Malonic a-

Aryl lead tncarboxylates have been shown to be intermediates in two new routes to phenols, and to have considerable potential as reagents for the C-arylation of carbon acids which are more acidic than diethyl malonate. A... 

Step A Ortho-Trif/uoromethy/anilinomethy/ene Ethyl Malonate - A mixture of 54.8 grams of ortho-trifluoromethylaniline and 73.5 grams of ethoxymethylene ethyl malonate was heated to 120°C under an inert atmosphere and maintained for 1 hour at this temperature while distilling off the ethanol formed. The mixture was cooled and the elimination of ethanol was completed by distillation under reduced pressure. The mixture was cooled to obtain 115 grams of ortho-trifluoromethylanilinomethylene ethyl malonate which was used as is for the following stage. A sample of the product was crystallized from petroleum ether (8P = 65° to 75°C) to obtain a melting point of 94°C. 

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. 

B. Di-tert-hutyl malonate. A 1-1. three-necked flask is fitted with a thermometer, a mercury- or rubber sleeve-sealed mechanical stirrer, a reflux condenser protected by a calcium chloride guard tube, and a dropping funnel (either pressure-equalized or protected by a calcium chloride guard tube). A mixture of 100 ml. (about 1 mole) of tert-butyl alcohol, dried by distillation from sodium,2 and 80 ml. (0.63 mole) of dry dimethylanilinc (Note 5) is placed in the flask, the stirrer is started, and a solu-... 

A. Malon, A. Radu, W. Qin, Y. Qin, A. Ceresa, M. Maj-Zurawska, E. Bakker, and E. Pretsch, Improving the detection limit of anion-selective electrodes an iodide-selective membrane with a nanomolar detection limit. Anal. Chem. 75, 3865-3871 (2003). 

The reaction was carried out with /3-keto esters, /3-diketones, malonate, a-formyl ketones, a-cyano and a-nitro esters, cyanoacetamide, and phen-ylsulfonylacetate. (PPh3)2PdCl2 was used with sodium phenoxide. Also, Pd(OAc)2 and PPh3 are good catalysts. When bidentate ligand was used, the 1 1 rather than 1 2 addition reaction took place (56). For example, bis(diphenylphosphino) 1,2-ethane (39) produced a mixture of the following 1,4- (59) and 1,2- (60) addition products ... 

Active methylene or methine compounds, to which two EWGs such as carbonyl, alkoxycarbonyl. formyl, cyano. nitro, and sulfonyl groups are attached, react with butadiene smoothly and their acidic hydrogens are displaced with the 2,7-octadienyl group to give mono- and disubstituted compounds[59], 3-Substituted 1,7-octadienes are obtained as minor products. The reaction is carried out with a /3-keto ester, /3-diketone, malonate, a-formyl ketones, a-cyano and a-nitro esters, cyanoacetamide, and phenylsulfonylacetate. Di(octadienyl)malonate (61) obtained by this reaction is converted into an... 

The activity of complex II (succinate dehydrogenase) is measured as the succinate-dependent reduction of decylubiquinone, which is in turn recorded spectro-photometrically through the reduction of dichlorophenol indophenol at 600 nm (e 19,100-M -cm Fig. 3.8.5). In order to ensure a linear rate for the activity, the medium is added with rotenone, ATP, and a high concentration of succinate. As noticed previously for complex I, decylubiquinone is not a perfect acceptor for electrons from the membrane-inserted complex II [70]. Malonate, a competitive inhibitor of the enzyme, is used to inhibit it. Rather than decylubiquinone, phenazine methosulfate can be utilized, which diverts the electrons from the complex before they are conveyed through subunits C and D, therefore allowing measurement of the activity of subunits A and B. 

CB585). In addition to the reductive cyclization included in Table 11, 1-hydroxyindole-2-carboxylate can also be prepared by base-catalyzed cyclization of dimethyl o-nitrobenzyl-malonate, a reaction which is formulated as involving a nucleophilic attack on the nitro group 72CRV627). 

Alkyl Diethyl malonate a-Alkylated Carboxylic acid... 

The self-complexed catalyst of ALB and a base was also successfully applied to the above-mentioned three-component coupling reaction of an enone, an aldehyde, and a malonate. A catalytic asymmetric synthesis of 11 -deoxy-PGFla was achieved by utilizing this reaction as the first key step (Scheme 8D.14) [31], Furthermore, a potential key intermediate 25 for the synthesis of PGFla was synthesized in relatively high yield with extremely high enantioselec-tivity (97%) by the kinetic resolution of the three-component coupling between racemic enone 24, aldehyde 22, and methyl dibenzylmalonate 23 [31],... 

The heart of the preparation of capsaicin is a malonic ester synthesis. The first step is bromination of the primary alcohol by phosphorous tribromide. The resulting primary alkyl bromide is used to alkylate the sodium salt of diethyl malonate. A substituted malonic acid derivative is obtained following basic hydrolysis of the ester groups. 

O Maille PE, Malone A, Dellas N, Andes Hess B Jr, Smentek L, Sheehan I, Greenhagen BT, Chappell J, Manning G, Noel JP (2008) Nat Chem Biol 4 617-623... 

Reaction of 7,7-dichlorobicycloheptane with base in the presence of malonate, a-cyanoacetate or CMe(CN)Ph ions leads initially to, eg., (277), Yields are not always high because of further reactions, but in some cases reach over 80% 151,202>. 

A classic example of competitive inhibition is the inhibition of succinate dehydrogenase by malonate, a structural analogue of succinate. Competitive inhibitors are usually structural analogues of the substrate, the molecule with which they are competing. They bind to the active site but either do not have a structure that is conducive to enzymatic modification or do not induce the proper orientation of catalytic amino acyl residues required to affect catalysis. Consequently, they displace the substrate from the active site and thereby depress the velocity of the reaction. Increasing [S] will displace the inhibitor. 

Hydrolysis of the alkylated diethyl malonate (a diethyl alkylmalonic ester) gives a malonic acid derivative. 

---