Substituted hydrazides of hydroxycarboxylic acids

A number of -chloroacetyl--tolylhydrazides of diaryl- and dialkylglycolic acids have been obtained by the reaction of the hydrazides with acetyl chloride. The chloroacetyl derivatives, on heating with piperidine, morpholine, or N-methylpiperazine, are converted into the corresponding -(aminoacetyl)--tolylhydrazides of diaryl- and dialkylglycolic acids. The IR and UV spectra of these compounds are examined, and also the spectra of their halochromic salts, and their basicity.For part LXIV, see [1].Translated from Gor'kii Perm State University. Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 5, pp. 633–636, May, 1970.     

Substituted hydrazides of hydroxycarboxylic acids

Under the action of concentrated sulfuric acid, a number of arylhydrazides of diarylglycolic acids are converted into 4,4-diaryl-3-oxo-1, 2, 3, 4-tetrahydrocinnolines. The cyclization reaction takes place through the intermediate formation of a halochromic salt. The UV and IR spectra of the cinnoline derivatives have been studied.For part XLV, see [1].     

Substituted hydroxycarboxylic hydrazides

The ethyl ester of oxalic acid piperylhydrazide has been synthesized, and its reactions with organomagnesium compounds investigated. The piperylhydrazides of diaryl-, dialkyl-, and dithienylglycolic acids have been obtained, and their properties examined. The IR and UV spectra of the compounds obtained, and the spectra of the halochromic salts and the basicity of the diaryl- and dithienylglycolic piperylhydrazides, were studied.For part LI, see [1].     

Substituted hydrazides of hydroxycarboxylic acids XXVIII. Morpholinoacetyl derivatives of phenylhydrazides of diaryl and dialkyl glycolic acids

The action of morpholine on chloroacetyl derivatives of phenylhydrazides of diaryl- and dialkylglycolic acids gives hitherto undescribed morpholinoacetyl derivatives of the phenylhydrazides. Methiodides of a number of these compounds are prepared. The hitherto undescribed chloroacetyl derivatives of the phenylhydrazides of di(m-tolyl)-, di(o-anisyl)-, diamyl-, diheptyl-, and dioctylglycolic acids, and also the phenylhydrazide of diheptylglycolic acid are described.     

Substituted hydrazides of hydroxycarboxylic acids XXVIII. Morpholinoacetyl derivatives of phenylhydrazides of diaryl and dialkyl glycolic acids

The action of morpholine on chloroacetyl derivatives of phenylhydrazides of diaryl- and dialkylglycolic acids gives hitherto undescribed morpholinoacetyl derivatives of the phenylhydrazides. Methiodides of a number of these compounds are prepared. The hitherto undescribed chloroacetyl derivatives of the phenylhydrazides of di(m-tolyl)-, di(o-anisyl)-, diamyl-, diheptyl-, and dioctylglycolic acids, and also the phenylhydrazide of diheptylglycolic acid are described.For Part XXVII see [1].     

Substituted hydrazides of hydroxy carboxylic acids

Under the action of concentrated sulfuric acid, a series of -alkyl--arylhydrazides of diarylglycolic acids is converted into 1-alkyl-1,2,3,4-tetrahydrocinnolin-3-ones. The reaction takes place through the intermediate formation of a halochromic salt.For Communication LXV, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 844–846, June, 1970.     

Substituted hydrazides of hydroxy carboxylic acids

The reaction of ethyl esters of arylhydrazides of oxalic acid with indolylmagnesium bromide has given arylhydrazides of N-indolylglyoxilic acid which, by reaction with benzoyl chloride, have been converted into -aryl--benzoylhydrazides of N-indolylglyoxilic acid. The reaction of arylmagnesium halides with arylhydrazides of indolylglyoxilic acid has given arylhydrazides of diarylglycolic acids. The spectra of the arylhydrazides of N-indolyglyoxilic acid have been studied.For Communication LXVI, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1079–1082, August, 1970.     

Determination of hydroxycarboxylic acids in food products by capillary electrophoresis

A procedure for the capillary-electrophoretic determination of lactic, malic, tartaric, and citric acids in food products was developed. The use of 3-nitrobenzoic acid as a light-absorbing component of the running buffer was proposed for the indirect photometric detection of these substances. This considerably increased the determination sensitivity (up to n × 10 ??g/L), as compared with currently available analogs. The composition of the running buffer was optimized: 3-nitrobenzoic acid, 10 mM; cetyltrimethylammonium bromide, 0.5 mM; EDTA, 0.1 mM; and monoethanolamine, to pH 5.3. The procedure was tested with the samples of food products: fruits, juices, nectars, wines, beer, etc. The accuracy of the analytical results was confirmed by the standard addition method.     

Preparation of hydrazides of amino acids and peptides

A new method of synthesizing hydrazides of amino acids and peptides is considered which involves the hydrazinolysis of the silyl esters of the corresponding compounds. A number of hydrazides of derivatives of amino acids and peptides has been obtained in high purity with yields close to quantitative. The physicochemical characteristics of the compounds synthesized are given.     

Preparation of hydrazides of amino acids and peptides

A new method of synthesizing hydrazides of amino acids and peptides is considered which involves the hydrazinolysis of the silyl esters of the corresponding compounds. A number of hydrazides of derivatives of amino acids and peptides has been obtained in high purity with yields close to quantitative. The physicochemical characteristics of the compounds synthesized are given.All-Union Scientific-Research Institute of the Technology of Blood Substitutes and Hormones Preparations, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 684–686, September–October, 1979.     

Synthesis and characterization of dioxoosmium(VI) complexes of hydroxycarboxylic acids

The synthesis and characterization of stable well-defined osmium(VI)-hydroxycarboxylic acid complexes is reported for the first time. The reaction of dipotassium tetramethylosmate(VI) with hydroxycarboxylic acids [glycolic, 2-hydroxyisobutyric, (S)-(+)-mandelic and o-salicylic] in the presence of pyridine led to the formation of trans-dioxo(oxoacidato)dipyridineosmium(VI) complexes. Elemental analysis, and IR, ¹H NMR, ¹³C NMR and mass spectrometer were used to characterize the new complexes. A structure in which OOsO group is perpendicular to the plane produced by the two nitrogen atoms of the pyridine ligands and the two oxygen atoms of the oxoacidato group is proposed for the complexes. In the structure, oxoacidato groups form five- or six-membered rings with the osmium atom.     

Lipase‐catalyzed polymerization of fluorinated lactones and fluorinated hydroxycarboxylic acids

Lipase‐catalyzed ring‐opening polymerization of 10‐fluorodecan‐9‐olide (1a), 11‐fluoroundecan‐10‐olide (1b), 12‐fluorododecan‐11‐olide (1c) and 14‐fluorotetradecan‐13‐olide (1d) gave optically active products with M_w of 3.000 to 8.000, while 10‐fluoroundecan‐11‐olide (3a) gave an optically inactive polymer with M_w = 11.000. On the other hand, Candida antarctica lipase‐catalyzed polymerization of 10‐ to 14‐membered ω‐fluoro‐(ω‐1)‐hydroxyalcanoic acids gave optically inactive oligomers with M_w of 3.000 to 11.000 in the presence of molecular sieves, while reactions without molecular sieves gave oligomers with lower molecular weight, but with small optical rotations. 9‐Fluoro‐10‐hydroxydecanoic acid, on the other hand, gave an optically inactive polyester with M_w = 7400. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2004–2012, 2000     

Substituted arylamides of dithiocarboxylic acids

The S-substituted derivatives formed by the reaction of arylamides of cyanothioacetic acid and the esters of arylamides of cyanomonothiomalonic acid with ethyl bromoacetate are cyclized to 2-cyanomethylidene-3-arylthiazolidin-4-ones (III) and 2-carbethoxycyanomethylidene-3-arylthiazolidin-4-ones (VI) rather than to tetrahydrothiophenone derivatives as previously proposed in [1,2].See Zh. Organ. Khim., 4, 234 (1968) for Communication XII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1621–1623, December, 1970.     

Quantitative determination of oxocarboxylic and hydroxycarboxylic acids in normal individuals and ketoacidotic patients

Oxo- and hydroxycarboxylic acids as metabolites of valine, leucine, and isoleucine and of ketogenesis are simultaneously quantitated in the form of their methyl esters and methyl esters/O-methyloximes by gas chromatography using internal and external standards. Normal values for the urinary excretions of the amino acid metabolites are between 3 ± 2 μmol/24 h (mean value ± standard deviation) for 2-oxoisocaproic acid and 122 ± 58 μmol/24 h for 3-hydroxyisobutyric acid. In diabetic ketoacidosis the values are increased by a factor of 2-10.     

Microwave-assisted one-step synthesis of fenamic acid hydrazides from the corresponding acids

A facile and efficient method for synthesis of fenamic acid hydrazides from their acids in one-step reaction under microwave irradiation and solvent-free conditions was developed. Compared with the two-step conventional heating method, the process was simple, the reaction time was very short and the yields were almost quantitative.     

Optimization of conditions for synthesizing sulfonated hydrazides of benzoic and benzenesulfonic acids

The kinetic relationships of arenesulfonation of benzoic and benzenesulfonic acid hydrazides were studied. Based on the data obtained, the conditions for synthesizing these products were optimized. The synthesis can be performed using aqueous-organic solvents containing 2-propanol, 1,4-dioxane, or tetrahydrofuran as nonaqueous component. The thermal stability of benzenesulfohydrazide and its sulfonation product was compared on the basis of data of gas chromatography–mass spectrometry. The fragmentation pathways of the reactants and target product, sulfonated benzenesulfohydrazide, were suggested.     

Optical activity in mixed-ligand terbium complexes containing 5-sulfosalicyclic acid and chiral hydroxycarboxylic acids

The optical activity associated with the f-f; emission bands of Tb(III) complexes which contain chiral hydroxycarboxylic acids has been studied by means of circularly polarized luminescence (CPL) spectroscopy. Complexes having the general formula Tb(SSA)₂(L) were studied (where SSA signifies 5-sulphosalicylic acid), with the chiral ligand (L) being L-lactic acid, L-mandelic acid, L-aspartic acid, and L-malic acid. The CPL spectra were found to be sensitive to the mode of bonding between the metal and the chiral ligand and therefore allowed predictions to be made regarding how the hydroxycarboxylic acid ligands attach to the Tb(III) ion. Also, the degree of optical activity varied systematically with the concentration of chiral ligand, and we have used this dependence to calculate formation constants for the addition of a hydroxycarboxylic acid ligand to the Tb/SSA complex. Finally, the line shape and magnitudes of the CPL spectra provide information regarding the type of chirality experienced by the Tb(III) ion.     

Unexpected cyclization route for o-ethynylbenzoic acids hydrazides in the presence of base

The reaction of o-ethynylbenzoic acids hydrazides with base has been studied. In the presence of a strong donor substituent (1,5-dimethylpyrazol-4-yl) it has been found that an unusual cyclization route occurs to give the corresponding benzopyridazinone instead of the expected isoindolinone. Dedicated to Academician B. A. Trofimov in his 70^th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 67-70, January, 2009.     

Improved procedure for the derivation and gas chromatographic determination of hydroxycarboxylic acids treated with chloroformates

Hydroxymonocarboxylic acids with a hydroxyl group adjacent to the carboxylic group can easily be converted with alkyl chloroformates into derivatives amenable to gas chromatography. However, the main reaction product, the O-alkoxycarbonylalkyl ester, is always accompanied by a certain amount of reaction side-products, by altering the sequence of addition of the organic base and the reagent. Under optimum conditions, >/94% of the mass of the analyte can be converted into the desired main product.