New Furopyridines Containing Pyridoxal and Pyrazolone Fragments

Reactions of pyridoxal hydrochloride with 5-pyrazolone derivatives in alcohol medium in the presence of concentrated hydrochloric acid led to the formation of new pyrazolones with pyridoxal fragments in the molecule. The corresponding diarylmethanes were formed when using pyridoxal and pyrazolone in a 1: 2 ratio.     

Introduction of functional groups into 6 position of pyridoxal

The synthesis of 6-acylpyridoxal, 6-carboxyethylpyridoxal and 6-(3′-aminopropyl)pyridoxal derivatives are described.     

Beta-replacement reaction of serine-O-carbonate derivatives with thiols catalyzed by a pyridoxal model having an ionophore side-chain

Serine-O-carbonate derivatives, including peptides having a serine-O-carbonate residue at the N-terminal position, are catalytically transformed into S-substituted cysteine derivatives employing the pyridoxal model having an ionophore function in the presence of Li+; this is the first artificial model mimicking cystathionine Beta-synthase.     

Kinetics and mechanism of the condensation of pyridoxal hydrochloride with L-tryptophan and D-tryptophan,and the chemical transformation of their products

The kinetics and mechanism of interaction between pyridoxal and L-tryptophan, D-tryptophan, and their derivatives are studied. It is found that condensation reactions proceed via three kinetically distinguishable stages: (1) the rapid intraplanar addition of the NH₂ groups of the amino acids to pyridoxal with the formation of amino alcohols; (2) the rotational isomerism of amino alcohol fragments with their subsequent dehydration and the formation of a Schiff base with a specific configuration; (3) the abstraction of α-hydrogen in the product of condensation of pyridoxal with L-tryptophan, or the abstraction of СО₂ in the product of condensation of pyridoxal with D-tryptophan with the formation of quinoid structures, hydrolysis of which results in the preparation of pyridoxamine and keto acid or pyridoxal and tryptamine, respectively. Schiff bases resistant to further chemical transformations are formed in the reaction with tryptophan methyl ester.     

Chemistry of pyridoxine in drug design

Russian Chemical Bulletin - Pyridoxine and its derivatives, pyridoxamine and pyridoxal, are the three main forms of vitamin B6, which play exceptionally important biological roles in living...     

Phosphorus containing pyrydoxal azomethines and alkoxyfuropyridines of salt structure

The reaction of azomethines of pyridoxal or alkoxyfuropyridines with phosphorus acids produces new salt derivatives.     

High antibacterial activity and low toxicity of pyridoxal derivatives of chitosan and their nanoparticles

The pyridoxal derivatives of chitosan with various degrees of substitution (DS) were synthesized from low-, moderate- and high-molecular-weight chitosans by their reaction with pyridoxal followed by treatment with NaBH₄. The derivative of moderate molecular weight and high DS demonstrated a maximum antibacterial activity against S. aureus and E. coli. The nanoparticles of this derivative obtained by ionic gelation are nontoxic, and they exhibit a high in vitro antibacterial effect, which slightly exceeds that of ampicillin and gentamicin.     

Phosphorylation of pyridoxal azomethines. Synthesis of phosphorus containing azomethines and furopyridines

New O-phosphorylated pyridoxal derivatives have been synthesized through the reaction of azomethines with Р^V acid chlorides. 2-Chloro-2-thioxo-5,5-dimethyl-1,3,2-dioxaphosphinanes and diethylchlorothiophosphate have been employed as phosphorylating agents. Regardless of the nature of the phosphorylating agent, the reaction is regioselective at phenolic hydroxyl group. The structure of final products is determined by the nature of the substituent at the nitrogen atom. If R is alkyl or cycloalkyl group, the products of the reaction represent phosphorylated pyridoxal imines, whereas phosphorylated furopyridines are formed in the case R is aryl substituent.     

Reactions of pyridoxal with aromatic carboxylic acids in alcoholic medium

Russian Journal of General Chemistry - Reactions of pyridoxal with benzoic acid and its derivatives in alcoholic medium afforded alkoxyfuropyridinium salts with potential biological activity.     

Effect of structure of the amino acids and amines on the rate and mechanism of their condensations with pyridoxal

Kinetics and mechanism of condensation of amino acids and amines of different structure and their derivatives with pyridoxal were studied. It was established that the amino acid with secondary amino group, proline, adds to pyridoxal with the formation of amino alcohol. α-Amino acids in the course of condensation with pyridoxal form amino alcohols which transform to Schiff bases. The latter compounds by elimination of the α-hydrogen atom or CO₂ from the amino acid fragment and the subsequent hydrolysis of the quinoid structure form the final products. β- And ɛ-amino acids react with pyridoxal to form Schiff bases which are stable to chemical transformations. The possibility was shown of their conversion to the quinoid structure. It was established that the guanidine structure of the molecule of L-arginine unlike its α-NH₂ group did not take part in the condensation with pyridoxal. The quantitative evaluation of the condensation rates of triptamine, Ltriptofane, and its methyl ester in the stage of dehydration of their amino alcohols was carried out.     

Synthesis of New Furopyridines Containing Carbonyl Group in Alkyl Substituent

Russian Journal of General Chemistry - The method was developed for the synthesis of previously unknown pyridoxal (vitamin B6) derivatives, containing a carbonyl group and a dihydrofuropyridine...     

Reactions of Pyridoxal with Heterocycles Containing Primary Amino Group

Russian Journal of General Chemistry - New nitrogen-containing derivatives of pyridoxal were obtained as a result of its reaction with various amines. The reactions with amines bearing a...     

Simple synthesis of functionalized 7-aza-2H-chromenes from pyridoxal and nitroalkenes in aqueous medium

A reaction of 1-nitro-3,3,3-trichloro(trifluoro)propenes and β-nitrostyrene with pyridoxal hydrochloride in the presence of sodium hydroxide in aqueous medium gives good yields of new derivatives of 7-aza-2H-chromene system.     

采用高效液相色谱技术分析生物体内维生素B6

维生素B6(VB6)是一类2-甲基-3-羟基吡啶类化合物的总称，基本类型有吡哆醇(PN)、吡哆醛(PL)和吡哆胺(PM)，磷酸酯型有磷酸吡哆醇(PNP)、磷酸吡哆醛(PLP)和磷酸吡哆胺(PMP)，其中磷酸吡哆醛和磷酸吡哆胺为活性形式，是多种酶的辅酶，哺乳动物尿中VB6的代谢产物主要是不具有生理活性的吡哆酸(PIC)，在植物体内还发现有数种吡哆醇的糖衍生物和氨基酸衍生物。     

A 13C n.m.r. study of the B6 vitamins and of their aldimine derivatives

The vitamins, pyridoxine, pyridoxal, pyridoxamine, pyridoxal-5′-phosphate and pyridoxamine-5′-phosphate, have been studied in aqueous solution over a pH range of 2–12 by ¹³C nuclear magnetic resonance spectroscopy. Resonance assignments are made primarily by the spin–spin coupling constants of carbons with protons and with phosphorus. The proton–carbon coupling constants show a marked conformational dependence in the hemiacetal form of pyridoxal. Furthermore, the H-6? C-5 coupling constant in the vitamins is much smaller than the corresponding constant in pyridine. This may be due either to an effect of the C-5 substituent in vitamins or to a different electronic configuration of the zwitterionic hydroxypyridine ring. The addition of manganese to a solution of pyridoxal phosphate causes line broadenings consistent with the interaction of the metal ion with this vitamin at the formyl and phenolic oxygens. The chemical shifts of the aromatic carbons of pyridoxine have been calculated, as a function of pH, by summing shielding parameters which were estimated empirically from pyridine derivatives. The calculated shifts agree well with the experimental data for C-3, C-5 and C-6, less well for C-2, and poorly for C-4. The deviation from additivity for C-4 indicates a preferred orientation for the 4-hydroxymethyl substituent caused by internal hydrogen bonding between the substituents at C-3 and C-4. Evidence is presented for the existence of the free aldehyde form of pyridoxal at alkaline pH. Aldimine complexes of pyridoxal and pyridoxal phosphate with amines and amino acids have also been studied. Characteristic chemical shift changes caused by both pyridinium and aldimine nitrogen deprotonations are seen. Additionally, the chemical shifts of carbons of the pyridine ring are dependent upon the structure of the imine, especially when the aldimine nitrogen is protonated. We conclude that this dependency is due to steric effects in an aldimine complex which is constrained by internal hydrogen bonding. We also discuss the merits of carbons 3 and 4 as possible sites of cofactor labeling for enzymatic studies.     

A New Pyridoxal Derivative for Transamination of N‐Terminus of Proteins

A new pyridoxal‐5‐phosphate (PLP) derivative FHMDP was developed for the transamination of different peptides with three most hindered amino acid residues (Leu, Ile, Val) as their N‐terminus. Compared to the previously reported reactions of PLP derivatives, the N‐terminus transamination could be accomplished efficiently with the new compound.     

Artificial model for cystathionine β-synthase: construction of a catalytic cycle with a pyridoxal model compound having an ionophore function

Catalytic transformation of serine-O-carbonate to S-aryl cysteine derivatives was successfully achieved in the presence of Li⁺ by the use of a pyridoxal model compound having an ionophore function, which is the first example mimicking cystathionine β-synthase, artificially.     

Spectrophotometric determination of gallium in alloys and fly-ash with pyridoxal derivatives of thiocarbohydrazide and carbohydrazide

The symmetric derivatives of pyridoxal with thiocarbohydrazide and carbohydrazide, and the asymmetric derivatives of pyridoxal and salicylaldehyde with the same hydrazides have been synthesized and their analytical potential for spectrophotometric and kinetic fluorimetric determination of metal ions was studied. Gallium(III) and PyMAU(1,3-bis{[4-(2-methyl-3-hydroxy-5-hydroxymethyl)pyridyl]methyleneaminourea at pH = 4.2 form a complex with a single absorption maximum at 425 nm, which can be extracted into cyclohexanone in the presence of a controlled amount of sodium perchlorate. The extract has maximum absorbance at 435 nm. Both systems can be used for determining gallium. The optimal range of gallium concentration for measurement in a 1-cm cell is 0.5-1.25 gmg/ml for the procedure in homogeneous medium ((425) = 3.76 x 10(4).mole(-1).cm(-1)) and 0.25-1.25 mug/ml for the extraction procedure ((435) = 5.30 x 10(4) 1.mole(-1).cm(-1). The latter procedure has been applied to the determination of gallium in alloys and fly-ash.     

Anticancer activity of novel 3-azaxanthenes

Novel 3-azaxanthenes have been synthesized via acid-catalyzed one-pot Friedel–Crafts reaction of pyridoxal/pyridoxal-5'-phosphate with naphthols followed by dehydration of the intermediate bis(2-hydroxyaryl)-(pyridin-4-yl)methane derivatives. The cytotoxicity of the obtained 3-azaxanthenes against M-HeLa and HuTu-80 tumor cell lines is comparable to that of tamoxifen, whereas the cytotoxicity against normal cell line is absent in the tested concentrations range, which makes this class of compounds interesting for further studies.     

Zur Analytik der Pyridoxine

4 selective tests for pyridoxal and pyridoxamine are described. In combination with the test by means of 2,6-dichloroquinone-4-chloroimine it is possible to determine pyridoxol, pyridoxamine and pyridoxal in presence of each other in mixtures. It is shown that the three components are able to be transformed into one another.