O－（3，4－二甲苯基）－苯基－硫代膦酰基氨基异马来酰胺的合成和晶体结构

标题化合物Ｃ_（１８）Ｈ_（１７）Ｎ_２Ｏ_３ＰＳ是Ｏ－芳基苯基硫代膦酰肼与马来酸酐加成后的关环产物，其晶体属于单斜晶系，空间群Ｐ２_１／ｃ，α＝１０．７２６（３），ｂ＝１０．２４８（２），ｃ＝１７．４５４（５）Ａ，　β＝１０４．０１（２）°，Ｍｒ＝３７２．３７，Ｖ＝１８６１．４Ａ３，Ｄｃ＝１．３３ｇ／ｃｍ￣３，Ｚ＝４，μ（ＣｕＫα）＝２４．６８ｃｍ￣（－１），Ｆ（０００）＝７７６，Ｒ＝０．０７０，Ｒｗ＝０．０６７。结构由直接法解出，分子中Ｐ原子与其相邻的Ｓ，Ｏ，Ｎ，Ｃ原子形成变形四面体构型。     

4－氨基－3，5－二甲基－1，2，4－三唑水杨亚胺合铜〔Ⅱ〕配合物合成及其单晶结构

４－氨基－３，５－二甲基－１，２，４－三唑（ＴＺ）与水杨醛缩合形成４－（邻羟苯基亚甲基）－亚胺－３，５－二甲基－１，２，４－三唑Ｓｃｈｉｆｆ碱（ＳＡＴＺ），该Ｓｃｈｉｆｆ碱与Ｃｕ（ＣｌＯ＿４）＿２·６Ｈ＿２Ｏ形成配合物Ｃｕ（ｓａｔｚ）＿２·６Ｈ＿２Ｏ，分子式为Ｃ＿（２２）Ｈ＿（２２）ＣｕＮ＿８Ｏ＿２·６Ｈ＿２Ｏ。经Ｘ射线晶体结构分析表明，晶体属于单斜晶系，空间群Ｐ２＿１／ｃ，Ｚ＝２，α＝８．２０２（１），ｂ＝１９．５６９（４），ｃ＝８．９７２（８）Ａ，β＝１０７．７２°（２），Ｖ＝１３７１．８（５）Ａ３，Ｄｃ＝１．４６ｇ／ｃｍ￣３，μ＝０．８５３ｍｍ￣（－１），Ｆ（０００）＝６３０，Ｒ＝０．０５１，Ｒ＿ｗ＝０．０６２。分子中２个偶氮甲碱（－Ｃ＝Ｎ－）中　　　的Ｎ原子及２个酚氧原子与中心Ｃｕ原子形成规则的菱形平面结构。     

［Mn_2（bzacen）_2（MeOH）_2（μ－4，4′－bipy）］（ClO_4）_2的合成、结构和谱学性质

合成了［Ｍｎ_２（ｂｚａｃｅｎ）_２（ＭｅＯＨ）_２（μ－４，４′－ｂｉｐｙ）］（ＣｌＯ_４）_２化合物，并测定其晶体结构。该晶体属单斜晶系，空间群Ｐ２_１／ｎ，晶胞参数：ａ＝１．３０８２（３）ｎｍ，ｂ＝１．２７１３（３）ｎｍ，ｃ＝１．８００６（５）ｎｍ，β＝１１０．９１（２）°，Ｚ＝２，μ＝５．９７ｃｍ－１，Ｒ＝０．０５８０，ＧＯＦ＝１．６６．在配合物阳离子中，４，４′－联吡啶桥联２个［Ｍｎ（ｂｚａｃｅｎ）（ＭｅＯＨ）］＋，而锰原子具有３个Ｎ原子和３个Ｏ原子形成的扭曲八面体配位构型。红外光谱和拉曼光谱均表明，形成配合物后，ｖ_（Ｃ＝Ｎ）、ｖ（Ｃ＝Ｏ）、和ｖ（Ｃ＝Ｃ）移向低频。红外光谱的１１１０ｃｍ￣（－１）谱带表明ＣｌＯ_４￣－未与Ｍｎ（Ⅲ）配位，８１２ｃｍ￣（－１）振动说明４，４′－ｂｉｐｙ充当桥联二齿配体。拉曼光谱中的４６３ｃｍ￣（－１）和４０１ｃｍ￣（－１）别为Ｍｎ－Ｏ和Ｍｎ－Ｎ的振动带。电子光谱证明存在ｄ－ｄ、ｄ－π和π－π跃迁。电极电位测定显示该配合物Ｍｎ（Ⅲ）的价态是稳定的。     

羰基三核钌簇Ru_3（CO）_9（C_6H_5）_2N_2HCS的合成和晶体结构

本文根道了Ｒｕ_３（ＣＯ）_９（Ｃ_６Ｈ_５）_２Ｎ_２ＨＣＳ的合成及晶体结构，晶体属单斜晶系，空间群Ｐ２_１／ｍ，晶胞参数ａ＝９．６０４（２），ｂ＝１４．２７９（５），ｃ＝９．９８６（１），β＝１０３．４５（１）°，Ｖ＝１３３１．９，Ｍ_ｒ＝７８２．６１，Ｚ＝２，Ｄ_ｘ＝１．９５１ｇ／ｃｍ~３，μ（ＭｏＫα）＝１７．７３ｃｍ~（－１），Ｆ（０００）＝７５４，Ｒ＝０．０３８．（Ｃ_６Ｈ_５）_２Ｎ_２ＨＣＳ通过Ｎ和Ｓ原子与３个钌原子成螯合配位，另外还有九个羰基与之配位。整个分子具有Ｃ_Ｓ对称性。     

混合三烃基锡有机酸酯化合物构效关系 （Ⅰ）二环己基－甲基－2，4－二溴－β－甲基苯氧乙酸锡酯 及二环己基－甲基－2－甲氧基－4－丙烯基苯氧乙酸锡酯的晶体结构和分子结构

报道２，４－Ｂｒ２Ｃ６Ｈ３ＯＣＨ（ＣＮ３）ＣＯ２Ｓｎ（Ｃ６Ｈ１１）２ＣＵ３（１）和２－ＯＣＨ３－４－ＣＨ３ＣＨ＝ＣＨＣ６Ｈ３ＯＣＨ２ＣＯ２Ｓｎ（Ｃ６Ｈ１１）２ＣＨ３（Ｈ２Ｏ）（Ⅱ）的晶体结构和分子结构。（Ⅰ）单斜晶系，空间群Ｐ２１／ｃ，ａ＝１３．０６７（３），ｂ＝１０．５９４（３），ｃ＝１８．１５７（４），β＝１０６．９９（２）°，Ｚ＝４，Ｄｃ＝１．６７２ｇ／ｃｍ３，Ｖ＝２４０３．７３，μ＝４３．７３１ｃｍ－１，Ｍｒ＝６２２．９９，Ｆ（０００）＝１２３２；（Ⅱ）单斜晶系，空间群Ｐ２１／ｎ，ａ＝１０．４０９（１），ｂ＝　１２．５７０（２），ｃ＝２０．６６４（２），β＝８３．５１（１）°，Ｚ＝４，Ｄｃ＝１．２８１ｇ／ｃｍ３，Ｖ＝２６８６．４Ａ３，μ＝９．７６１ｃｍ－１，Ｍｒ＝５３９．２８，Ｆ（０００）＝１１２０．最后的偏离因子，化合物（Ⅰ）Ｒ＝０．０４６，Ｒω＝０．０４６；化合物（Ⅱ）Ｒ＝０．０４９，Ｒω＝０．０４７。晶体结构解析表明，化合物（Ⅰ）和（Ⅱ）中的锡均被配体的３个碳和２个氧原子配位，配位原子呈畸变三角双锥构型；化合物中的环己基均为椅式构象；化合物（Ⅱ）中，配位水分子和另一分子的羰基氧与芳环上的甲基氧?     

Cu（sahm）_2·4H_2O的合成及晶体结构

标题化合物Ｃｕ（ｓａｈｍ）_２·４Ｈ_２Ｏ，Ｃ_（２２）Ｈ_（３０）Ｎ_８Ｏ_（１０），Ｍ_ｒ＝６２９．５（ｓａｈｍ＝４－（邻羟基苯基亚甲基）－亚胺－３．５－二羟甲基－１，２，４－三唑）被合成并得到单晶。Ｘ－衍射结构分析表明，晶体属单斜晶系，空间群Ｐ２_１／ｃ，晶体学数据：ａ＝８．３１８９（８）Ａ，ｂ＝９．８２７（１）Ａ，ｃ＝１６．１２６（２）Ａ，β＝１０２．５８５（９）°，Ｖ＝１２８６．６（３）Ａ~３，Ｚ＝２，Ｄ_ｘ＝１．４８ｇ／ｃｍ~３，μ＝０．９０７ｍｍ（－１），Ｆ（０００）＝５９８。最终偏离因子Ｒ＝０．０４２，Ｒ_ｗ＝０．０５７。结构分析表明，分子中两个偶氮甲碱的Ｎ原子及两个酚氧原子与中心Ｃｕ原子配位，形成规则的菱形平面结构。     

镉－硫氰酸根与铵－苯并15－冠－5配合物的合成与结构研究

用凝胶法生长了标题配合物［ＮＨ_４（Ｂ１５Ｃ５）_２］［Ｃｄ（ＳＣＮ）_３］的晶体，并对其进行了红外光谱，元素分析等各项物理性质的测试。经Ｘ射线单晶结构分析得到了配合物的全部晶体学数据：Ｍ_ｒ＝８４１．３１，正交晶系，空间群Ｐ２_１２_１２_１，晶胞常数ａ＝１０．９７０（３），ｂ＝２１．８３４（３），ｃ＝１５．５６３（４），Ｖ＝３７２７（３），Ｚ＝４，Ｄ_ｘ＝１．５０ｇ／ｃｍ￣３，Ｆ（０００）＝１７３６，μ＝７．０９ｃｍ￣（－１），Ｒ＝０．０７０，Ｒ_ｗ＝０．０６３。结构分析结果表明，配阳离子［ＮＨ_４（Ｂ１５Ｃ５）_２］￣＋和配阴离子［Ｃｄ（ＳＣＮ）_３］￣－间靠静电力结合成配合物。     

（四甲基二硅撑）双（3－三甲硅基环戊二烯基）－四羰基二铁的反应性

标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２／（μ－ＣＯ）_２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ_２Ｃｌ、ＣｌＣＨ_２ＣＯＯＣ_２Ｈ_５和Ｐｈ_３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２Ｒ］_２（Ｒ：ＭｅＣＯ（１），ＰｈＣＯ（２），ＰｈＣＨ_２（３），ＣＨ_２ＣＯＯＣ_２Ｈ_５（４），Ｐｈ_３Ｓｎ（５），Ｉ（６））。Ａ在氯仿中与碘反应，得到Ｆｅ－Ｆｅ断裂的双铁碘化物，但在苯中与过量碘反应，则得到Ｆｅ－Ｉ－Ｆｅ桥联的离子型化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２Ｉ·Ｉ（７）。化合物６的晶体和分子结构经Ｘ射线衍射测定，６属单斜晶系，Ｐ２１／ｃ空间群，ａ＝１．７２１７（４）ｎｍ，ｂ＝０．７７５３（２）ｎｍ，Ｃ＝１．３６２９（７）ｎｍ，β＝１０３．８０（３）°，Ｖ＝１．７６７（２）ｎｍ３，Ｚ＝４，Ｄｃ＝１．６２９９·ｃｍ－１，最终偏差因子Ｒ＝０．０５４。     

大环硫氮冠醚金属配合物的研究──Ⅱ．1，4，10，13－四硫－7，16－二氮杂环十八烷硝酸铜配合物的合成、结构及立体化学

作为系统研究大环硫氮杂冠醚配合物的第二部分，合成了四硫二氮杂环十八冠的硝酸铜配合物［Ｃｕ（Ｃ＿（１２）Ｈ＿（２６）Ｎ＿２Ｓ＿４）］·（ＮＯ＿３）＿２·Ｈ＿２Ｏ，测定了元素分析和红外光谱。利用Ｘ－射线衍射分析方法，测定其晶体结构。晶体学参数ａ＝１７．５７６（４），ｂ＝１１．７５３（３），ｃ＝１０．４８５（５），Ｖ＝２１６３．９（７），Ｚ＝４，Ｄ＿ｃ＝１．６３２ｇ／ｃｍ￣３，Ｆ（０００）＝１１０８，μ＝１．４２ｃｍ￣（－１）（ＭｏＫα），最终偏离因子Ｒ＝０．０３２和Ｒｗ＝０．０３４。晶体测定结果表明：有杂原子组成的四硫二氮大环冠醚比含氧冠醚有更大的柔变性；四硫二氮大环冠醚与Ｃｕ离子配位前后，大环的构象发生了变化。     

等瓣置换反应的研究──手性簇合物［（η~5－MeO_2CC_5H_4）（CO）_2Mo］·［（η~5－MeO_2CC_5H_4）（CO）_2W］Fe（CO）_3（μ_3－S）的分子结构及晶体结构

用Ｘ射线衍射法测定了由η~５－ＭｅＯ_２ＣＣ_５Ｈ_４）（ＣＯ）_３ＭｏＮａ和［（η~５－ＭｅＯ_２ＣＣ_５Ｈ_４）（ＣＯ）_２Ｗ］Ｆｅ－（ＣＯ）_３Ｃｏ（Ｃｏ）_３（μ_３－Ｓ）的等瓣置换反应所生成的手性簇合物──［（η~５－ＭｅＯ_２ＣＣ_５Ｈ_４）（ＣＯ）_２Ｍｏ］－［（η~５－ＭｅＯ_２ＣＣ_５Ｈ_４）（ＣＯ）_２Ｗ］Ｆｅ（ＣＯ）_３（μ_３－Ｓ）的分子结构及晶体结构。晶体属Ｐ１空间群，晶胞参数α＝０．８７１６２（５）ｎｍ，ｂ＝０．７６２１８（４）ｎｍ，ｃ＝１．８７１１１（８）ｎｍ；α＝９４．１６４（４）°，β＝９７．９７９（２）°，γ＝９９．１０８（２）°，Ｚ＝２，μ＝５．９ｃｍ~（－１）。最终的一致性因子Ｒ＝０．０３６，Ｒｗ＝０．０３７．该簇合物含ＭｏＷＦｅＳ四面体簇核，其中Ｍｏ、Ｗ原子以１：１的比例无序地分占了四面体的２个顶点．     

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.