Syntheses and Characterization of 2D and 3D Organotin Polymers with Phenylsuccinic Acid and Trimethyltin Chloride Under Different Conditions

Two types of di- and trimethyltin(IV) polymers [(Me₂Sn)₄O₂(C₁₀H₈O₄)₄] _n 1 and [(Me₃Sn)₂(C₁₀H₈O₄)] _n ·DMF 2 have been synthesized by the reaction of trimethyltin chloride with (±)-phenylsuccinic acid under two different experimental conditions. Both of the complexes are characterized by elemental analysis, IR, NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy and X-ray crystallographic diffraction analysis. The structural analyses show that complex 1 is a two-dimensional corrugated sheet polymer consisting of dimeric tetraorganodistannoxane units and bridging ligands. Complex 2 is a 3D corrugated polymer in which the deprotoned acid occurs as a tetradentate ligand and is bonded by the four oxygen atoms. It is worth noting that the X-ray diffraction study reveals that complex 2 crystallizes in the orthorhombic space group P212121, which is chiral space group.     

苯并咪唑-5,6-二羧酸的研究进展

苯并咪唑-5,6二羧酸是一种重要的有机合成中间体,在医药、农药等行业有广泛的应用前景。苯并咪唑-5,6二羧酸可合成分子生物学中的二维探针。本文对苯并咪唑-5,6二羧酸的合成方法及在医药、农药、生物化学和分析化学等方面的具体应用进行了概括。     

Syntheses, Characterization and Crystal Structures of 1D and 2D Organotin Polymers Containing 3-Methyladipic Acid Ligand

Four new organotin (IV) complexes of two types [(R₂Sn)₂(C₇H₁₀O₄)(μ₃-O)] _n (R = Me: 1; nBu: 2; and {(R₃Sn)₂[C₅H₁₀(COO)₂]} _n (R = Me: 3; nBu: 4) have been synthesized by the reaction of 3-methyladipic acid with the corresponding R₃SnCl (R = Me, nBu) under two different experimental conditions. All the complexes were characterized by elemental analysis, FT-IR, and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy. Except for 2, all of the complexes were also characterized by X-ray crystallography. The structural analyzes show that complex 1 is a 1D infinite chain polymer and forms a 2D organotin framework through intermolecular C–H···O interactions and weak Sn···O interactions. Complexes 3 and 4 are 2D network polymers in which 3-methyladipic acid acts as a tetra dentate ligand coordinated to the trialkyltin (IV) ion.     

2-甲基-苯并咪唑-5-羧酸的合成与表征

文章以3,4-二氨基苯甲酸和乙酸为主要原料,合成了2-甲基-苯并咪唑-5-羧酸,并探讨了反应温度、反应物料摩尔比以及反应时间对目标产物的影响。通过红外、熔点、元素分析等方法对产物进行了表征。得到合成2-甲基-苯并咪唑-5-羧酸的最佳条件为以4 mol/L HCl溶液作为溶剂,同时作为催化剂,反应温度为140℃,反应时间14 h,3,4-二氨基苯甲酸与乙酸的最佳摩尔比为1∶5,反应条件温和,产物收率达到75%。     

SO42-/Fe2O3固体酸催化合成香叶基氯

香叶基氯是一种由异戊二烯为原料合成香料香叶醇的中间体,今以SO42-/Fe2O3固体酸为催化剂,在溶剂环己烷的存在下,异戊二烯与异戊烯氯反应合成了香叶基氯.考察了催化剂制备过程中浸渍H2SO4浓度和焙烧温度对固体酸表面硫含量和反应结果的影响,得到比较好的催化剂制备条件浸渍硫酸浓度和焙烧温度550℃.还考察了反应温度、反应时间、催化剂用量和溶剂环己烷的用量对反应的影响.实验结果表明,当,WCatWC5Hs=130,WC6H12WC5Hs=10.8,在反应温度18℃时反应2h,异戊二烯的转化率为18.3%,生成香叶基氯的选择性可达到75.2%.     

Ru/Al_2O_3催化剂上邻苯二甲酸二丁酯加氢合成1,2-环己烷二甲酸二丁酯

以浸渍法制备Ru/Al2O3催化剂,研究在高压反应釜中Ru/Al2O3上催化加氢邻苯二甲酸二丁酯(DBP)合成1,2-环己烷二甲酸二丁酯(CDADE)。采用X射线衍射(XRD)、H2程序升温还原(H2-TPR)、扫描电镜(SEM)、X射线能谱仪(EDS)和透射电子显微镜(TEM)对催化剂进行表征。结果表明,Ru负载量为3.0%(质量分数),200℃氢气气氛中还原的Ru/Al2O3催化剂,在催化DBP合成CDADE的反应中具有较高的催化活性。在反应温度80℃、反应压力2.0~2.5 MPa和搅拌转速800 r/min下,DBP转化率和CDADE选择性分别达到99.972%和99.904%,催化剂重复使用9次后仍有较高活性,但继续使用,由于活性组分Ru部分流失、团聚和催化剂表面积炭,催化剂活性有所下降。     

Synthesis, crystal structures and photoluminescence of Zn–Ln heterometallic polymers based on pyridine-2,3-dicarboxylic acid

Three new two-dimensional 3d–4f isostructural heterometallic coordination polymers, namely [Ln₂Zn(2,3-pydc)₄(H₂O)₄·4H₂O]_n (Ln = Sm (1), Eu (2), Gd (3), 2,3-pydcH₂ = pyridine-2,3-dicarboxylic acid) have been successfully synthesized by the hydrothermal reactions of Ln₂O₃, Zn(NO₃)₂·6H₂O, H₂pydc and H₂O. X-ray diffraction analyses reveal that they possess a 2D heterometallic framework containing 1D lanthanide chains based on dimeric [Ln(2,3-pydc)₂(H₂O)₂]₂ unit. The Zn(II) ion, which is six-coordinated by four oxygen and two nitrogen atoms from four 2,3-pydc²⁻ ligands, as a bridge, links the lanthanide chains to make the 1D chains further extend into 2D layer framework. Furthermore, the neighboring layers are assembled into three-dimensional supramolecular network through inter-layer O–HO and C–HO hydrogen-bond interactions. In addition, the solid-state luminescent property of complex 2 was investigated.     

合成吡咯-2,5-二甲酸及其酯的新方法

亚氨基二乙酸与二氯亚砜在过量的甲醇或乙醇溶剂中回流8h合成了亚氨基二乙酸二甲酯或亚氨基二乙酸二乙酯,然后与二水合三聚乙二醛在强碱甲醇钠或乙醇钠的作用下,合成了吡咯-2,5-二甲酸二甲酯或吡咯-2,5-二甲酸二乙酯,产率分别为67.6％和70.2％;吡咯-2,5-二甲酸二甲酯或吡咯-2,5-二甲酸二乙酯经碱性条件下水解、酸化合成了吡咯-2,5-二甲酸,总产率为62.4％～66.5％.     

Hydrothermal synthesis of 3D TiO2 nanostructures using nitric acid: Characterization and evolution mechanism

Various morphologies of TiO₂ nanostructures were synthesized by HNO₃ assisted hydrothermal treatment with respect to the acid molarity (1 M, 3 M, and 8 M), temperature (110, 140, and 180 °C), and time (1, 3, and 6 h). An additional sample was synthesized inside the protonated titanate nanoribbon coated vessel with the acid molarity of 8M at 140 °C for 3 h. The crystal structure and morphology of the nanostructures synthesized were investigated using X-Ray diffractometer, scanning electron microscope, and transmission electron microscope. The results revealed that lower acid concentrations, longer synthesis durations and higher temperatures favored anatase phase formation. Meanwhile, a phase pure 3D lotus structure rutile TiO₂ could be obtained by hydrothermal synthesis at 8M HNO₃ concentration at 140 °C for 3 h using protonated H-titanate nanoribbons. A probable mechanism for the evolution of 3D rutile lotus structure was highlighted.     

Hydrothermal Synthesis and Characterization of Trimethyltin(IV) Derivatives with 2-Carboxyethylphosphonic and Benzylphosphonic acid: X-ray Crystal Structures of 2D Network Polymers

Two organotin(IV) derivatives, {[(CH₃)₃Sn]₆·[O₃P(CH₂)₂CO₂]₂·3H₂O} _n 1 and {[(CH₃)₂Sn]₄·[O₃PCH₂Ph]₄} _n 2, were synthesized by the reaction of trimethyltin(IV) chloride, 2-carboxyethylphosphonic acid and benzylphosphonic acid, respectively. Characterization of complexes 1 and 2 were achieved using elemental analysis, IR, TGA, NMR (¹H, ¹³C, ³¹P and ¹¹⁹Sn) spectroscopy and X-ray crystallography diffraction analysis. X-ray characterization show that complexes 1 and 2 are 2D network structures.     

Photocatalytic Oxidation of Dichloroacetic Acid and Dichloroacetyl Chloride on TiO2: Active Sites, Effect of H2O, and Reaction Pathways

Photocatalytic oxidation (PCO) quickly oxidizes dichloroacetyl chloride and dichloroacetic acid to phosgene (COCl₂) and CO₂ on TiO₂. At least two types of active sites exist for PCO on TiO₂ and their activities differ by more than an order of magnitude; the more-active sites comprise approximately 30 of the adsorption sites. Water redistributes adsorbed dichloroacetyl chloride and dichloroacetic acid to more-active sites during transient PCO, yet does not change PCO activity or selectivity. Dichloroacetyl chloride oxidizes through parallel pathways, one of which forms dichloroacetic acid as an intermediate. The -carbon in dichloroacetic acid quickly oxidizes to CO₂ without forming any long-lived intermediates, whereas the -carbon forms CO₂ and COCl₂ in parallel reactions.     

苄基磺酸化MCM-41介孔分子筛的合成、表征及催化酯化性能

MCM-41介孔分子筛先后与苄基氯和氯磺酸接枝反应,得到苄基磺酸介孔分子筛(SBM)。通过X射线多晶衍射(XRD)、氮气吸附脱附、红外光谱(IR)、有机元素分析、扫描电镜(SEM)等方法对所得样品进行了表征。研究结果表明,MCM-41表面硅羟基与苄基氯反应,接枝量w(C)=6.68%;进一步磺化,接枝率w(S)=8.46%。XRD等分析结果表明,经过两步接枝反应,SBM仍然具有介孔结构特征,比表面积和孔容分别为366.9 m2/g、0.349 cm3/g。以SBM为催化剂,催化合成柠檬酸三丁酯;在n(酸)∶n(醇)=1.0∶9.0,w(催化剂)=3%,反应温度110℃,回流时间7 h的条件下,柠檬酸转化率可达93.2%;催化剂重复使用4次柠檬酸转化率为76.3%。     

Syntheses and Structural Characterization of Triorganotin Derivatives of Bis(carboxymethyl)trithiocarbonate: X-ray Crystal Structures of 2D Network Polymers

Six triorganotin(IV) complexes of the type {(R₃Sn)₂[C₃S₃(COO)₂]}_n (R = C₆H₅ 1; n-Bu 2; PhCH₂ 4; p-F-PhCH₂ 5; o-F-PhCH₂ 6) and {(R₃Sn)₂[C₃S₃(COO)₂]}_n·[EtOH] (R = Me 3) have been synthesized by the reaction of bis(carboxymethyl)trithiocarbonate with triorganotin(IV) chloride in the presence of sodium ethoxide. All complexes were characterized by elemental analysis IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Except for 4–6, all complexes were also characterized by X-ray crystallography. The X-ray date revealed that complexes 1–3 show two-dimensional network polymeric structure in which the geometries of tin atoms are trigonal bipyramid with the axial positions occupied by carboxylic oxygen atoms.     

D,L-乳酸-肌醇星形聚合物的合成与表征

以廉价易得的D,L-乳酸和无毒的肌醇(Ins)为原料,采用工艺简单、成本低廉的直接熔融聚合法合成了肌醇聚乳酸酯——以肌醇为核的星形聚D,L-乳酸(SPDLLA)。当n(Ins)∶n(LA)=1∶120时,SPDLLA较合适的合成工艺为:140℃预聚8 h后,在w(SnCl2)=0.3%催化下,170℃熔融聚合8 h,可获得最大特性黏数[η]为1.208 dL/g的共聚物。改变投料摩尔比,合成了系列SPDLLA,并用[η]、FTIR、1HNMR、GPC、XRD等手段进行了结构与性能表征,发现不同投料比所得的SPDLLA均为无定形态,它们的Tg(35~42℃)均低于线形聚D,L-乳酸(LPDLLA),最高Mw可达8 600,可望应用于药物缓释等领域。     

Synthesis,Crystallization Studies,and in vitro Characterization of Cinnamic Acid Derivatives as SmHDAC8 Inhibitors for the Treatment of Schistosomiasis

Schistosomiasis is a neglected parasitic disease that affects more than 265 million people worldwide and for which the control strategy relies on mass treatment with only one drug: praziquantel. Based on the 3‐chlorobenzothiophene‐2‐hydroxamic acid J1075 , a series of hydroxamic acids with different scaffolds were prepared as potential inhibitors of Schistosoma mansoni histone deacetylase 8 (SmHDAC8). The crystal structures of SmHDAC8 with four inhibitors provided insight into the binding mode and orientation of molecules in the binding pocket as well as the orientation of its flexible amino acid residues. The compounds were evaluated in screens for inhibitory activity against schistosome and human HDACs. The most promising compounds were further investigated for their activity toward the major human HDAC isotypes. The most potent inhibitors were additionally screened for lethality against the schistosome larval stage using a fluorescence‐based assay. Two of the compounds showed significant, dose‐dependent killing of the schistosome larvae and markedly impaired egg laying of adult worm pairs maintained in culture.     

Synthesis and Characterization of Thiophen-3-yl Acetic Acid 4-Pyrrol-1-yl Phenyl Ester and its Conducting Polymers

ABSTRACT

Thiophen-3-yl acetic acid 4-pyrrol-1-yl phenyl ester (TAPE) monomer was synthesized via reaction of thiophen-3-yl acetyl chloride with 4-pyrrol-1-yl phenol. Homopolymers were achieved by using electrochemical and chemical polymerization techniques. Copolymers of TAPE with bithiophene or pyrrole were synthesized by potentiostatic electrochemical polymerization in acetonitrile-tetrabutylammonium tetrafluoroborate (TBAFB) solvent-electrolyte couple. The chemical structures were confirmed by both Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Differential Scanning Calorimetry (DSC) and Thermal Gravimetry Analysis (TGA) were used to examine the thermal behavior of the polymers. The morphologies of the films were investigated by Scanning Electron Microscope (SEM). Two-probe technique was used to measure the conductivities of the samples. Moreover, investigations of electrochromic and spectroelectrochemical properties of poly(TAPE-co-BiTh) carried out and the characteristics of dual type electrochromic device based on poly(TAPE-co-BiTh) and poly(3,4-ethylenedioxythiophene) (PEDOT) were reported.     

间溴苯氧丙酸与7-溴苯并二氢吡喃-4-酮的合成

以间溴苯酚和3-溴丙酸为原料,合成了间溴苯氧丙酸,并以间溴苯氧丙酸为原料,进一步合成了7-溴苯并二氢吡喃-4-酮。探讨了投料比、反应时间、反应温度、氢氧化钠的质量分数和加料顺序等因素对间溴苯氧丙酸收率的影响。适宜的反应条件为:n(间溴苯酚)∶n(氢氧化钠)∶n(3-溴丙酸)=1∶1∶1.3,反应温度95℃,氢氧化钠的质量分数8%,反应时间7 h,间溴苯氧丙酸收率71.4%。以间溴苯氧丙酸为原料,以85%的收率合成了7-溴苯并二氢唑喃-4-酮。     

A Novel 3D Europium (III) Coordination Polymer Constructed from 3,5-Pyridinedicarboxylate Acid: Synthesis, Crystal Structure and Emission Spectrum

Abstract  A novel 3D coordination polymer Eu₂(PDC)₃(H₂O)₃ (1) has been synthesized by hydrothermal reaction of europium chloride with 3,5-pyridinedicarboxylate acid (H₂PDC) under acidic condition (pH 2–3). Complex 1 is a 3D coordination polymer via 1D infinite chains built by the pyridinium moieties of the PDC²⁻ anions. The thermal analyses and luminescent properties of 1 have also been investigated. Graphical Abstract   A novel 3D coordination polymer Eu₂(PDC)₃(H2O)₃ has been synthesized by hydrothermal reaction of europium chloride with 3,5-pyridinedicarboxylate acid under acidic conditions (pH 2–3). The formation of the title complex demonstrates that pH plays an important role during the synthesis.      

Radical Ring Opening and Vinyl Copolymerization of 2,3,4,5,6-pentafluorostyrene with 5,6-Benzo-2-methylene-1,3-dioxepane: Synthesis and Structural Characterization Using 1D and 2D NMR Techniques

Radical ring opening polymerisation behaviour of 5,6-Benzo-2-methylene-1,3-dioxepane (BMDO) during its copolymerisation with 2,3,4,5,6-pentafluorostyrene (PFS) is reported using t-butyl peroxide (TBPO) conventional radical initiator. The reactivity behaviour of PFS for its copolymerisation is compared with that of the corresponding non-fluorinated monomer styrene. The presence of five fluorine atoms affected the course of polymerisation and led to the synthesis of well defined copolymers as compared to the formation of only homo poly styrene. Structural characterisation of the copolymers was done using 1D and 2D NMR spectroscopic techniques. The microstructural characterisation showed the formation of gradient copolymers with increased reaction time and/or increased amount of BMDO in the feed. The reactivity ratios for the copolymerisation of BMDO and PFS were determined using Kelen-Tüdos method and was found to be r _BMDO = 0.35 and r _PFS = 9.9. Thermal stabilities of copolymers are also compared with that of the homopolymers.     

无水三氯化铝催化合成3-乙酰氨基-N，N-二丙酸甲酯基苯胺的研究

报道了用无水AlCl3作催化剂在低温下将3-氨基乙酰苯胺和丙烯酸甲酯转化为3-乙酰氨基-N,N-二丙酸甲酯基苯胺的新方法,其产品收率达到90%,纯度高于94%。