二苄基锡双(吗啉荒酸酯)的合成、表征及晶体结构

Dibenzyltin bis(dithiomorpholinocarbamate) was synthesized by the reaction of dibenzyltin dichloride with dithiomorpholinocarbamate. The compound was characterized by elemental analysis, IR, ¹H NMR and MS. and the crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to orthorhombic with space group Pca2₁, a=1.8327(3)nm, b= 0.65678(12)nm, c=2.2583(4)nm, Z=4, V=2.718 (9)nm³, D_x=1.528g·cm^-3,μ=1.271mm^-1, F(000)=1272, R₁=0.0434, wR₂=0.1152. In the crystals, the structures consist of discrete molecules containing six-coordinate tin atoms in a distorted octahedron configuration.     

二苄基锡双(四氢吡咯荒酸酯)的合成、表征和晶体结构

Dibenzyltin bis(dithiotetrahydropyrrolocarbamate) was synthesized by the reaction of dibenzyltin dichloride with dithiotetrahydropyrrolocarbamate. The compound was characterized by elemental analysis, IR, ¹H NMR and MS. and the crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to or-thorhombic with space group Pccn, a=2.1665(6)nm, b=0.9932(3)nm, c=1.1979(3)nm,α=90°,β=90°,γ=90°,Z=2,V=2.5777(12)nm³,D_c=1.529g·cm^-3,μ(MoKα)=1.330mm^-1,F(000)=1208,R₁=0.0341, wR₂=0.0627. In the crystals, the structures consist of discrete molecules in which the tin atom is six-coordinate in a distorted octahedron configuration. CCDC: 179919.     

二苄基锡N,N-二甲基氨荒酸酯的合成及晶体结构

利用二苄基二氯化锡和N, N-二甲基氨荒酸钠反应, 合成了二苄基锡N, N-二甲基氨荒酸酯(C20H26N2S4Sn, Mr = 541.36)。通过元素分析、红外光谱、核磁共振氢谱和质谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体结构。化合物为单斜晶系, 空间群P21/n, a = 1.3926(5), b = 0.9832(4), c = 1.7080(7) nm, b = 103.541(6), V = 2.274(2) nm3, Z = 4, Dc = 1.581 g/cm3, m(MoKa) = 1.500 mm-1, F(000) = 1096, R = 0.0482, wR = 0.1162. 在化合物的晶体中, 锡原子为六配位的畸变八面体构型。     

二苄基锡双氨荒酸酯的合成

由二苄基二氯化锡与氨荒酸盐反应，合成了１０个新的二苄基锡双氨荒酯化合物，利用元素分析，ＩＲ和＾１ＮＮＭＲ表征了这些化合物的结构。     

二丁基锡磺酸酯催化酯交换合成碳酸二苯酯

研究了不同类型的酸催化剂对碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的影响. 实验结果表明, 碳酸二甲酯与苯酚的酯交换反应是软碱(酚氧)亲硬酸(羰基碳)的反应; 硬Lewis酸比软Lewis酸、交界Lewis酸和Brönsted酸有更高的酯交换选择性. 将不同的磺基引入n-Bu₂SnO分子中, 制得一系列硬Lewis酸催化剂[n-Bu₂Sn(OH)OS(O)₂R(H₂O)]₂[R=p-NH₂C₆H₄(Ⅰ), p-CH₃C₆H₄(Ⅱ), C₆H₅(Ⅲ), p-ClC₆H₄(Ⅳ), Me(Ⅴ), CF₃(Ⅵ)]. 在酯交换反应中, 由于磺基的强吸电子效应增强了[n-Bu₂Sn(OH)OS(O)₂R(H₂O)]₂中Sn的Lewis酸性, 其催化活性比n-Bu₂SnO的高, 而且磺基上取代基的吸电子效应越强, 催化剂中Sn的Lewis酸性越强, 催化活性越高, 但取代基的吸电子效应过强会降低其对酯交换反应的选择性.     

三(邻甲基苄基)氯化锡和二(对甲基苄基)二氯化锡的合成和晶体结构

将邻甲基氯苄和对甲基氯苄在适当的溶剂中与锡粉反应，合成了三(邻甲基苄基)氯化锡1和二(对甲基苄基)二氯化锡2，用X射线衍射方法测定了化合物的晶体结构。化合物(1)的晶体属三方晶系，空间群为R3，晶体学参数：a=1.329 36(8) nm，b=1.329 36(8) nm，c=2.147 0(3) nm，α=β=90°，γ=120°，V=3.285 8(5) nm³，Z=6，D_c=1.424 g·cm^-3，μ(Mo Kα)=12.93 cm^-1，F(000)=1 428，R₁=0.037 1，wR=0.110 2。化合物2的晶体属单斜晶系，空间群为C2/c，晶体学参数：a=2.850 4(3) nm，b=0.491 23(5) nm，c=1.215 32(12) nm，β=112.517(2)°，V=1.571 9(3) nm³，Z=4，D_c=1.690 g·cm^-3，μ(Mo Kα)=19.49 cm^-1，F(000)=792，R₁=0.038 0，wR₂=0.109 4；中心锡原子为畸变四面体配位构型。     

钛酸酯催化碳酸二甲酯与苯酚酯交换反应的研究

用Ti(OBu)4、Ti[OCH(CH3)2]4和T(OPh)43种钛酸酯作催化剂,对碳酸二甲酯（DMC）与苯酯的酯交换反应进行了研究。以Ti(OBu)4为催化剂,对反应的热力学、原料配比、催化剂用量、反应温度和反应时间等工艺条件进行了考察 。实验表明,当DMC：苯酚：Ti(OBu)4(摩尔比）＝1.5:1:0.05、反应温度175℃、反应时间为25h时,酯交换反应基本上达到平衡,苯酚的转化率为47.4％,MPC的选择性为90.9%,DPC的选择性为9.14%.     

三苄基锡羧酸酯的合成

合成了三苄基锡苯甲酸酯,三苄基锡水扬酸酯,三苄基锡3－羟基－4－羧基苯磺酸酯和三苄基锡对氯苯氧乙酸酯4种化化合物,对其进行了IR,1H NMR表征,发现苯甲酸,水扬酸和对氯苯氧乙酸与三苄基锡氧化物反应生成三苄基锡羧酸酯,而对磺基水杨酸与三苄基锡氧化物反应生成三苄基锡3－羟基－4－羧基苯磺酸酯,4种化合物对苯甲醛,庚醛和乙二醇缩合反应的催化活性测试表明,其活性次序为：三苄基锡3－羟基－4－羧基苯磺酸酯＞三苄基锡水杨酸酯＞三苄基锡苯甲酸酯＞三苄基锡对氯苯氧乙酸酯。     

三(邻甲基苄基)锡和二(间氟苄基)锡硫代水杨酸酯配合物的合成、结构及性质

合成了三(邻甲基苄基)锡硫代水杨酸酯配合物(1)和一维链状二(间氟苄基)锡硫代水杨酸酯配合物(2),经元素分析、IR、NMR、X射线衍射等技术手段表征了其结构。配合物1属三斜晶系,空间群Pī,晶体学参数a=1.00221(5)nm,b=1.48934(8)nm,c=1.71789(9)nm,α=78.3120(10)°,β=85.6560(10)°,γ=80.2580(10)°,V=2.4725(2)nm~3,Z=2,Dc=1.371 g/cm~3,μ(Mo Kα)=10.91 cm~(-1),F(000)=1040,R_1=0.0439,wR_2=0.1119。配合物2属单斜晶系,空间群为P21/n,晶体学参数:a=1.17827(5)nm,b=2.11945(9)nm,c=1.55970(7)nm,β=93.4510(10)°,V=3.8880(3)nm~3,Z=4,Dc=1.671 g/cm~3,μ(Mo Kα)=14.53 cm~(-1),F(000)=1936,R1=0.0323,wR2=0.0927。配合物1中锡原子呈四配位畸变四面体构型,配合物2中锡原子呈五配位畸变三角双锥构型。配合物1和2分别在152和195℃下稳定,电化学性质不可逆,对人体癌细胞Colo205、Hep G2、MCF-7、Hela和NCI-H460具有体外抗癌活性,配合物2的抗癌活性远大于配合物1。     

二苄基二氯化锡三苯基氧膦的合成及晶体结构研究

利用二苄基二氯化锡与三苯基氧膦反应 ,合成了目标化合物二苄基二氯化锡三苯基氧膦 ,其结构经元素分析表征。用X 射线单晶衍射测定其晶体结构属于三方晶系 ,空间群为P2 1,a =2 .0 2 7( 4 )nm ,b =0 .9714 ( 17)nm ,c =1.5 5 9( 3)nm ,α =90° ,β =90° ,γ =90° ,Z =4 ,V =3.0 4 9( 10 )nm3 ,Dc =1.4 0 7mg·m-3 ,u =1.0 81mm-1,F( 0 0 0 )=1312 ,R1=0 .0 370 ,wR2 =0 .0 6 88,晶体中心的Sn原子为五配位的畸变三角双锥构型     

Synthesis,Crystal Structure and Quantum Chemistry of a Hydration Dibenzyltin Dichloride

A novel organotin hydration dibenzyltin dichloride has been synthesized and its crystal structure was determined by X-ray diffraction. The crystal belongs to monoclinic, space group Pc with a = 1.1918（5）, b = 0.6199（2）, c = 1.1074（5）nm, β = 106.899（7）°, V= 0.7828（8）nm3, Z = 2, Dc = 1.654 g/cm3,μ（MoKa） = 19.59 cm^-1, F（000） = 384, R = 0.0564 and RwR = 0.1427. The Sn-C bonds are 0.2140（9） and 0.2152（5） nm, Sn-Cl are 0.2385（4） and 0.2497（3） nm, and Sn-O is 0.2388（7） nm. The tin atom is five-coordinated in a distorted trigonal bipyramidal configuration. The study on the title complex has been performed with quantum chemistry calculation by means of G98W package on the Lanl2dz basis set. The stability of the complex as well as the orbital energies and composition characteristics of some frontier molecular orbitals has been investigated.     

碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的热力学性质及均相催化剂

在298.15K,101.325kPa条件下,液态碳酸二甲酯(DMC)的标准Gibbs自由能和熵分别估算为-472.3kJ*mol-1和245.2J*mol-1*K-1.在298K～523K计算了由DMC和苯酚生成碳酸二苯酯(DPC)和苯甲醚反应的热力学性质(ΔrH0m,ΔrS0m,ΔrG0m和平衡常数).计算出的热力学性质表明,DMC和苯酚酯交换合成DPC反应是吸热的,并且在热力学上是不利的.研究了n-Bu2SnO, Ti(OC4H9)4, AlCl3和ZnCl2四种酯交换法合成DPC反应的催化剂,其中n-Bu2SnO具有最高的催化活性.热力学计算和实验结果均表明,合成DPC反应的最佳温度为453K.当以n-Bu2SnO为催化剂,n(苯酚)∶n(DMC)＝4∶1时,DPC的产率和选择性分别为43.0%和88.7%.     

有机锡化合物[n-Bu2Sn(OH)OS(O)2(p-ClPh)]2的合成、晶体结构和催化性能

An organotin compound, [n-Bu₂Sn(OH)OS(O)₂(p-ClPh)]₂, has been synthesized by the reaction of n-Bu₂SnO with p-ClPhSO₃H and characterized by IR, elemental analysis and X-ray diffraction single crystal structure analysis. The results show that it possesses a polymeric sheet structure with repeating 20-membered macrocycles by virtue of the bridging bidentate sulfonate groups; the crystal belongs to monoclinic, space group P2₁/c with a=1.460 72(12) nm, b=0.897 41(11) nm, c=2.896 94(14) nm, β=107.629(4)°, V=3.619 2(6) nm^-3, Z=4; all the tin atoms are six-coordinated in a distorted octahedral geometry. The compound showed the very high catalytic activity in the transesterification of dimethyl carbonate and phenol to diphenyl carbonate. CCDC: 751163.     

类水滑石催化酯交换反应活性、寿命及失活原因研究

研究了5种不同阳离子组合的类水滑石对碳酸二甲酯与苯酚酯交换反应的催化活性和ZnAl, MgAl水滑石的使用寿命. 结果显示, 类水滑石的催化性能与组成的阳离子性质有关: 三价阳离子的性质影响类水滑石的催化活性高低, 二价阳离子的性质则影响其使用寿命长短. 通过对失活原因的研究发现, 特征的层状结构形式是类水滑石具有活性的关键: 层状结构塌陷, 活性随之消失; 层状结构稳定, 使用寿命长. 当苯酚与碳酸二甲酯的摩尔比为2∶1, 催化剂的质量分数为原料总质量的1%, 反应时间8 h时, MgAl水滑石具有最优的催化性能: 碳酸二甲酯转化率51.8%, 酯交换产物选择性94.2%, 5次循环使用后催化活性保持稳定. 其催化性能明显优于文献报道的其它相关固体催化剂.     

乙醇热法制备纳米二氧化钛及其对酯交换反应合成碳酸二丁酯的催化性能

 The preparation of nano-TiO2 powder by the alcohol-thermal method at atmospheric pressure using ethanol as the solvent, H2TiO3 as the precursor, and KOH, NaOH or NH3·H2O as the mineralizer has been presented. XRD result showed that the structure of TiO2 is anatase, and with the increase of mineralizer alkalinity, the average diameter of TiO2 becomes smaller, and the crystallinity of TiO2 becomes higher. The diameter and the crystallinity of TiO2 affect the catalytic activity of TiO2 for the synthesis of dibutyl carbonate (DBC) from dimethyl carbonate (DMC) and butyl alcohol. The anatase TiO2 obtained from KOH exhibits high catalytic activity, giving 61.9% conversion of DMC, 100% selectivity for DBC, and 61.9% yield of DBC. The conversion of DMC, selectivity and yield of DBC remain almost unchanged through four reuses.     

有机阴离子柱撑水滑石催化酯交换合成碳酸二苯酯

 A series of organic anion-pillared hydrotalcites were synthesized by the ion exchange method and characterized by X-ray diffraction and Fourier transform infrared spectroscopy. The hydrotalcite precursor and pillared hydrotalcites with different anions was tested as catalysts in transesterification of dimethyl carbonate (DMC) with phenol. The results show that the catalytic selectivity of this transesterification reaction over these organic anion-pillared hydrotalcites is significantly improved. The catalytic selectivities of C4H4O4-, C6H8O4-, C10H16O4-, 1,4-C8H4O4-, and C7H5O2-pillared hydrotalcites for transesterified products (diphenyl carbonate and methyl phenyl carbonate) are all greater than 90%, at least 10% higher than that of the hydrotalcite precursor. Under the conditions of n(phenol)/n(DMC)=4, catalyst amount=1.5%, and t=10 h, the C6H8O4-pillared hydrotalcite presents the best catalytic performance, and the DMC conversion and the selectivity for transesterified products reach 43.8% and 93.2%, respectively.     

杂原子介孔分子筛Me-HMS催化酯交换合成碳酸二苯酯

以水热合成法制备了杂原子介孔分子筛Me-HMS(Me指金属杂原子),用于催化碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的反应.小角度的X射线衍射显示,所有样品均具有典型的HMS介孔结构.Me-HMS中,Ti-HMS显示最好的催化性能,其活性与骨架钛含量密切相关,当溶胶中Ti/Si比达1/30时,骨架钛趋于饱和,苯酚转化率达到最大值31.4%,酯交换选择性为99.9%.