Acids malonic

The Np02 oxidation of oxalic acid in aqueous perchloric acid provides one of the few examples of redox kinetic studies of Np(VI) . The rate law is 

Admixture of the reactants caused the pink colour of NpO to change to yellow, suggesting complex formation, and one mole of oxalic acid consumed four moles of oxidant to give Np(V) as the final product, identified optically, k is independent of ionic strength and is 0.012 + 0.001 sec at 25 °C ( = 1 M) with E = 15.5 kcal.mole . Breakdown of an oxalatoneptunium(VI) complex of low formation constant is presumably the mechanism. 

Kinetics of the reactions with all the oxidants have been reported (Table 16). The usual product is formic acid, which is the first molecule formed resistant to very rapid secondary oxidation. Six equivalents of Ce(IV) are destroyed in oxidising one molecule of substrate to one of HC02H °, viz. 

The readily oxidised intermediates are probably tartronic and glyoxylic acids in all the oxidations, viz. 

The kinetics are straightforward only in the case of Co(IIl) oxidation, which involves slow breakdown of a malonato complex, viz. 

The biologically active form of malonic acid, malonyl-CoA, is essential for the biosynthesis of fatty acids and for the elongation of carbon chains including the formation of a variety of aromatic secondary metabolites. Malonyl-CoA is formed from acetyl-CoA and bicarbonate in the cytosol by the action of acetyl-CoA carboxylase. 

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Blauc s rule Ail dicarboxyiic acids, with the exception of oxalic and malonic acids, up to... 

Carbon suboxide, C3O2, OCCCO. M.p. — 107 C, b.p. 6-8°C. A toxic gas (malonic acid plus P2O5) which polymerizes at room temperature. Reforms malonic acid with water. 

CH OfiSj, H2C(S03H)2- a colourless, crystalline solid which readily absorbs water vapour decomposes on distillation. The potassium salt is prepared by heating methylene chloride with an aqueous solution of potassium sulphite under pressure at 150-I60" C. The free acid is obtained by decomposing the sparingly soluble barium salt with sulphuric acid. The aryl esters are very stable, but the alkyl esters decompose on heating to give ethers. Resembles malonic acid in some of its reactions. 

The BZ reaction involves the oxidation of an organic molecule (citric acid, malonic acid (MA)) by an... 

The reaction involving chlorite and iodide ions in the presence of malonic acid, the CIMA reaction, is another that supports oscillatory behaviour in a batch system (the chlorite-iodide reaction being a classic clock system the CIMA system also shows reaction-diffusion wave behaviour similar to the BZ reaction, see section A3.14.4). The initial reactants, chlorite and iodide are rapidly consumed, producing CIO2 and I2 which subsequently play the role of reactants . If the system is assembled from these species initially, we have the CDIMA reaction. The chemistry of this oscillator is driven by the following overall processes, with the empirical rate laws as given ... 

Lengyel I, Rabai G and Epstein I R Experimental and modelling study of oscillations in the chlorine dioxide-iodine-malonic acid reaction J. Am. Chem. See. 112 9104-10... 

Patel H M, Didymus J M, Wong K K W, Hirsch A, Skiebe A, Lamparth I and Mann S 1996 Fullerates interaction of divalent metal ions with Langmuir monolayers and multilayers in mono-substituted Cgg-malonic acid J. Chem. Soc., Chem. Commun. 611-2... 

The existence of chaotic oscillations has been documented in a variety of chemical systems. Some of tire earliest observations of chemical chaos have been on biochemical systems like tire peroxidase-oxidase reaction [12] and on tire well known Belousov-Zhabotinskii (BZ) [13] reaction. The BZ reaction is tire Ce-ion-catalyzed oxidation of citric or malonic acid by bromate ion. Early investigations of the BZ reaction used tire teclmiques of dynamical systems tlieory outlined above to document tire existence of chaos in tliis reaction. Apparent chaos in tire BZ reaction was found by Hudson et a] [14] aiid tire data were analysed by Tomita and Tsuda [15] using a return-map metliod. Chaos was confinned in tire BZ reaction carried out in a CSTR by Roux et a] [16, E7] and by Hudson and... 

Consequently, when D /Dj exceeds the critical value, close to the bifurcation one expects to see the appearance of chemical patterns with characteristic lengtli i= In / k. Beyond the bifurcation point a band of wave numbers is unstable and the nature of the pattern selected (spots, stripes, etc.) depends on the nonlinearity and requires a more detailed analysis. Chemical Turing patterns were observed in the chlorite-iodide-malonic acid (CIMA) system in a gel reactor [M, 59 and 60]. Figure C3.6.12(a) shows an experimental CIMA Turing spot pattern [59]. 

The crude product is evaporated to dryness and then heated with a mixture of ethanol and sulphuric acid the cyano group is thus hydrolysed giving malonic acid, which then undergoes esterification to give diethyl malonate. 

The term Knoevenagel Condensation was originally applied to the base-catalysed condensation of the carbonyl ( CO) group of aldehydes and ketones with the reactive methylene group of malonic acid, with loss of w ater ... 

It is now applied more widely to include malonic acid derivatives, such as diethyl monoethyl-malonate, ethyl cyanacetate, etc. Various amines may be used as catalysts, and usually the most effective is piperidine (hexahydro-pyridine) a mixture of piperidine and pyridine, or pyridine alone, is also often used. 

The role of the base is apparently primarily that of a proton remover from the reactive methylene group thus if B represents the base, reaction (i) gives the carbanion, which then combines with the positive carbon of the carbonyl group (reaction ii) the product regains a proton from the piperidinium ion, and then by loss of water followed by mono-decarboxylation of the malonic acid residue gives the final acid. 

The reaction is readily illustrated by the formation of crystalline sorbic acid by the condensation of crotonaldehyde and malonic acid in hot pyridine solution ... 

Add 4 g. of malonic acid to 4 ml. of pyridine, and then add 3 1 ml. of crotonaldehyde. Boil the mixture gently under reflux over an asbestos-covered gauze, using a small Bunsen flame, for 40 minutes and then cool it in ice-water. Meanwhile add 2 ml. of concentrated sulphuric acid carefully with shaking to 4 ml. of water, cool the diluted acid, and add it with shaking to the chilled reaction-mixture. Sorbic acid readily crystallises from the solution. Filter the sorbic acid at the pump, wash it with a small quantity of cold water and then recrystallise it from water (ca, 25 ml.). The colourless crystals, m.p. 132-133°, weigh ro-i-2 g. 

Ootonic acid may be prepared by condensing acetaldehyde with malonic acid in pyridine solution in the presence of a trace of piperidine (Doebner reaction see discussion following Section IV,123). 

Mix together in a 250 ml. flask carrying a reflux condenser and a calcium chloride drying tube 25 g. (32 ml.) of freshly-distilled acetaldehyde with a solution of 59-5 g. of dry, powdered malonic acid (Section 111,157) in 67 g. (68-5 ml.) of dry pyridine to which 0-5 ml. of piperidine has been added. Leave in an ice chest or refrigerator for 24 hours. Warm the mixture on a steam bath until the evolution of carbon dioxide ceases. Cool in ice, add 60 ml. of 1 1 sulphuric acid (by volume) and leave in the ice bath for 3-4 hours. Collect the crude crotonic acid (ca. 27 g.) which has separated by suction filtration. Extract the mother liquor with three 25 ml. portions of ether, dry the ethereal extract, and evaporate the ether the residual crude acid weighs 6 g. Recrystallise from light petroleum, b.p. 60-80° the yield of erude crotonic acid, m.p. 72°, is 20 g. 

This preparation is another example of the condensation of an aldehyde with malonic acid and pyridine to 3neld ultimately an ap-unsaturated acid (Doebner reaction). It is included here because, unlike the acids prepared from many of the lower aUphatic aldehydes, the product consists largely (about 95 per cent.) of the ap-isomeride and only about 5 per cent, of the PY-isomeride is present ... 

Dissolve 57 g. of dry malonic acid in 92 5 ml. of dry P3rridine contained in a 500 ml. round-bottomed flask, cool the solution in ice, and add 57 g. (70 ml.) of freshly distilled n-heptaldehyde (oenanthol) with stirring or vigorous shaking. After a part of the aldehyde has been added, the mixture rapidly seta to a mass of crystals. Insert a cotton wool (or calcium chloride) tube into the mouth of the flask and allow the mixture to stand at room temperature for 60 hours with frequent shaking. Finally, warm the mixture on a water bath until the evolution of carbon dioxide ceases (about 8 hours) and then pour into an equal volume of water. Separate the oily layer and shake it with 150 ml. of 25 per cent hydrochloric acid to remove pyridine. Dissolve the product in benzene, wash with water, dry with anhydrous magnesium sulphate, and distil under reduced pressure. Collect the ap-nonenoic acid at 130-13272 mm. The yield is 62 g. 

Sorbic acid is prepared by the condensation of crotonaldehj de with malonic acid ill the presence of pyridine at 100° (Doebner reaction) ... 

Malonic acid may be prepared from chloroacetic acid by the following series of reactions (compare Diethyl Malonate, Section 111,153) —... 

Knoevenagel reaction. The condensation of an aldehyde with an active methylene compound (usually malonic acid or its derivatives) in the presence of a base is generally called the Knoevenagel reaction. Knoevenagel found that condensations between aldehydes and malonic acid are effectively catalysed by ammonia and by primary and secondary amines in alcoholic solution of the organic amines piperidine was regarded as the best catalyst. 

Dissolve 50 g. of piperonal and 75 g. of malonic acid in a mixture of 160 ml. of pyridine and 2-5 ml. of piperidine contained in a 500 ml. round-bottomed flask, and heat under reflux for 1 hour on a water bath. A rapid evolution of carbon dioxide takes place. Complete the reaction by boiling the solution for 5 minutes. Cool, pour into excess of water containing enough hydrochloric acid to combine with the pyridine, filter ofiFthe piperonylacrylic acid, wash with a little water, and dry. The yield is almost quantitative and the acid is practically pure. It may be recrystallised from glacial acetic acid m.p. 238°. 

The acid may also be prepared by the condensation of furfural with malonic acid in the presence of pyridine fiiiylmalonic acid is intermediately formed, which is decomposed upon heating In the presence of the base ... 

Method 2. Place 48 g. (41 -5 ml.) of freshly-distilled furfural, 52 g. of dry malonic acid (1), and 24 ml. of dry pyridine (2) in a 500 ml. round-bottomed flask, fitted with a reflux condenser. Heat the flask on a boiling water bath for 2 hours, cool the reaction mixture and dilute with 50 ml. of water. Dissolve the acid by the addition of concentrated ammonia solution, filter the solution and wash the filter paper with a... 

Synthesis No control is needed in the first step there is only one enolisable H atom on eitlier aldehyde. If we use malonic acid for the second step, cychsation and decarboxylation will be spontaneous (Monatshefte, 1904, 2 13). 

A classical way to achieve regioselectivity in an (a -i- d -reaction is to start with a-carbanions of carboxylic acid derivatives and electrophilic ketones. Most successful are condensations with 1,3-dicarbonyl carbanions, e.g. with malonic acid derivatives, since they can be produced at low pH, where ketones do not enolize. Succinic acid derivatives can also be de-protonated and added to ketones (Stobbe condensation). In the first example given below a Dieckmann condensation on a nitrile follows a Stobbe condensation, and selectivity is dictated by the tricyclic educt neither the nitrile group nor the ketone is enolizable (W.S. Johnson, 1945, 1947). 

Thiazolomonomethine cyanines result from the condensation of 2 moles of 2-alkylmercaptothiazolium on 1 mole of malonic acid in pyridine (method C) but could not be obtained from this intermediate in acetic anhydride as is the case for other rings (26). 

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