Heck反应一锅法合成3-乙氧羰基-2-甲基吲哚的研究

吲哚以其独特的化学结构使其衍生出的化合物都具有独特的生理活性,它们在医药、农药、香料、色氨酸等领域发挥着重要的作用,是一类非常重要的杂环类精细化工中间体。因此,长久以来发展简单、通用,特别是具有区域选择性的方法合成吲哚类化合物一直吸引了人们的研究兴趣[1]。在已经发展起来的合成吲哚类化合物的许多方法中,Heck反应[2],即Pd催化卤代物与烯烃构筑碳碳键的方法,由于其温和的反应条件和广泛的官能团相容性,已经成为合成吲哚及其衍生物采用最多的方法[3]。早在1984年,Suzuki[4]就报道合成了化合物3-乙氧羰基-2-甲基吲哚,其是由…     

3-取代吲哚衍生物的合成

目前吲哚化学的研究是杂环化学中最活跃的领域之一,特别是3-取代吲哚衍生物,已用于许多天然产物和相应具有生物活性化合物重要骨架的构筑,其合成方法的研究格外令人注目。近年来,由吲哚一步合成3-取代吲哚衍生物的报道剧增。本文按合成过程中所用催化剂的种类,综述近几年来由吲哚为原料一步合成二吲哚甲烷、β-吲哚酮、β-吲哚醇、β-吲哚硝基化合物和α-吲哚甲胺等为代表3-取代吲哚衍生物的研究进展。     

3-硫化吲哚类化合物合成方法的研究进展

硫化吲哚类化合物作为合成天然化合物的重要中间体,被广泛应用于有机合成化学.近年来,由于3-硫化吲哚类化合物有良好的药用价值而被广泛关注.目前,硫醇或硫酚、二硫醚、硫氯等硫化试剂被广泛应用于3-硫化吲哚类化合物合成中,3-硫化吲哚类化合物的合成方法随硫化试剂的不同而异,文章综述了3-硫化吲哚类化合物合成方法的研究进展.     

吲哚-2,3-二酮衍生物抗病毒活性研究进展

吲哚-2,3-二酮是一种广泛存在于天然产物中的化合物,基于其结构特点可以发生不同类型的反应,为其衍生物的合成提供了便利的条件,因此目前其合成和活性的研究备受关注.本文对近年来吲哚-2,3-二酮衍生物抗病毒活性研究情况进行了综述,分别介绍了对HIV、痘病毒、SARS病毒、柯萨奇病毒B3和烟草花叶病毒的抑制活性.重点介绍了吲哚-2,3-二酮衍生物对HIV病毒的作用以及对HIV病毒进入人体破坏人体的免疫功能后容易感染的细菌和结核病的作用.     

3-芳亚甲基吲哚-2-酮类化合物的合成及其抑菌活性研究

在超声辐射和哌啶催化反应条件下,1,3-二氢吲哚-2-酮(1)与芳香醛2a~2m发生Knoevenagel缩合反应,合成了一系列3-芳亚甲基吲哚-2-酮衍生物3a~3m。该方法具有产率高、反应时间短、后处理简单和环境友好等优点,产物通过~1H NMR、~(13)C NMR和HRMS手段进行结构表征,并通过核磁2D NOESY确定了所有化合物几何构型。初步抑菌活性测试结果表明,化合物3d对革兰氏阳性菌具有较好的抑制作用,最小抑菌浓度(MIC)为15.6μg/m L,化合物3f、3g、3h和3k对油菜菌核病菌表现出良好的抑制活性,MIC为62.5μg/m L,与阳性对照多菌灵相当。此外,对此类化合物的构效关系进行了讨论。     

无过渡金属催化条件下合成3,3'-二吲哚甲烷衍生物的最新进展（英文）

3,3'-二吲哚甲烷类化合物是一类重要的吲哚生物碱,其结构单元广泛存在于天然产物、功能性材料以及合成药物分子中.因其具有多样的生物活性和功能,如抗氧化、抗炎症、抗血管生成、抗菌以及抗癌活性等,构筑3,3'-二吲哚甲烷类杂环化合物备受关注.传统的合成方法,尤其是对称结构的3,3'-二吲哚甲烷类化合物的合成主要在化学量的Br?nsted酸或Lewis酸存在下,吲哚衍生物与羰基化合物经傅-克反应缩合得到.而过渡金属的使用可引起化合物中金属残留以及环境污染.总结和探讨了从2010年至今3,3'-二吲哚甲烷类化合物的合成方法,尤其是对无过渡金属参与条件下,对称结构的3,3'-二吲哚甲烷类化合物以及非对称结构3,3'-二吲哚甲烷类化合物制备的最新进展以及相应的反应机理,旨在为该类化合物生物活性测试提供重要的理论依据和技术支持.     

二氢吲哚-2,3-二酮衍生物抑菌活性研究进展

二氢吲哚-2,3-二酮是一种结构简单且应用广泛的药物小分子,其衍生物的合成、结构和药理活性等备受关注。已有报道表明二氢吲哚-2,3-二酮具有抗菌、抗衰老、降血脂、抗癫痫、抗病毒等多种生物活性。本文主要围绕抑菌生物活性,对国内外关于二氢吲哚-2,3-二酮类化合物的构效关系进行分析总结,为后期该类新型抗菌化合物的设计合成提供参考。     

自由基加成/关环反应合成1,3-二氢吲哚-2-酮的研究进展

近两年来,关于自由基加成/关环反应合成1,3-二氢吲哚-2-酮的报道屡见不鲜.它们大多以N-芳基取代的丙烯酰胺类化合物为底物,在各种不同的金属、无金属和光的催化作用下,与不同的自由基反应,可以一步生成3,3-二取代的吲哚-2-酮衍生物.该类方法现已成为合成含氮五元杂环的一个重要手段,用来合成1,3-二氢吲哚-2-酮及其衍生物.目前对自由基加成/关环反应合成该类化合物的研究多集中在不同催化手段引发不同的自由基和反应机理上.按催化剂类型的不同,对近年来自由基加成/关环反应合成吲哚-2-酮的研究进展进行了综述.     

磷酸二氢钾催化Yonemitsu缩合反应合成5-[(3-吲哚基)-芳甲基]-2,2-二甲基-1,3-二噁烷-4,6-二酮衍生物

以醛、吲哚和麦氏酸为原料,水和乙醇混合液为溶剂,在室温搅拌条件下以磷酸二氢钾为催化剂通过Yonemitsu缩合反应,合成了一系列的5-[(3-吲哚基)-芳甲基]-2,2-二甲基-1,3-二噁烷-4,6-二酮衍生物,产率为48%~98%,并通过X射线单晶衍射仪测定了化合物4o的晶体结构。 该方法能够有效的促使反应活性较低的4-甲基苯甲醛和4-甲氧基苯甲醛参与反应,以83%和60%的收率获得相应的目标产物,并具有反应条件温和、催化剂廉价易得、后处理简单、产物易于纯化、产率较高等优点,可用于合成3-取代吲哚类化合物。     

吲哚与亚胺的Friedel-Crafts反应的研究进展

由于吲哚类化合物具有许多生物特性等优点,在众多天然产物和相应的具有生物活性的化合物中起重要的骨架构筑作用,其合成方法的研究格外令人注目.近年来,关于吲哚与亚胺在催化剂作用下发生Friedel-Crafts反应来制备3-取代吲哚甲胺衍生物的报道剧增.对近年来吲哚与亚胺Friedel-Crafts反应的研究情况进行了综述.     

2-烷基-2-(芳磺酰基)乙酸酯的高效共轭加成

本文报道在固-液相转移催化的温和条件下2-烷基-2-(芳磺酰基)乙酸酯(1)与α, β-不饱和酯、腈、酮(2)的高选择性和高效率共轭加成反应。成功地合成了2, 2-二取代戊二酸二酯(3a~d)、4-氰基丁酸酯(3e~g)和5-氧代己酸酯(3h~j)。对它们的结构作了表征。初步讨论了本合成法的特点。Michael受体、相转移催化剂和溶剂等对共轭加成反应的影响。     

[O(S),O=P]型配体修饰的单氯单茂锆催化剂的高温乙烯聚合

以Ph3CB(C6F5)4/iBu3Al作为助催化体系,研究了单氯半茂型催化剂,ClCp′Zr[X-2-R1-4-R2-6-(Ph2P=O)C6H2]2(Cp′=C5H5,a:X=O,R1=Ph,R2=H;b:X=O,R1=F,R2=H;c:X=O,R1=tBu,R2=H;d:X=O,R1=R2=tBu;e:X=O,R1=SiMe3,R2=H;f:X=S,R1=SiMe3,R2=H;Cp′=C5Me5;g:X=O,R1=SiMe3,R2=H)的乙烯高温（50~125 ℃）聚合行为。 结果表明,催化剂a~d可在高温(50~100 ℃)下高效引发乙烯聚合,最佳反应温度为75 ℃。 适当增大R1取代基的位阻或引入吸电子取代基均有利于提高催化活性。 三甲基硅烷基取代的催化剂[WTHZ]e[WTBZ]耐高温性能较催化剂a~d大大提升,在100 ℃时,乙烯聚合活性可达5628 kg/(mol Zr·h)。 金属中心的配位原子及茂环上取代基团的改变对催化活性和聚合物的相对分子质量分布有一定的影响。     

Electrochemical and Theoretical Studies of 1-Alkyl-2-substituted Benzimidazoles as Corrosion Inhibitors for Carbon Steel Surface in HCl Medium

The inhibition efficiencies of newly synthesized four 1-alkyl-2-substituted benzimidazole compounds(a~d) have been studied for the corrosion of carbon steel in 1.0 M HCl by using potentiodynamic polarization measurement. The four inhibitors act as mixed-type inhibitors,which mainly inhibit cathodes. The inhibition efficiency of these compounds enhanced when the concentration of the inhibitors increased. A theoretical study of the corrosion inhibition efficiency of these compounds was carried out by using the B3 LYP level with the 6-31+G* basis set. Considering the solvent effect,the IEFPCM model was selected. Furthermore,the adsorption energies of the inhibitors with the iron(001) surface were studied by using molecular dynamic(MD) simulations. The theoretical results show that these inhibitors all exhibit several adsorption active-centers. Meanwhile,the MD simulations indicate that the adsorption occurs mostly through benzene ring and the lone pair electrons of the nitro atoms. These results demonstrated that the theoretical studies and MD simulations are reliable and promising methods for analyzing the inhibition efficiency of organic inhibitors.     

Synthesis of 5-Deoxy-5-Acyloxyiminoavermectin B1 Derivatives

The avermectins1 are a unique collection of naturally occurring macrocyclic lactones with broad spectrum of anthelmintic and insecticidal activities. Their remarkable biological activity and complex molecular architecture stimulated significant interest in the scientific community. Much research has been carried out on these compounds. Many derivatives of avermectin have much more bioactivities and have been commercially utilized2-5. Here we describe the synthesis of 5-deoxy-5-acyloxyimi…     

Synthesis and characterization of benzyl and benzoyl substituted oxime-phosphazenes

Two oxime-cyclophosphazenes were prepared from hexakis(4-formylphenoxy)cyclotriphosphazene (2) and hexakis(4-acetylphenoxy)cyclotriphosphazene (7). The reactions of these oximes with benzyl chloride, benzenesulfanoyl chloride, benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride were studied. Hexa and pentasubstituted compounds were obtained from the reaction of hexakis(4-[(hydroxyimino)methyl]phenoxy)cyclotriphosphazene (3) with benzyl chloride (4) and benzoyl chloride, respectively. However, the oxime groups on 3 rearranged to nitrile (5) in the reaction of 3 with benzenesulfanoyl chloride and 1-napthalenesulfanoyl chloride. Hexasubstituted compounds were also obtained from the reactions of hexakis(4-[(1)-N-hydroxyethaneimidoyl]phenoxy)cyclotriphosphazene (8) with benzoyl chloride (10), 4-methoxybenzoyl chloride (11) and 2-chlorobenzoyl chloride (12). A trisubstituted compound was obtained from the reaction of 8 with benzyl chloride (9). All the products were generally obtained in high yields. Pure and defined products could not be obtained from the reaction of 3 with 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. The structures of the compounds were defined by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy.     

Cyclization of electron-deficient cyclopentadienone with 2-alkenyl and 2-alkynylamines via sequential pericyclic reaction pathway.

The pericyclic reactions of 2,5-bis(methoxycarbonyl)-3,4-diphenylcyclopentadienone (1a) with both allylic and propargylic amines have been investigated. The reaction proceeded via initial formation of the 1,4 adducts followed by the ene cyclization and/or sequential pericyclic reactions depending upon the structures of the amines. The reaction of 1a with diallylamine (2a) gave the tetracyclic compound (3a). On the other hand, the reaction of 1a with 2-propynylamine (2c) gave exclusively the bicyclic compound (5c). In the reactions with the secondary 2-propynylamines (2d,e), the tetracyclic compounds (3d,e) were exclusively formed. The reactions of 1a with alpha-branched primary 1,1-dialkyl-2-propynylamines (2f,g) gave mixtures of 3- and 5-type compounds. The tetracyclic compounds 3 were formed from the intramolecular [4+2]pi cycloadditions of the [1,5]-sigmatropic rearrangement products of the 1,4 adducts of 1a and 2, followed by the [1,5]-sigmatropic rearrangement of hydrogen and dehydrogenation. The bicyclic compounds 5 were derived from the [2pi+2pi+2sigma] reaction of the 1,4 adducts of 1a and 2. The one-pot multistage sequential pericyclic reactions were discussed on the basis of the X-ray crystallographic structures and the MO calculation data.     

Tuning of spin crossover behaviour in iron(III) complexes involving pentadentate Schiff bases and pseudohalides

Investigations on a series of eight novel mononuclear iron(III) Schiff base complexes with the general formula [Fe(L(5))(L(1))]·S (where H(2)L(5) = pentadentate Schiff-base ligand, L(1) = a pseudohalido ligand, and S is a solvent molecule) are reported. Several different aromatic 2-hydroxyaldehyde derivatives were used in combination with a non-symmetrical triamine 1,6-diamino-4-azahexane to synthesize the H(2)L(5) Schiff base ligands. The consecutive reaction with iron(III) chloride resulted in the preparation of the [Fe(L(5))Cl] precursor complexes which were left to react with a wide range of the L(1) pseudohalido ligands. The low-spin compounds were prepared using the cyanido ligand: [Fe(3m-salpet)(CN)]·CH(3)OH (1a), [Fe(3e-salpet)(CN)]·H(2)O (1b), while the high-spin compounds were obtained by the reaction of the pseudohalido (other than cyanido) ligands with the [Fe(L(5))Cl] complex arising from salicylaldehyde derivatives: [Fe(3Bu5Me-salpet)(NCS)] (2a), [Fe(3m-salpet)(NCO)]·CH(3)OH (2b) and [Fe(3m-salpet)(N(3))] (2c). The compounds exhibiting spin-crossover phenomena were prepared only when L(5) arose from 2-hydroxy-1-naphthaldehyde (H(2)L(5) = H(2)napet): [Fe(napet)(NCS)]·CH(3)CN (3a, T(1/2) = 151 K), [Fe(napet)(NCSe)]·CH(3)CN (3b, T(1/2) = 170 K), [Fe(napet)(NCO)] (3c, T(1/2) = 155 K) and [Fe(napet)(N(3))], which, moreover, exhibits thermal hysteresis (3d, T(1/2)↑ = 122 K, T(1/2)↓ = 117 K). These compounds are the first examples of octahedral iron(III) spin-crossover compounds with the coordinated pseudohalides. We report the structure and magnetic properties of these complexes. The magnetic data of all the compounds were analysed using the spin Hamiltonian formalism including the ZFS term and in the case of spin-crossover, the Ising-like model was also applied.     

1-脱氢松香酰基-3-取代硫脲以及5-(脱羧脱氢松香-4-基)-3-芳氨基- 1H-1,2,4-三唑化合物的合成与生物活性

以广西的优势资源松香为原料, 脱氢松香酸与亚硫酰氯、硫氰化钾分别在回流条件下反应6 h和1.5 h, 得到脱氢松香酰异硫氰酸酯, 产率52%; 然后与胺在加热回流条件下反应1.5 h, 得到11种1-脱氢松香酰基-3-取代硫脲4, 产率63%～94%; 4a～4f 分别与水合肼在搅拌下回流反应3～6 h, 得到6种5-(脱羧脱氢松香-4-基)-3-芳氨基-1H-1,2,4-三唑化合物5, 产率70%～94%; 所有化合物的结构均经IR, 1H NMR, 13C NMR和元素分析确认. 初步生物活性测试表明, 4e, 4f, 4j, 5b对枯草杆菌抑菌率较高, 特别是4j在浓度为50 mg/L时就达到较好效果; 4b, 4h, 4i, 5e在100 mg/L时对大肠杆菌的抑菌效果较好.     

Sequential amination/annulation/aromatization reaction of carbonyl compounds and propargylamine: a new one-pot approach to functionalized pyridines

A general one-pot synthesis of pyridines 4a-t from the reaction of dialkyl acyclic/cyclic ketones 1a-i, methyl, aryl/heteroaryl ketones 1m-r, and aldehydes bearing alpha-hydrogens 1s,t with propargylamine 2 is described. Gold and copper salts are efficient catalysts for the reaction of ketones with 2. The formation of the pyridines 4 is suggested to proceed through the sequential amination of carbonyl compounds followed by regioselective 6-endo-dig cyclization of the N-propargylenamine (N-propargyldienamine) intermediate 3(5) and aromatization reaction. Whereas the preparation of linear polycyclic pyridine 4i can be carried out by reacting cholestan-3-one 1i with 2, the angular polycyclic pyridine 4j has been obtained starting from cholest-5-en-3-one 1j. Selectivity of the reaction of polycyclic dicarbonyls 1k,l with 2 has also been investigated.     

Preparation and structure of (η-cyclopentadienyl)(η-tetraphenylcyclobutadiene) cobalt coordinated by four Cr(CO)3 units at the phenyl rings

The reaction of (η⁵-cyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt (1) with excess Cr(CO)₆ yielded several heterometallic compounds: 2, 3 (3′ and 3″), 4 and 5 with, respectively, one, two, three and four phenyl rings complexed with Cr(CO)₃ fragment(s). These compounds were characterized by mass, infrared, ¹H and ¹³C NMR spectra. The crystal structure of 5 was determined. In 5 the four Cr(CO)₃ fragments are on the same side of the CpCo fragment; whereas, the two Cr(CO)₃ fragments of 3′, the precursor of 5, are pointed in a different direction from the CpCo fragment. The cyclopentadienyl ring shows a static disorder around the axis that passes through the cobalt and the centre of the ring.