分子内催化硅氢化合物的脱氢偶联反应

通过分子内五配位硅烷和多种取代酚的等摩尔反应，研究了Ｘ－Ｃ６Ｈ４ＯＨ在与硅烷的脱氢缩合反应中的取代基效应。结果表明，它与氟化物催化的这类反应的活性顺序一致，这说明两种体系具有相似的催化机理，本文还比较了两种不同分人五配位硅烷的反应活性，结果表明，其活性上的差异与它们分子内对Ｓｉ的配位程度有关。     

二高氯酸四（2－羟基吡啶）二水合钴的单晶制备及结构分析

２－羟基吡啶（ＨＬ）、Ｔｂ（ＣｌＯ_４）_３·６Ｈ_２Ｏ和Ｃｏ（ＣＨ_３ＣＯＯ）_２·４Ｈ_２Ｏ在乙腈中反应，制备了［Ｃｏ（ＨＬ）_４（Ｈ２Ｏ）_２］（ＣｌＯ_４）_２，并且测定了它的晶体结构。［Ｃｏ（ＨＬ）_４（Ｈ_２Ｏ）_２］（ＣｌＯ_４）_２的晶体为单斜晶系，ｐ２１／ｎ空间群，晶胞参数为α＝０．９３１３（３）ｎｍｂ＝１．１５８６（１）ｎｍ，ｃ＝１．２９８４（２）ｎｍ，β＝９７．２４（２）°。［Ｃｏ（ＨＬ）_４（Ｈ_２Ｏ）_２］￣（２＋）为六配位畸变八面体构型，２－羟基吡啶的氧原子同钴配位。     

新芽前,芽后早期稻田除稗剂MY—100

新芽前、芽后早期稻田除稗剂ＭＹ－１００１理化性质结构式：ＯＮＨ３ＣＯＣＨ３ＣＨ３Ｃ１Ｃ１化学名称（ＩＵＰＡＣ）：３－〔１－（３,５－二氯苯基）－１－甲基乙基〕－２,３－二氢－６－甲基－５－苯基－４Ｈ－１,３－嗪－４－酮通用名：ｏｘａｚｉｃｌｏｍｅｆ...     

光催化氧化法处理活性染料水溶液

在开放的光催化反应器中,以紫外光为光源,ＴｉＯ２ 为催化剂,考察了催化剂用量、反应液的起始质量浓度、反应液的起始ｐＨ 及Ｈ２Ｏ２ 的加入等因素对光催化氧化反应的影响。结果表明,在一定的光强度下,催化剂的投加量存在一最佳范围（２ ～４ ｇ／Ｌ） ;加入Ｈ２Ｏ２ 可加快染料分子的脱色速度,但对染料废水的ＣＯＤｃｒ的去除影响不大。同时,也考察了活性艳黄Ｘ－ ６Ｇ、活性艳蓝Ｘ－ ＢＲ 及活性艳红Ｘ－ ３Ｂ的ＣＯＤｃｒ的去除情况,反应７５ ｍｉｎ ,可以使上述３ 种染料的ＣＯＤｃｒ的去除率均达６０ ％ 以上。     

新试剂2-[2''''-(6''''-取代苯并噻唑)偶氮]-5-二甲氨基苯甲酸的合成及其光度特性的研究

合成了６种２－［２＇－（６’－取代苯并噻唑）偶氮］－５－二甲氨基苯甲酸（６－Ｒ－ＢＴＡＭＢ，其中Ｒ＝ＣＨ３，ＯＣＨ３，Ｃｌ，Ｂｒ，ＣＨ３ＳＯ２，ＮＯ２）新试齐４。初步研究了６－ＣＨ３－ＢＴＡＭＢ与Ｆｅ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）和Ｐｄ（Ⅱ）等离子的络合显色反应的光度特性。     

CaO—SiO2—P2O5—H2O系统中CBC材料的溶胶—凝胶过程研究：I.溶胶的形…

以溶胶－凝胶方法制备ＣａＯ－ＳｉＯ２－Ｐ２Ｏ５－Ｈ２Ｏ系统中ＣＢＣ材料工艺流程为基础，利用ＸＲＤ，ＩＲ及固体核磁共振（＾２９Ｓｉ，＾３１Ｐ－ＮＭＲ）等测试方法研究了溶胶的形成及溶胶－凝胶转变过程中的物相变化及物相间发生的化学反应，结果表明，在多组分溶胶的形成过程，由Ｃａ（ＮＯ３）２．４Ｈ２Ｏ和Ｈ３ＰＯ４反应生成Ｃａ２Ｏ２Ｏ７和Ｃａ１０（ＰＯ４）６（ＯＨ）２（羟基磷灰石，简写为ＯＨＡｐ，下同），两者     

不同引发体系下明胶的接枝改性

本文系统地研究了ＡＩＢＮ，Ｈ_２Ｏ_２－ＦｅＳＯ_４，Ｋ_２Ｓ_２Ｏ_８，Ｈ_２Ｏ_２－抗坏血酸以及Ｃｅ（ＮＨ_４）２（ＮＯ_３）_６等五种引发体系对乙烯基吡咯烷酮在明胶上的接枝共聚反应。并以接枝率、接枝效率和侧链分子量为参数比较了前三种引发体系的引发效果。结果表明乙烯基吡咯烷酮与明胶的接枝共聚反应可在弱酸性水溶液中进行，在强酸性介质中单体严重水解而失去聚合能力。通过选择合适的引发体系，调整反应条件可以控制接枝共聚物的组成。     

固体酸催化合成无毒增塑剂柠檬酸三正丁酯

研究了柠檬酸（２－羟基丙烷三羧酸）与丁醇在固体酸催化作用下合成柠檬酸三正丁酯（２－羟 基丙烷三羧酸三正丁酯）的工艺条件，找到了一种工艺简单、反应时间短、酯化率高的合成方法。 实验结果表明：４种固体酸催化剂对反应的催化活性大小依次为ＨＰＷ（磷钨酸）＞ＦｅＣｌ_３·６Ｈ_２Ｏ＞ ＮＨ_４Ｆｅ（ＳＯ_４）_２ １２Ｈ_２Ｏ＞ＳＯ_４~（２－）／ＺｒＯ_２；ＨＰＷ催化合成柠檬酸三正丁酯的的最佳反应条件为：醇酸摩 尔比５０：１，ＨＰＷ用量３％（以酸质量为基准），反应温度１１０～１６０℃，反应时间４～５ｈ，转化率达 ９８％以上，产品纯度＞９９％。     

聚甲基四苯基苯硅烷的合成及非线性光学性质的研究

在甲苯中，将甲基四苯基苯二氯硅烷与金属钾反应，或甲基四苯基苯二氯硅烷分别与甲基乙烯基二氯硅烷、甲基苯基二氯硅烷、二甲基二氯硅烷和二苯基二氯硅烷按摩尔比１∶１混合，再与金属钾反应，合成了聚硅烷１、２、３、４和５，分别用元素分析、ＩＲ、ＵＶ、１ＨＮＭＲ和ＧＰＣ作了表征，并测得它们的非线性谐波极化率Ｘ（３）的值分别为８．６×１０－１２、７．９×１０－１２、９．１×１０－１２、６．５×１０－１２和９．３×１０－１２ｅｓｕ。     

以氨基羟基琥珀酸为基础的水系统缓蚀剂

９４─０３５以氨基羟基琥珀酸为基础的水系统缓蚀剂用作水系统缓蚀剂的氨基羟基琥珀酸具有通式（Ⅰ）。式中Ｒ＝Ｈ，Ｃ＿（１～６）烷基（常任意取代基），Ｃ＿（４～７）环烷基，或苯基（常任意取代基）；Ｒ￣１＝Ｈ或Ｃ＿（１～６）烷基（常任意ＯＨ或ＣＯ＿２Ｈ取代基...     

硅上取代基对氟化钾催化下取代硅烷酚解反应活性的影响

本文通过色谱定量监测，研究了多种取代硅烷ＲＲ１Ｒ２ＳｉＨ（Ｒ、Ｒ１、Ｒ２分别为Ｈ、Ｍｅ、Ｅｔ、Ｂｕｉ、Ｐｈ和ＥｔＯ）与苯酚，在氟化钾存在下，于相同条件下的反应，定量地表征了Ｓｉ上取代基对其脱氢偶联反应活性的影响。结果表明，Ｓｉ上连有吸电子基团或多个Ｈ原子时有利于反应     

Deoxygenative reduction of organometallic compounds by hydrosilanes — an organometallic approach to reaction mechanisms of catalytic CO hydrogenation

Elementary steps of catalytic CO hydrogenation are reproduced on organometallic systems by using hydrosilane (HSiR₃) as an equivalent for H₂. These transformations are based on the features of hydrosilanes, i.e. (1) the reactivity of the H–Si bond in hydrosilane to that of the H–H bond and (2) the Lewis acidic activation of oxygen-containing functional groups by silyl metal species resulting from oxidative addition of hydrosilane.     

First Example of Monomeric Hydrosilane Stabilized Redispersible Silver Nanoparticles

The direct production of silver nanoparticles in organic media is achieved via a simple one pot protocol using long chain hydrosilanes both as reducing and stabilizing agents. This synthetic strategy leads to highly efficient production of stable yet reactive silver nanoparticles. This synthesis is unique in terms of stabilization mechanism, where a very weak passivation is used to produce dispersible but highly active nanoparticles. The effect of hydrosilane alkyl chain length on the growth mechanism, reactivity, dispersibility and stability of the nanoparticles are also investigated.     

N-Heterocyclic Carbene Iron Silyl Hydride Complexes

Reaction of N-heterocyclic carbene iron(0) tetracarbonyl complexes with hydrosilanes (triphenylsilane, methyldiphenylsilane and diphenylsilane) under UV irradiation (350 nm) afforded the octahedral N-heterocyclic carbene iron(II) silyl hydride complexes in yields up to 95 %, resulting from the oxidative addition of the hydrosilane. Eight iron silyl hydrides were obtained and characterized by NMR and X-ray diffraction analysis. Noticeably, the geometry of the iron-hydride complexes and the bent structures of the carbonyl ligands were rationalized by DFT calculations.     

Second row transition metal sulfides for the hydrotreatment of coal derived naphtha III. Removal of individual nitrogen compounds

The disappearance of individual nitrogen compounds is followed during the hydrotreatment of a coal-derived naphtha containing a mixture of nitrogen-, sulfur- and oxygen-containing heteroatom compounds over bulk second row transition metal sulfides. The naphtha contains mainly three types of nitrogen compounds: pyridines, anilines and quinolines. While quinoline is the least reactive of the three simplest compounds in these compound classes, substituted anilines are the compounds most difficult to remove from the naphtha. The presence or absence of an alkyl substituent exerts a strong influence on the reactivity of individual compounds and can over-shadow the differences between compound types. The reactivity patterns of the methyl-substituted pyridines indicate a steric hindrance about the nitrogen atom. The order of reactivity between alkyl-substituted anilines is different over the various sulfides with steric hindrance about the nitrogen atom indicated for only the higher activity catalysts. Except for molybdenum sulfide, the reactivity of quinoline is less than or equal to that of methyl-substituted quinolines. The individual nitrogen compounds do not disappear according to a first order rate expression but indicate strong product inhibition of the reaction rate. The overall removal of nitrogen does not follow simple first, zero or second order kinetics and shows similar kinetic behavior as for the disappearance of individual nitrogen compounds.     

Oligomer and Polymer Formation in Hexamethylcyclotrisiloxane (D<Subscript>3</Subscript>) – Hydrosilane Systems Under Catalysis by tris(pentafluorophenyl)borane

Summary Reactions of hexamethylcyclotrisiloxane, D₃, with 1,1,3,3-tetramethyldisiloxane, ^HMM^H, 1,1,1,3,3-pentamethyldisiloxane, ^HMM, phenyldimethylsilane and phenylmethylsilane catalyzed by tris(pentafluorophenyl)borane were studied. These reactions lead to ring opening of D₃ by the SiH reactant producing open chain oligomers with hydrosilane functionality at one or both chain ends. The reactivity of the hydrosilanes toward D₃ decreases in the series: PhMeSiH₂ > ^HMM^H > PhMe₂SiH > ^HMM. Competitive self-oligomerization of ^HMM^H and ^HMM also occurs. Primary products of these processes are able to enter into reactions with the SiH and D₃ reactants; some also undergo cyclization. Thus, consecutive and competitive processes lead to a series of various oligohomologues. Gas chromatography in conjunction with chemical ionization mass spectroscopy permitted identification of structure and determination of the basic directions of these oligomerization processes. Polysiloxanes of higher molecular weight may be also formed in some of these systems. The reactions, which occur in the systems studied, are rationalized on the basis of the mechanism involving the hydride transfer from silicon to trivalent boron. This includes the transient formation of tertiary trisilyloxonium borate which decomposes by the hydride transfer to one of the silicon atoms of the trisilyloxonium center. Footnote: This paper is dedicated to Professor Ian Manners in recognition of his significant contributions to the field of organometallic polymers.     

Hydrodechlorination of para-substituted chlorobenzenes over a ruthenium/carbon catalyst

The hydrodechlorination (HDC) of chlorobenzene (abbreviated as CLB) and seven types of para-substituted chlorobenzenes (para-amino, -methoxy, -methyl, -chloro, -trifluoromethyl, -acetyl and -cyano: abbreviated as CLAN, CLAS, CLTN, DCLB, CLTF, CLAP and CLBN, respectively) were performed over 5%-ruthenium/carbon (Ru/C) under a hydrogen pressure of 0.5–1.5 MPa at 523 K.In the HDC of these model compounds, except for CLAP and CLBN, reductive cleavage between the carbon and chlorine atoms took place and dechlorinated compounds were produced preferentially. In the reaction of CLAP and CLBN, on the other hand, hydrogenation and/or hydrogenolysis of the substituent coincided with the HDC and a wide variety of products was observed accompanying the HDC product.For the chlorobenzenes of the simple HDC, the HDC reaction rate constants decreased in the orders of CLAN  CLB ≈ CLTN ≈ CLAS and CLB > DCLB  CLTF, respectively.In the reaction of the chlorobenzenes of the electron-donating substituent, the reaction constant (ln k/k₀) has no relevance to the Hammett substituent constant (). In the case of the chlorobenzenes possessing the electron-withdrawing substituent, on the other hand, it was indicated that the electron-withdrawing substituent suppressed the HDC reactivity of chlorobenzenes, although no proportional relationship was observed between the reaction rate constant and the Hammett substituent constant.To explore the factors affecting the HDC reactivity, quantum calculation according to the DFT method (B3LYP/LANL2DZ) was applied to the “chlorobenzenes-Ru₁₀” complex. As a result of the calculation, chlorobenzenes were adsorbed through a chlorine atom on the edge atom of the Ru₁₀ cluster. The magnitude of the adsorption energy, moreover, decreased in the order of CLAN > CLAS ≈ CLB ≈ CLTN and CLB > DCLB > CLTF, respectively. These orders of adsorption energy are similar to that of the HDC reaction rate constant. It was concluded that adsorption energy is a useful parameter for the reactivity index of the HDC.     

酚醛树脂用生物油反应活性的测试与分析

生物油的反应活性是制备生物油-PF(酚醛树脂)的关键因素。首先利用酚单体取代基共轭效益参数(Rc)评价了生物油中主要酚类物质的理论反应活性,然后测定了生物油/甲醛的实际反应能力,并与苯酚/甲醛的反应能力进行了对比,以此来评价生物油的整体反应活性。结果表明:生物油中酚类物质的理论反应活性为苯酚的29%;在10 g生物油中加入2.0 g NaOH,并且当反应温度为80℃和反应时间为90 min时,生物油的实际反应能力是苯酚的31%左右。     

Substituent effect on the oxidation of azaferrocene studied by 1H NMR and 57Fe Mössbauer spectroscopy

The substituent effect on the oxidation site of azaferrocene was studied by using ¹H NMR and ⁵⁷Fe Mössbauer spectroscopy. An introduction of methyl substituent to the cyclopentadienyl ring promotes the oxidation of the central iron atom of azaferrocene more than the nitrogen atom in pyrrole ring, which is contrary to the introduction of methyl substituent to the pyrrole ring. Broadening and shift of NMR signals were observed by successive adding of iodine into the 1^′,2,2^′,3^′,4^′,5,5^′-heptamethylazaferrocene and then narrowing was observed by further adding of iodine, suggesting a structural change by iodine oxidation.     

Competitive silylation of olefins with vinylsilanes and hydrosilanes photocatalyzed by iron carbonyl complexes

Fe(CO)₅ appeared to be a good catalyst for competitive silylation of olefins (vinylsilanes, styrene) by vinylsilanes and hydrosilane (e.g. Et₃SiH). The catalytic measurements for Fe(CO)₅+ Et₃SiH system and a stoichiometric study on the insertion of olefin into Fe–Si bond in CpFe(CO)SiMe₃ confirm the mechanism of catalysis involving the first reported β-silyl transfer (from carbon of β-silylethyliron) to iron atom accompanied by dehydrogenative silylation of the olefin.