An Efficient Synthesis of [1,2,4]Triazolo[3,2-d][1,5]benzoxazepin-2-thiones, a Kind of Novel Tricyclic O,N-Heterocycles

A series of novel tricyclic O,N-heterocycles, [1,2,4]triazolo[3,2-d][1,5]benzoxazepin-2-thiones 7 were achieved via acid-induced ring closure of the geminal arylazo isothiocyanate compounds 5 which were derived from substituted chroman-4-ones, followed by feasible ring expansion with simultaneous insertion of the nitrogen atom into the carbon skeleton. The X-ray crystal structure of 7d was also described.     

A Convenient Synthesis of 2-Arylnaphtho[1,2-d]oxazole Derivatives Promoted by Triethylamine

A variety of 2-arylnaphtho[ 1,2-d]oxazole derivatives were efficiently synthesized in moderate to high yields by the reaction of aromatic aldehydes with 1-amino-2-naphthol derivatives in the presence of triethylamine in refluxing ethanol in air. Seven new 2-arylnaphtho[1,2-d]oxazole derivatives were obtained and characterized by the spectral data and elemental analysis. In addition, the X-ray crystal structures of 2-[4-（N,N-dimethylamino）phenyl]naphtho[ 1,2-d] oxzole （3d） and 1, 1＇-bis（naphtho[ 1,2-d]oxazol-2-yl）ferrocene （3n） have been determined.     

Synthesis of Certain 3-Aminopyrazolo[5,4-b]pyridine and 3,4-Substituted Pyrido[2′,3′：3,4]pyrazolo[5,1-c][1,2,4]triazine Derivatives

2-Thioxo-1,2-dihydropyridine derivatives 2a, 2b were reacted with methyl iodide to give 2-methylthiopyridines 3a, 3b, which were reacted with hydrazine hydrate to produce 3-aminopyrazolo[5,4-b]pyridines 4a, 4b. Compounds 4a, 4b were diazotized to afford the corresponding diazonium salts 5a, 5b, which were reacted with some active methylene compounds 6a-6h to give the corresponding pyrido[2′,3′ ： 3,4]pyrazole[5,1-c][1,2,4]triazines 7-14.     

Comparative Studies of 1,4-Bis[2-（4-Pyridyl）ethenyl]-benzene Using Density Functional Theory

The optimized molecular structure and harmonic vibrational frequencies of a 1,4-bis[2-(4-pyridyl)ethenyl]-benzene(BPENB)molecule were calculated via five popular density functional theory(DFT)methods.On the basis of the comparison between calculated and experimental results,it is concluded that the B3PW91 and B3LYP methods are superior to the others in optimizing structures,and the BPW91 method reproduces the observed fundamental frequencies most satisfactorily.     

Fe3O4@MCM-48–SO3H:合成苯并[f]色烯并[2,3-d]嘧啶酮的高效、可磁性分离纳米催化剂（英文）

Sulfonic acid groups were grafted onto three different types of synthesized magnetic nanoparticles, namely Fe3O4, Fe3O4@SiO2, and Fe3O4@MCM‐48. The sulfonic acid‐functionalized nanoparticles were evaluated as catalysts for the synthesis of 5‐aryl‐1H‐benzo[f]chromeno[2,3‐d]pyrimidine‐2,4(3H,5H)‐dione derivatives in terms of activity and recyclability. Their catalytic activities were compared with that of the homogeneous acid catalyst 1‐methylimidazolium hydrogen sulfate ([HMIm][HSO4]). The activity of Fe3O4@MCM‐48–SO3H was comparable to those of the other heter‐ogeneous and homogeneous catalysts.     

Synthesis and Characterization of a Novel Copoly(aryl ether ketone) Containing 4,4′-Biphenyl-bis[4-phthalazin-1(2H)-one] moiety

A new monomer of 4,4′-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenly and phthalic anhydride,and a novel copoly(aryl ether ketone)(PPEK) was synthesized from 2,2-bis(4-hydroxyphenyl)-propane(BPA),4,4′-biphenyl-bis-[4-phthalazin-1(2H)pne],4,4′-difluorodiphenylketone(DFK).The monomer and copolymer were characterized by FT-IR and ^1H-NMR.DSC and TGA were used to the novel polymer.     

Mass Spectral Fragmentation of （S, S）-N,N＇-Bis [1-（hydroxymethyl） alkyl ] anthracene/Naphthalene-1, 8-dicarboxamides under Electron Impact Ionization Conditions

The mass spectrometric fragmentation of （ S, S） -N, N＇-bis [ 1- （hydroxymethyl） alkyl] anthracene/naphthalene-1, 8-dicarboxamides was investigated with the aid of mass-analyzed ion kinetic energy spectrometry and the elemental compositions of important fragment ions were determined by accurate mass measurement under electron impact ionization conditions. All the compounds could eliminate formaldehyde. The [ M-CH2O] ions could also eliminate imine, aziridine, aziridinone, 2-amonoalkan-1-ol, water, and other fragments. Several cyclizations were observed under electron impact ionization.     

Synthesis of a Tweezer—like Bis（Phenylthiapropoxy）calix[4]—arene as a Cation／π Enhanced Sensor for Ion—Selective Electrodes

Two novel 25,27-dihydroxy-26,28-bis(3-phenylthiapropxy)-calix[4]arene(3) and 25,27-dihydroxy-26,28-bis(3-phenylthiapropoxy)-5,11,17,23-tetra-tert-butylcalix[4] arene (4) were synthesized for the evaluation of their ion-selectivity in ion-selective electrodes(ISEs).ISEs based on 3 and 4 as neutral ionophores were prepared,and their selectivity coefficients for Ag^ (lg KAg,M^pot)were investigated against other alkali metal,alkaline-earth metal,aluminum,thallium(Ⅰ）,Lead and some transition metal ions using the separate solution method (SSM).These ISEs showed excellent Ag^ seletivity over most of the interfering cations examined,except for Hg^2 and Fe^2 having relative smaller interference(lg KAg,M^pot≤-2.1).     

Study on Interaction of L-Tryptophan with p-Suffonatocalix[4]arene by Spectrofluorometry

The interactions between L-tryptophan（L-Trp） and water-soluble p-sulfonatocalix[4]- arene （SCX4） were investigated by spectrofluorometry. The effect of pH was discussed. The interaction process was estimated from the thermodynamic viewpoint. The SCX4 was found to be able to adjust its conformation to fit the size of L-Trp, and the benzene of L-Trp penetrated into the hydrophobic cavity of SCX4. Meanwhile, the binding mechanism was further elucidated by IHNMR and molecular mechanics calculations.     

单氧代-二硒烷基-1, w-二氧取代杯[4]衍生物的合成,结构及萃取性能研究

Novel macrocyclic monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a were synthesized by the reaction of calix[4]arene dibromides 1-5 with the disodium salt of bis（2-selenylethyl）ether in the yields between 28% and 64%. Their structures were characterized by proton and carbon NMR spectra. X-Ray structure analysis of la further confirmed the cone conformation of compounds 1a-5a. An interesting host-guest complex of la with dichloromethane via CH/π and C1/π interactions was elucidated. Extraction experiments showed that these novel monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a had strong extraction ability towards mercury ion. The interaction of Hg^2＋with the calix ligand has also been investigated by 1^H NMR titration.     

An Interesting Approach to Bis-calix[5]arene Analogue from Calix[6]arene

Calix [n] arenas {n = 4, 6 or 8} are easily prepared from formaldehyde and para-substituted phenols via cyclic condensation under alkaline conditions in one step. It is not surprising that the calyx [n] arene (n = 4, 6, 8) chemistry has been developing very rapidly during the latest 20 years1. However, it is not the case for calixarenes with odd benzene rings (for example, n = 5). The yield of p-tert-butylcalix [5] arene synthesized in one-step from p-tert-butylphenol and formaldehyde was a…     

Cycloaddition reactions of 2,3-dihydro-1H-1,4-diazepines with nitrile oxides and imines. Synthesis of bis[1,2,4]oxadiazolo-and bis[1,2,4]triazolo[1,4]diazepine derivatives

New heterotricyclic systems, 6,10a,11,11a-tetrahydro-5H-bis[1,2,4]oxadiazolo[4,5-d:5′,4′-g][1,4]diazepines 6,7,9-11 and 5,6,10,10a,11,11a-hexahydro-1H-bis[1,2,4]triazolo[4,3-d:3′,4′-g][1,4]diazepines 8,12 have been obtained by double site- and regie-specific 1,3-dipolar cycloaddition of mesitylnitrile oxide ( 1 ) or diphenylnitrile imine ( 2 ) to 5,7-disubstituted 2,3-dihydro-1H-1,4-diazepines 3-5. The structure of the synthesized bis-adducts 6-12 shows that the hetero double bonds are much more reactive than the olefinic ones in the dipolarophiles under study. No evidence for the formation of mono-adducts was obtained.     

Synthesis of 1,3-Bis[(3-aryl)-S-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]benzenes

1,3-bis[(3-aryl)-s-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]benzenes 2 were synthesized in high yields by the reaction of 3-aryl 4-amino-5-mercapto-1,2,4-triazole 1 with m-phthalic acid.     

The Synthesis and Fungicidal Activities of 2,6-Bis[(3-aryl)-s-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]pyridines

In search of better bioactive compounds, a series of novel 2,6-bis[(3-aryl)-s-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]pyridines 2 were synthesized in high yields by the cyclization of 3-aryl-4-amino-5-mercapto-1, 2, 4-triazoles 1 with 2,6-pyridine dicarboxylic acid. 2 exhibited good fungicidal activities against Cerospora beticola sacc.     

5,6-2H-1,2,4-三唑[3,4-b][1,3,4]噻二嗪衍生物的合成及抗癌活性测定

取代苯甲醛与4-氨基-5-(3,4,5-三甲氧基苯基)-1,2,4-三唑-3-硫酮(2)缩合生成5-(3,4,5-三甲氧基苯基)-4-取代苯基亚胺基-1,2,4-三唑-3-硫酮(3),再烷基加成化为新型5,6-2H-1,2,4-三唑[3,4-b][1,3,4]噻二嗪衍生物4.化合物结构经1HNMR 13C NMR,IR以及元素分析确认.采用噻唑兰(MTT)比色法进行化合物抑制人体前列腺癌细胞(PC3)体外活性测试,结果表明所合成的化合物具有不同程度的抑制PC3活性,其中化合物4a在10μmol·L-1浓度下对PC3的抑制率为75.9%.     

硫(硒)杂多杯[4]芳烃合成及其络合性能研究

合成了下缘硫、硒杂杯[4]芳烃, 然后与杯芳烃片段2,6-二(溴甲基)-4-甲氧基-甲苯在NaH存在条件下缩合得到硫、硒杂多杯[4]芳烃5a和5b. 离子萃取实验表明硫、硒杂多杯[4]芳烃显著增加了对Ag＋和Hg2＋重金属离子的萃取效果.     

One-pot synthesis of [1+1] and 62-membered [2+2] Schiff base macrocycles

New [1+1] and 62-membered [2+2] Schiff base macrocycles containing a 2,6-diamidopyridine subunit have been synthesized by condensation reaction of the precursors pyridine-2,6-dicarboxamide and 1,10-bis(20-formylphenyloxy)decane in the presence of phosphoric acid via a one-pot process. The cyclocondensed products were effectively isolated by gel column chromatography and characterized by ~1H NMR, FTIR, mass spectrometry and X-ray analysis. The two macrocycles have a twisted structure, and not an open ‘circular' conformation in the solid state.     

Photochemistry of 3,7-Bis(arylmethylene)bicyclo[3.3.1]nonane Derivatives

UV irradiation of trans-trans-3,7-bis(arylmethylene)bicyclo[3.3.1]nonane-2,6-diones leads to their complete or partial transformation into the corresponding cis-cis isomers. Irradiation of trans-trans-3,7-bis(arylmethylene)bicyclo[3.3.1]nonane-2,6-diol in ether in the presence of CuCl results in intramolecular cyclization involving the exocyclic double bonds and one benzene ring to give exo-7endo-10-dihydroxy-2-phenyl-3,4-benzotetracyclo[4.3.3.18,11.01,6]tridecane.     

Reactivities of novel [hydroxy(tosyloxy)iodo]arenes and [hydroxy(phosphoryloxy)iodo]arenes for alpha-tosyloxylation and alpha-phosphoryloxylation of ketones

Novel [hydroxy(tosyloxy)iodo]arenes bearing 2-thienyl, 3-thienyl, N-tosyl-4-pyrazolyl, 3-trifluoromethylphenyl, and 3,5-bis(trifluoromethy)phenyl as an aromatic group, and [hydroxy(phosphoryloxy)iodo]arenes bearing N-tosyl-4-pyrazolyl, 3-trifluoromethylphenyl, and 3,5-bis(trifluoromethy)phenyl as an aromatic group, were prepared. alpha-Tosyloxylation and alpha-phosphoryloxylation of ketones with these compounds were carried out, respectively. Their reactivities were compared with that of the parent [hydroxy(tosyloxy)iodo]benzene and [hydroxy(phosphoryloxy)iodo]benzene, respectively, and consequently [hydroxy(tosyloxy)iodo]arenes and [hydroxy(phosphoryloxy)iodo]arenes bearing 3-trifluoromethylphenyl and 3,5-bis(trifluoromethy)phenyl as an aromatic group showed the best reactivity. These new compounds can be used as powerful alpha-tosyloxylation and alpha-phosphoryloxylation reagents, instead of the parent [hydroxy(tosyloxy)iodo]benzene and [hydroxy(phosphoryloxy)iodo]benzene.     

Enhancement of luminescence lifetimes of mononuclear ruthenium(II)-terpyridine complexes by manipulation of the sigma-donor strength of ligands

The synthesis and characterization of mixed ligand 2,2';6',2' '-terpyridine (tpy) ruthenium complexes with 2,6-bis([1,2,4]triazol-3-yl)pyridine, 2,6-bis(5-phenyl-[1,2,4]triazol-3-yl)pyridine, and 2,6-bis([1,2,3,4]tetrazol-5-yl)pyridine are reported. The species are characterized by HPLC, 1H NMR, UV/vis, and emission spectroscopy. The photophysical properties of the complexes are investigated as a function of temperature over the range 80-320 K. The emission lifetime observed for the fully deprotonated compounds at room temperature is about 80 ns. This increase by 2 orders of magnitude with respect to the parent "[Ru(tpy)2](2+)" complex is rationalized by an increase in the energy of the metal based dsigma orbital, rather than by manipulation of the pi* orbitals on the ligands. The acid-base and electrochemical properties of the compounds are reported also.