修饰NADH模拟物的金属-有机三元环光催化制氢

将含有不同还原型烟酰烟腺嘌呤二核苷酸(NADH)活性中心模拟物的有机配体H2L1和H2L2与钴离子配位自组装获得2例具有氧化还原活性且带有正电荷的金属-有机大环Co-L1和Co-L2.选择阴离子型钌基光敏剂[Ru(dcbpy)3]4-(dcbpy=2,2'-联吡啶-4,4'-二羧酸)作为光敏中心,金属-有机大环结构作为...     

取代联吡啶钌配合物对末端炔烃的催化环三聚作用

RuCl3·3H2O分别与6,6’-二甲基-2,2’-联吡啶(dmbp)和2,2’-联吡啶-6,6’-二甲醛(bpda)反应生成[cisRu(L)2Cl2]Cl·2H2O(L=dmbp,bpda),进一步用CF3SO3Ag脱氯得到[cis-Ru(L)2(H2O)2](CF3SO3)3.研究了4种配合物对1-己炔、苯乙炔和丙炔酸乙酯的催化环三聚作用,发现脱氯后的含水配合物催化活性有显著提高;体系中有水存在时,丙炔酸乙酯环三聚具有很强的区域选择性.催化机理研究表明,该催化过程为催化[2+2+2]环加成反应.钌杂环庚三烯或7-钌杂双环[2.2.1]-2,5-庚二烯是关键中间体,联吡啶配体上的6-甲酰基取代基水合后通过与丙炔酸乙酯的羰基形成分子内氢键影响环三聚产物的区域选择性.     

钌亚丙二烯基配合物与肼的反应性质:丙烯腈配合物的生成（英文）

以双齿P,N-配体8-(二苯基膦基)喹啉(DPPQ)为支撑配体的钌亚丙二烯基配合物[RuCl(=C=C=CR_2)(DPPQ)_2]-[BPh_4](3a:R=苯基;3b:CR_2=FN=亚芴基)可由双核钌配合物[Ru(μ-Cl)(DPPQ)_2]_2[BPh_4]_2(1)分别与过量的1,1-二苯基炔丙醇(2a)或9-乙炔-9-芴醇(2b)反应得到.配合物3易与肼在室温下反应生成丙烯腈的钌配合物[RuCl(N≡C—CH=CR)2)(DPPQ))2][BPh)4](4a:R=苯基;4b:CR)2=FN=亚芴基),该反应涉及肼对亚丙二烯基配体α-碳原子的分子间亲核进攻,是首例肼对金属亚丙二烯基加成生成丙烯腈的反应.配合物4与过量的丙炔醇2反应可释放出3,3-二苯基丙烯腈(5a)或3-芴基丙烯腈(5b),并再生亚丙二烯基配合物3.此外,初步考察了配合物1对端基炔丙醇与肼反应生成丙烯腈的催化活性,结果表明该催化反应的确可以进行,但是得到的丙烯腈产物的产率不高.尽管结果不是很理想,但是这些研究表明可望发展端基炔丙醇与肼经由过渡金属亚丙二烯基中间体转化为丙烯腈的新催化反应.     

咪唑/三唑羧酸配体配合物的合成及性能研究

本文以含咪唑/三唑基的两种有机羧酸H2L1和H2L2(H2L1=2-(4-(1H-1,2,4-三唑-1-基)苯基)-1H-苯并[d]咪唑-5-羧酸;H2L2=2-(4-(1H-咪唑-1-基)苯基)-1H-苯并[d]咪唑-5-羧酸)为配体,在溶剂热条件下合成三种新的金属配合物[Co(HL1)2(H2O)4] (1),[N...     

双核钌(II)多吡啶配合物与酵母RNA的相互作用研究

用紫外-可见吸收光谱和荧光光谱滴定、稳态荧光淬灭和反向盐滴定实验研究了双核钌(II)配合物[(bpy)2Ru(ebipcH2)Ru(bpy)2](ClO4)4 {bpy=2,2'-联吡啶; ebipcH2=N-乙基-4,7-二(咪唑-[4,5-f]-(1,10-邻菲啰啉)-2-基)咔唑}与酵母RNA 的相互作用. 结果表明该双核配合物以插入方式与酵母RNA 作用, 在生理盐浓度下(≈150 mmol/L NaCl)该配合物与RNA 的相互作用明显强于DNA.     

钌(Ⅲ)-二安替比林对氯苯甲烷-高碘酸钾体系催化分光光度法测定痕量钌

在磷酸介质中及加热条件下,钌(Ⅲ)对高锰酸钾氧化二安替比林对氯苯基甲烷(DApCM)显色反应有强烈的催化作用,由此建立了测定痕量钌的方法.体系的最大吸收波长为500nm,钌的含量在0.0～4.0μg/L范围内具有线性关系,检测限为1.94×10-10g/mL,反应的表观活化能为88.20kJ/mol,反应表观速率常数为7.7×10-4/s.本方法用于矿样中痕量钌的测定得到了满意的结果.     

樟脑磺酸噻唑腙类化合物的设计、合成及抗氧化应用

以樟脑衍生物樟脑磺酸为原料,经缩合、环化等反应,合成了22个樟脑磺酸噻唑腙类化合物,采用~1H NMR、~(13)C NMR、HR-MS等方法对产物的结构进行表征,并研究了它们的抗氧化活性.结果表明,不同取代基的樟脑磺酸噻唑腙类化合物表现出不同的抗氧化活性,其中(2-(2-(4-(4-氰基苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q19)消除1,1-二苯基-2-三硝基苯肼(DPPH)自由基的IC_(50)值可达到176μmol/L,(2-(2-(4-(4-氟苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q3)消除2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)二铵盐(ABTS)自由基的IC_(50)值可达到20.6μmol/L,(E)-(7,7-二甲基-2-(2-(4-(3-甲苯基)噻唑-2-基)亚肼基)双环[2.2.1]庚-1-基)甲磺酸(Q8)对羟基自由基的消除率可达到66.2%,(2-(2-(4-(4-联苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q20)消除过氧自由基的IC_(50)值可达到20.7μmol/L,均远超过阳性对照trolox的抗氧化活性.(2-(2-(4-(2-羟基苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q16)抑制酪氨酸酶的IC_(50)值可达154.9μmol/L,也优于阳性对照曲酸.对樟脑磺酸基噻唑腙类化合物的抗氧化机理进行了探索.     

钌（Ⅲ）—二安替比林对氯苯甲烷—高碘酸钾体系催化分光光度法？…

在磷酸介质中及加热条件下,钌(Ⅲ)对高锰酸钾氧化二安替比林对氯苯基甲烷(DApCM)显色反应有强烈的催化作用,由此建立了测定痕量钌的方法.体系的最大吸收波长为500nm,钌的含量在0.0～4.0μg/L范围内具有线性关系,检测限为1.94×10-10g/mL,反应的表观活化能为88.20kJ/mol,反应表观速率常数为7.7×10-4/s.本方法用于矿样中痕量钌的测定得到了满意的结果.     

单核、对称双核钌配合物在铂电极上的电化学行为

利用循环伏安、循环交流伏安和微分电容测定等电化学方法研究了由2,2'-联吡啶(bpy)和桥联配体1,4-二(2-咪唑并[4,5-f][1,10]邻菲咯啉)苯(DIPB)配位而成的单核钌配合物[Rul:Ru(bpy)~2(DIPB)(ClO~4)~2]和对称双核钌配合物[Ru2:(bpy)~2Ru(DIPB)Ru(bpy)~2(ClO~4)~4]在铂电极上的电化学行为。研究结果表明,在0.1mol/L高氯酸四丁基铵(TBAP)的乙腈溶液中,这两种配合物的中心钌离子在铂电极上均呈现一对氧化还原峰,而配体2,2'-联吡啶则呈现两对氧化还原峰。单核Ru1和双核Ru2所对应的各组氧化还原峰分别符合可逆的单电子和二电子传递反应过程的特征,所对应的条件电位(FormalPotential)Ru2较ru1有轻微正移。Ru1和Ru2所对应的配位阳孩子的扩散系数分别为9.93×10^-^6cm^2/s和3.50×10^-^6cm^2/s。在循环交流法和微分电容法确定的时间量程内,两中心钌离子在桥联配体间的电子传递过程较它与电极间的慢。     

新型1,2,4-三唑三氮烯衍生物的合成及其生物活性

以对氨基苯甲酸为原料,经多步反应合成了16个未见文献报道的1,2,4-三唑三氮烯衍生物.利用~1H NMR~,(13)C NMR和HRMS对标题化合的结构进行了表征.衍生物的细胞毒活性测试结果表明,2-[4-(3,3-二甲基三氮烯-1-基)苯基]-3-氨基-4-S-(4-氯基苄基)-1,2,4-三唑(6g)、2-[4-(3,3-二甲基三氮烯-1-基)苯基]-3-氨基-4-S-(2,4-二氯基苄基)-1,2,4-三唑(6h)、2-[4-(3,3-甲基苯甲基三氮烯-1-基)苯基]-3-氨基-4-S-苄基-1,2,4-三唑(6i)、2-[4-(3,3-甲基苯甲基三氮烯-1-基)苯基]-3-氨基-4-S-(4-甲基苄基)-1,2,4-三唑(6j)、2-[4-(3,3-甲基苯甲基三氮烯-1-基)苯基]-3-氨基-4-S-(4-甲氧基苄基)-1,2,4-三唑(6l)、2-[4-(3,3-甲基苯甲基三氮烯-1-基)苯基]-3-氨基-4-S-(2,4-二氯基苄基)-1,2,4-三唑(6p)对膀胱癌细胞具有较好的抑制作用,其IC50值分别为23.883,5.512,8.731,8.077,5.590和12.195μmol/L,化合物6h,6i,6j,6l对前列腺癌细胞具有较好的抑制作用,其IC50值分别为13.690,21.908,10.772和4.827μmol/L.     

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.     

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.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.