Synthesis of 4-Acyl-2-amino-6-(arylsulfanyl)pyridine-3,5-dicarbonitriles

Russian Journal of Organic Chemistry - The reaction of 4-acyl-2-amino-6-chloropyridine-3,5-dicarbonitriles with aromatic thiols in 1,4-dioxane in the presence of triethylamine led to the formation...     

Modification of pyridine-3-carboxamide (nicotinamide) by radical substitution

Pyridine-3-carboxamide ( 1 ) was reacted with alkyl radicals to give mono-, di-, and tri-alkylated products. The t-butyl radical gives only 6-t-butylpyridine-3-carboxamide ( 4a ). The reactivity decreases in the order of t-butyl, isopropyl, and ethyl radicals. The product 4a reacts further with the 2-phthalimidoethyl radical to give 2- and 4-substituted products 9 and 10 , which were transformed into tetrahydronaphthyridinone derivatives 11 and 12 .     

Synthesis and solid-state fluorescence of 2-alkylamino-4-aminopyridine-3,5-dicarbonitriles

Reactions of 4-amino-2-aryl-6-chloropyridine-3,5-dicarbonitriles with primary and secondary amines afforded 2-alkylamino-4-amino-6-arylpyridine-3,5-dicarbonitriles which showed solid-sate fluorescence in the violet or blue region with the emission maxima in the λ range 400–460 nm.     

One-Pot Synthesis of 6-Alkyl-4-amino-2-bromopyridine-3,5-dicarbonitriles

Russian Journal of Organic Chemistry - A one-pot procedure has been proposed for the synthesis of 6-alkyl-4-amino-2-bromopyridine-3,5- dicarbonitriles by reaction of malononitrile dimer with...     

Ion recognition properties of new pyridine-2,6-dicarboxamide bearing propeller-like pendant residues: multi-spectroscopic approach

The synthesis and ion binding properties of new amide derived from propeller-like tris(2-pyridyl)amine and 2,6-pyridinedicarboxylic acid chloride were described. Amide binds divalent metal cations: copper(II), nickel(II), zinc(II), and lead(II) in acetonitrile. In acetonitrile:water mixture (9:1 v/v) amide interacts only with copper(II) and nickel(II) cations forming complexes of 1:1 stoichiometry. It was found that the introduction of bulky, nitrogen donor atom bearing pendant groups can influence coordination mode of pyridine-2,6-dicarboxamides. The probable model of ligand-ion interactions is proposed on the basis of 1H NMR and FT-IR spectroscopy.     

Synthesis of N-unsubstituted and N-methyl derivatives of 4-aryl-2,6-dimethyl-1,2-dihydropyridine-3,5-dicarbonitriles

In the reduction of 2,6-dimethyl-4-arylpyridine-3,5-dicarbonitriles or their N-oxides by sodium borohydride, a mixture of 1,2- and 1,4-dihydropyridine-3,5-dicarbonitriles is formed. 1,2,6-Trimethyl-4-aryl-1,2-dihydropyridine-3,5-dicarbonitriles were obtained by reducing the corresponding pyridinium perchlorates or by alkylating 4-aryl-2,6-dimethyl-1,2-dihydropyridine-3,5-dicarbonitrile derivatives by methyl iodide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 81–85, January, 1987.     

Syntheses and characterizations of four metal coordination polymers constructed by the pyridine-3,5-dicarboxylate ligand

A series of metal-organic frameworks, namely [Ni(PDB)(H₂O)]_n (1), [Pb(PDB)(H₂O)] · (H₂O) (2), [Co₂(PDB)₂(bpy)₂(H₂O)₄] · 4H₂O (3) and [Co₂(PDB)₂(phen)₂]_n (4) (H₂PDB = pyridine-3,5-dicarboxylic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized based on pyridine-3,5-dicarboxylate acid and two neutral chelate ligands, with different metal ions such as Ni^II, Co^II and Pb^II, under hydrothermal conditions. The framework structures of these polymeric complexes have been determined by the X-ray single crystal diffraction technique. In the four complexes, the pyridine-3,5-dicarboxylate acid ligand exhibits diverse coordination modes, which play an important role in the construction of metal-organic frameworks. The thermal analyses of these four complexes have been measured and discussed. In addition, complex 2 shows strong phosphorescent emission at room temperature and the magnetic measurement of the polymer of 4 reveals a typical antiferromagnetic exchange.     

Annulation of pyrrole ring in 4-acylpyridine-3,5-dicarbonitriles in the presence of ammonia

Chemistry of Heterocyclic Compounds - 4-Acyl-2-amino-6-chloropyridine-3,5-dicarbonitriles underwent heterocyclization in the presence of ammonia in aqueous dioxane medium, involving the...     

Multi-component synthesis of 2-amino-6-(alkylthio)pyridine-3,5-dicarbonitriles using Zn(II) and Cd(II) metal-organic frameworks (MOFs) under solvent-free conditions

Multi-component synthesis of 2-amino-3,5-dicarbonitrile-6-thio-pyridines has been developed by using the reaction of aldehydes, malononitrile, and thiophenols in the presence of a Zn(II) or a Cd(II) metal-organic framework (MOF) as the heterogeneous catalyst. This protocol tolerates different functional groups on the substrates and does not require the use of any organic solvent. Moreover, the Zn(II) and Cd(II) MOF catalysts can be recovered and reused for a number of runs without loss of activity.     

Reaction of 2-Chloropyridine-3,4-dicarbonitrile with Anilines. Synthesis of 2-(Arylamino)pyridine-3,4-dicarbonitriles

Russian Journal of Organic Chemistry - The reaction of 2-chloropyridine-3,4-dicarbonitrile with anilines in propan-2-ol in the presence of N,N- diisopropylethylamine (DIPEA) in a sealed vial at...     

Synthesis of Linear and V-Shaped Carbazolyl-Substituted Pyridine-3,5-dicarbonitriles Exhibiting Efficient Bipolar Charge Transport and E-Type Fluorescence

With the aim of developing all-organic bipolar semiconductors with high charge mobility and efficient E-type fluorescence (so-called TADF) as environmentally friendly light-emitting materials for optoelectronic applications, four noble metals-free dyes with linear and V-shapes were designed using accepting pyridine-3,5-dicarbonitrile and donating carbazole units. By exploiting a donor-acceptor design strategy and using moieties with different donating and accepting abilities, TADF emitters with a wide variety of molecular weights were synthesized to achieve the optimum combination of charge-transporting and fluorescent properties in one TADF molecule. Depending on molecule structures, different TADF emitters capable of emitting in the range from 453 to 550 nm with photoluminescence quantum yields up to 98 % for the solutions in oxygen-free toluene were obtained. All compounds showed bipolar charge-transport. Hole mobility of 2.8×10⁻³ cm²/Vs at 7×10⁵ V cm⁻¹ was observed for the compound containing two di-tert-butyl-substituted carbazole moieties. The compounds were tested in both non-doped and doped organic light-emitting diodes using different hosts. It was shown that the developed TADF emitters are suitable for different color devices with electroluminescence ranging from blue to yellow and with brightness, maximum current and external quantum efficiencies exceeding 10 000 cd m⁻², 15 cd/A, and 7 %, respectively.     

Synthesis and Structural Characterization of Pyridine-2,6-dicarboxamide and Furan-2,5-dicarboxamide Derivatives

Derivatives based on pyridine-2-6- and furan-2,5-dicarboxamide scaffolds reveal numerous chemical properties and biological activities. This fact makes them an exciting research topic in supramolecular and coordination chemistry and in discovering new pharmacologically-active compounds. This work aimed to obtain a series of symmetrical pyridine-2-6- and furan-2,5-dicarboxamides through a condensation reaction of the appropriate acyl chlorides and aromatic amides. Successful syntheses were confirmed with NMR spectroscopy. We solved their crystal structures for seven compounds; two pyridine and five furan derivatives. Based on our crystallographic studies, we were able to indicate supramolecular features of the crystals under investigation. Additionally, Hirshfeld surface analysis allowed us to calculate a distribution of intermolecular contacts in the dicarboxamide crystals.     

4-Ferrocenylpyridine- and 4-Ferrocenyl-3-ferrocenylmethyl-3,4-dihydropyridine-3,5-dicarbonitriles: Multi-Component Synthesis, Structures and Electrochemistry

The reactions of 2-cyano-3-ferrocenylacrylonitrile (1) with malononitrile (2) in a MeOH/H₂O or 2-PrOH/H₂O medium in the presence of Na₂CO₃ afforded 6-alkoxy-2-amino-4-ferrocenylpyridine-3,5-dicarbonitriles 3a,b (multi-component condensation) and 6-alkoxy-2-amino-4-ferrocenyl-3-ferrocenylmethyl-3,4-dihydropyridine-3,5-dicarbonitriles 4a,b (multi-component cyclodimerization). Analogous reactions of 1 with 2 in an MeOH/H₂O medium in the presence of NaOH, piperidine, or morpholine gave compounds 3a, 4a and 2-amino-4-ferrocenyl-6-hydroxy-, 6-piperidino- and 6-morpholinopyridine-3,5-dicarbonitriles 3c-e, respectively. The structures of the compounds 3b, 4a and 4b were established by the spectroscopic data and X-ray diffraction analysis. The electrochemical behaviour of compounds 3b, 3d and 4b was investigated by means of cyclic voltammetry.     

Synthesis,antibacterial and antitumor activity of methylpyridinium salts of pyridoxine functionalized 2-amino-6-sulfanylpyridine-3,5-dicarbonitriles

A library of 29 2-amino-6-sulfanylpyridine-3,5-dicarbonitriles functionalized with a pyridoxine moiety was synthesized using a three-component one-pot reaction of aldehyde derivative of pyridoxine, malononitrile, and thiophenol. The obtained bipyridine structures were converted into methylpyridinium salts. Several compounds demonstrated expressed antibacterial activity with MICs (minimum inhibitory concentrations) in the range of 0.5–4?µg/mL against the three studied Gram-positive strains and 8–64?µg/mL against the Gram-negative E. coli strain, which was comparable or better than the activity of the reference antimicrobial agents. At the same time, all the synthesized compounds were inactive against the Gram-negative P. aeruginosa. Several compounds also demonstrated high cytotoxic activity against the studied tumor cells, but without selectivity for the normal HSF (human foreskin fibroblast) cells. Despite the preliminary character of the performed biological studies, the obtained results make the obtained structural chemotype a promising starting point for the design of physiologically active compounds.     

Alkylation of acyl and sulfonyl derivatives of 3,5-diamino-1-phenyl-1,2,4-triazole

Alkylation of 3-acylamino-, 5-amino-1-phenyl-3-tosylamino-1,2,4-triazoles and 3,5-diacetylamino-1-phenyl-1,2,4-triazole in the presence of an equimolar amount of sodium methylate in DMSO occurs regioselectively at the amide (sulfamide) group nitrogen atom. The benzylation of 3-acetylamino-5-amino-1-phenyl-1,2,4-triazole with excess base and benzyl chloride also alkylates the amino group at position 5. Alkylamino-1-R-1,2,4-triazoles can be conveniently prepared by alkylation of the corresponding acetylamino-1,2,4-triazoles in the presence of base and subsequent acid hydrolysis of the N-acetyl-N-alkyl derivatives. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 557–567, April, 2009.     

3,5-二甲基-亚硝基哌嗪代谢物对DNA烷化作用的理论研究

用从头计算法在MP2/6-311＋G(d,p)水平上对3,5-二甲基-亚硝基哌嗪(DMNP)及其类似物经代谢生成DNA烷化剂的机理进行了研究. 探讨了N’原子上取代基的变化对DMNP代谢物生成α-位和γ-位两个烷化中心的影响, 解释了两个烷化中心的生成活性与化合物的致癌性之间的关系. 结果表明, α-位和γ-位代谢物越容易生成活泼亲电中间体, 其母体化合物的致癌活性越高. 但如果有一个烷化中心丧失活性, 就会明显减弱化合物的致癌活性. 因此, DMNP类化合物的致癌性取决于其α-位和γ-位的协同烷化作用, 在评价DMNP的致癌强度时需同时考虑两个烷化中心的烷化能力以及二者之间的关系.     

Enhanced gelation property due to intra-molecular hydrogen bonding in a new series of bis(amino acid)-functionalized pyridine-2,6-dicarboxamide organogelators

A series of pyridine-2,6-dicarboxamide derivatives containing two α-amino acid pendant groups was prepared and characterized. Three of the synthesized compounds obtained from this series, all having aromatic amino acid side chains, were found to be excellent organogelators toward aromatic solvents (mgc∼10-20 mg/mL), alcoholic solvents (mgc∼4-15 mg/mL), and CCl₄ (mgc∼4-10 mg/mL). It was found that the intra-molecular hydrogen bonds between the pyridine dicarboxamide N-Hs and the pyridine N atom were the key structural elements for gel formation. This series of compounds represented one of the rare examples where both inter- and intra-molecular hydrogen bonds were needed for effective gel formation. FTIR, ¹H NMR, and CD spectroscopy revealed that both hydrogen bonding and π-π aromatic stacking were the driving forces for gelation.     

Alkylation of 3,5-Dimethylisothiazole. A Regioselective Synthesis of S-Alkyl-3-methylisothiazoles

3,5-Dimethylisothiazole reacts sequentially with lithiumdiisopropylamide (molar ratio 1:1) and alkyl halides (in excess) affording 5-alkyl-3-methylisothiazoles in excellent yields. When a two-fold excess of base is used, a mixture of 5-monoalkylated and 3,5-dialkylated products is obtained. Sodium amide was also tried as deprotonating agent, but the yield in final products was lower.