2，6─二甲酸─4─取代苯酚双缩苯甲酰肼双核铜（Ⅱ）配合物的合成与磁性

本文合成并表征了两个新的双核铜（Ⅱ）配合物：〔Ｃｕ２（Ｌ）（μ─Ｃｌ）Ｃｌ２〕，配体Ｌ为２，６─二甲酰─４─甲基苯酚双缩苯甲酰肼，取代基分别为氯（Ｌ１）和叔丁基（Ｌ２）．配合物具有相同的组成和配位构型．变温磁化率（４－３００Ｋ）测定结果表明，由于取代基不同，其磁交换参数分别为－４６．２ｃｍ（－１）（Ｌ１）和－５７．６ｃｍ（－１）（Ｌ２）．     

多核配合物中金属间相互作用的电化学研究：取代三联吡？…

报道了２个取代三联吡啶配体（４′－苯基－２，２′：６′，２″－三联吡啶（Ｌ１）和４′－二茂铁基－２，２′：６′，２″－三联吡啶（Ｌ２）的Ｃｏ（Ⅱ）配合物（Ｃｏ（Ⅱ）（Ｌ１）２）（ＣｌＯ４）２．４ＣＨ３ＣＮ（１）和（Ｃｏ（Ⅱ）（Ｌ２）２）（ＣｌＯ４）２Ｈ２Ｏ（２）的合成及配体Ｌ２的配合物１和配合物２的晶体结构，电化学研究表明：在配合物２中，由于Ｃｏ＾２＋的作用，二茂铁基的氧化电位较配体Ｌ２中的二茂铁     

Mn（Ⅲ）—苯甲酰丙酮缩乙二胺—有机碱配合物的合成及结构

合成了４种锰（Ⅲ）－苯甲酰丙酮缩乙二胺－有机碱配合物：Ｍｎ（ｂｚａｃｅｎ）ＬＣｌＯ４．（Ｌ为哌嗪，吡啶，γ－甲基吡啶和乙腈）。测定了配合物［Ｍｎ（ｂｚａｃｅｎ）（ＣＨ３ＣＮ）ＣｌＯ４］的结构，晶体属正交晶系。空间群Ｐｎｍａ。晶胞参数：ａ＝０．９０７７（１），ｂ＝１．５５６３（１）ｎｍ，ｃ＝１．７２０５（２）ｎｍ，Ｖ＝２．４３０５ｎｍ＾３，Ｚ＝４，Ｄｃ＝１．４８ｇ／ｃｍ＾３，Ｄｍ＝１．４９ｇ／ｃｍ＾     

1，2－亚丙基双（草酰胺根）桥联的线性三核铜（Ⅱ）配合物的合成与磁性

本文合成和表征了四种新的三核铜（Ⅱ）配合物｛［Ｃｕ（Ｌ）］２［Ｃｕ（ＣＨ３－ｅｂｏ）］｝（ＣｌＯ４）２（ＣＨ３ｅｂｏ表示１，２－亚丙基双（草酰胺根），Ｌ表示１，１０－菲咯啉（ｐｈｅｎ）（１），５－硝基－１，１０－菲咯琳（ＮＯ２－ｐｈｅｍ）（２），２，２’－联吡啶（ｂｐｙ）（３）和４，４’－二甲基－２，２’－联吡啶（Ｍｅ２ｐｙ）（４））．测定了四种配合物的变温磁化率（７７－３００Ｋ），求得交换参数分别为Ｊ１＝－２１９．６ｃｍ－１，Ｊ２＝－１９１．７ｃｍ－１，Ｊ３＝－２００．８ｃｍ－１，Ｊ４＝－１８５．５ｃｍ－１，表明Ｃｕ（Ⅱ）－Ｃｕ（Ⅱ）离子间存在着强的反铁磁交换相互作用．     

双臂套索冠醚双核铜（II）配合物的磁性质研究

测定了双臂套索冠醚双核铜（Ⅱ）配合物［Ｃｕ２Ｌ（ＯＨ）］（ＣｌＯ４）３Ｍｅ２ＣＯ（Ｌ－Ｎ，Ｎ＇－二（８－喹啉甲基）－１，４，１０，１３－四氧－７，１６－二氮环八环）的变温磁化率（４￣３００Ｋ），所加场强为５．０×１０＾５Ａ／ｍ，拟合了变温磁化率数据，得到Ｊ＝－２７９．４ｃｍ＾－２；加上分子场校正后，得Ｊ＝－２５７．７ｃｍ＾－１，Ｚｊ＇＝－３０．１ｃｍ＾－１。拟合结果表明，分子间存在反铁磁性交换作用     

用钼酸盐和罗丹明B连续光度法测定铈和钪

聚乙烯醇存在下，铈或钪钼杂多酸与罗丹明Ｂ（ＲＢ）形成离子缔合物，最大吸收均位于５７０ｎｍ，摩尔吸光系数分别为１．１６×１０＾６和５．６２×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，ｃｍ＾－１，０－１．２μｇ／２５ｍＬＣｅ和０－２．０μｇ／ｍＬＳｃ服从比耳定律，检测限１．５ｎｇ／ｍＬＣｅ（ｎ＝１０）和１．１ｎｇ／ｍＬＳｃ（ｎ＝９）。缔合物的摩尔比为Ｃｅ：ｍＯ：ＲＢ＝１：６：３和 Ｓｃ：Ｍｏ：ＲＢ＝１：１     

新试剂（MSBTAMB）双波长光度法测定微量铜（II）的研究

研究了新试剂２－〔２＇－（６＇－甲磺酰－苯并噻唑）偶氮〕－５－二甲氨基苯甲酸（ＭＳＢＴＡＭＢ）与铜（Ⅱ）的显色反应。试验表明，在ｐＨ２．０￣５．１和４０％乙醇介质中，Ｃｕ（Ⅱ）与ＭＳＢＴＡＭＢ形成１＋１稳定的配合物，其最大吸收波长为６４２ｎｍ，用单波长法测得配合物的Σ６４２＝６．７４×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，双波长法测得的Σ６４２．５４６＝１．０９×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－     

具有不同类型桥基的双核Cu（Ⅱ）—Schiff碱配合物的合成 …

合成了３个分别以Ｃ２Ｏ＾２－４（「Ｃｕ２（Ｌ１）２（ｏｘ）」，１），ＡｃＯ＾－（「Ｃｕ２（ＡｃＯ）（Ｌ２）２」ＢＦ４，２）和酚氧（「Ｃｕ２９Ｌ３０２」（ＣｌＯ４）２，３）为桥基的双核铜配合物，并测定了１的复配合物「Ｃｕ２（Ｌ１）２（ｏｘ）」「Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４」ＣｌＯ４．Ｈ２Ｏ及２和３的晶体结构。     

对称三唑Schiff碱与铜的配合物合成及性能

合成了４种新型对称三唑水杨醛Ｓｃｈｉｆ碱的铜配合物［ＣｕＬ１Ｃｌ２］（Ⅰ）和三核配合物［Ｃｕ３（Ｌ２－Ｌ４）２Ｃｌ４］·ｎＨ２Ｏ（Ⅱ～Ⅳ），其中Ｌ１，Ｌ２，Ｌ３和Ｌ４分别为４－氨基－１，２，４－三唑、４－氨基－３，５－二甲基－１，２，４－三唑、４－氨基－３，５－二乙基－１，２，４－三唑和４－氨基－３，５－二羟甲基－１，２，４－三唑的水杨醛Ｓｃｈｉｆｆ碱．经元素分析、电导、红外光谱、热重分析、电子光谱、ＥＳＲ和变温磁化率表征，该类配合物为畸变四方构型．配合物Ⅱ的变温磁化率表明，铜离子间存在弱的反铁磁相互作用，Ｊ＝－１８．９ｃｍ－１，ｇ＝２．０８，Ｆ＝２．７×１０－３．配合物对Ｂ细胞增殖有抑制作用．     

Grignard试剂同6,6—二烷基富烯反应的研究

烯丙基卤化镁和环戊二烯基溴化镁同６，６－二烷基富烯分别进行富烯环外双键的加成和还原反庆，生成的取代环戊二烯基负离子用（ＣｐＴｉＣｌ２）２Ｏ（Ｃｐ＝环戊二烯基）或ＴｉＣｌ４配合，合成式为Ｃｐ（Ｃ６Ｈ４－ＣＲＲ＾１－ＣＨ２Ｃｈ－ＣＨ２）ＴｉＣｌ２和（Ｃ６Ｈ４ＣＨＲＲ＾１）２ＴｉＣｌ２的化合物，对烯丙基卤化镁、环戊二烯基溴化镁同富烯的反应机理进行了探讨。     

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%.     

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.     

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.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.