Intermediates in the transformation of 1,2-dialkylpyrimidinium iodides in the Kost-Sagitullin rearrangement

Intermediate recyclization products were obtained in a study of the Kost-Sagitullin rearrangement of a series of 1,2-dialkylpyrimidinium iodides. The initial attack of the nucleophile leads to the formation of products of the addition of the hydroxyl group, namely, the corresponding pseudo bases. Heating one of these intermediates in ethanol or in the presence of primary amines leads to rearrangement to give a pyridone derivative. Upon heating in chloroform, the pseudo bases readily lose a water molecule and are converted to anhydro bases, namely, derivatives of 1-alkyl-1,2-dihydro-2-methylidenepyrimidine. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 894–900, May, 2006.     

Oxidative cleavage of a tricyclic pyridone to a bicyclic lactam-dione

Two equivalents cf anhydrous m-chloroperbenzoic acid (m-CPBA) cleaved the pyridone ring of 10-(3-chlorophenyl)-6,8,9,10-tetrahydrobenzo[b][1,8]naph forming; the ten-membered lactam α-diketone 12-(3-chlorophenyl)-7,8,9,10-tetrahydropyrido[2,3-b]azecine-5,6,11(12H)-trione. Under aqueous conditions, one equivalent of m-CPBA and the same pyridone formed the lactam α-ketol 12-(3-chlorophenyl)-7,8,9,10-tetrahydro-6-hydroxypyrido[2,3-b]azecine-5,11(6H, 12H)-dio     

Synthetic Access to New Pyridone Derivatives through the Alkylation Reactions of Hydroxypyridines with Epoxides

General methods for the preparation of a variety of pyridone and oxypyridine derivatives are described. 2‐,3‐,4‐Hydroxy pyridine and 2‐pyridinemethanol were alkylated with ethylene‐, propylene‐, and stryrene‐oxide and epichlorohydrin in the presence of different Lewis acids as a catalyst. The best yield of 3a was achieved in the presence of CdI₂/BF₃ · OEt₂. The corresponding pyridone derivatives (3a–d, 7a–d) were obtained from the reaction of 2‐and 4‐hydroxypyridine with oxiranes in good yields, whereas oxypyridine derivatives (5a–d, 9a,b) were obtained from reactions of 3‐hydroxypyridine and 2‐pyridinemethanol with oxiranes. Chlorohydrines (3d, 5d, 7d) were easily converted to corresponding epoxy derivatives (10, 11, 12) in basic medium; then amino alcohols (13–17) were obtained from the reaction of these epoxy derivatives with amines.     

Rational Development of Remote C−H Functionalization of Biphenyl: Experimental and Computational Studies

A simple and efficient nitrile‐directed meta‐C?H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U‐shaped template to achieve a molecular U‐turn and assemble the large‐sized cyclophane transition state for the remote C?H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta‐C?H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta‐selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand‐containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta‐selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non‐directed meta‐C?H activation. Substituted 2‐pyridone ligands were found to be key in assisting the cleavage of the meta‐C?H bond in the concerted metalation–deprotonation (CMD) process.     

1,4-Diaza-bicyclo[2,2,2]octane as a Novel and Efficient Catalyst for the Synthesis of 3,4,6-Trisubstituted 2-Pyridone Derivatives

3,4,6‐Trisubstituted 2‐pyridone derivatives have been synthesized in good to excellent yields through a condensation reaction of various 1,3‐diketones with amides in the presence of 1,4‐Diaza‐bicyclo[2,2,2]octane (DABCO) at reflux temperature.     

Synthesis,Characterization, and Antibacterial Activity of Novel Pyridones

Novel ethyl 2-oxo-4,6-diaryl-1,2,3,4-tetrahydropyridine-3-carboxylate and 4,6-diaryl-3,4-dihydropyridine-2(1H)-one derivatives have been synthesized from the cyclization of adducts of diethylmalonate to chalcones with ammonium acetate. The structures were established on the basis of extensive spectroscopic methods and further confirmed by X-ray crystallographic analysis. Antibacterial activity of obtained pyridones was investigated against four human pathogen microorganisms and the compounds showed poor activity.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Cyanoacetanilides Intermediates in Heterocyclic Synthesis. Part 2: Preparation of Some Hitherto Unknown Ketene Dithioacetal,Benzoazole and Pyridone Derivatives

Ketene dithioacetal 3 , aminopyrazole 5 , tetrazine 7 , benzoazole 9 and pyridone 11 , 12 , 13 and 16 derivatives were prepared from cyanoacetanilide 1 as a starting material.     

吡啶酮偶氮分散染料光谱性能

吡啶酮分散染料应用性能优异 ,其色谱主要为黄色及橙色 ,尤以黄色为主 [1～ 3]。Cheng和 Peng等 [2 ,3] 对以氨基噻二唑类和苯系芳胺为重氮组分的吡啶酮类染料的可见光谱及互变异构进行了研究 ,Ertan等 [4 ] 研究了以氨基噻唑和氨基苯并噻唑为重氮组分的吡啶酮偶氮染料的可见光谱 ,结果表明上述染料色谱主要仍为黄色。为得到具有更深色谱的吡啶酮类染料 ,我们用不同的重氮组分合成了一系列吡啶酮分散染料 ,研究了其在不同溶剂及不同 p H值下的光谱 ,发现该类染料亦可达到红、甚至蓝色谱 ,其中染料 1 a、1 b及 2 b3个染料结构未见报道。O2 …     

Simultaneous determination of niacin and its metabolites—nicotinamide,nicotinuric acid and N‐methyl‐2‐pyridone‐5‐carboxamide—in human plasma by LC‐MS/MS and its application to a human pharmacokinetic study

An LC‐MS/MS method for the simultaneous quantitation of niacin (NA) and its metabolites, i.e. nicotinamide (NAM), nicotinuric acid (NUA) and N‐methyl‐2‐pyridone‐5‐carboxamide (2‐Pyr), in human plasma (1 mL) was developed and validated using nevirapine as an internal standard (IS). Extraction of the NA and its metabolites along with the IS from human plasma was accomplished using a simple liquid–liquid extraction. The chromatographic separation of NA, NAM, NUA, 2‐Pyr and IS was achieved on a Hypersil‐BDS column (150 ¥ 4.6 mm, 5 mm) column using a mobile phase consisting of 0.1% formic acid : acetonitrile (20:80 v/v) at a flow rate of 1 mL/min. The total run time of analysis was 2 min and elution of NA, NAM, NUA, 2‐Pyr and IS occurred at 1.37, 1.46, 1.40, 1.06 and 1.27 min, respectively. A detailed validation of the method was performed as per the FDA guidelines and the standard curves were found to be linear in the range of 100–20000 ng/mL for NA; 10–1600 ng/mL for NUA and NAM and 50–5000 ng/mL for 2‐Pyr with mean correlation coefficient of ≥0.99 for each analyte. The method was sensitive, specific, precise, accurate and suitable for bioequivalence and pharmacokinetic studies. The developed assay method was successfully applied to a pharmacokinetic study in humans. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and spectroscopic properties of cross-conjugated ketones and meso-substituted tridecamethine salts containing the pyran or pyridone fragment

The reactions of substituted 4H-pyrones and N-methyl-2,6-dimethylpyridone with dimethylformamide acetal and aminal acetals of conjugated -dimethylaminoaldehydes were studied. Cross-conjugated ketones and meso-ethoxy(dialkylamino)tridecamethine salts containing the pyran or pyridone fragment were synthesized and their spectroscopic properties were investigated. The replacement of the bridging O atom by the NMe group precludes an interaction between chromophores in cross-conjugated ketone and the related tridecamethine salt. In addition, the insertion of a meso-amino substituent into the polymethine chain of the salts containing the central pyrylium fragment leads to a sharp weakening of the chromophore interaction. In spite of the dramatic differences in the UV spectra of ketocyanines containing the bridging O or NMe fragments, these dyes have similar ¹³C NMR spectra.