1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5镉配合物的合成和晶体结构

1苯-基-3甲-基-4苯-甲酰基-吡唑啉酮-5(HPMBP)是一类含有氮杂环的β-二酮螯合剂,现在已经广泛应用于金属离子的分离和分析[1-4]。它与许多金属离子生成的配合物的生物活性明显增强,显示了广谱的抗菌、抗病毒和抗肿瘤等性质,引起了化学家对它与金属离子的配位作用以及配合物的晶     

酚醛型苯基硫脲树脂对Pt4+、Pd2+的吸附性能

螯合树脂是一类具有螯合功能基,能从含有金属离子的溶液中有选择的捕集、分离特定金属离子的功能高分子。含N、S、O配位原子的螯合树脂对贵、重金属离子有良好的吸附性能和吸附选择性。利用螯合树脂的吸附性能,     

含咪唑功能基螯合树脂的研究进展

咪唑环是一种含有两个配位原子的功能基,能与重金属离子形成稳定配合物。将其接枝到有机或无机高分子上,制得的含咪唑功能基的螯合树脂,不仅对重金属离子表现出良好的吸附选择性能,且回收操作简单、回收利用率高。本文对该类螯合树脂的研究进展进行了综述。     

N,N′-二(对甲基苯磺酰基)-3-甲氧亚胺基-1,5-二氮环辛烷的合成

多氮杂大环及其衍生物能够与金属离子形成多齿配合物 ,而中环二胺则是一种重要的双齿配体 ,能够与金属离子形成“夹心状”配合物[1] 。氮杂环化合物能够与许多重金属离子形成稳定配合物 ,该性质使其具有很有意义的应用前景 ,如在医药、诊断方面具有实用性 ,也可用于金属离子的分离和回收[2 ] 。本文合成了环上含有羟亚胺基烷氧亚胺基取代的八元环二胺衍生物 ,该化合物中亚胺基中的氮原子带有一对孤电子 ,可参与形成氢键或配位键 ,该化合物可用于有机合成中的中间体 ,其合成路线如下 :1　实验部分1 .1　仪器与试剂熔点仪为Ｂ櫣ｃｈｉ 5 1 0 ,…     

2-氧代-2-(2-氯-5-吡啶甲氨基)4-取代苯基-5,5-二甲基-1,3,2-二氧磷杂环己烷的合成

新烟碱类杀虫剂是人们对天然烟碱研究开发的一类超高效杀虫剂,是烟碱乙酰胆碱受体(nAchR)的效应剂,具有活性高,广谱杀虫,对对抗性昆虫有良好的防效,并且对哺乳动物毒性低.人们对该类杀虫剂的构效关系研究表明:活性化合物均具有3-氨甲基吡啶结构单元,氮原子上连有强吸电子基,氮原子带有部分正电荷.1,3,2-二氧磷杂环以其广泛的生物活性使其成为农药、医药合成中的重要活性结构单元.     

1,4,7-三氮杂环壬烷-N,N'',N"-三取代化合物的合成

本文报道母体化合物1,4,7-三氮杂环壬烷以及六种新的1,4,7-三氮杂环壬烷-N,N′,N″-三取代物(9～14)的合成方法,其中每个取代基的碳链均含有三个碳原子。它们都可以作为过渡金属离子Co~(2+)、Ni~(2+)、Cu~(2+)、Zn~(2+)、Co~(3+)、Fe~(3+)、Cr~(3+)的配体。     

某些氮杂环烷衍生物的合成

多氮杂环多羧酸及其氮取代化合物因其特殊的螯合能力近年来得到了日益广泛的研究,多氮杂环烷多乙酸的合成及其应用研究报道较多[1～3],而多氮杂环多丙酸及氮上带3个碳原子以上取代基的化合物研究较少,随着氮原子上碳链的增长,此类化合物作为配体其硬度下降,有助于分离某些金属离子.我们以Cyelen.4HCl及Cyclam为原料以LiOH为碱在水溶液中与氯丙酸反应合成了化合物Ⅰ,Ⅱ,用Cyclen和Cyclam为原料与丙烯腈回流合成了化合物Ⅲ,Ⅳ.     

3-杂环基硫取代-1,3,4,5-四氢-2-氧代-苯并氮杂衍生物的合成

以芳酰肼为原料, 合成了一系列3-巯基-5-芳基-1,2,4-三唑、2-巯基-5-芳基-1,3,4-噁二唑和2-巯基-5-芳 基-1,3,4-噻二唑, 并通过硫原子对3-溴-2-氧代-苯并氮杂3-位上的亲核取代反应将杂环化合物引入了苯并氮杂的结构当中, 合成了32个新的苯并氮杂杂环衍生物. 为提高其在有机溶剂中的溶解性, 在苯并氮杂的N原子上引入乙酸乙酯和乙酸叔丁酯基取代基, 合成了36个新衍生物. 所有化合物经质谱、核磁共振谱及元素分析确证了结构并初步测定了抗菌活性.     

X射线单晶衍射研究系列功能七元杂环桥联联苯构象

含有七元杂环桥联联苯的π-共轭聚合物是重要的宽禁带光电材料, 其发光性质决定于两苯环间扭曲角. 利用X射线单晶衍射仪确定了系列功能的七元杂环桥联联苯化合物的晶体结构, 比较了桥联原子, 6,6位取代基及分子间弱氢键对这类桥联联苯扭曲构象的影响. 桥联键是—CH2—O—CH2—和—CH2—S—CH2—的七元杂环桥联联苯两苯环间的扭曲角分别为39°和51°, 在6,6位上含有不同取代基的双氧桥联七元杂环桥联联苯的扭曲角存在5°的差异. 在双氧桥联的七元杂环桥联联苯的二聚物中, 桥联的氧原子与非桥联的苯亚基-苯亚基2,2’位置上的两个氢原子之间形成的氢键网络结构导致中心联苯呈现平面构象, 但氢键并没有改变桥联联苯的构象. 七元杂环桥联联苯的构象主要由桥联原子决定, 同时分子间相互作用亦能轻微调控这类桥联联苯的扭曲角.     

2,3-二苯基-1,4-二氮杂-1,3-环庚二烯和2,3-取代喹(口恶)啉的铜(Ⅱ)配合物研究

1,4-二氮杂环配体有两个可以与金属配位的N原子,配位后可能呈现链状形式.当金属离子含未成对电子时,由于M_1—L—M_2链中超交换作用的存在,可能会产生反铁或铁磁性相互作用,即M_1与M_2中的未成对电子呈反平行或平行排列.这决定于电子构型和链的几何排列,可以用ESR和变温磁化率测定.我们制备了四个二氮杂环配体L、MQ、dMQ和dPQ,使之与CuX_2(X=Cl,Br)反应,对生成配合物的结构进行了讨论.     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.