Selenium-catalyzed oxidative carbonylation of 2-aminobenzyl alcohol to give 1,4-dihydro-2H-3,1-benzoxazin-2-one

An efficient,economical,and phosgene-free approach was developed for the preparation of l,4-dihydro-2H-3,l-benzoxazin-2-one from 2-aminobenzyl alcohol.In terms of its key features,this reaction uses the cheap and recyclable non-metal selenium as a catalyst instead of the noble metal palladium;carbon monoxide as a carbonylation agent instead of virulent phosgene or one of its derivatives;and oxygen as an oxidant.The selenium-catalyzed oxidative carbonylation reaction of2-aminobenzyl alcohol proceeded efficiently in a single pot in the presence of triethylamine to afford l,4-dihydro-2H-3,l-benzoxazin-2-one in 87%yield.Furthermore,the selenium catalyst was readily recovered and recycled,affording a product yield of 80%after five cycles.

Synthesis, Structural Characterization and Antimicrobial Activity of a Novel Cobalt(II) Complex Based on 3-Methyl-1-Phenyl-4-(2-Thienoyl)-Pyrazol-5-One

New cobalt(II) complex, [Co(O2C15H11N2S)2(OH2)2]∙2H2O (1∙2H2O), has been synthesized upon reaction of cobalt chloride hexahydrate (Co(Cl)2∙6H2O) with 3-methyl-1-Phenyl-4-(2-thienoyl)-pyrazol-5-one (referred as HL) in ethanol at room temperature. Single crystal X-ray diffraction (XRD), spectroscopic methods, and microelemental analyses were used to characterize 1∙2H2O. Compound 1∙2H2O crystallizes in the orthorhombic crystal system with a Pbca space group and with the cobalt atom being pseudo-octahedral coordinated. The broth microdilution technique was used to screen the free ligand (HL) and the complex (1∙2H2O) for antimicrobial activities. HL has a low activity (MIC > 100 μg/mL) on all microorganisms, whereas compound 1∙2H2O displayed moderate activity (10 ∙2H2O exhibited bactericidal and fungicidal activity respectively on all the bacteria and yeasts tested. These findings reveal that the antimicrobial activity of HL was enhanced upon coordination to Co(II) ion against all microorganisms (bacteria and fungus).

Synthesis, Structural Characterization and Antimicrobial Activity of a Novel Cobalt(II) Complex Based on 3-Methyl-1-Phenyl-4-(2-Thienoyl)-Pyrazol-5-One

New cobalt(II) complex, [Co(O2C15H11N2S)2(OH2)2]∙2H2O (1∙2H2O), has been synthesized upon reaction of cobalt chloride hexahydrate (Co(Cl)2∙6H2O) with 3-methyl-1-Phenyl-4-(2-thienoyl)-pyrazol-5-one (referred as HL) in ethanol at room temperature. Single crystal X-ray diffraction (XRD), spectroscopic methods, and microelemental analyses were used to characterize 1∙2H2O. Compound 1∙2H2O crystallizes in the orthorhombic crystal system with a Pbca space group and with the cobalt atom being pseudo-octahedral coordinated. The broth microdilution technique was used to screen the free ligand (HL) and the complex (1∙2H2O) for antimicrobial activities. HL has a low activity (MIC > 100 μg/mL) on all microorganisms, whereas compound 1∙2H2O displayed moderate activity (10 ∙2H2O exhibited bactericidal and fungicidal activity respectively on all the bacteria and yeasts tested. These findings reveal that the antimicrobial activity of HL was enhanced upon coordination to Co(II) ion against all microorganisms (bacteria and fungus).

STUDY ON THE CHAIN-EXTENDING REACTION OF POLY (ETHYLENE TEREPHTHALATE) WITH 2, 2′-BIS (4H-3, 1-BENZOXAZIN-4-ONE)

2,2'-Bis (4H-3,1-benaoxazin-4-one) (BBON) has been proved to be an effective chain extender for poly (ethylene terephthalate) (PET). In order to study the reaction mechanism and kinetics of chain-extending reaction, beta-bishydroxyethylene terephthalate (BHET) was selected as model compound. The NMR data, IR spectra and number average molecular weight (<(M)over bar (n)>) of the products obtained from the reaction of BBON and BHET verify that BBON is a hydroxyl-reactive extender. The mechanism was discussed. Kinetics data indicate that extending reaction is a second order reaction, and BBON has high reactivity. The activation energy (E(a)) was measured.

UPLC-MS/MS法测定槲寄生抗肿瘤成分1,7-bis(4-hydroxyphenyl)-1,4-heptadien-3-one的含量

目的建立超高效液相色谱-串联质谱法(UPLC/MS/MS)测定槲寄生中具有抗肿瘤活性的新化合物1,7-bis(4-hydroxyphenyl)-1,4-heptadien-3-one(BHPHD)的含量,并通过多因素方差分析比较产地与寄主对药材抗肿瘤成分含量的影响。方法以Thermo Hypersil GOLD C18(50 mm×2.1 mm,1.9μm)为分离色谱柱,乙腈-体积分数0.1%甲酸水溶液为流动相,流速0.2 m L·min-1,梯度洗脱,质谱检测器,电喷雾正离子,多反应监测模式,监测离子对m/z 295.09→106.99。结果BHPHD在质量浓度为0.050~2.5 mg·L-1内线性关系良好,精密度、重复性、稳定性试验的RSD均≤3.5%,平均加样回收率(n=9)为97.2%(RSD=1.6%)。结论该方法可满足定量要求。多因素方差分析表明槲寄生中BHPHD的含量受产地影响较大(P<0.01),受寄主影响不大。

Highly efficient synthesis of 2,3-dihydroquinazolin-4(1H)-ones catalyzed by heteropoly acids in water

Heteropoly acids efficiently catalyzed the cyclocondensation reaction of anthranilamide with aldehydes in water at ambient temperature and afforded the corresponding 2,3-dihydro-4（1H）-quinazolinones compounds in good to excellent yields.This method provides mild reaction conditions and clean reaction profiles,using a small quantity of catalyst and a simple workup procedure.

Synthesis and Crystal Structure of 1-(4-Fluorophenyl)-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H)-one

The crystal structure of the title compound 1-（4-fluorophenyl） -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H） -one（C23H21FN4O2S,Mr = 436.5） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854（3） ,b = 17.2678（4） ,c = 18.1828（5）A,β = 99.364（2） °,V = 4332.58（18） A^3,Z = 4,Dc = 1.338,F（000） =1824,μ = 0.185 mm^-1,MoKa radiation（λ = 0.71073） ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I 〉 2σ（I） . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5（1H） -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.

Synthesis, Crystal Structure and Fungicidal Activity of (Z)-3,3-Dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one O-2-Chlorobenzyl Oxime Nitrate

The title compound has been synthesized by the reaction of 3,3-dimethyl-1-（1H-1,2,4-triazol-1-yl）butan-2-one oxime with 2-chlorobenzyl chloride, and then treated with 65～68% HNO3. Its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 14.5481（8）, b = 9.3351（5）, c = 13.1911（7） , β = 98.9450（10）°, Z = 4, V = 1769.67（17） 3, Mr = 369.81, Dc = 1.388 g/cm3, S = 1.06, μ = 0.247 mm-1, F（000） = 776, the final R = 0.0352 and wR = 0.0960 for 3069 observed reflections （I 2σ（I））. X-ray crystal structure presents the intramolecular N–H…O hydrogen bond. The packing is nearly parallel without π-π stacking interactions between two adjacent phenyl rings and stabilized by Van der Waals force. The preliminary bioassay shows that the title compound possesses fungicidal activity against Gibberella zeae at the dosage of 25 mg/L.

An efficient synthesis of 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one catalyzed by recyclable solid superacid SO_4^(2-)/TiO_2 under grinding condition

An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.

Synthesis of some new bis-3,4-dihydropyrimidin-2(1H)-ones by using silica-supported tin chloride and titanium tetrachloride

Silica-supported tin chloride and titanium tetrachloride were prepared by the reaction of tin chloride and titanium tetrachloride with activated silica gel in refluxing toluene.These solid acids have been employed as the catalysts for the synthesis of bisdihydropyrimidin -2(1H)-ones from aromatic dialdehydes,1,3-dicarbonyl compounds and urea at 90℃under solvent-free conditions.

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.

SYNTHESIS OF 4,6-DISUBSTITUTED 5-THIOXO-1,2,4-TRIAZIN-3-ONE FROM BENZOTHIOFORMANILIDE

A method of synthesis of 4,6-disubstituted 5-thioxo-1,2,4-triazin- 3-ones from benzothioformanilides and semicarbazide is described.And six new compounds were synthesized by this method.

SINGLE LANTHANUM TRIS(N-PHENYLETHYL-3,5-DI-t-BUTYLSALICYLALDIMINATO)S INITIATOR FOR RING-OPENING POLYMERIZATION OF 1,4-DIOXAN-2-ONE IN BULK

A rare earth Schiff base complex:lanthanum tris(N-phenylethyl-3,5-di-t-butylsalicylaldiminato)s [La(OPEBS)_3] was successfully applied as single component initiator for the ring-opening polymerization of 1,4-dioxan-2-one (PDO) in bulk.The influence of reaction conditions,such as polymerization temperature,the molar ratio of the monomer to initiator (M/I) on the monomer conversion and molecular weight of the polymer has been investigated.Poly(1,4-dioxan-2-one) with a viscosity-average molecular weight (My) o...

Design and Synthesis of 3,4-Dihydropyrrolo[2, 1-c][1, 4]oxazin-1-oneand its 7-Acyl Derivatives

Starting from 1H-pyrrole, unreported 3, 4-dihydropyrrolo[2, 1-c][l, 4]oxazin-1-one 4, 7-(4-chlorobenzoyl)-3, 4-dihydropyrrolo[2, 1-c][1, 4]oxazin-1-one 5 and 7-benzoyl-3, 4-dihydro-pyrrolo [2, 1-c][1, 4]oxazin-1-one 9 were designed and synthesized. They may have antipyretic and analgesic activities.

The First Total Synthesis of Natural 6β-Cinnamoyloxy-1α- hydroxy-5, 10-bis-epi-eudesm-4-en-3-one

The first total synthesis of natural 6β-cinnamoyloxy-1α-hydroxy-5, 10-bis-epi- eudesm-4-en-3-one （1）, a highly complex natural eudesmane, was described.

H_3PMo_(12)O_(40) catalyzed three-component one-pot synthesis of 4,6-diarylpyrimidin-2(1H)-ones under solvent-free conditions

4,6-Diarylpyrimidin-2(1H)-one derivatives have been synthesized from three-component one-pot condensation of acetophe-none derivatives,aldehydes and urea in the presence of trimethylsilyl chloride and a catalytic amount of HPMoOunder solvent-free conditions.

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 biphenyl 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)-one], 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.

Synthetic Approach for Novel Fluorine Substituted <i>α</i>-Aminophosphonic Acids Containing 1,2,4-Triazin-5-One Moiety as Antioxidant Agents

Novel fluorine substituted α-amino phosphonic acids containing 1,2,4-triazin- 5-one (6a-f) have been obtained from fluoroacylation of 6-(2&prime;-amino-5&prime;-nitrophenyl)-3-thioxo-1,2,4-triazin-5(4H)-one (1) followed by ammonilysis to give the corresponding 3-amino-derivative 3. Condensation of compound 3 with nitro/halogenated aromatic aldehydes yielded the Schiff bases 4. The simple addition of diethyl phosphonate to compound 4 produced the α-amino phosphonates 5. Acidic hydrolysis of compound 5 produced the fluorine substituted α-amino acids derivatives 6. Structures of the new compounds have been established with the help of elemental analysis and spectral measurements. Also, the products evaluated as antioxidants, where the fluorinated α-amino phosphonic acids 6 are more active than the other synthesized systems.

Various Routes to Synthesise 3-Thioxo-1,2,4-Triazine-5-One Derivatives as Antimicrobial Agents

A simple condensation afforded some new 3-thioxo-1,2,4-triazin-5-one derivatives (4, 6 and 8). Utilizing a facile condensation of (E)-4-(4’-bromo styryl)-2-oxo-3-buteneoic acid with thiosemicarbazide, dithioic formic acid hydrazide, and thiocarbahydrazide in different conditions. Structures of these compounds were confirmed by elemental and spectral analysis. The preliminary biocidal activity of these products were evaluated against some microbial and compared to Mycostatine and piperacillin as antibiotics were most of derivatives exhibited good activity.