2-羧基苯甲醛缩二乙烯三胺钙(Ⅱ)配合物的合成、结构表征和抗肿瘤活性的研究

在乙醇溶剂中, 以高氯酸钙、2-羧基苯甲醛缩二乙烯三胺为原料, 合成了一个新型钙配合物。对其进行了元素分析、红外光谱分析、摩尔电导、差热-热重分析, 并用X-射线单晶衍射测定了它的单晶结构。结果表明:在配合物分子中, 每个钙原子分别与希夫碱配体中的6个氧原子配位, 形成了变形的八面体构型。配合物属三方晶系, P31c空间群, 配合物分子通过氢键和苯环的π-π堆积作用形成了三维网状结构。初步研究了配合物对肝癌、肺腺癌、白血病和结肠癌的抗肿瘤活性。     

以4,4’-联苯咪唑及间苯二甲酸根为配体构筑的Ni(Ⅱ)配位聚合物的合成、晶体结构及光学性质

以4,4'-联苯咪唑(4,4'-bibp)和间苯二甲酸(H₂MPA)为配体,采用水热法合成了1个二维镍(Ⅱ)配位聚合物[Ni(H₂O)(MPA)(4,4'-bibp)]_n(1)。通过元素分析、红外光谱、热重(TGA)和X-射线粉末衍射(PXRD)等手段对其进行了表征,并用X-射线单晶衍射法测定了配合物的单晶结构。该配合物属于单斜晶系,Pc空间群,为二维层状结构。我们研究了配体和配合物在室温下的固体紫外光谱性质。     

镉配合物的合成、晶体结构与荧光性质

用水热合成法得到了镉的2个配合物[CdCl(pybma)·H₂O]_n (1)和[Cd₂(pybma)₂(OH-BDC)]_n (2)(Hpybma=2-(2-吡啶基)苯并咪唑基乙酸, OH-H₂BDC=5-羟基-1,3-苯二酸),对它们进行了元素分析、红外光谱、XRD,热重,荧光等表征,并用X-射线单晶衍射测定了配合物的单晶结构。配位聚合物1属单斜晶系,P2₁/c空间群, 配位聚合物2属三斜晶系,P1 空间群。2个配合物都是二维层状结构,其中配合物1通过氢键作用形成三维网状结构。实验结果表明2个配合物都具有较好的荧光性质,可以作为潜在的荧光光学材料。     

喹啉酰腙铜锌配合物的结构及荧光性质

合成了配合物{[Cu（L）（OAc）]·MeOH}_n（1）和[Zn（L）（OAc）]_n（2）（HL为喹啉-8-甲醛缩异烟肼）,并通过单晶X射线衍射、元素分析、红外光谱表征了结构。单晶衍射结果表明,除了结晶溶剂不同,2个配合物结构类似。每个配合物中,中心金属离子与来自烯醇化脱质子配体L^-的2个O原子和1个N原子,1个单齿配位的醋酸根和相邻配体4-吡啶N原子配位,形成一维链状结构。但配合物中金属离子的配位构型分别为扭曲的四方锥和三角双锥。在360 nm紫外光激发下,甲醇溶液中配合物2在510 nm左右有很强的荧光发射,这是由锌离子配位荧光增强效应所导致。     

N-O螯合配体协同膦配体的银(Ⅰ)混配配合物的设计、结构和生物活性

合成了一种Ag （Ⅰ）配合物[Ag （Qina）（Tpp）₂]·1.5H₂O （Qina=2-喹啉羧酸根,Tpp=三苯基膦）。运用单晶X射线衍射、IR、NMR和粉末X射线衍射对配合物的结构进行了表征。配合物属于单斜晶系,C2/c空间群,晶胞参数：a=3.195 90（13） nm,b=1.210 96（4） nm,c=2.319 74（7） nm,β=102.166（4）°,V=8.776 0（5） nm³,Z=8。通过Hirshfeld表面分析,推导出配合物的超分子结构和分子间弱作用力。同时,通过DNA结合活性测试、抗菌活性和癌细胞体外毒活性测试,评价了配合物的生物活性。     

3-乙基-2-乙酰吡嗪缩4-甲基氨基硫脲Ni（II）/Zn（II）配合物的合成、结构和DNA结合性质

合成并通过单晶衍射、元素分析、红外光谱表征了配合物[NiL（HL）]（OAc）（1）和[ZnL（OAc）]_n（2）的结构（HL=3-乙基-2-乙酰吡嗪缩4-甲基氨基硫脲）。单晶衍射结果表明,配合物1中的Ni（II）离子与来自2个缩氨基硫脲配体的4个N原子和2个S原子配位,其中一个配体为阴离子。而配合物2中,五配位的Zn（II）离子采取扭曲的四方锥配位构型,与2个μ-OCO桥联的醋酸根,一个三齿配位的缩氨基硫脲阴离子配位,形成沿a轴方向的一维链状结构。此外,荧光光谱结果表明,配合物与DNA的相互作用强于配体。     

喹啉酰腙铜锌配合物的结构及荧光性质

合成了配合物{[Cu（L）（OAc）]·MeOH}_n（1）和[Zn（L）（OAc）]_n（2）（HL为喹啉-8-甲醛缩异烟肼）,并通过单晶X射线衍射、元素分析、红外光谱表征了结构。单晶衍射结果表明,除了结晶溶剂不同,2个配合物结构类似。每个配合物中,中心金属离子与来自烯醇化脱质子配体L^-的2个O原子和1个N原子,1个单齿配位的醋酸根和相邻配体4-吡啶N原子配位,形成一维链状结构。但配合物中金属离子的配位构型分别为扭曲的四方锥和三角双锥。在360 nm紫外光激发下,甲醇溶液中配合物2在510 nm左右有很强的荧光发射,这是由锌离子配位荧光增强效应所导致。     

基于二苯甲酰酒石酸构筑的钴（Ⅱ）、镍（Ⅱ）配合物的合成、结构、荧光及磁性质

在室温条件下合成了2个配合物[Ni（DBTA）（DMF）（H₂O）₄]（1）和[Co（DBTA）（DMF）（H₂O）₄]（2）（D-H₂DBTA=D-（+）-二苯甲酰酒石酸,DMF=N,N-二甲基甲酰胺）,并通过元素分析、FT-IR光谱、X射线单晶及粉末衍射表征了2个配合物的结构。X射线单晶衍射结果表明,2个配合物同构,属于单斜晶系,P2₁空间群。配合物由配位键形成零维结构,再通过分子间氢键形成三维网状结构。荧光分析表明当激发波长为280 nm时,配合物1和2具有较强的荧光。尽管2个配合物同构,但表现出不同的磁性质：配合物1主要表现出Ni²⁺离子间弱的反铁磁相互作用,而配合物2则表现为Co²⁺离子的磁各向异性以及Co²⁺离子间强的反铁磁相互作用。     

钴(Ⅱ)、锰(Ⅱ)与4-吡啶甲醛缩4-氨基安替比林配合物的合成、晶体结构与磁性

以希夫碱衍生物4-氨基安替比林缩吡啶-4-甲醛为配体(L),采用溶剂热合成法,成功合成了2个Schiff碱Co(Ⅱ)配合物[CoLCl₂](1)、Mn(Ⅱ)配合物[MnLCl₂](2),通过元素分析、红外光谱IR、XRD、TG和磁性分析等测试手段对2个配合物进行表征,并用X-射线单晶衍射测得Co(Ⅱ)、Mn(Ⅱ)配合物的晶体结构。单晶结构表明,配合物1的晶体属于单斜晶系,空间群为Cc;配合物2的晶体属于三斜晶系,空间群为P1。配合物1是以Co(Ⅱ)为中心的扭曲四面体构型,配合物2是以Mn(Ⅱ)为中心的扭曲八面体构型。     

以2,2’-联吡啶-4,4’-二甲酸和2-甲基吡嗪[3,2-f：2’,3’-h]喹喔啉为配体的三维锰（Ⅱ）配位聚合物的合成、晶体结构和荧光性质

采用水热法合成了一个锰的配合物[Mn（bpydc）（Medpq）]_n（1）（H₂bpydc=2,2’-联吡啶-4,4’-二甲酸,Medpq=2-甲基吡嗪[3,2-f：2’,3’-h]喹喔啉）,并利用元素分析、红外光谱、紫外可见光谱、热分析和X-射线单晶衍射对其结构进行了表征。单晶结构分析表明配合物1属于正交晶系,Cc空间群,晶胞参数a=2.0316（4）nm,b=1.5645（3）nm,c=0.71926（14）nm,β=103.97（3）,V=2.2185（8）nm³,Z=4。配合物1是一个锰(Ⅱ)离子经由bpydc^2-连接形成的三维网络结构。配合物1的固体荧光光谱表明它具有很强的荧光性。应用Gaussian03W程序,在HF/LANL2DZ水平上对标题化合物的自然键轨道（NBO）进行了分析,结果表明Mn(Ⅱ)与配位原子间的价键类型都属于共价键范畴。     

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.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

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.