三嗪吡唑类铜配合物的合成、结构及光谱研究

以三齿吡唑-三嗪(类蝎型)化合物2,4-二(3,5-二甲基吡唑)-6-二乙基胺-1,3,5-三嗪(bpz*eaT)为配体,在无水乙醇和甲醇溶剂中,合成了2个配合物Cu2(mpz*eaT-EtO)2(N3)2Cl2(1)和Cu2(mpz*eaT-MeO)2(N3)4(2)(mpz*eaT-EtO:2-(3,5-二甲基吡唑)-4-乙醇-6-二乙基胺-1,3,5-三嗪;mpz*eaT-MeO:2-(3,5-二甲基吡唑)-4-甲醇-6-二乙基胺-1,3,5-三嗪)。通过元素分析、红外光谱、紫外光谱、热重分析以及X-ray单晶衍射方法对配合物进行了表征,并分析了其光谱及结构特征。晶体结构表明,配合物1属于三斜晶系,P1空间群,a=0.994 9(2)nm,b=1.021 6(2)nm,c=1.148 0(2)nm,α=115.11(3)°,β=106.99(3)°,γ=100.39(3)°,V=0.946 0(3)nm3,Z=1;配合物2属于单斜晶系,P21/c空间群,a=1.546 4(5)nm,b=1.400 8(5)nm,c=0.890 5(3)nm,β=103.227(5)°,V=1.877 9(10)nm3,Z=2。配合物1和2中的中心铜原子均为五配位,形成扭曲的四角锥构型。     

3,5-二氨基苯甲酸构筑的Zn(Ⅱ)、Cd(Ⅱ)两种配合物的合成及晶体结构(英文)

利用3,5-二氨基苯甲酸配体合成了2种新的配合物[Cd(diaba)(phen)2]NO3·H2O(1)和[Zn(diaba)(2,2′-bipy)2](2)(H2diaba=3,5-diaminobenzoic acid;phen=1,10-phenanthroline,2,2′-bipy=2,2′-bipyridine),并对其进行了元素分析、红外光谱和X射线单晶衍射测定。配合物1属于正交晶系,空间群为Fddd,a=1.425 81(7)nm,b=2.564 62(13)nm,c=3.092 47(17)nm。配合物2属于单斜晶系,空间群为C2/c,a=1.273 62 nm,b=1.592 78 nm,c=1.519 35 nm,β=107.334°。配合物1和2都为单核晶体。配合物1的结构单元由1个CdII、1个3,5-二氨基苯甲酸和2个phen构成。配合物2的结构单元由1个ZnII、1个3,5-二氨基苯甲酸和2个2,2′-bipy构成。两种配合物再通过氢键或π-π堆积形成三维超分子网络。研究了配合物的热稳定性和荧光性质。     

两个异亚硝基乙酰丙酮-n-芳基亚胺Pd(Ⅱ)配合物的合成、谱学性质和PdCl(C6H5一IAI)(C6H5NH2)的晶体结构

合成了两个异亚硝基乙酰丙酮-n-芳基亚胺的Pd(Ⅱ)配合物,PdCl(C6H5一IAI)(C6H5NH2)(1)和PdCl(P-CH3C6H4－IAI)(P-CH3C6HtNH2)(2),并测定了配合物1的晶体结构.配合物1晶体属正交晶系,空间群为Pca2l,晶胞参数a一1.858 7(4)nm,b＝0.938 0(2)nm,c一2.123 7(4)nm,2=8,F(000)一1 760,μ＝1.160 mm-1,R1＝O.027 二齿Schiff碱配体的异亚硝基(肟基)的N原子和亚胺的N原子,苯胺基N原子和CL-离子与Pd(Ⅱ)配位,形成PdN3Cl平面正方形配位构型.红外和喇曼光谱表明,形成配合物后νC=O和νc=N 移向低频,而vN-.o则移向高频.电子光谱说明存在π-π*和d-π*跃迁     

基于吡啶多羧酸和N，N′-桥联混合配体的钴配合物的合成及结构分析

将吡啶-2,4,6-三羧酸(2,4,6-pytaH3),4-氨基-3,5-二(4-吡啶基)-1,2,4-三氮唑(4,4′-abpt)和CoCl2在不同的pH条件下发生水热反应,得到2个新的配位聚合物[Co(2,4,6-pytaH)(4,4′-abpt)(H2O)](1)和[Co1.5(2,4,6-pyta)(4,4′-abpt)(H2O)3].3.5H2O(2)。配合物1是在吡啶-2,4,6-三羧酸酸性环境下产生的,吡啶-2,4,6-三羧酸在水热条件下只脱去2个羧基上的质子变成2,4,6-pytaH2-,而配合物2是在NaOH碱性溶液下反应得到的,其中吡啶-2,4,6-三羧酸完全脱去3个羧基上的质子变成2,4,6-pyta3-。配合物1中包含一维Co-羧酸链,2中存在具有(4,4)拓扑网络的二维层。1和2中的一维链和二维层通过π-π堆积和丰富的氢键作用分别拓展成三维超分子网络。单晶结构分析表明,配合物1结晶于单斜晶系,P21/n空间群,a=0.961 30(10)nm,b=0.632 09(6)nm,c=3.372 9(4)nm,β=95.104(2)°,V=2.041 3(4)nm3,Z=4。而配合物2结晶于单斜晶系,P21/c空间群,a=1.795 2(2)nm,b=0.729 62(8)nm,c=2.078 7(2)nm,β=112.323(2)°,V=2.518 6(5)nm3,Z=4。     

芳香碘基辅助的配位超分子自组装--锌(Ⅱ)、镉(Ⅱ)与7-碘-8-羟基喹啉-5-磺酸配合物的合成和结构

合成了锌(Ⅱ)、镉(Ⅱ)与7-碘-8羟基喹啉-5-磺酸(IHQS)的两种单晶配合物[Zn(IHQS)(H2O)3]2·4H2O(1)和[Cd-(IHQS)(H2O)2]n·2nH2O(2),用X射线衍射法确定了结构.结果表明,1和2均由一对对映体配合物构成1中两个[Zn-(IHQS)(H2O)3]对映体通过磺酸基-锌(Ⅱ)八面体轴向互补配位形成中心对称双分子聚合体,该聚合体通过分子间磺酸基氧-配位水氢键形成独特的二维层状结构;2的两个[Cd(IHQS)(H2O)2]对映体通过镉(Ⅱ)-磺酸基-镉(Ⅱ)双向互补配位形成一维直线型聚合配位结构.芳香碘基呈现新颖的碘-芳环氢和碘-磺酸基氧等弱相互作用模式,并对上述结构的支撑稳定发挥重要的结构辅助作用.本文展示了芳香碘基、磺酸基和喹啉环三种弱相互作用基团在配位超分子自组装中的形状、空间匹配和协同促进模式.结晶学参数配合物1单斜晶系,C2/c空间群,a=2.2243(7)nm,b=1.0053(3)nm,c=1.3468(4)nm,β=102.267(5)°,V=2.9428(16)nm3和Z=4.配合物2三斜晶系,P1空间群,a=0.6949(2)nm,b=1.0183(3)nm,c=1.0989(3)nm,α=76.069(5)°,β=75.294(5)°,γ=84.747(5)°,V=0.7295(4)nm3和Z=2.     

一维链状镍配位聚合物{[Ni(DNBC)2(Im)(H2O)]·0.25H2O}n的合成、晶体结构及热学性质研究

在水和乙醇混合溶液中合成了配合物{[Ni(DNBC)2(Im)(H2O)]·0.25H2O}n(DNBC=3,5-二硝基苯甲酸,Im=咪唑),并进行了元素分析、红外光谱、热重分析(TG)对其进行了表征,用单晶X-射线衍射测定了配合物的晶体结构。结果表明此配合物属正交晶系,空间群为Pbca,a=1.5022(6)nm,b=1.5146(6)nm,c=1.9269(7)nm,V=4.384(3)nm3,Z=8,F(000)=2320。配合物中金属镍原子采用五配位,分别与4个氧原子和1个咪唑氮原子配位,形成1个扭曲的四方锥体。     

含2,6-萘二甲酸及2,2′-联吡啶的双核钴配合物的合成和晶体结构

溶液法合成了配合物[Co2(NDC)(BIPY)2(H2O)6]·(NDC)(NDC=2,6-萘二甲酸根,BIPY=2,2′-联吡啶),用X-射线单晶衍射分析确定了该配合物的晶体结构。配合物为三斜晶系,P1空间群,a=0.92239(4)nm,b=1.12616(5)nm,c=1.22119(6)nm,α=94.857(3)°,β=111.843(2)°,γ=112.200(3)°,V=1.05205(8)nm3,Z=2,Dc=1.526Mg·m-3。该配合物由[Co2(NDC)(BIPY)2(H2O)6]2+阳离子和1个游离的2,6-萘二甲酸根阴离子组成。Co2+离子与2,6-萘二甲酸根的1个氧原子,2,2′-联吡啶的2个氮原子和3个水的氧原子配位,形成扭曲的八面体构型。2,6-萘二甲酸根的2个羧基分别以单齿方式桥连2个Co2+离子形成双核配合物。配合物中,配位水分子之间,配位水分子和2,6-萘二甲酸根阴离子之间,以及配位水分子和未配位的2,6-萘二甲酸根阴离子之间形成了丰富的O-H…O氢键,进而将双核配合物连接成三维超分子。     

基于一种酰腙和咪唑配体的铜(Ⅱ)、镍(Ⅱ)配合物的水热合成、晶体结构及体外抗癌活性

采用水热法合成了5-硝基水杨醛缩噻吩-2-甲酰腙的铜和镍配合物[Cu(Him)L]2(1)和[Ni(Him)L](2)(H2L=5-硝基水杨醛缩噻吩-2-甲酰腙,Him=咪唑)并经元素分析、红外光谱和紫外光谱表征。X射线单晶衍射分析表明,1的晶体属单斜晶系,空间群P21/c,晶胞参数:a=1.135 68(12)nm,b=0.770 45(8)nm,c=2.140 4(2)nm,β=97.405(3)°。2的晶体属三斜晶系,空间群P1,晶胞参数:a=0.726 91(4)nm,b=0.976 34(6)nm,c=1.265 74(8)nm,α=79.533(2)°,β=82.862(2)°,γ=68.985(2)°。1是中心对称的双核配合物,Cu(Ⅱ)处于四方锥配位环境;2是单核配合物,Ni(Ⅱ)处于平面四边形的配位环境。化合物1通过N-H…O氢键形成一维超分子链,而化合物2通过N-H…O和C-H…O氢键形成二维超分子网络。初步研究了配体和配合物的体外抗癌活性。结果表明,配合物1和2对人肝癌细胞HEPG2和人结肠癌细胞SW620均有较强的增殖抑制作用。     

基于环己二酸和双苯并咪唑配体的一维钴(Ⅱ)配位聚合物的合成、结构和催化性能研究

水热条件下,合成了钴(Ⅱ)配位聚合物{[Co(L)(chdc)].2H2O}n(1)(L=1,3-二(苯并咪唑-1-甲基)苯,H2chdc=1,4-环己烷二酸)。结构分析表明,配合物1的晶体属于单斜晶系,C2/c空间群,晶胞参数为a=1.4504(1)nm,b=1.834 9(2)nm,c=2.128 7(2)nm,β=94.325(1)°,V=5.649 2(9)nm3,Z=4。该配合物为一维环状链结构,并进一步通过链间的π-π作用自组装成二维超分子结构。配合物1作为类芬顿反应的催化剂降解刚果红显示较高的活性。     

由5-硝基间苯二甲酸和1，4-双(咪唑基-1-甲基)-苯配体构筑的镍配位聚合物的水热合成及晶体结构

通过水热法合成了一个新的金属-有机配位聚合物[Ni(NIPH)(bix)(H2O)2]n(H2NIPH=5-硝基间苯二甲酸,bix=1,4-双(咪唑基-1-甲基)-苯)。并对其进行了元素分析、红外光谱、热重、紫外光谱表征和X-射线单晶衍射测定。该配合物属于正交晶系,Pnma空间群。晶体学数据:a=1.743 62(8)nm,b=2.128 96(9)nm,c=0.568 59(3)nm,V=2.110 66(17)nm3,C22H21N5NiO8,Mr=542.15,Dc=1.706g.cm-3,μ(Mo Kα)=0.984 mm-1,F(000)=1 120,Z=4,最终R=0.032 4,wR=0.081 9用于1 703个可观测点,该配合物为一维链状结构。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.