On the structural and spectroscopic properties of the thienyl chalcone derivative: 3-(5-Bromo-2-thienyl)-1-(4-nitrophenyl)-prop-2-en-1-one

In this study, we investigate the structural and spectroscopic properties of the thienyl chalcone derivative 3-(5-Bromo-2-thienyl)-1-(4-nitrophenyl)-prop-2-en-1-one, C₁₃H₈BrNO₃S, using nuclear magnetic resonance (¹H and ¹³C NMR), UV–vis and Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy at room conditions combined with density functional theory (DFT) and time-dependent DFT (TD-DFT) augmented with B3LYP/6-311G(d,p) and CAM-B3LYP/6-311G(d,p) basis sets, yielding valuable information on the molecular conformational preferences, vibrational assignments, optical properties and electronic transitions. The vibrational mode assignments of the most stable conformer of C₁₃H₈BrNO₃S are discussed based on potential energy distribution (PED) analysis and establishing a comparison with a similar chemical structure. The temperature dependence on the Raman spectra of the C₁₃H₈BrNO₃S shows a reversible phase transition in the range 443–443 K pointed out by the discontinuity in the dω/dT of bands in the external and internal modes region. The UV–vis spectrum of the C₁₃H₈BrNO₃S indicates a semiconductor behavior with an optical band gap of 2.6 eV, corresponding to the predicted value of 3.42 eV assigned as the electronic transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). TD-DFT calculations reveal that the electron donor and acceptor group substitution on the 1-phenyl-3-(thiophen-2-yl)prop-2-en-1-one affects its absorption and nonlinear activity.     

Synthesis,Characterization, Antimicrobial Activities,and Structural Studies of Lanthanide (III) Complexes with 1-(4-Chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone

Twelve coordinate lanthanide (III) complexes with the general composition [Ln L₃X_n(H₂O)_n] where Ln = Pr(III), Sm(III), Eu (III), Gd (III), Tb (III), Dy (III), X = Cl^?1, NO₃ ^?2, n = 2–7, and L is 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1- thiosemicarbazone have been prepared. The lanthanide complexes (5) were derived from the reaction between 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone (4) with an aqueous solution of lanthanide salt. Chalcone thiosemicarbazone ligand (4) was prepared by the reaction of [1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)]prop-2-enone (chalcone) (3) with thiosemicarbazide in the presence of hot ethanol. All the lanthanide-ligand 1:3 complexes have been isolated in the solid state, are stable in air, and characterized on the basis of their elemental and spectral data.

Thiosemicarbazone ligands behave as bidentate ligands by coordinating through the sulfur of the isocyanide group and nitrogen of the cyanide residue. The probable structure for all the lanthanide complexes is also proposed. The chalcone thiosemicarbazone ligands and their lanthanide complexes have been screened for their antifungal and antibacterial studies. Some of the synthesized lanthanide complexes have shown enhanced activity compared with that of the free ligand.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis and characterization of beta-cyclodextrin inclusion complex containing di(8-hydroxyquinoline) magnesium

The beta-cyclodextrin (beta-CD) inclusion complex containing di(8-hydroxyquinoline)magnesium was prepared. The product was characterized by NMR, IR, differential thermal thermogravimetric analysis (DT-TGA), spectrofluorimetry, and elemental analysis, indicating the formation of inclusion complex in which the quinoline rings of the guest were encapsulated within the beta-CD cavities. The Job's method provided 2:1 stoichiometry for the inclusion complex between beta-CD and di(8-hydroxyquinoline)magnesium. The association constant calculated with the modified Benesi-Hildebrand equation at 25 degrees C was determined. And the mean association constant was 3577 (L/mol)2, R.S.D. was 2.58%. The thermal stability and solubility of di(8-hydroxyquinoline)magnesium were improved when forming inclusion complex.     

Preparation of 3-(3′-,4′-Hydroxyphenyl)sydnones

3-(3′-,4′-Hydroxyphenyl)sydnones were prepared by dealkylation of 3-(3′-,4′-alkoxyphenyl)sydnones with concentrated sulfuric acid at room temperature in a range of 59 to 86% yield.     

One-pot synthesis of 3-(2-cyanophenyl)quinazolin-4(3H)-one

Anthranilonitrile reacting with formic acid at room temperature for three days gave 64% of 3-(2-cyanophenyl)quinazolin-4(3H)-one. Under similar conditions anthranilic acid. 4-nitroaniline, and 2,5-dichloroaniline were N-formylated in good yields.Institute of Organic Chemistry and Technology, Silesian Technical University, Krzywoustego, 4, 44–100 Gliwice, Poland; e-mail: wojtex@zeus.polsl.gliwice.pl. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 922–924, July, 2000.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

Synthesis of Gingerenone C and 5-Hydroxy-1-(4'-hydroxy- 3'-methoxyphenyl)-7-(4"-hydroxyphenyl)-3-heptanone

The two diarylheptanoids (E)-1-(4'-hydroxy-3'-methoxyphenyl)-7-(4"-hydroxyphenyl) hept-4-en-3-one 1 (Gingerenone C) and (±)-5-hydroxy-1-(4'-hydroxy-3'-methoxyphenyl)-7-(4"-hydroxyphenyl)-3-heptanone 2 were synthesized from vanillin 3 and 4-hydroxybenzaldehyde 9.     

超声技术合成1,5-二-(4-羟基苯基)-1,4-戊二烯-3-酮

利用对羟基苯甲醛和丙酮为原料,以氯化氢气体为催化剂,超声波辐射下成功合成了1,5-二-(4-羟基苯基)-1,4-戊二烯3-酮(HPD).与传统方法相比,该方法具有反应时间短,操作简便及产率高等优点,并讨论了影响产率的因素.     

The Synthesis of 3-(2'-Hydroxybutyl) isobenzofuran-1 (3H)-one

l（3H】．Isobenzoturans（Dhthalldes】werereDortedtoexhibitawiderangeofbiologicalactivities．Forexample,3－n－butylphthallde（NB）exhibitsantlasthmatlc’,antlconvuls－ant“actlvltles．PenEandZhouhavestudiedonthemetabolismofNBPInrats‘．Theyfoundthat...     

离子液体中脂肪酶催化拆分外消旋烯丙酮醇反应

 以离子液体为溶剂,考察了溶剂类型、水活度、温度、 pH值和共溶剂等因素对脂肪酶催化拆分外消旋烯丙酮醇(R,S)-4-羟基-3-甲基-2-(2-丙烯基)-2-环戊烯-1-酮反应的影响,并与常用于外消旋烯丙酮醇拆分的有机溶剂乙酸乙烯酯进行了比较. 结果表明,在离子液体［bmim］PF6中脂肪酶的催化性能较好,酶初始反应速率为18.48 μmol/(g·min), 半衰期为74.53 h, 高于在乙酸乙烯酯中的相应值(9.18 μmol/(g·min)和64.29 h). 但离子液体中拆分反应的转化率低于在乙酸乙烯酯中的转化率,可以通过向离子液体中补加酰基供体来提高外消旋烯丙酮醇的转化率. 两种反应介质中最佳酶反应条件均为水活度0.17, 温度40 ℃和pH=7, 但加入共溶剂后,离子液体中脂肪酶催化拆分外消旋烯丙酮醇的效率降低,而在乙酸乙烯酯中则有所提高.     

Synthesis of propyl O-(α-L-rhamnopyranosyl)-(1→3)-[2,4-di-O-(2s-methylbutyryl)-α-L-rhamnopyranosyl]-(1→2)=(3-O-acetyl-β-D-glucopyranosyl)-(1→2)-βp-D-fucopyranoside,the tetrasaccharide moiety of Tricolorin A

Propyl O-(α-L-rhamnopyranosyl)-(1→3)-[2,4di-O-(2s-methylbutyryl)-α-L-rhamnopyranosyl]-(1→2)-(3-O-acetyl-β-glucopyranosyl)-(1→2)-β-D-fucopyranoside (1), the tetrasaccharide moiety of Ricolorin A, was synthesized in total 23 steps with a longest linear sequence of 10 steps, and overall yield of 3.7% from D-Glucose. The isomerization of the dioxolane-type benzylidene in the prance of NIS/AgOTf was observed. Tetrasaccharide 1 exhibited no activity against the cultured P388 cell as Tricolorin A did.     

Synthesis,characterization, NLO study,and antimicrobial activities of metal complexes derived from 3-(3-(2-hydroxyphenyl)-3-oxoprop-1-enyl)-4H-chromen-4-one and sulfanilamide

A series of metal(II) complexes ML (where M?=?Cu(II), Co(II), Ni(II), Zn(II), Mn(II), Cd(II), and VO(II)) have been prepared from 3-(3-(2-hydroxyphenyl)-3-oxoprop-1-enyl)-4H-chromen-4-one and sulfanilamide. The structures of the complexes have been investigated by elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, NMR, mass, and ESR spectral studies. Conductivity measurements reveal that the complexes are non-electrolytes, except the oxovanadium complex. Spectral and other data show square pyramidal geometry for oxovanadium and octahedral for the other complexes. The redox behaviors of the copper and vanadyl complexes have been studied through cyclic voltammetry. Antimicrobial activities of the compounds against several microorganisms indicate that some complexes have higher activity than free ligand. The compounds may serve as photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation efficiency of the ligand was found to be higher than that of urea and KDP.     

Condensation reactions at the methylene group of 1-(4-nitrophenyl)-pyrrolin-2-one and 1-(4-nitrophenyl)-pyrrolin-2-onium perchlorate

The interaction has been investigated of 1-(4-nitrophenyl)pyrrolin-2-one with aromatic aldehydes in acetic anhydride in the presence of catalytic amounts of pyridine. 1-(4-Nitrophenyl)pyrrolinium perchlorate has been synthesized and was put into a condensation reaction with aromatic aldehydes. As a result 5-arylidene-1-(4-nitrophenyl)pyrrolin-2-onium perchlorates were obtained. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1015–1021, July, 2006.     

Synthesis and Crystal Structure of a New Quinazolinone Compound 2,3-Dihydro-2-（2-hydroxyphenyl）-3-phenyl-quinazolin-4（1H）-one

A new quinazolinone compound 2,3-dihydro-2-(2-hydroxyphenyl)-3-phenylquinazolin-4(IH)-one 3 ([C2oH16O2N2]-C2H5OH, Mr = 362.42) and compound 2-(2-hydroxybenzylidene-amino)-N-phenyl-benzamide 2 (C2oH16O2N2, Mr = 316.34) were prepared from a precursor of 2-amino-N-phenyl-benzamide 1 (C13H12ON2, Mr = 212.25). Compound 3 was characterized by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic,space group Pbca with a = 1.2889(11), b = 1.6170(14), c = 1.7729(15) nm, V= 3.695(6) nm^3, Z= 8, F(000) = 1536, Mr = 362.42, Dc = 1.303 g/cm^3, μ(MoKa) = 0.087 mm^-1, R = 0.0447 and wR= 0.0879. The crystal structure analysis indicates that the title compound has a two-dimensional network structure formed by hydrogen bonds and electrostatic interactions.     

合成3-羟基-2-(4-吡啶基)-1H-茚-1-酮的工艺改进

以邻苯二甲酸酐和4-甲基吡啶为起始原料,正十二烷为溶剂,氯化锌为催化剂,于190℃反应24 h合成了抗癌药物瓦他拉尼的关键中间体——3-羟基-2-(4-吡啶基)-1H-茚-1-酮,收率90.6%,其结构经1H NMR,IR和MS确证。     

用Heck反应合成1-羟基-4-(3-吡啶基)丁-2-酮

在Heck反应条件下,以Ph3P为催化剂配体,由3-卤代吡啶和3-丁烯-1,2-二醇进行偶合可以得到1-羟基-4-(3-吡啶基)丁-2-酮,具有原料易得、合成方法简单的优点.     

Synthesis, Crystal Structure and Antibacterial Activity of 1-（（2-Chloroquinolin-3-yl）-methyl）-pyridin-2（1H）-one

On the basis of the interesting structures and biological activities exhibited by several heterocyclic systems possessing the pyridone nucleus such as mappcine and camptothecin, we have planed to design the synthesis, crystal studies and antibacterial activity of the new 1-((2- chloroquinolin-3yl)-methyl)-pyridine-2(1H)-one building block. An X-ray analysis has provided valuable insight into the effect of steric factors on the three-dimensional shape of this compound which serves as a useful advanced intermediate in the synthesis of these biologically active molecules. A multistep synthesis of camptothecin (5) has been designed by retrosynthetic analysis as part of an ongoing program on lead anticancer drug.     

Spectral characteristics of tramadol in different solvents and β-cyclodextrin

Effect of solvents and β-cyclodextrin on the absorption and fluorescence spectra of tramadol drug has been investigated and compared with anisole. The solid inclusion complex of tramadol with β-CD is investigated by FT-IR, ¹H NMR, scanning electron microscope (SEM), DSC and semiempirical methods. The thermodynamic parameter (ΔG) of inclusion process is determined. A solvent study shows (i) the spectral behaviour of both tramadol and anisole molecules is similar to each other and (ii) the cyclohexanol group in tramadol is not effectively conjugated with anisole group. However, in β-CD, due to space restriction of the CD cavity, a weak interaction is present between the above groups in tramadol. β-Cyclodextrin studies show that tramadol forms 1:2 inclusion complex with β-CD. A mechanism is proposed for the inclusion process.     

(3-氮-吗啉)-1-(4-氯)-苯基-1-丙酮不对称还原产物光学活性的理论计算

采用AM1方法对(S)-4-苄基-5,5-二苯基-1,3,2-噁唑硼烷催化(3-氮-吗啉)-1-(4-氯)-苯基-1-丙酮不对称还原反应的立体控制步骤进行了计算,获得了R和S型过渡态的优化构型及其热焓和熵等热力学参数,计算得到了该步反应中生成R和S型对映体的反应速率常数之比,据此得到的不对称还原反应最终产物的光学活性e.e.的理论计算值,与实验结果相近.     

Synthesis, Characterization, Spectroscopic Properties of 2-（4-Dimethylaminophenyl）-5-fluoro-6-（morpholin-4-yl）-1H-benzimidazole and its Interaction with Calf Thymus DNA

Benzimidazole compounds have attracted a renewed interest recently owing to theirpotential applications in high-performance composite materials, electronic chemicals,photosensitive materials, and their special potentials in biological and/or medicinalapplication1,2. Typically, aromatic compounds with near planar structures and contain-ing hydrogen-donor groups or groups, which are capable of being protonated, havespecial interactions with DNA via intercalation, hydrogen-bonding, and so on3.Me…