Synthesis,Structure and Photoluminescence of a New Pb(Ⅱ)Coordination Polymer[Pb(1,4-chdc)(L)]n·nH2O Based on a Flexible 1,4-Cyclohexanedicarboxylic Acid

A new Pb（Ⅱ） coordination polymer, [Pb（1,4-chdc）（L）]_n·nH_2O（1）, was synthesized under hydrothermal condition（1,4-H2 chdc = 1,4-cyclohexanedicarboxylic acid and L = 2-（3-fluorophenyl）-1H-imidazo[4,5-f][1,10]phenanthroline）. Its crystal structure was determined by singlecrystal X-ray diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 9.1182（8）, b = 11.3249（10）, c = 12.7326（12） A, α = 77.897（2）, β = 81.644（2）, γ = 84.491（2）°, V = 1269.0（2） A^3, Z = 2, C_（27）H_（24）FN_4O_5Pb, M_r = 710.69, D_c = 1.860 g/cm^3, F（000） = 690, μ（MoKa） = 6.701 mm^（-1）, R = 0.0349 and wR = 0.0746. In 1, each 1,4-chdc anion bridges two neighboring Pb（Ⅱ） atoms in a bidentate chelating coordination mode to give a chain structure. The L ligands are attached on one side of the chain through chelating the Pb（Ⅱ） atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. The O-H···O and N-H···O hydrogen bonding interactions further stabilize the supramolecular layer structure of 1. Moreover, solid state luminescent property of 1 was also studied.

可见光促进三组分合成C3-芳甲基取代的咪唑并[1,2-a]吡啶衍生物

C3-芳甲基取代的咪唑并[1,2-a]吡啶衍生物在材料及药物化学领域有着广泛应用。基于自由基对亚胺C=N键的插入串联环化策略,以2-氨基吡啶衍生物、芳基甲醛为原料、芳基溴乙炔为自由基源,在可见光促进和路易斯酸协同作用下,通过三组分串联反应,以70%~78%的产率实现了C3-芳甲基取代的咪唑并[1,2-a]吡啶衍生物的构建。目标产物结构经^(1)H NMR、^(13)C NMR和HR-MS确证。本方法无需额外添加光催化剂,操作简便、反应条件温和,具有较好的底物适用性和官能团耐受性,并且可以应用于唑吡坦的一步合成。

Cu,N codoped carbon nanosheets encapsulating ultrasmall Cu nanoparticles for enhancing selective 1,2-propanediol oxidation

In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.

A New Co(Ⅱ) Coordination Polymer Based on a Flexible 1,4-Cyclohexanedicarboxylic Acid: Synthesis, Structure and Thermal Behavior

A new Co（Ⅱ） coordination polymer, [Co（1,4-chdc）（L）（H2O）]n（1）, was synthesized under hydrothermal condition（1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid, L = 2-（4-fluoro-phenyl）-1 H-imidazo[4,5-f][1,10]phenanthroline）. Its crystal structure was determined by single-crystal X-ray diffraction. 1 crystallizes in triclinic, space group P1 with a = 8.790（5）, b = 10.486（5）, c = 13.305（5） ?, α = 87.391（5）, β = 82.925（5）, γ = 81.841（5）o, V = 1204.2（10） ?3, Z = 2, C27H23FN4O5Co, Mr = 561.42, Dc = 1.548 g/cm3, F（000） = 578, μ（Mo Ka） = 0.769 mm-1, R = 0.0415 and wR = 0.1043. In 1, each 1,4-chdc anion bridges two neighboring Co（Ⅱ） atoms to give a chain structure. The L ligands are attached on one side of the chain through chelating the Co（Ⅱ） atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a double-chain structure. The double-chain structures are linked into a supramolecular layer structure through N–H···O hydrogen-bonding interactions between the adjacent double-chain structures. Moreover, the thermal behavior of 1 was also studied.

豹皮菌中2－Amino－3－（1，2－dicarboxyethylthio）propanoic Acid非对映异构体的分离和鉴定

从豹皮菌中的新鲜子实体的乙醇提取物中分离得到一种ＮＭＤＡ受体格抗剂，经理化常数和波谱数据的测定鉴定为２－Ａｍｉｎｏ－３－（１，２－ｄｉｃａｒｂｏｘｙｅｔｈｙｌｔｈｉｏ）ｐｒｏｐａｎｏｉｃａｃｉｄ非对映异构体的混合物，该化合物是首次从豹皮菌中得到，经进一步分离，得到两种非对映体异构体。

磺酸型离子液体催化合成脂肪族1,2-二醇

以磺酸型离子液体1-(3-丙烷磺酸)吡啶磷酸氢盐[PyPS]H2PO4为催化剂催化甲酸-双氧水氧化端烯烃合成相应的1,2-二醇,采用1H NMR对产物的结构进行了表征。以1-己烯合成1,2-己二醇为模型反应,得到了反应的优化条件,即:n(1-己烯)∶n(H2O2)∶n(甲酸)=1∶1.1∶2,催化剂[PyPS]H2PO42.5 mol%,反应温度50℃,反应6 h。在此条件下,1,2-己二醇、1,2-戊二醇、1,2-辛二醇、1,2-环己二醇以及苯乙二醇收率分别为78.2%,74.7%,68.8%,76.2%和74.0%。[PyPS]H2PO4容易回收,在循环使用中催化活性未见明显降低。

Crystal Structure and Magnetic Property of 2-（Imidazo[1,2-α]pyri-din-2-yl）- 2-oxoacetic Acid and Its Perchlorate

We herein report two crystals based on 2-（imidazo[1,2-a]pyridin-2-yl）-2-oxoacetic acid rad- ical and its perchlorate, and investigate the relationship between magnetic properties and crystal stacking structures or supramolecular interactions. 2-（imidazo[1,2-a]pyridin-2-yl）- 2-oxoaeetic acid radical in two crystals mainly exist as diamagnetic dimer formed via short atomic contacts or supramolecular interactions （hydrogen bonds, anion-Tr or lone- pair-~r interactions）, leading to low magnetic susceptibilities. 2-（imidazo[1,2-a]pyridin-2-yl）- 2-oxoaeetic acid radical crystal exhibits quasi-one-dimensional columnar stacking chain and weak antiferromagnetism. However, its perchlorate crystal possesses one-dimensional double- stranded chain structure assembled through double hydrogen bonds and anion-To interactions, and reveals weak ferromagnetism.

TiSiW_(12)O_(40)/TiO_2催化合成环己酮1,2-丙二醇缩酮

以固载杂多酸盐TiSiW1 2 O4 0 /TiO2 为多相催化剂 ,通过环己酮和 1 ,2 丙二醇反应合成了环己酮 1 ,2 丙二醇缩酮 ,探讨TiSiW1 2 O4 0 /TiO2 对缩酮反应的催化活性 ,较系统地研究了酮醇量比 ,催化剂用量 ,反应时间诸因素对产品收率的影响。实验表明 :TiSiW1 2 O4 0 /TiO2 是合成环己酮 1 ,2 丙二醇缩酮的良好催化剂 ,在n(酮 )∶n(醇 ) =1 0∶1 5 ,催化剂用量为反应物料总质量的 0 6 % ,环己烷为带水剂 ,反应时间 40min的优化条件下 ,环己酮 1 ,2 丙二醇缩酮的收率可达 92 2 %。

铌酸催化合成环己酮1,2-丙二醇缩酮

将铌酸应用于催化缩酮反应 ,以环己酮和 1 ,2 -丙二醇的缩酮反应为探针 ,详细探索了影响缩合反应的各种因素 ,并得出了铌酸催化环己酮与丙二醇反应的最佳条件 :mol环己酮 ∶ mol丙二醇 =1∶ 1 .5 ,环己烷作带水剂 ,环己烷和铌酸催化剂的用量分别为反应物总体积、总质量的 35 %和 1 .2 % ,回流搅拌反应 3.5 h,产品环己酮 1 ,2 -丙二醇缩酮的总收率为 73.5 %

反1,2-环己二醇的合成新工艺

采用硫酸作催化剂,以1,2-环氧环己烷为原料经水解合成了反1,2-环己二醇。考察了催化剂用量、原料摩尔比、反应温度、反应时间等条件对产物收率的影响;以二氯乙烷为溶剂对产物进行萃取、重结晶提纯。实验结果表明,在水与1,2-环氧环己烷的摩尔比为20∶1、反应温度为(45±2)℃、pH为3.0左右、反应时间为60m in的条件下,产物反1,2-环己二醇的收率在80%左右,纯度达到99%以上。并通过红外光谱与气相色谱-质谱方法对产物进行了表征,证实了产物的结构与纯度。

MCM-48分子筛负载硅钨酸催化合成环己酮1,2-丙二醇缩酮

采用浸渍法制备了MCM-48分子筛负载硅钨酸催化剂(H4SiW12O40/MCM-48);采用该催化剂,以环己酮和1,2-丙二醇为原料合成了环己酮1,2-丙二醇缩酮;采用傅里叶变换红外光谱、X射线衍射、核磁共振等方法对试样进行了表征;研究了原料配比、催化剂用量、带水剂环己烷用量、反应时间等因素对合成反应的影响;比较了H4SiW12O40/MCM-48、铌酸、硫酸铁、维生素C催化剂催化该合成反应的活性。表征结果表明,H4SiW12O40在MCM-48分子筛上具有较高的分散度,负载后H4SiW12O40仍保持着Keggin结构。实验结果表明,H4SiW12O40/MCM-48催化剂是合成环己酮1,2-丙二醇缩酮的良好催化剂,在n(环己酮):n(1,2-丙二醇)=1:1.6、催化剂用量为反应物质量的0.6%、带水剂环己烷用量10mL、反应时间45min的优化条件下,环己酮1,2-丙二醇缩酮的收率可达87.2%。

AlCl_3/Al固体酸催化合成1，2-二苯乙烷

以苯和1,2-二氯乙烷为原料,以AlCl_3/Al新型固体酸为催化剂合成了1,2-二苯乙烷,并采用正交实验得到了的最优工艺条件,即反应温度65℃、每100 mL苯的催化剂用量1.4 g、n(苯):n(二氯乙烷)=5:1、反应时间20 min。在此条件下,产物的单程收率可达35.75%。

环保增塑剂环己烷1,2-二甲酸二异辛酯的合成

以1,2-环己二甲酸和异辛醇为原料,浓硫酸为催化剂,酯化合成环保增塑剂环己烷1,2-二甲酸二异辛酯,考察了反应时间、醇酸物质的量比、反应温度等对酯化率的影响,并对产物进行了1 H-NMR、IR、TG及气相定性分析。结果表明,反应时间6h,反应温度170℃,醇酸物质的量比为2.5∶1时,酯化率可达99.5%,收率95%,产品为无色油状液体。核磁氢谱显示与酯基相连的亚甲基的多重峰信号δ在4.0处,红外谱图显示酯羰基的伸缩振动峰出现在1 735cm-1处,这些结果表明得到了预期产物。产物的TG曲线显示其外延起始温度为215℃,其气相出峰时间为14.310min和14.505min,能够与邻苯二甲酸二异辛酯(DOP)有效分离。

强酸性阳离子交换树脂催化合成异丁醛1，2-丙二醇缩醛的研究

在强酸性阳离子交换树脂催化剂存在下,以异丁醛、1,2-丙二醇为原料,直接合成异丁醛1,2-丙二醇缩醛.分别研究了反应温度、反应时间、原料配比、带水剂、催化剂用量等条件对合成反应的影响,确定了最佳工艺条件:反应温度90～95℃,反应时间2.5 h,n(异丁醛):n(1,2-丙二醇)=1:1.2,催化剂用量1.5 g,带水剂环己烷40 mL (异丁醛为0.1 mol的情况下).异丁醛1,2-丙二醇缩醛的收率达到91.16%,产品纯度w(异丁醛1,2-丙二醇缩醛)达到98.5%以上.催化剂不经处理可多次循环使用.该催化剂具有价廉易得、催化活性好、不腐蚀设备、无环境污染等优点.

Interaction between Pd and Cu nanoparticles in bimetallic CuPdx nanoparticles and its impact on oxidation of 1,2-propanediol to aliphatic acids

Bimetallic CuPdx nanoparticles synthesized by the wet chemical reduction method were used as the catalysts in the catalytic oxidation of 1,2-propanediol with gaseous oxygen to aliphatic acids.The palladium and copper nanoparticles in the bimetallic CuP dxnanoparticles had an alloying trend.The catalytic activity of the palladium nanoparticles in the bimetallic CuP dxnanoparticles was enhanced by the interaction between the palladium and copper nanoparticles.When the bimetallic CuPd7 nanoparticles catalyzed the oxidation of 1,2-propanediol in an alkaline aqueous solution at 100℃for 3h,lactic,formic,and acetic acids were dominantly produced with the total selectivity of above 99%at the 1,2-propanediol conversion of 85.9%.The simulation of the reaction kinetic equation on the CuPd7 catalyst showed that the reaction activation energy was 29.4kJ·mol^-1,indicating that the bimetallic CuPd7 nanoparticles had a high catalytic activity in the oxidation reaction between 1,2-propanediol and gaseous oxygen.

AB INITIO STUDY OF 1,2-DITHIOSQUARIC ACID

Result of ab initio SCF calculation of 1,2-dithiosquaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dithione) are reported. The ZZ isomer is found to be the most stable of the three isomers. An isodesmic energy analysis has been carried out at the HF 6-31G*//6-31G* level for the three planar isomers. The three isomers have positive isodesmic energies or small negative ones, suggesting that 1,2-dithiosquaric acid is not aromatic. Vibrational frequencies have also been calculated for the three isomers.

三维配位聚合物[Cu_(1.5)(opda)(tib)(Ac)]的合成及其电化学传感嘧霉胺

金属-有机骨架(MOFs)作为传感器在电化学检测污染物方面备受关注,为达到灵敏检测嘧霉胺,通过水热法合成了配位聚合物[Cu_(1.5)(opda)(tib)(Ac)](tib=均苯三咪唑,mpda=间苯二乙酸,Ac=醋酸),利用元素分析、红外光谱、热重分析和X-射线单晶衍射等进行表征,并研究了其对嘧霉胺的电化学传感响应。结果表明,该配位聚合物属于三斜晶系、Pī空间群,具有3D网络配位结构。该配位聚合物的比表面积为5 m^(2)/g,属于介孔材料,平均孔径为15.8 nm。配位聚合物修饰电极传感器对嘧霉胺的电化学传感响应良好,且具有良好的选择性、重复性和稳定性,检出限为0.09μmol/L(S/N=3)。该配位聚合物可能在电化学传感检测嘧霉胺方面具有较好的应用前景。

强酸性阳离子交换树脂催化合成香兰素1,2-丙二醇缩醛

以香兰素、1,2-丙二醇为原料在强酸性阳离子交换树脂催化作用下合成香兰素1,2-丙二醇缩醛,分别研究了原料配比、反应温度、反应时间和催化剂用量等条件对合成反应的影响。结果表明,在香兰素用量0.1 mol,n(1,2-丙二醇):n(香兰素)2.2,强酸性阳离子交换树脂用量1 g,带水剂环己烷30 mL,反应温度90～95℃,反应时间3.5 h,香兰素1,2-丙二醇缩醛的收率可达到84.86%,产品纯度98.5%。催化剂重复使用多次仍保持较高的催化活性,且催化剂易处理。

聚苯并[1,2-d∶5,4-d′]二噁唑-2,6-二(1,4-亚萘基)的合成及表征

采用4,6-二氨基-1,3-苯二酚盐酸盐和1,4-萘二甲酸为原料,在磷酸、多聚磷酸介质中经溶液缩聚,制得聚苯并[1,2-d∶5,4-d′]二噁唑-2,6-二(1,4-亚萘基)(PNBO),并对制得的PNBO进行表征。研究结果表明:在P_2O_5添加量为84%(wt,质量分数),减压、氮气保护条件下,制得的PNBO产率达到86.73%,黏度达到17.95dL/g,并具有较好的耐热性能。

聚己二酸-1,2-环己二醇酯的合成

聚酯多元醇是合成聚氨酯的主要原料,该文对1,2-环己二醇的衍生物聚己二酸-1,2-环己二醇酯的合成进行了较为详细的研究.考察了醇酸摩尔比、反应温度、反应升温方式、反应时间、减压时间、催化剂的用量和稳定剂的用量等因素对所合成的聚酯多元醇的酸值、羟值、相对分子质量和反应程度的影响.采用单因素优选法对合成工艺条件进行了优化,得到了合成聚己二酸-1,2-环己二醇酯的较佳工艺条件:缩聚反应温度180 ℃,反应时间3 h,n(1,2-环己二醇)∶ n(己二酸)=1.6∶ 1,催化剂的用量为己二酸投料质量的0.8%,稳定剂用量为己二酸投料质量的0.3%.在此条件下合成出的聚己二酸-1,2-环己二醇酯为淡黄色、透明黏稠液体,酸值＜9.3 mg/g,羟值50～70 mg/g,相对分子质量1 000～2 000.