环己烯催化氧化产物的气相色谱-红外光谱联用分析

环己烯的催化双氧水氧化产物经气相色谱－红外光谱联用分析为２－环己烯－１－醇、２－环己烯－１－酮及２,３－环氧－１－环己酮３种产物。其中２,３－环氧－１－环己酮是首次检测到的产物,推测为２－环己烯－１－酮的深度氧化产物。     

A multisite molecular mechanism for Baeyer-Villiger oxidations on solid catalysts using environmentally friendly H2O2 as oxidant

The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO2(rutile). The tin active site has been modeled by means of a Sn(OSiH3)3OH cluster, which includes a defect in the framework that provides the flexibility necessary for the interaction between the adsorbates and the Lewis acid center. Two possible reaction pathways have been considered in the computational study, one of them involving the activation of the cyclohexanone carbonyl group by Sn (1) and the other one involving hydrogen peroxide being activated through the formation of a tin-hydroperoxo intermediate (2). Both the quantum-chemical results and the kinetic study indicate that the reaction follows mechanism 1, and that the catalyst active site consists of two centers: the Lewis acid Sn atom to which cyclohexanone has to coordinate, and the oxygen atom of the Sn-OH group that interacts with H2O2 forming a hydrogen bond.     

TS-1分子筛催化双氧水氧化环己烷(英文)

系统地研究了ＴＳ－１分子筛催化双氧水氧化环己烷的反应。制备了三种ＴＳ－１分子筛,它们具有窄的粒径分布,在６０℃表现出高的活性和选择性。考察了溶剂、催化剂、反应温度、反应时间、ＴＳ－１中Ｔｉ含量及Ｈ２Ｏ７用量对氧化反应的影响。对具有完好晶型的ＴＳ－１分子筛役有必要进行预处理。最佳反应温度为８０～１１０℃,丙酮为最佳溶剂。环己酮的选择性与ＴＳ－１粒子大小有关,而Ｈ２Ｏ２选择性与ＴＳ－１用量无关。实验结果显示．溶剂在反应中间体的形成中起重要作用,Ｔｉ与丙酮配体的过氧配合物具有活化环己烷的活性。关键词 ＴＳ－１ 环己烷 催化氧化 Ｈ２Ｏ２     

环己酮氨肟化反应中失活TS-1催化剂上沉积物的物化表征

在液相环己酮氨肟化反应中，有机物在钛硅分子筛催化剂（TS-1）上的沉积是造成失活的原因之一。采用傅里叶变换红外光谱、热重-差热、色谱-质谱联用、X-射线衍射、固体核磁共振、N2物理吸附和扫描电镜等分析手段，对失活TS-1的骨架结构及表面沉积物分子的结构和物化性质进行了表征。结果表明，引起催化剂失活的沉积物富集在分子筛的孔道内，主要有环己酮的氧化或还原产物、环己酮的二聚物、环己酮肟深度反应产物、叔丁基环己酮等可溶性沉积物以及它们缩聚而成的不溶性沉积物，其量可占失活催化剂总质量的5.0%。TPO烧炭时靠近Ti中心处的沉积物可以在较低温度下脱除，而孔道内的其他沉积物需要在较高温度下脱除，650℃沉积的炭可完全脱除。失活催化剂经700℃煅烧再生后，催化活性可恢复到新鲜催化剂的水平。     

用双氧水绿色氧化环己酮合成己二酸的研究

以30%的双氧水为氧化剂, 钨酸钠与含N或O的双齿有机配体(草酸)形成的络合物为催化剂, 在无有机溶剂、无相转移剂的条件下, 研究了环己酮氧化制己二酸的反应. 研究结果表明, 用廉价的草酸为配体, 最佳反应条件为钨酸钠∶草酸∶环己酮∶30%的双氧水的物质的量比为2.0∶3.3∶100∶350, 在92 ℃下反应12 h, 可制得80.6%的己二酸; 用GC-MS跟踪了氧化过程中三种主要物质环己酮、己内酯及己二酸含量随反应时间的变化关系, 提出了其主要氧化机理为环己酮首先经Beayer-Villiger氧化反应生成己内酯, 己内酯进一步氧化成己二酸.     

TS-1催化丙烯环氧化过程中环氧丙烷的开环反应研究

环氧丙烷的开环反应是TS-1催化丙烯环氧化制备环氧丙烷过程的副反应,本文对醇溶剂中开环反应进行了研究,分析了该反应的酸性催化机理,酸性主要来自TS-1与H2O2的相互作用产生的质子酸,醇溶剂能显著增强体系酸性从而加快环氧丙烷的开环反应速度。三种醇按酸性增强程度的顺序为甲醇>异丙醇>仲丁醇。根据反应的Eley-Rideal 机理（吸附态的PO与游离态的醇发生开环反应,表面反应为控制步骤）再考虑各组分在TS-1上的吸附特点提出反应的机理模型。用实验数据进行了回归,得到了令人满意的动力学方程式,实验数据与模型计算值平均偏差小于10％。     

环己酮绿色氧化合成己二酸质谱分析

己二酸是合成尼龙-66的主要原料,同时在低温润滑油、合成纤维、油漆、聚亚胺酯树脂及食品添加剂的制备等方面也有重要用途,目前己二酸的世界年产量估计已达220万吨。工业上已二酸的生产是以环己烷经两步氧化合成,第一步为环己烷在金属离子催化下用氧气氧化为环己醇、环己酮,第二步用浓HNO3氧化环己醇、环己酮制得己二酸。在第二步氧化时由于用了浓HNO3故产生大量的CO、NOx、N2O等有毒气体,其中N2O是比CO2还强310倍的温室气体。在当今普遍提倡绿色化学的时代,如何减少化工生产对环境的污染是当前化学工作者首要解决的任务。过氧化氢是一种理想的清洁氧化剂,其反应的唯一预期副产物是水,反应后处理容易,同时过氧化氢的价格相对低廉,氧化成本低。为此,许多化学工作者对环己酮绿色氧化制剂己二酸已有研究。但环己酮氧化为己二酸的反应产物的研究未见报道,本文报道环己酮氧化为己二酸的12种产物。     

Study on the Ammoximation of Cyclohexanone to Cyclohexanone Oxime Catalyzed by Titanium Silicalite-1 Formed in Inorganic System

The conventional and modified synthesis of titanium silicalite-1 is in the organic system^[1,2]. We have reported the TS-1 could be prepared with colloidal SiO₂ and TiCl₃ as Si source and Ti source respectively in inorganic system^[3]. The present paper deals with the ammoximation of cyclohexanone to cyclohexanone oxime over TS-1 prepared by the method described above. Tests are carried out for 5 hours at 65℃,with NH₃ and H₂O₂ in the liquid phase, acetone as solvent, reactants adding to reactor all at once over these two kinds of TS-1. The results show that oxime yield over TS-1 produced in inorganic system is as good as or better than that catalyzed by conventional TS-1 at the same conditions. More over, more satisfied yield of oxinone could be achieved if it reacts at some optimal reaction conditions^[4,5]. In addition, the same result has been reached at the epoxidation of propylene catalyzed by these two kinds of TS-1 Following table is the results of reaction catalyzed by these two kinds of TS-1.     

Si(001)-(2×2×1):H表面O2吸附的密度泛函理论研究

A novel model was developed to theoretically evaluate the O2 adsorption on H-terminated Si(001)-(2*2*1) surface. The periodic boundary condition, the ultrasoft pseudopotentials technique based on density functional theory (DFT) with generalized gradient approximation (GGA) functional were applied in our ab initio calculations. By analyzing bonding energy on site, the favourable adsorption site was determined. The calculations also predicted that the adsorption products should be Si=O and H2O. This theoretical study supported the reaction mechanism provided by Kovalev et al. The results were also a base for further investigation of some more complex systems such as the oxidation on porous silicon surface.     

Kinetic Studies of Picolinic Acid Catalyzed Chromic Acid Oxidation of Cyclohexanone

The chromic acid oxidation of cyclohexanone catalyzed by picolinic acid in water undergoes a change from first-to zero-order dependence in both cyclohexanone and acidity. The mechanism proposed indicates the formation of an intermediate C₁ by picolinic acid and chromic acid. Then C₁ would react with enol form of cyclohexanone to give another intermediate C₂. C₂ finally cleaves into products.     

钛硅沸石中的一种非活性钛物种

Synthesis of the titanium silicalite TS-1 was first reported by Taramasso et al[1]in 1983. TS-1 has received considerable interest during the last decade because of its unique catalytic properties in oxidation reactions involving H2O2 as the oxidant. It is accepted that the extraframework Ti species in TS-1 favor the decomposition of H2O2and should be avoided. But in the present study, it was observed that there was a kind of Ti species inactive in both the oxidation reaction and the decomposition of H2O2.     

杂原子Sn-β分子筛的脱铝补位两步法制备、表征及其催化环己酮Baeyer-Villiger氧化性能

采用酸处理Al-β脱铝以产生T"空位",再高温焙烧插入Sn,即脱铝补位两步法制备了杂原子Sn-β分子筛.考察了β沸石中T"空位"数量、母体硅铝比和焙烧温度等因素对Sn-β分子筛形成与性能的影响,并利用X射线衍射、红外光谱、紫外-可见光谱、扫描电镜、X射线荧光光谱和电感耦合等离子体原子发射光谱等手段及环己酮Baeyer-Villiger(B-V)氧化反应,对催化剂进行了表征和评价.结果表明,脱铝补位两步法可以制备Sn-β分子筛,且Sn以四配位形式存在于分子筛骨架中,在对环己酮B-V氧化反应中表现出较高的催化活性.     

Efficient catalytic oxidation of alkanes by Lewis acid/[Os(VI)(N)Cl4]- using peroxides as terminal oxidants. Evidence for a metal-based active intermediate

The oxidation of alkanes by various peroxides ((t)BuOOH, H2O2, PhCH2C(CH3)2OOH) is efficiently catalyzed by [Os(VI)(N)Cl4](-)/Lewis acid (FeCl3 or Sc(OTf)3) in CH2Cl2/CH3CO2H to give alcohols and ketones. Oxidations occur rapidly at ambient conditions, and excellent yields and turnover numbers of over 7500 and 1000 can be achieved in the oxidation of cyclohexane with (t)BuOOH and H2O2, respectively. In particular, this catalytic system can utilize PhCH2C(CH3)2OOH (MPPH) efficiently as the terminal oxidant; good yields of cyclohexanol and cyclohexanone (>70%) and MPPOH (>90%) are obtained in the oxidation of cyclohexane. This suggests that the mechanism does not involve alkoxy radicals derived from homolytic cleavage of MPPH but is consistent with heterolytic cleavage of MPPH to produce a metal-based active intermediate. The following evidence also shows that no free alkyl radicals are produced in the catalytic oxidation of alkanes: (1) The product yields and distributions are only slightly affected by the presence of O2. (2) Addition of BrCCl3 does not affect the yields of cyclohexanol and cyclohexanone in the oxidation of cyclohexane. (3) A complete retention of stereochemistry occurs in the hydroxylation of cis- and trans-1,2-dimethylcyclohexane. The proposed mechanism involves initial O-atom transfer from ROOH to [Os(VI)(N)Cl4](-)/Lewis acid to generate [Os(VIII)(N)(O)Cl4](-)/Lewis acid, which then oxidizes alkanes via H-atom abstraction.     

Redox‐Neutral Rhodium‐Catalyzed CH Functionalization of Arylamine N‐Oxides with Diazo Compounds: Primary C(sp3)H/C(sp2)H Activation and Oxygen‐Atom Transfer

An unprecedented rhodium(III)‐catalyzed regioselective redox‐neutral annulation reaction of 1‐naphthylamine N‐oxides with diazo compounds was developed to afford various biologically important 1H‐benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by‐products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp³)? H bond and C(sp²)? H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)‐catalyzed coupling of readily available tertiary aniline N‐oxides with α‐diazomalonates was also developed under external oxidant‐free conditions to access various aminomandelic acid derivatives by an O‐atom‐transfer reaction.     

Redox‐Neutral Rhodium‐Catalyzed C?H Functionalization of Arylamine N‐Oxides with Diazo Compounds: Primary C(sp3)?H/C(sp2)?H Activation and Oxygen‐Atom Transfer

An unprecedented rhodium(III)‐catalyzed regioselective redox‐neutral annulation reaction of 1‐naphthylamine N‐oxides with diazo compounds was developed to afford various biologically important 1H‐benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by‐products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp³) H bond and C(sp²) H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)‐catalyzed coupling of readily available tertiary aniline N‐oxides with α‐diazomalonates was also developed under external oxidant‐free conditions to access various aminomandelic acid derivatives by an O‐atom‐transfer reaction.     

Mechanism of homogeneously and heterogeneously catalysed Meerwein-Ponndorf-Verley-Oppenauer reactions for the racemisation of secondary alcohols

The mechanism of hydrogen transfer from alcohols to ketones, catalysed by lanthanide(III) isopropoxides or zeolite Beta has been studied. For the lanthanide catalysed reactions, (S)-1-phenyl-(1-(2)H(1))ethanol and acetophenone were used as case studies to determine the reaction pathway for the hydrogen transfer. Upon complete racemisation all deuterium was present at the 1-position, indicating that the reaction exclusively takes place via a carbon-to-carbon hydrogen transfer. Zeolite Beta with different Si/Al ratios was applied in the racemisation of (S)-1-phenylethanol. In this case the racemisation does not proceed via an oxidation/reduction pathway but via elimination of the hydroxy group and its re-addition. This mechanism, however, is not characteristic for all racemisation reactions with zeolite Beta. When 4-tert-butyl cyclohexanone is reduced with this catalyst, a classical MPV reaction takes place exclusively. This demonstrates that zeolite Beta has a substrate dependent reaction pathway.     

Reaction mechanism of the ammoximation of ketones catalyzed by TS-1

Summary The liquid-phase adsorption of acetone, butanone, cyclohexanone, 3-methylcyclohexanone and 4-butylcyclohexanone on TS-1 were measured, and the direct ammoximation reactions of these ketones with H₂O₂and NH₃catalyzed by TS-1 were studied. The catalysts after reaction were characterized by TGA. The adsorption results showed that acetone, butanone, cyclohexanone and 3-methylcyclohexanone could enter into the cavity of TS-1, while 4-butylcyclohexanone could not. In the ammoximation reactions, all the ketones were converted into the corresponding oximes in highconversions and selectivities. In combination with the TGA results, it is inferred thatthe ammoximation reactions of acetone and butanone may occur to some extent inside the pores of TS-1. For cyclohexanone and 3-methylcyclohexanone, the ketone-involving step may occur inside the pores of TS-1 to a limited extent but for 4-butylcyclohexanone, may only occur outside the catalyst.</o:p>     

Coverage dependence and hydroperoxyl-mediated pathway of catalytic water formation on Pt (111) surface

Hydrogen oxidation on Pt (111) surface is modeled by density functional theory (DFT). Previous DFT calculations showed too large O2 dissociation barriers, but we find them highly coverage dependent: when the coverage is low, dissociation barriers close to experimental values (approximately 0.3 eV) are obtained. For the whole reaction, a new pathway involving hydroperoxyl (OOH) intermediate is found, with the highest reaction barrier of only approximately 0.4 eV. This may explain the experimental observation of catalytic water formation on Pt (111) surface above the H2O desorption temperature of 170 K, despite that the direct reaction between chemisorbed O and H atoms is a highly activated process with barrier approximately 1 eV as previous calculations showed.     

Water oxidation catalyzed by the tetranuclear Mn complex [Mn(IV)4O5(terpy)4(H2O)2](ClO4)6

The tetranuclear manganese complex [Mn(IV)(4)O(5)(terpy)(4)(H(2)O)(2)](ClO(4))(6) (1; terpy = 2,2':6',2″-terpyridine) gives catalytic water oxidation in aqueous solution, as determined by electrochemistry and GC-MS. Complex 1 also exhibits catalytic water oxidation when adsorbed on kaolin clay, with Ce(IV) as the primary oxidant. The redox intermediates of complex 1 adsorbed on kaolin clay upon addition of Ce(IV) have been characterized by using diffuse reflectance UV/visible and EPR spectroscopy. One of the products in the reaction on kaolin clay is Mn(III), as determined by parallel-mode EPR spectroscopic studies. When 1 is oxidized in aqueous solution with Ce(IV), the reaction intermediates are unstable and decompose to form Mn(II), detected by EPR spectroscopy, and MnO(2). DFT calculations show that the oxygen in the mono-μ-oxo bridge, rather than Mn(IV), is oxidized after an electron is removed from the Mn(IV,IV,IV,IV) tetramer. On the basis of the calculations, the formation of O(2) is proposed to occur by reaction of water with an electrophilic manganese-bound oxyl radical species, (?)O-Mn(2)(IV/IV), produced during the oxidation of the tetramer. This study demonstrates that [Mn(IV)(4)O(5)(terpy)(4)(H(2)O)(2)](ClO(4))(6) may be relevant for understanding the role of the Mn tetramer in photosystem II.     

用H2O2氧化苯乙烯合成苯甲酸

摘要：以30％H2O2做为氧化剂,钨酸钠与含O双齿有机配体(草酸)形成的络合物为催化剂,在无有机溶剂、无相转移剂的条件下,研究了苯乙烯氧化制苯甲酸的反应。研究结果表明,最佳反应条件为：苯乙烯100．0mmol,n(钨酸钠)：n(草酸)：n(苯乙烯)：n(30％H2O2)=2．0：3．2：100．0：440．0,于92℃反应24h,苯甲酸收率98．6％。用GC—MS跟踪了氧化过程中4种主要物质苯乙烯、1-苯基邻二醇、羟基苯乙酮及苯甲酸含量随反应时间的变化关系,提出了其主要氧化机理为苯乙烯经过环氧化反应、水解生成生成1-苯基邻二醇,1-苯基邻二醇再氧化为羟基苯乙酮、最后氧化为苯甲酸。