Microwave promoted one-pot synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins

A facile procedure for the synthesis of 3-（2′-amino-3′-cyano-4′-arylpyrid-6′-yl） coumarins are being reported starting from 3- acetylcoumarin, aromatic aldehydes and malononitrile. The reactions were carried out on microwave irradiation in good yield with short time and easy work-up. The structures of all the compounds have been confirmed on the basis of their analytical, IR, ^1H NMR, and mass spectral data.

Synthesis,Crystal Structure and Plant Growth Regulatory Activity of 1-(3-Amino-[1,2,4]triazol-1-yl)-3,3-dimethyl-butan-2-one

The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with equal amount of K_2CO_3 as acid acceptor. The structure of compound 3 was characterized by ~1H NMR, 13 C NMR, HRMS and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n with a = 5.7227（8）, b = 27.924（4）, c = 6.2282（7） ？, β = 101.892（11）°, V = 973.9（2） ？~3, Z = 4, T = 180.00（10） K, μ（MoKα） = 0.087 mm^（-1）, Dc = 1.243 g/cm^3, 3832 reflections measured（3.648≤θ≤26.022°）, 1916 unique reflections（Rint = 0.0359, Rsigma = 0.0572） used in all calculations. The final R = 0.0557（I 〉 2σ（I）） and w R = 0.1276（all data）. Bioassay showed that 3 displayed excellent activity as plant growth regulator with inducing lateral root formation and enhancing primary root elongation at 0.27 mmol/L（50 ppm） in soybeen（He Feng-50）. Good water solubility was found with 50 mg in 1 m L of water. Therefore, application of 3 in agriculture is more environmentally friendly due to cosolvent-free condition, and results in improved abiotic-stress tolerance by affecting the root growth. And furthermore, it can be used as a precursor to investigate the function of regulating plant root growth.

Theoretical Study on the Reaction Mechanism of 2-Methoxybenzaldehyde,4-Bromo-indanone,Malononitrile and Ammonium Acetate One-pot to Form 6-(2-Methoxyphenyl)-2-amino-6-bromo-5H-indeno[1,2-b]pyridine-3-carbonitrile

The reaction mechanism of 2-methoxybenzaldehyde, 4-bromo-indanone, malononitrile and ammonium acetate one-pot to form 6-（2-methoxyphenyl）-2-amino-6-bromo-5 Hindeno[1,2-b]pyridine-3-carbonitrile was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Reaction pathways were investigated in this study. The result indicates that the reaction Re→ TSB1→IMB1→ TSB2→ IMB2→TSB3→IMB3→TSB4→IMB4→TSB5→IMB5→TSB6→IMB6→TSB7→IMB7→ TSB8→IMB8→TSB9→IMB9→P2 is the main pathway, the activation energy of which is the lowest. The dominant product predicted theoretically is in agreement with the experiment results.

Synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with potential bioactivity in PEG-400

An environmental benign procedure for synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles has been developed by reaction of 2-amino-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with formic acid in PEG-400.The key advantages of this protocol are the shorter reaction time,higher yields,lower cost,simple workup,and environment-friendly compared to conventional organic solvent reaction.The present method does not involve any hazardous organic solvent or catalyst.

Crystal Structure and Biological Activities of (R)-N′-[2-(4-Methoxy-6-chloro)-pyrimidinyl]-N-[3-methyl-2-(4-chlorophenyl)butyryl]-urea

The title compound （R）-N′-[2-（4-methoxy-6-chloro）-pyrimidyl]-N-[3-methyl-2-（4- chlorophenyl）butyryl]-urea has been synthesized, and its crystal structure and biological behaviors were studied. Crystallographic data： C17H18C12N4O3, Mr = 397.25, monoclinic, space group P21/c, a = 12.331（2）, b = 14.025（3）, c = 23.085（5） A, β = 99.607（4）°, Z = 8, V = 3936.2（13） A3, Dc = 1.341 g/cm^3, F（000） = 1648, R = 0.0718, wR = 0.1585 and/t（MoKα） = 0.353 mm^-1. The preliminary biological tests showed that the title compound has definite insecticidal and fungicidal activities.

Synthesis, Crystal Structure, Antibacterial Activities and Theoretical Computation of 3-(2-Hydroxybenzly)-4-(4-isopropylbenzyl- ideneamino)-(1H)-1,2,4-triazole-5-thione

The title compound C18H18N4OS has been synthesized by the reaction of 3-（2-hydroxy- benzyl）-4-amino-（1H）-1,2,4-triazole-5-thione with 4-isopropylbenzaldehyde in ethanol and characterized by IR, ^1H NMR spectra and elemental analysis. Its structure was determined by X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 11.605（2）, b = 7.401（1）, c = 20.339（2） A, β= 103.05（2）°, V= 1701.8（4） A^3, Z = 4, Mr = 338.42,μ = 0.202 mm^-1, Dc = 1.321 g/cm^3 and F（000） = 712. The structure was solved by direct methods and refined to R = 0.0428 and wR = 0.1069. Due to the intramolecular O-H…N hydrogen bond and π-π stacking interactions between the benzene （C（1）～C（6）） and triazole rings, the two planes are essentially coplanar. Their biological activities have been measured, showing this type of compound has certain antibacterial activity for Staphylococous aureus and Bacillus subtilis. Based on the quantum chemistry calculation at the RHF/6-31G level, the frontier orbitals and electrostatic potential of the title compound were also discussed.

Synthesis and Crystal Structure of Ethyl 2-(6-(1,3-Dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) Butanoate

The title compound ethyl 2-（6-（1,3-dioxo-4,5,6,7-tetrahydro-lH-isoindol-2（3H）- yl）-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4（3H）-yl） butanoate 3 was synthesized by the reaction of ethyl 2-（6-amino-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4（3H）-yl） butanoate with 4,5,6,7- tetraydrophthalic anhydride, and its structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P2 1/n with a = 9.3469（2）, b = 16.7715（5）, c = 13.7153（4） A, β= 104.9680（10）°, μ = 0.107 mm^-1, Mr = 430.42, V= 2077.08（10） ,A3, Z= 4, Dc = 1.376 g/cm3, F（000） = 904, T= 296（2） K, R = 0.0508 and wR = 0.1478.

豹皮菌中2－Amino－3－（1，2－dicarboxyethylthio）propanoic Acid非对映异构体的分离和鉴定

从豹皮菌中的新鲜子实体的乙醇提取物中分离得到一种ＮＭＤＡ受体格抗剂，经理化常数和波谱数据的测定鉴定为２－Ａｍｉｎｏ－３－（１，２－ｄｉｃａｒｂｏｘｙｅｔｈｙｌｔｈｉｏ）ｐｒｏｐａｎｏｉｃａｃｉｄ非对映异构体的混合物，该化合物是首次从豹皮菌中得到，经进一步分离，得到两种非对映体异构体。

Preparation of 2-amino-5,7-dimethoxy-4-aryl/alkyl-4H-chromene-3-carbonitriles using Na_2O-Al_2O_3-P_2O_5 glass–ceramic system

A highly efficient and environmentally benign protocol for the synthesis of 2-amino-5,7-dimethoxy-4- aryl/alkyl-4H-chromene-3-carbonitrile derivatives by one-pot three-component coupling reacting of aromatic aldehydes, malononitrile and 3,5-dimethoxy phenol under reflux condition has been developed in aqueous EtOH media using Na2O-Al2O3-P2O5 glass-ceramic system.

Improvement in the synthesis of 2-(5-amino-1,2,4-thiadiazol-3- yl)-2-(Z)-methoxyiminoacetic acid 2-benzothiazolyl thioester

2-(5-Amino-1,2,4-thiadiazol-3-yl)-2-(Z)-meth-oxyiminoacetic acid 2-benzothiazolyl thioester(III),an important intermediate of the fourth generation cephalos-porins,was efficiently synthesized by reacting 2-(5-amino-1,2,4-thiadiazol-3-yl)-2-(Z)-methoxyiminoacetic acid(I)with 2,29-dibenzothiazole disulfide(II)in the presence of triphenylphosphine.Effects of reaction time,temperature,solvents,catalysts and feeding molar ratio on the yield and quality of products were investigated,and an im-proved procedure suitable for industrial production was established.Using 1,2-dichloroethane as solvent,triphe-nylphosphine as reducer,and triethylamine as catalyst,n(I):n(II):n(triphenylphosphine)51.0:1.0:1.0,the product was obtained at room temperature in 98.1%yield.The purity of the product without further purification is 98.7%determined by HPLC method.This procedure could be a suitable alternative to the traditional processes because of its easy handling,high yield and low cost.

A New Two-dimensional Coordination Polymer Based on Trinuclear Manganese Clusters

A novel two-dimensional Mn（II） coordination polymer, [Mn3（L）R（cis-chdc）fftrans- chdc）]n （L = 2-amino-4-（1H-imidazo[4,5-J][1,10]phenanthrolin-2-yl）phenol and chdc = 1,4-cyclo- hexanedicarboxylate）, has been hydrothermally synthesized and characterized by elemental analysis, IR, TG PL and single-crystal X-ray diffraction. Crystallographic data for this compound： monoclinic space group P2/n with a = 11.0058（13）, b = 9.0179（11）, c = 28.431（3） A, β = 92.850（2）°, V = 2818.3（6） A3, Z = 2, C62Hs6Mn3N10O14, Mr = 1329.99, Dc = 1.567 g/cm3, F（000） = 1370, p（MoKa） = 0.742 mm-1, R = 0.0553 and wR = 0.1421. The chdc carboxylates bridge the Mn（II） atoms to form a trinuclear Mn（lI） cluster. The cis-chdc ligands are held together by the trinuclear Mn（II） clusters to result in a chain structure. Further, the trans-chdc ligands link adjacent chains to furnish a two-dimensional network. The π-π interactions between neighboring layers link the adjacent layers into a three-dimensional supramolecular architecture. Moreover, the N-H...O and O-H...O hydrogen bonds further stabilize the 3D supramolecular architecture.

A Sensitive HPLC-MS/MS Analysis of Dencichine in Rat Plasma and Its Application to Pharmacokinetics

In order to quantitate dencichine in biological samples, a selective and sensitive method for the determination of dencichine in rat plasma based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed and validated. (l)-2-amino-3-(carboxymethylthio)propionic acid was used as the internal standard (I.S.). After a protein precipitation extraction with acetonitrile, dencichine and the I.S. were chromatographed on an Xterra MS-C18 column. The mobile phase was consisted of 20mmol/L ammonium acetate solution-acetonitrile (35:65, V/V) at a flow rate of 0.2 mL/min. The detection was performed on a triple quadrupole mass via electrospray ionization (ESI) source in the positive mode. The intra- and inter-day precision (relative standard deviation, R.S.D.) values of dencichine were below 6.7%. The extraction recoveries were up 85%. The lower limit of quantification was 20 ng/ml, which was sensitive enough to detect the analyte. The HPLC-MS/MS method was successfully applied to the pharmacokinetic study after an intravenous administration of dencichine in Sprague-Dawley (SD) rat.

Syntheses, Characterization and Biological Activity of Novel Thiazoylazo Dye and Its Coordination Compounds

The present work describes the synthesis of a novel heterocyclic azo dye by general diazonization of 2-amino-4,5-dimethylthiazole followed by the diazo- coupling of the resulting diazonium ion with 5-methyl-2-(propan-2-yl)phenol to obtain ligand L. This was characterized using Fourier-transformed infrared and electronic spectrophotometry. Ligand L was further coordinated with five metal ions, M:L, 1:2 [M = Cu(II), Mn(II), Zn(II), Ni(II) and Co(II)]. The coordination compounds obtained were characterized by electronic, IR spectrophotometry, magnetic susceptibility and percentage metal analyses. The results obtained suggested that a thiazoylazo dye was obtained as ligand L. It was proposed that two molecules of the solvent coordinated to the metal ion in addition with the ligands to give an octahedral geometry for copper(II), manganese(II) and nickel(II) complexes. On the other hand, square planar geometry was suggested for zinc(II) and cobalt(II) complexes. The anti-infla- mmatory activity of the ligand and coordination compounds was evaluated using four in vitro-based assays viz: xanthine oxidase and lipoxygenase inhibition assay, membrane stability and protein denaturation assay. The synthesized compounds generally exhibited good anti-inflammatory activity in all the assays carried out. However, the reference standards, in this instance, were more effective in the case of xanthine oxidase, lipoxygenase and protein denaturation inhibitory assays. For the membrane stability study, the coordination compounds and ligand L elicited more potent anti-inflammatory activity than the standard drug.