Reaction of α,β‐unsaturated ketones using cerium (IV) sulfate tetrahydrate in acetic acid

The reaction of α,β‐unsaturated ketones with cerium (IV) sulfate tetrahydrate [Ce(SO₄)₂·4H₂O, CS] in acetic acid gave the corresponding β‐acetoxy ketones. In the case of 2‐cyclohexen‐1‐one with CS in acetic acid, benzobicyclo[2.2.2]octen‐2‐one was obtained. The reaction mechanism also was proposed. Moreover, we report the aromatization and esterification of (R)‐(?)‐carvone by CS in acetic acid. Copyright © 2007 John Wiley & Sons, Ltd.     

Preparative conversion of oximes to parent carbonyl compounds by cerium(IV) sulfate in acetonitrile and alcohol

A new method for the direct conversion of oximes into aldehydes and ketones by treatment with cerium(IV) salts is described. Cerium(IV) salts can be used as an effective and mild oxidizing agent for the regeneration of carbonyl compounds from oximes in good yield. The solvent effects are discussed. Copyright © 1999 John Wiley & Sons, Ltd.     

Cerium(IV) sulfate tetrahydrate: a catalytic and highly chemoselective deprotection of THP,MOM, and BOM ethers

Tetrahydropyranyl (THP), methoxymethyl (MOM), and benzyloxymethyl (BOM) phenyl/alkyl ethers were efficiently cleaved to the corresponding parent hydroxyl compounds in good yields using catalytic amounts of Ce(SO₄)₂·4H₂O by microwave-assisted or conventional heating in methanol solution. Intramolecular and competitive experiments demonstrated the chemoselective deprotection of THP ethers in the presence of triisopropylsilyl (TIPS) and tert-butyldiphenylsilyl (TBDPS) phenyl ethers.     

硫酸高铈催化炔烃的水合反应研究

炔烃经水合反应生成酮是有机合成中最重要和最基本的进行官能团转换的方法之一. 我们提供了一种价廉且具有高选择性的硫酸高铈催化炔烃水合方法. 实验结果表明: 在硫酸高铈(0.1 mmol)、浓硫酸(0.06 mL)、水(0.02 mL)和苯(5 mL)且反应温度为70 ℃的反应条件下, 炔烃(1 mmol)可以顺利发生水合反应生成酮.     

Facile synthesis of 1-(arylimino)naphthalen-2(1H)-ones from anilines and 2-naphthols promoted by NaBr/K2S2O8/CAN

An efficient method has been developed for the synthesis of 1-(arylimino)naphthalen-2(1H)-ones through the cascade reaction of anilines and 2-naphthols promoted by NaBr/K₂S₂O₈/Ce(NH₄)₂(NO₃)₆. Using this protocol, a series of 1-(arylimino)naphthalen-2(1H)-ones was obtained in good to excellent yields (17 examples, 70–92% yields). The reactions may proceed through the following steps: bromination of 2-naphthols by in-situ-generated bromine from NaBr and K₂S₂O₈ to afford 1-bromonaphthalen-2-ols, coupling of 1-bromonaphthalen-2-ols with anilines to afford the corresponding amines, and subsequent oxidation of the amines into the products by Ce(NH₄)₂(NO₃)_6. These newly obtained α-imine ketones have great potentials for synthesis of special optical materials bearing naphthalene moiety.     

New Borate‐citrate: Synthesis,Structure, and Properties of Sr[B(C6H5O7)2](H2O)4·3H2O

Single crystals of Sr[B(C₆H₅O₇)₂](H₂O)₄ · 3H₂O, a new borate‐citrate material, were grown with sizes up to 8 × 6 × 2 mm by slow evaporation of water at room temperature. The structure of Sr[B(C₆H₅O₇)₂](H₂O)₄ · 3H₂O was determined by single‐crystal X‐ray diffraction. It crystallizes in the monoclinic space group P2₁/c, with a = 11.363(3) Å, b = 18.829(4) Å, c = 11.976(3) Å, β = 110.736(3)°, and Z = 4. The SrO₈ dodecahedra, BO₄ tetrahedra and citrate groups are linked together to form chains. The compound was characterized by IR and UV/Vis/NIR transmittance spectroscopy as well as thermal analysis.     

Einkristalle des Cer(IV)–Oxotellurats(IV) CeTe2O6

Single Crystals of the Cerium(IV) Oxotellurate(IV) CeTe₂O₆ Orange‐red, coffin‐shaped single crystals of CeTe₂O₆ (monoclinic, P2₁/n; a = 703.71(5), b = 1106.32(8), c = 735.24(5) pm, β = 108.066(6)°; Z = 4) were obtained by the reaction of admixtures of cerium dioxide and tellurium dioxide (CeO₂, TeO₂; molar ratio 1 : 2) in the presence of fluxing CsCl (750 °C, 4 d) in evacuated silica tubes. The crystal structure contains eightfold coordinated Ce⁴⁺ cations, which are surrounded by irregular trigonal dodecahedra of oxygen atoms. The interconnection of these [CeO₈] polyhedra occurs via two edges (O2–O2′ and O3–O3′) with equatorial orientation relative to each other forming zigzag chains {[CeO_4/1O_4/2]^8–} which run parallel to [100] and arrange as a hexagonal packing of rods. Both crystallographically different Te⁴⁺ cations exhibit trigonal non‐planar coordination figures (ψ¹ tetrahedra) with three oxygen atoms each as a result of the stereochemical activity of the non‐binding electron pairs (“lone pairs”). They also are responsible for the necessary cross‐linkage of the anionic {[CeO₆]^8–} chains. The isotypical relationship with Ce(SeO₃)₂ therefore justifies the formulation Ce(TeO₃)₂ for CeTe₂O₆.     

Oxidation of alcohols using cerium(IV) alkyl phosphonate modified silica

The oxidation of a range of alcohols to ketones or carboxylic acids proceeds in good yield using catalytic quantities of cerium(IV) phosphonate modified silica and sodium bromate as the re-oxidant.     

稀土钬及铒钇丙氨酸配合物的量热与热分析研究

合成了两种固态稀土丙氨酸配合物[Ho2(Ala)4(H2O)8]Cl6和[ErY(Ala)4(H2O)8](ClO4)6 (Ala为丙氨酸),用量热和热分析方法研究了这两种配合物的热力学性质.用全自动高精密绝热量热计测定了在78～377 K温区内的低温热容.对于[Ho2(Ala)4(H2O)8]Cl6,在214～255 K温区内发现一固-固相变,其相变温度为235.09 K.对于[ErY(Ala)4(H2O)8](ClO4)6,在99～121 K温区内也发现一固-固相变,其相变温度为115.78 K. [Ho2(Ala)4(H2O)8]Cl6固-固相变焓为3.02 kJ• mol－1,相变熵为12.83 J•K－1•mol－1； [ErY(Ala)4(H2O)8](ClO4)6 固-固相变焓为1.96 kJ•mol－1,相变熵为16.90 J•K－1•mol－1.同时,用TG技术在40～800 ℃温区研究了两配合物的热稳定性.由TG/DTG曲线分析可知, [Ho2(Ala)4(H2O)8]Cl6从80 ℃到479 ℃热分解分两步完成, [ErY(Ala)4(H2O)8](ClO4)6从120 ℃到430 ℃热分解分三步完成.     

Low-Temperature Heat Capacities and Thermodynamic Properties of Hydrated Nickel L-Threonate Ni（C4H7O5）2·2H2O（S）

Low-temperature heat capacities of the compound Ni（C4H7O5）2·2H2O（S） have been measured with an auto- mated adiabatic calorimeter. A thermal decomposition or dehydration occurred in 350--369 K. The temperature, the enthalpy and entropy of the dehydration were determined to be （368.141 ±0.095） K, （18.809±0.088） kJ·mol ^-1 and （51.093±0.239） J·K^-1·mol^-1 respertively. The experimental values of the molar heat capacities in the temperature regions of 78-350 and 368-390 K were fitted to two polynomial equations of heat capacities （Cp,m） with the reduced temperatures （X）, [X=f（T）], by a least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound were calculated on the basis of the fitted polynomials. The smoothed values of the molar heat capacities and fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated with an interval of 5 K.     

搅拌釜中制备草酸铈的团聚尺寸模型研究

以硝酸铈和草酸铵反应生成草酸铈沉淀为研究对象，探讨了搅拌釜中输入功率、溶液过饱和度与产物团聚尺寸之间的变化关系并在团聚和破碎动力学的基础上建立了团聚尺寸模型。根据草酸铈沉淀实验中得到的实验结果求得了一定反应体系浓度下的模型K1，K2和K3值，最后通过－↑LtE,max的模型计算值与实验值，ε--↑LtE的模型曲线与实验曲线的比较初步证明了该模型的实际适用性。     

Neue Halogenochalkogen(IV)‐Säuren: [H3O(Benzo‐18‐Krone‐6)]2[Te2Br10] und [H5O2(Dibenzo‐24‐Krone‐8)]2[Te2Br10]

Novel Halogenochalcogeno(IV) Acids: [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] Systematic studies on halogenochalcogeno(IV) acids containing tellurium and bromine led to the new crystalline phases [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] ( 1 ) and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] ( 2 ). The [Te₂Br₁₀]^2‐ anions consists of two edge‐sharing distorted TeBr₆ octahedra, the oxonium cations are stabilized by crownether. ( 1 ) crystallizes in the monoclinic space group P2₁/n with a = 14.520(5) Å, b = 22.259(6) Å, c = 16.053(5) Å, β = 97.76(3)° and Z = 4, whereas ( 2 ) crystallizes in the triclinic space group with a = 11.005(4) Å, b = 12.103(5) Å, c = 14.951(6) Å, α = 71.61(3)°, β = 69.17(3)°, γ = 68.40(3)° and Z = 1.     

Syntheses and Structures of Na2Mg3(OH)2(SO4)3·4H2O and K2Mg3(OH)2(SO4)3·2H2O

The crystal structures of Na₂Mg₃(OH)₂(SO₄)₃ · 4H₂O and K₂Mg₃(OH)₂(SO₄)₃ · 2H₂O, were determined from conventional laboratory X‐ray powder diffraction data. Synthesis and crystal growth were made by mixing alkali metal sulfate, magnesium sulfate hydrate, and magnesium oxide with small amounts of water followed by heating at 150 °C. The compounds crystallize in space group Cmc2₁ (No. 36) with lattice parameters of a = 19.7351(3), b = 7.2228(2), c = 10.0285(2) Å for the sodium and a = 17.9427(2), b = 7.5184(1), c = 9.7945(1) Å for the potassium sample. The crystal structure consists of a linked MgO₆–SO₄ layered network, where the space between the layers is filled with either potassium (K⁺) or Na⁺‐2H₂O units. The potassium‐bearing structure is isostructural to K₂Co₃(OH)₂(SO₄)₃ · 2(H₂O). The sodium compound has a similar crystal structure, where the bigger potassium ion is replaced by sodium ions and twice as many water molecules. Geometry optimization of the hydrogen positions were made with an empirical energy code.     

Pectin based cerium (IV) and thorium (IV) phosphates as novel hybrid fibrous ion exchangers synthesis,characterization and thermal behaviour

Summary Pectin based cerium (IV) and thorium (IV) phosphates have been synthesized as new phases of hybrid fibrous ion exchangers. Both materials were characterized using X-ray diffraction, infrared (IR) spectra, thermogravimetric analysis (TG), differntial thermogravimetry (DTG), differntial thermal analysis (DTA) and scanning electron microscopy (SEM), as well as the determination of their ion exchange capacity, elution and pH titration. The X-ray study reveals the amorphous nature of the materials, while SEM studies confirm the fibrous nature of the materials. The thermal studies of these materials indicate that both of them are highly stable on heating as they retain about 97% of their ion-exchange capacity (i.e.c.) on heating up to 100°C and about 81% on heating up to 200°C.     

配合物Zn(His)SO4·H2O(s)的低温热容和热力学性质

通过精密自动绝热热量计测定了配合物Zn(His)SO4*H2O(s)在78～390K温区的摩尔热容,由热容曲线得到其起始脱水温度328.90K;用最小二乘法拟合得到摩尔热容(Cp,m)对温度(T)的多项式方程,并在此基础上计算了它的各种热力学函数.此外,研究了其在惰性气氛下的热分解过程.     

17O NMR spectra of some butyltin(IV) acetates

The ¹⁷O NMR spectra of ¹⁷O isotope‐enriched tributyltin(IV) acetate (1) and dibutyltin(IV) diacetate (2) were recorded in various solvents over wide temperature ranges. Only a single ¹⁷O signal was observed for both oxygen atoms of the —COOSn—groups under these experimental conditions, in both non‐coordinating and coordinating solvents. The ¹⁷O NMR spectra of tert‐butyl acetate (3) were obtained for comparison. Copyright © 2002 John Wiley & Sons, Ltd.     

First-principles Calculations of H2O Adsorption Reaction on the GaN（0001） Surface

The adsorption and decomposition of H2O on GaN（0001） surface have been explored employing density functional theory （DFT）. Two distinct adsorption features of H2O on GaN（0001） corresponding to molecular adsorption and H-OH dissociative adsorption are revealed by our calculations. The activities of the surface reactions of H2O on GaN（0001） surface are investigated. For the stepwise processes of H2O decomposition into H2 in gas phase and adsorbed O atom （H2O（g）→H2O（chem）→OH（chem） ＋ H（chem）→2H（chem） ＋ O（chem）→H2（g） ＋ O（chem））, the first and second steps are facile and can even occur at room temperature; while the last two have high barriers and thus are difficult to proceed, especially the fourth step is endothermic. In short, H2O adsorption and decomposition into H2 in gas phase and adsorbed O atom on GaN（0001） surface are exothermic by -43.98 kcal/mol.     

Theoretical investigation of the structures and spectroscopic properties of (H2O4)n (n = 1–4) clusters

Density functional theory and ab initio calculations were performed to elucidate the hydrogen interactions in (H₂O₄)_n (n = 1–4) clusters. The optimized geometries, binding energies, and harmonic vibrational frequencies were predicted at various levels of theory. The trans conformer of the H₂O₄ monomer was predicted to be the most stable structure at the CCSD(T)/aug‐cc‐pVTZ level of theory. The binding energies per H₂O₄ monomer increased in absolute value by 9.0, 10.1, and 11.8 kcal/mol from n = 2 to n = 4 at the MP2/cc‐pVTZ level of theory (after the zero‐point vibrational energy and basis set superposition error corrections). This result implies that the intermolecular hydrogen bonds were stronger in the long‐chain clusters, that is, the formation of the longer chain in the (H₂O₄)_n clusters was more energetically favorable.     

Identification of Saturating Solid Phases in the System Ce2(SO4)3-H2O from the Solubility Data

Saturating solid phases, Ce₂(SO₄)₃·hH₂O, with hydrate numbers h equal to 12, 9, 8, 5, 4 and 2, have been identified by critical evaluation of the solubility data in the system Ce₂(SO₄)₃—H₂O over the temperature range 273–373 K. The results are compared with the respective TG—DTA—DSC and X-ray data. The solubility smoothing equations, transition points and solution enthalpy estimators of the identified hydrates are given. The stable equilibrium solid phases are concluded to be only Ce₂(SO₄)₃·9H₂O at 273–310 K, Ce₂(SO₄)₃·4H₂O at 310–367 K and Ce₂(SO₄)₃·2H₂O at 367–373 K. Divergencies of up to 185% in the reported solubility data are mainly due to a variety of metastable equilibria involved in the close crystallization fields, and incorrect assignments of the saturating solid phases. Since a similar variety of the hydrate numbers exists for the analogous La(III) system, it most probably also occurs for the corresponding Pu(III), Np(III) and U(III) systems. This revised version was published online in July 2006 with corrections to the Cover Date.