三羰基环戊二烯基钼负离子与1，3－二卤丙烷的反应

三羰基环戊二烯基钼负离子与１，３－二卤丙烷在一缩二乙二醇二甲醚介质中反应，生成环卡宾配合物ＣｐＭｏＸ（ＣＯ）＿２ＣＯ（ＣＨ＿２）＿２ＣＨ２（Ｘ＝Ｂｒ，Ｉ）．硅桥连双环戊二烯基三羰基钼负离子与１，３－二卤丙烷顺利地进行类似反应，生成相应的硅桥连双［环卡宾钼配合物］──Ｅ［Ｃ＿５Ｈ＿４ＭｏＸ（ＣＯ）＿２］ＣＯ（ＣＨ＿２）＿２ＣＨ＿２］＿２（Ｅ＝Ｍｅ＿２Ｓｉ，Ｍｅ２ＳｉＳｉＭｅ＿２，Ｍｅ２ＳｉＯＳｉＭｅ＿２）．化合物硅氧硅桥联二茂二钼环卡宾配合物１１的晶体结构经Ｘ射线衍射测定，晶体属三斜晶系，Ｐ１空间群，晶体学数据：ａ＝０．８１８８（１）ｎｍ，ｂ＝１．０４５（３）ｎｍ，ｃ＝２．３２５２（４）ｎｍ，α＝９４．１４（２）°，β＝９４．０９（１）°，γ＝１０２．４８（２）°，Ｖ＝１．９３０６ｎｍ￣３，Ｚ＝２，Ｄ＿ｃ＝１．８５４ｇ／ｃｍ￣３。     

含杂环卡宾碳的铁羰基簇合物的结构化学研究Ⅱ．—Fe_3(CO)_8[:CNHC(S)C(CH_3)_2NH]的合成和晶体结构

Ｆｅ３（ＣＯ）＿（１２）和取代２，４＿二硫代乙内酰脲反应，得到新的取代物Ｆｅ３（ＣＯ）＿８－［：ＣＮＨＣ（Ｓ）Ｃ（ＣＨ＿３）＿２ＮＨ］（μ＿３－Ｓ）＿２，并进行了ＩＲ、１￣ＨＮＭＲ、ＭＳ表征，测定了它的分子和晶体结构，讨论了杂环卡宾碎片：ＣＮＨＣ（Ｓ）Ｃ（ＣＨ＿３）＿２ＮＨ的取代位置，它是通过卡宾碳原子与Ｆｅ配位。     

聚苯乙烯固载聚乙二醇催化环己烯与二氯卡宾的加成反应

本文报道了聚苯乙烯固载聚乙二醇催化环己烯与二氯卡宾的加成反应，考察了聚乙二醇固载前后的催化活性、聚苯乙烯国载聚乙二醇上的聚乙二醇摩尔量、催化剂用量和反应时间等对产品收率的影响，并对催化剂的重复使用活性进行了研究。催化剂首次使用，产品７，７－二氯双环［４，１，０］庚烷的收率为８５．４％。     

微波场中二氯卡宾产生的研究

二氯卡宾是应用最为广泛的活性中间体,早期制备二氯卡宾的方法为氯仿与叔丁醇钾等强碱作用,条件苛刻。一直到1969年Makosza和Wawrzyniewicz的著名论文发表后,用强碱水溶液和相转移催化剂制取二氯卡宾被认为是最简捷的方法。另据文献报道,以聚氧乙烯类表面活性剂作催化剂进行固-液相反应制备二氯卡宾也可获得较理想的结果。但广泛的实     

四氯化碳与镁的反应及其反应机理的研究──产生二氯卡宾的新方法

四氯化碳与镁的反应及其反应机理的研究──产生二氯卡宾的新方法林海霞,徐良衡,黄乃聚（温州师范学院化学系,温州,３２５００３）（复旦大学化学系）关键词二氯卡宾,偕二氯环丙烷衍生物,单电子转移偕二氯环丙烷衍生物是一类重要的有机合成中间体,它主要通过二氯卡...     

开环移位聚合研究进展

关于开环移位聚合（Ｒｉｎｇ－ＯｐｅｎｉｎｇＭｅｔａｔｈｅｓｉｓＰｏｌｙｍｅｒｉｚａｔｉｏｎ,ＲＯＭＰ）的报导,最早始于５０年代末．１９６０年,Ｅｌｅｕｔｅｒｉｏ［１］用ＬｉＡｌＨ４激活的氧化铝催化降冰片烯（Ｎｏｒｂｏｒｎｅｎｅ,ＮＢＥ）、环戊烯的开环...     

含杂环卡宾碳的铁羰基簇合物的结构化学研究Ⅱ.—Fe3（CO）8（：CNH（S）C（…

Ｆｅ３（ＣＯ）１２和取代２，４－二硫代乙内酰脲反应，得到新的取代物Ｆｅ３（ＣＯ）８＾－（：ＣＮＨＣ（Ｓ）Ｃ（ＣＨ３）２ＮＨ（μ３－Ｓ２），并进行了ＩＲ，＾１ＨＮＭＲ，ＭＳ表征，测定了它的分析和晶体结构，讨论了杂环卡宾碎片：ＣＮＨＣ（Ｓ）Ｃ（ＣＨ３）２ＮＨ的取代位置，它是通过卡宾碳原子与Ｆｅ配位。     

卡宾的钨配合物与二氯甲基Wittig试剂的反应

卡宾的过渡金属配合物是一个十分活跃的研究领域,有关它们的制备方法及性质的研究工作正日益引起人们的注意。Burkhardt等发现,卡宾的钨配合物能与Witting试剂反应,生成烷氧基取代烯烃。本文将卡宾的钨配合物进一步用于与二氯甲基Wittig试剂的反应,合成1,1-二氯-2-烷氧基烯烃。众所周知,1,1-二卤代烯烃是一类产生不饱和卡宾的前体化合物。因此,通过对卡宾的钨配合物与二氯代Wittig试剂之间的反应研究,还可以为进一步研究烷氧基取代不饱和卡宾的性质提供方便。     

利用质谱—质谱法进行稠环芳烃化合物的结构解析

应用（ＥＩ）ＭＳ／ＭＳ法研究了吡啶并苯并蒽酮以及苯并苯并蒽酮类异构体的裂解方式及其与结构之间的相关性，探讨了不同异构体中由Ｍ＾ｉ＋产生的［Ｍ－Ｈ］＾＋、［Ｍ－ＨＣＮ］＾＋、［Ｍ－ＣＯＨ］＾＋、［Ｍ－ＣＯ］＾ｉ＋、［Ｍ－（ＣＯ＋２Ｈ）］＾ｉ＋以及［Ｍ－（ＣＯ＋ＨＣＮ）］＾ｉ＋（ｉ＝１，２）等１价及２价离子在ＭＳ／ＭＳ－ＣＩＤ谱上的强度差异和裂解方式，发现是否含有氮原子以及氮原子和苯环位置的差异，是支     

过渡金属卡宾正离子的从头算研究

过渡金属卡宾正离子被认为是如烯烃的聚合和烷基金属的分解过程等许多反应的中间体．较为稳定的环丁烷金属离子和环戊烷金属离子已从相应酮的脱羰反应获得［１］．Ｊａｃｏｂｓｏｎ等［２］研究了ＦｅＣＨ＋２和ＣｏＣＨ＋２与烯烃和环烷烃的气相反应．Ｍｃｋｅｅ［３］在...     

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.