 870-23-5) see Altizide allyl(l-methyl-2-pentynyl)malonic acid diethyl ester (C16H24O4 101448-52-6) see Methohexital 4-allyloxy-3-chlorobenzaldehyde (CigH Cl02, 58236-91-2) see Alclofenac 4-allyloxy-3-chlorobenzyl chloride (C Hi()Cl20 20788-43-6) see Alclofenac 4-allyloxy-3-chlorobenzyl cyanide (C, H C1N0 20788-44-7) see Alclofenac... 

Monoanions derived from nitroalkanes are more prone to alkylate on oxygen rather than on carbon in reactions with alkyl halides, as discussed in Section 5.1. Methods to circumvent O-alkylation of nitro compounds are presented in Sections 5.1 and 5.4, in which alkylation of the a.a-dianions of primary nitro compounds and radial reactions are described. Palladium-catalyzed alkylation of nitro compounds offers another useful method for C-alkylation of nitro compounds. Tsuj i and Trost have developed the carbon-carbon bond forming reactions using 7t-allyl Pd complexes. Various nucleophiles such as the anions derived from diethyl malonate or ethyl acetoacetate are employed for this transformation, as shown in Scheme 5.7. This process is now one of the most important tools for synthesis of complex compounds.6811-1 Nitro compounds can participate in palladium-catalyzed alkylation, both as alkylating agents (see Section 7.1.2) and nucleophiles. This section summarizes the C-alkylation of nitro compounds using transition metals. 

Microwave-mediated transesterification of commercially available neat poly(styr-ene-co-allyl alcohol) with ethyl 3-oxobutanoate, ethyl 3-phenyl-3-oxopropanoate, and diethyl malonate provided the desired polymer-supported /i-dicarbonyl compounds (Scheme 12.18) [65]. Multigram quantities of these interesting building blocks for heterocycle synthesis were obtained simply by exposing the neat mixture of reagents to microwave irradiation in a domestic microwave oven for 10 min. 

The research group of Van Leeuwen reported the use of carbosilane de-ndrimers appended with peripherial diphenylphosphino end groups (i.e. 25, Scheme 26) [37]. After in situ complexation with allylpalladium chloride, the resultant metallodendrimer 25 was used as catalyst in the allylic alkylation of sodium diethyl malonate with allyl trifluoroacetate in a continuous flow reactor. Unlike in the batch reaction, in which a very high activity of the dendrimer catalyst and quantitative conversion of the substrate was observed, a rapid decrease in space time yield of the product was noted inside the membrane reactor. The authors concluded that this can most probably be ascribed to catalyst decomposition. The product flow (i.e. outside the membrane reactor)... 

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