Phenyl malonic acid

It is noteworthy that the value of this substrate is smaller by one order compared to non-cyclic compounds. According to the discussions proposed above, this is considered to be due to its conformation already being fixed to the one that fits to the binding site of the enzyme. This estimation was demonstrated to be true by the examination of the effect of temperature on the kinetic parameters. Arrhenius plots of the rate constants of indane dicarboxylic acid and phenyl-malonic acid showed that the activation entropies of these substrates are —27.6 and —38.5 calmol K , respectively. The smaller activation entropy for the cyclic compound demonstrates that the 5yn-periplanar conformation of the substrate resembles the one of the transition state. 

Fig. 7. Hammett plot of k at for the AMDase catalyzed decarboxylation of a series of X-phenyl-malonic acids...

Carbenicillin can be viewed as a phenyl malonic acid derivative, thus is prone to COi loss. 

In order to label in the 2 position, [ " C]nrea is condensed with ethyl phenyl malonic acid diethyl ester, according to the plan in Fig. 1. 

C]benzyl alcohol [7- " C]benzyl chloride [l- Clphenyl acetic acid ethyl ester [2- " C]phenyl malonic acid diethyl ester... 

The diazo compound from methyl benzoylacetate gives phenylcarbo-methoxyketene in 70% jdeld when the final decomposition is carried out in refluxing xylene, but it is converted largely to the ester of phenyl-malonic acid by heating in the absence of a solvent. The ethyl ester of ethylmalonic acid is the principal product from the decomposition (in the absence of a solvent) of the diazo compoimd obtained from ethyl pro-pionylacetate. A small amoimt of the ketene evidently was formed also. The diazo compound obtained from ethyl ethoxalylacetate on decomposition in warm xylene gives 54% of dicarbethoxyketene. ... 

Miyamoto K, Tsuchiya S, Ohta H. Stereochemistry of enzyme-catalyzed decarboxylation of a-methyl- a-phenyl-malonic acid. 7. Aw. Chem. Soc. 1992 114 6256-6257. 

C13H16 04 phenyl-malonic acid diethyl ester 83-13-6 ... 

With malonic acid in a mixture of pyridine and piperidine 2-phenyl-4-formyl-5-chlorothiazole yields 2-phenyl-5-chloro-4-thiazoleacrylic acid (103). 

A-Fluoro-2,4,6-tnmethylpyndmium inflate (1 mmol) is added m several portions at room temperature to a tetrahydrofuran solution of sodium diethyl phenyl-malonate, obtained from 1 mmol of diethyl phenyl malonate and sodium hydnde at 0 C in tetrahydrofuran The reaction imxture is poured mto dilute hydrochlonc acid and extracted with ether The ether extract is washed with sodium bicarbonate and water and dned over magnesium sulfate The oily residue obtamed after removal of tihe ether is chromatographed on sihca gel (dichloromethane-hexane, 1 1) to give diethyl fluorophenylmalonate in 83% yield... 

Methyl- and 3-phenyl-4-hydroxy-2-oxo-2//-pyrido[2,1 -Z)]oxazinium inner salts were prepared in the reaction of 2-pyridone and 2-substituted malonyl chloride, prepared in situ from 2-substituted malonic acid with PCI5 in CH2CI2 (00JCS(P2)2096). 

N-Phenyl-N-(2-emino5malonic acid ethyl ester amide... 

To obtain a better understanding of the reaction mechanism, some compounds that are considered to he intermediates were subjected to the reaction. Various reaction courses can be considered as illustrated in Fig. 21. Path A a-Methyltropic acid is oxidized to a-phenyl-a-methylmalonic acid. Then, the malonate is converted to optically active a-phenylpropionate hy arylmalonate decarboxylase. In order to confirm this assumption, incubation of the malonic acid with Rhodococcus sp. was carried out. The result obtained was the total recovery of the substrate, indicating that no decarboxylase is present in this bacterium. Path B a-Methyltropic acid is converted to racemic a-phenylpropionic acid, which is deracemized to optically active propionic acid. To examine the possibility of this route, racemic a-phenylpropionic acid was subjected to the reaction to observe... 

Bohman and Allenmark resolved a series of sulphoxide derivatives of unsaturated malonic acids of the general structure 228. The classical method of resolution via formation of diastereoisomeric salts with cinchonine and quinine has also been used by Kapovits and coworkers " to resolve sulphoxides 229, 230, 231 and 232 which are precursors of chiral sulphuranes. Miko/ajczyk and his coworkers achieved optical resolution of sulphoxide 233 by utilizing the phosphonic acid moiety for salt formation with quinine. The racemic sulphinylacetic acid 234, which has a second centre of chirality on the a-carbon atom, was resolved into pure diastereoisomers by Holmberg. Racemic 2-hydroxy- and 4-hydroxyphenyl alkyl sulphoxides were separated via the diastereoisomeric 2- or 4-(tetra-0-acetyl-D-glucopyranosyloxy)phenyl alkyl sulphoxides 235. The optically active sulphoxides were recovered from the isolated diastereoisomers 235 by deacetylation with base and cleavage of the acetal. Racemic 1,3-dithian-l-oxide 236... 

Room temperature conditions affected only the conversion, the reaction rate being smaller (entry 6). Noticeably, cyclization of 2-prop-2-ynyl-malonic acid monomethyl ester le and 2-phenyl-pent-4-ynoic acid If, also occurred with very good results (entries 7, 8). The obtained results may be ascribed to the LDH support, which exhibits enough basic properties to activate the unsubtituted acetylenic carboxylic acids. Basically, the composition of the LDH exhibits only a very minor influence in these reactions. 

From the fore gut of Laccophilus minutus, a Bacillus pumilus strain was isolated which produced maculosin, the diketopiperazine formed from proline and tyrosine [103] 24, phenyl malonate 25, N-acetylphenylalanine 26, N-acetyl-tryptophane 27 and 3,4-dihydroxybenzoic acid [ 103]. Maculosin which has also been isolated from several microorganisms and sponges shows phytotoxic and cytotoxic properties [103], 3,4-dihydroxybenzoic acid shows antioxidant properties and was already found in pygidial defensive glands of several dytis-cid beetles. 

C) Preparation of Dipotassium Salt of [2-Phenyl-2-(2-Amino-5-Chlorophenyl)-1-Azavinyl] Malonic Acid (4306 CB) 50 g of caustic potash are dissolved in 1,350 ml of 96% ethyl alcohol, and 82 g (0.25 mol) of compound 4347 CB are then added all at once at a temperature of about 70°C. The solid dissolves rapidly to form a yellow solution which then loses color while simultaneously an abundant colorless precipitate appears. 

Phenyl ethyl malonic acid diethyl ester Methylurea... 

Thiocarbamoylation of malonic acid derivatives with phenyl isothiocyanate gives the sodium salts 193 which are not isolated. Alkylation of these salts in situ using dibromomethane or bromochloromethane yields the 1,3-thiazetidine derivatives 40 (Scheme 63) <2005MI499>. 

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