A New Zn(Ⅱ) Coordination Polymer Constructed from 4-(1H-pyrazol-3-yl)pyridine as Fluorescent Sensor for Fe^(3+)

A new Zn(Ⅱ) coordination polymer, [Zn(4-PP)(1,4-BDC)?(H_2O)]_n(1, 4-PP = 4-(1 H-pyrazol-3-yl)pyridine, 1,4-H_2BDC = 1,4-benzenedicarboxylic acid), has been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis, IR spectra, XRPD and TG. Structural analysis reveals that Zn(Ⅱ) ions are bridged by COO-from 1,4-BDC^(2-)to form a binuclear structure as the second building units(SBUs). Zn_2 clusters can be clarified as 4-connected nodes, so the framework of 1 can be considered as a 2 D(44?62)-sql sheet. Fluorescence measurements show that 1 has highly selective and sensitive detection of Fe^(3+) in water medium.

Self-aggregating behavior of poly(4-vinyl pyridine)and the potential in mitigating sand production based onπ-πstacking interaction

Unconsolidated sandstone reservoirs are most susceptible to sand production that leads to a dramatic oil production decline.In this study,the poly(4-vinyl pyridine)(P_(4)VP)incorporated with self-aggregating behavior was proposed for sand migration control.The P_(4)VP could aggregate sand grains spontaneously throughπ-πstacking interactions to withstand the drag forces sufficiently.The influential factors on the self-aggregating behavior of the P_(4)VP were evaluated by adhesion force test.The adsorption as well as desorption behavior of P_(4)VP on sand grains was characterized by scanning electron microscopy and adhesion force test at different pH conditions.The result indicated that the pH altered the forms of surface silanol groups on sand grains,which in turn affected the adsorption process of P_(4)VP.The spontaneous dimerization of P_(4)VP molecules resulting from theπ-πstacking interaction was demonstrated by reduced density gradient analysis,which contributed to the self-aggregating behavior and the thermally reversible characteristic of the P_(4)VP.Dynamic sand stabilization test revealed that the P_(4)VP showed wide pH and temperature ranges of application.The production of sands can be mitigated effectively at 20-130℃ within the pH range of 4-8.

A New Diiminopyridyl Cobalt Complex [CoCl_2L](L=2,6-Bis(N,N'-bis(2,6-diisopropyl-4-(2,3-dimethyoxylbenzoylamide)phenylimino))pyridine)

The reaction of CoCl2·6H2O with 2,6-bis（N,N＇-bis（2,6-diisopropyl-4-（2,3-dimethy-oxyl-benzoylamide）phenylimino））pyridine（L） afforded the complex [CoCl2L],which was fully characterized by elemental analysis,UV-vis,IR spectroscopy,fluorescence,and X-ray diffraction analysis.The compound is of triclinic system,space group P1 with a = 13.058（3）,b = 13.798（3）,c = 16.695（3） ,α = 98.191（3）,β = 102.792（3）,γ = 101.820（3）°,V = 2815.0（9） 3,Z = 2,F（000） = 1122,μ = 0.45 mm-1,R = 0.061 and wR = 0.1349 for 9842 observed reflections（Ⅰ 〉 2σ（Ⅰ））.The Co（Ⅱ） center adopts a distorted square-pyramidal coordination geometry.The extended structure shows a one-dimensional zigzag double chain linked by hydrogen bonds and π-π stacking interactions.

Synthesis, Reactions and Characterization of 1,1’-(1,4-Phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(ethan-1-one)

Reaction of 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile) (1) with methyl iodide afforded the 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-(methylthio)nicotinonitrile) (2). The reaction of 2 with hydrazine hydrate followed by diazotization reaction af-forded the 1,1’-(1,4-phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(e-than-1-one) (3) and 1,1’-(1,4-phenylenebis(3-(chlorodiazenyl)-6-methyl-1H-pyrazolo[3,4-b]-pyridine-4,5-diyl))bis(ethan-1-one) (4) respectively. On the other hand, reaction of 4 with malononitrile, 2-cyanoethanethioamide, ethyl acetoacetate, acetyl acetone, ethyl benzoylacetate, diethylmalonate, ethyl cyanoacetate and phenacylbromide aiming to build up pyrazolotriazine or pyrazole ring on the ring system of 4. Structures of all newly synthesized heterocyclic compounds in the present study were confirmed by considering the data of IR, 1H NMR, mass spectra as well as that of elemental analyses.

Synthesis,Crystal Structure and Fluorescent Properties of 1-(4-(Dimethylamino)benzylidene)-4-(naphthalen-1-yl) Thiosemicarbazide

The title compound, 1-4-（dimethylamino）benzylidene）-4-（naphthalene-1-yl） thiosemicarbazide （DMABNTS, C20H20N4S, Mr = 348.47）, was synthesized and characterized by elemental analysis, 1R, ^1H NMR and MS. The crystal structure of DMABNTS with 1,4-dioxane （Diox, C4H8O2） solvent molecules （DMABNTS·2Diox, C28H36N4O4S, Mr = 524.67） was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic system, space group P21/c with a = 14.418（4）, b = 7.1702（19）, c = 28.350（7）°A,β= 101.154（6）°, V= 2875.4（13） °A^3, Z= 4, Dc= 1.212 g/cm^3, F（000） = 1120 and μ= 0.151 mm^-1. A total of 6458 reflections were collected, of which 4671 were unique. The structure was solved by direct methods and refined to the final R = 0.0732 and wR = 0.2127 for 3921 observed reflections （I〉 2σ（I））. There exist intermolecular hydrogen bonds （N（2）-H（2B）…S（1A）and N（1）-H（1A）…O（4B）） in the structure. The study of fluorescent properties ＇shows that DMABNTS emits bright solid-state fluorescence in the visible region and exhibits blue photoluminescence.

Bis(1-(4-(dimethylamino)benzylidene)-4-phenylthiose micarbaznato)palladium(Ⅱ):Synthesis,Crystal Structure and Its Dual Fluorescence Property

The title compound bis（1-（4-（dimethylamino）benzylidene）-4-phenylthiosemicar-bazato）-palladium（Ⅱ）（PdL2） was obtained by reacting 1-（4-（dimethylamino）benzylidene）-4-phenyl-thiosemicarbazide with dichlorobis（benzonitrile）palladium（Ⅱ） in methanol,and its structure was characterized by single-crystal X-ray diffraction.The crystal of PdL2 was obtained in dimethyl-formamide（DMF） solvent with solvent molecules involved in the cell and crystallizes in the monoclinic system,space group C2 with a = 18.485（15）,b = 7.090（5）,c = 17.595（11） ,β = 121.21（3）o,V = 1972（2） 3,Z = 2,Mr = 847.40,Dc = 1.427 g/cm3,μ = 0.624 mm-1,F（000） = 880,R = 0.0607 and wR = 0.1358.The Pd atom adopts a distorted square planar coordination geometry with two Pd-N and two Pd-S bonds.The ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via mercapto sulfur and the imine nitrogen atom,which binds to palladium as bidentate N,S-donors forming five-membered chelate rings.The complex formed hydrogen bonding interaction with solvent DMF molecules from the hydrogen of phenylamine to the oxygen of DMF and several intramolecular hydrogen bonds.Pd（Ⅱ） perturbed ligand π-π＊ transition and metal-to-ligand charge transfer（MLCT） transition are observed in its electronic absorption spectra.The complex exhibits intraligand 1π-π＊（IL） state and MLCT state dual fluorescent emissions in organic solvent at room temperature.

Nonlinear Optical Properties and Optical Limiting Measurements of {(1Z)-[4-(Dimethylamino)Phenyl]Methylene} 4-Nitrobenzocarboxy Hydrazone Monohydrate under CW Laser Regime

We report results from the investigation of the nonlinear refractive index and nonlinear absorption coefficient of {(1Z)-[4-(Dimethylamino)phenyl]methylene} 4-nitrobenzocarboxy hydrazone mono-hydrate (DMPM4NBCHM) solution using Z-scan technique with a continuous wave (CW) Argon ion laser. The results show that this type of organic material has a large nonlinear absorption and nonlinear refractive index at 488 nm and 514 nm. The origin of the nonlinear effects was discussed. We demonstrate that the light induced nonlinear refractive index variation, leads to limiting effect. The results indicated that DMPM4NBCHM could be promising candidates for application on nonlinear photonic devices and optical limiters.

4-二甲氨基吡啶合成工艺条件优化

以吡啶为原料,乙酸乙酯做溶剂,两步法合成高效酰化催化剂4-二甲氨基吡啶.采用正交实验法考察了各种因素对反应的影响,得到了最佳合成条件,该法具有原料易得,条件温和等优点。

[5C+1N]成环反应:吡啶-4(1H)酮类化合物的一种简便合成方法

用N,N-二甲基丙烯酰基二硫缩烯酮类化合物2与各种脂肪胺类化合物3在N,N-二甲基甲酰胺溶剂中60℃条件下,氮乙烯基发生分子内的亲核取代反应,通过[5C+1N]成环反应,合成了系列吡啶-4(1H)酮类化合物4,产率在75%～95%之间。

4-N,N-二甲胺基吡啶促进乙酸钴—溴苄催化甲苯氧化

以乙酸钴和溴苄为催化剂,考察了三乙胺、2,6-二甲基吡啶、吡啶、4-羧基吡啶和4-N,N-二甲氨基吡啶等不同含氮有机化合物对甲苯氧化反应的影响.结果发现4-N,N-二甲氨基吡啶表现出促进效应,并探讨了其促进机制.

4-二甲氨基吡啶和乙醇胺催化苯并噁嗪开环聚合的研究

采用差示扫描量热(DSC)、傅里叶变换红外光谱(FTIR)和原位傅里叶变换红外光谱(in-situ FTIR)研究了4-二甲氨基吡啶(DMAP)、乙醇胺对苯酚-苯胺型苯并噁嗪(pa)开环聚合过程的影响。结果表明,DMAP、乙醇胺及其混合物可使pa开环聚合的起始、峰值温度及其活化能明显降低,其起始温度甚至可降至80℃以下;同时,这些物质的加入还改善了pa聚合放热集中的不足;但它们基本不影响pa开环聚合过程中的化学结构演变及最终固化物结构。热重分析(TGA)结果表明,DMAP、乙醇胺几乎不影响pa固化物的热稳定性。上述结果说明,DMAP、乙醇胺只催化了pa的开环聚合,而基本不影响其聚合物结构及性能,因而是一类适宜于工业化应用的苯并噁嗪开环聚合催化剂。

(苯-1,3,5-三酰基)三乙腈的合成

以1,3,5-三(溴甲基)苯和氰化钾为原料,4-二甲氨基吡啶催化作用下,经亲核取代反应制得目标化合物。产物结构经~1H NMR、IR和电子碰撞质谱法(EI-MS)确证。通过对反应条件研究,确定了最佳反应条件为:n(1,3,5-三(溴甲基)苯)∶n(KCN)=1∶3.1,二甲基亚砜(DMSO)和水为反应溶剂,n(4-二甲氨基吡啶)∶n(1,3,5-三(溴甲基)苯)=0.05,40℃反应2 h,产物收率为97%。

(R)-3-叔丁基二甲基硅氧丁基苯硫醚的合成方法改进

以4-(二甲氨基)吡啶为催化剂,通过(R)-3-叔丁基二甲基硅氧丁醇与甲磺酰氯之间的改进烷基磺酰化反应得到(R)-3-叔丁基二甲基硅氧丁基甲磺酸酯(2b,收率98%),2b再与苯硫酚钠反应生成(R)-3-叔丁基二甲基硅氧丁基苯硫醚(3,总收率89%)。2和3的结构经1H NMR,IR和MS表征。

“一勺烩”工艺合成4－二甲氨基吡啶

以吡啶、氯化亚砜、二甲胺盐酸盐为主要原料，＂一勺烩＂工艺合成高效酰化催化剂４－二甲氨基吡啶，收率达到１３．３％。

Synthesis of FER Zeolite Using 4-(Aminomethyl)pyridine as Structure-directing Agent

This paper describes the synthesis of FER zeolite using commercially available 4-(aminomethyl)pyridine as organic structure-directing agent(OSDA). FER zeolites were prepared in mixtures with SiO2/Al2O3 molar ratios in a narrow range and the resultant products possessed a typical flake-shaped morphology. The crystallization of FER zeolite was tracked in order to better understand the formation mechanism and the products obtained at different crystallization time were systematically characterized using multiple techniques. It showed that a majority of Si atoms and nearly all the Al atoms transformed into the solid phase during the hydrothermal synthesis. The rearrangement of inorganic species gave rise to zeolitic 5-membered rings(5-MRs) and 6-membered rings(6-MRs). Consequently, FER zeolite crystals were formed by the consumption of amorphous bulky gel/solid matrix. Tracking the synthesis process of FER can help.

Simple HPLC Analysis of Hinokitiol in Skin Lotion with Visible Light Detection after Pre-Column Dabsylation

Hinokitiolis frequently added to personal care products as an antibacterial agent. We previously established an HPLC-UV method for determination of hinokitiol in skin lotion after pre-column derivatization with 4-fluoro-7-nitro-2,1,3-benzoxadiazole. However, the labeling reagent is expensive, and derivatives of degradation products of parabens, which may be added to skin lotion as general preservatives, interfered with the peak of the hinokitiol derivative. In this study, the concentration of hinokitiol in skin lotions was determined by HPLC with a visible light detector (450 nm) after pre-column derivatization with 4-(dimethylamino)azobenzene-4’-sulfonyl chloride (Dabsyl-Cl), a more economical reagent. A standard curve was obtained after derivatization with Dabsyl-Cl in borate buffer (pH 9.5) at 55°C for 10 min. The retention time of Dabsyl-hinokitiol was 6.8 min. The calibration plot was linear in the range of 1.25 to 40 μg/mL with a r2 value of 0.9991, and the lower limit of quantification and detection were 0.60 μg/mL (absolute amount of 0.86 ng/20μL injection, signal-to-noise ratio of 10:1) and 0.18 μg/mL (absolute amount of 0.26 ng/20μL injection, signal-to-noise ratio of 3:1), respectively. The coefficient of variation was less than 8.8%. Seven Dabsyl-paraben derivatives showed little interference with the peak of Dabsyl-hinokitiol. The developed system was used to determine the content of hinokitiol in two skin lotions. Addition-recovery tests gave satisfactory results.

环氧/酸酐/DMPA体系固化动力学与溶解性研究

在环氧/酸酐固化体系中引入4-二甲氨基吡啶(DMPA)作为酯交换反应催化剂和固化反应促进剂,以制备具有动态交联网络的环氧树脂。用差示扫描量热仪(DSC)对环氧/酸酐/DMPA体系的固化行为进行了研究,考察了催化剂的含量和固化剂比例对环氧/酸酐/DMPA体系固化行为的影响和固化动力学。通过乙二醇溶解实验,研究交联网络中的可交换键。结果表明反应体系中有高温和低温两种固化机理发生反应,催化剂和固化剂含量较少时,固化反应温度高,固化反应中含较多环氧自聚反应,不利于酯交换反应,溶解效果差;反之,固化反应温度向低温移动,利于酯键的形成,样品的溶解速度就越快。当环氧/酸酐为1:1.5,催化剂用量为3%时,具有较好的溶解性能。

高效高分子酰化催化剂——含超亲核试剂聚酰胺的合成与表征

以４氨基吡啶为原料，制备各种含烷氨基吡啶基团的二元酰氯和二元胺反应性单体，再经缩聚反应得到聚酰胺型高分子超亲核催化剂．用气相色谱跟踪以聚酰胺催化的叔丁醇反应，结果表明，聚酰胺在酰化反应体系中有着良好的溶解性，含烷氨基吡啶基团的线型聚酰胺具有比４（ Ｎ，Ｎ二甲基氨基） 吡啶（ＤＭＡＰ） 更高的催化能力，而交联型树脂较其线型聚合物活性有所降低．

水杨酸甲酯的合成新方法

以水杨酸和甲醇为原料催化合成水杨酸甲酯的实验中,考察了对甲苯磺酸、浓硫酸和N,N-二环己基碳酰亚胺(DCC)、4-二甲氨基吡啶(DMAP)等在反应中的催化活性。结果表明,DCC/DMAP的催化活性高,是较好的酯化反应催化剂,适用于催化合成水杨酸甲酯。还考察了醇酸摩尔比、反应时间和反应温度等条件对合成水杨酸甲酯产率的影响。以DCC/DMAP为催化剂,甲醇与水杨酸摩尔比为1.2∶1,在20℃下反应4h,水杨酸甲酯的收率可达到80.2%。

超亲核催化剂:含烷氨基吡啶功能基团的化合物和聚合物(英)

本文参考了51篇文献，对超亲核酰化反应催化剂4-二烷基氨基吡啶系列化合物和聚合物进行了综述．其中包括：4-（N，N-二甲基氨基）吡啶（DMAP），4-（N，N－二烯丙基氨基）吡啶（DAAP），聚合物负载烷氨基吡啶，烷氨基吡啶高分子化合物等．此外，叙述了该类催化剂的合成及应用．