Clean and selective oxidation of alcohols with n-Bu4NHSO5 catalyzed by ionic liquid immobilized TEMPO in ionic liquid [bmim][PF6]

An efficient oxidation of alcohols with tetra-n-butylammonium peroxymonosulfate catalyzed by ionic liquid immobilized TEMPO in ionic liquid [bmim][PF₆] was reported. TEMPO-IL serves as a homogeneous catalyst to enhance the reaction remarkably. The oxidation proceeded to afford aldehydes or ketones in excellent yields and high selectivity without remarkable over-oxidation to carboxylic acids. It is noteworthy to mention that the catalyst and solvent could easily be recycled and reused without loss of activity. A possible mechanism for the oxidation is proposed.     

2,2,6,6-Tetramethyl piperidine-1-oxyl (TEMPO)-mediated catalytic oxidation of benzyl alcohol in acetonitrile and ionic liquid 1-butyl-3-methyl-imidazolium hexafluorophosphate [BMIm][PF6]: Kinetic analysis

TEMPO (2,2,6,6-tetramethyl piperidine-1-oxyl) is electrochemically oxidized to a stable form of the cation (TEMPO⁺) in acetonitrile (CH₃CN) or 1-butyl-3-methyl-imidazolium hexafluorophosphate ([BMIm][PF₆]) media. Cyclic voltammograms were characterized by a well-defined one-electron reversible redox couple in both media at low scan rates. The reduced form of TEMPO⁺ is catalytically regenerated in a follow-up chemical reaction with benzyl alcohol (BA) in the presence of 2,6-lutidine. It was observed that in [BMIm][PF₆], the redox currents are largely suppressed compared to that in CH₃CN. The apparent heterogeneous electron-transfer rate constant () of the quasi-reversible redox reaction of TEMPO was determined at a Pt electrode and found to be 1.9 × 10⁻³ cm s⁻¹ and 4.5 × 10⁻² cm s⁻¹ in [BMIm][PF₆] and CH₃CN, respectively. With the aid of chronoamperometry (CA), the homogeneous rate constant for the catalytic oxidation of benzyl alcohol by TEMPO, in the presence of 2,6-lutidine in CH₃CN was estimated to be 5.53 × 10¹ M⁻¹ s⁻¹ which is approximately double, relative to the value of 2.91 × 10¹ M⁻¹ s⁻¹ determined in [BMIm][PF₆].     

配位离子液体［3（CH3CH2）4N+Cl-·（NH2）2CO］的合成及表征

采用尿素和氯化四乙基铵为原料，合成了一种新型的配位离子液体，并通过红外和X－射线粉末衍射对其结构进行了表征。结果表明，尿素和氯化四乙基铵发生反应，使得原来尿素羰基峰由1690.72cm－1转移到了1619.10cm－1。由X－射线粉末衍射图可以看出，在2θ = 30.37°处有新的衍射峰。通过差热－热重分析，配位离子液体在室温到250℃可以稳定存在，与其他有机溶剂相比具有良好的稳定性。     

TEPA与[MI][C6H2(OH)3COO]复配对小桐子生物柴油抗氧化性的影响

将四乙烯五胺（TEPA）抗氧化剂与[MI][C₆H₂(OH)₃COO]离子液体抗氧化剂进行不同比例复配,旨在研究其抑制金属设备对生物柴油的催化氧化作用以及减轻生物柴油对金属的腐蚀。本文利用Rancimat测定法检测添加复配抗氧化剂前后小桐子生物柴油氧化安定诱导期的变化,研究复配抗氧化剂对小桐子生物柴油的抗氧化性、铜片腐蚀性及铁片腐蚀性、油溶性能的影响。结果表明,复配抗氧化剂可以有效地提高生物柴油的氧化稳定性能,在1∶1复配抗氧化剂添加量为0.01%时,小桐子生物柴油诱导期为11.63h,超过了国家标准（6h）,比小桐子生物柴油的诱导期提高了473%。复配抗氧化剂对生物柴油的铜片腐蚀、铁片腐蚀都有良好的抑制作用,对生物柴油中的Cu²⁺、Fe³⁺的催化氧化也有良好的抑制效果。在TEPA与[MI][C₆H₂(OH)₃COO]复配比例为1∶1、3∶1、5∶1时,5∶1的油溶性能最佳。     

Highly efficient oxidation of organic halides to aldehydes and ketones with H5IO6 in ionic liquid [C12mim][FeCl4]

A simple, mild, and efficient procedure for the oxidation of organic halides to aldehydes and ketones with H₅IO₆ in ionic liquid [C₁₂mim][FeCl₄] has been developed. The oxidation reactions afford the target products in good to high yields and no overoxidation was observed. The products can be separated by a simple extraction with organic solvent, and the catalytic system can be recycled and reused without loss of catalytic activity.     

Stability and activity of cellulase modified with polyethylene glycol (PEG) at different amino groups in the ionic liquid [C2OHmim][OAc]

Polyethylene glycol (PEG), as a suitable tool to improve enzyme stability, such as monomethoxyl-polyethylene glycol aldehyde (mPEG-ALD) and monomethoxyl-polyethylene glycol succinimide (mPEG-SPA), has been appended at the ε-amino group of lysine or the N-terminal α-amino acid residue of commercial cellulase. The modified cellulases thus obtained are designated as Cell-ALD and Cell-SPA, respectively. The stabilities and activities of these modified cellulases have been studied in the ionic liquid [C₂OHmim][OAc]. Cell-ALD showed excellent stability and activity in [C₂OHmim][OAc], such as the activity of Cell-ALD 5k (molecular weight of ALD is 5000), which can reach above 80% of its original value after remaining in [C₂OHmim][OAc] for 24?h, and outstanding performance in the hydrolysis of natural cellulose.     

Extracting Cu(II) from aqueous solutions with hydrophobic room-temperature ionic liquid in the presence of a pyridine-based ionophore to attempt Cu recovery: A laboratory study

Extraction of Cu(II) from neutral aqueous solutions with the hydrophobic room-temperature ionic liquid (IL) N-butyl-N-methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide (BMP-TFSI) in the presence of the pyridine-based ionophore N¹,N¹,N⁴,N⁴-tetrakis(2-(pyridin-2-yl)ethyl)butane-1,4-diamine (C₄N₂Py₄) is demonstrated in this study. Although the distribution coefficients, D_M, of Cu(II) extraction depend on the concentration of Cu(II) in aqueous solutions, all values were higher than 200, indicating extremely high extraction efficiency. Based on spectrophotometric, electrochemical, and X-ray crystallography studies, the coordination number of the C₄N₂Py₄-coordinated Cu(II) ions was determined as 2. The voltammetric behavior of Cu(I), Cu(II), and their C₄N₂Py₄ complex ions were also studied. The recovery of Cu from the IL was conducted by washing the IL phase containing the extracted Cu(II) complex with an acidic aqueous phase or by controlled-potential electrolysis. The IL containing C₄N₂Py₄ was employed for two complete rounds and a decrease in extraction efficiency was only observed when higher concentration of Cu(II) was used.     

固载离子液体［HSO3-BMIM］［HSO4］/SiO2的制备及其催化乙酸乙醇酯化反应的研究

为使离子液体(ILs)在保持催化活性的前提下更易分离回收,减轻ILs的腐蚀,制备了固载ILs,并用于催化酯化反应合成乙酸乙酯(EtAc)。通过红外光谱、热失重、N₂吸附-脱附、扫描电镜等对固载ILs进行表征分析,发现溶胶-凝胶(Sol-Gel)法比浸渍法能更有效地固载ILs于二氧化硅(SiO₂)载体上,在催化乙酸乙醇酯化合成EtAc时催化效果较好。反应条件为酸醇比R⁰_A∶E = 1,反应温度T在323.15~338.15 K范围内,催化剂与乙酸质量比x_cat∶HAc在5%~15%范围内时,Sol-Gel法制备的[HSO₃-BMIM][HSO₄]/SiO₂初始反应速率较快,反应30 min时乙酸转化率(X_HAc)超过50%,达到平衡转化率(68%)的约70%。使用LHHW模型拟合[HSO₃-BMIM][HSO₄]/SiO₂催化酯化反应的速率,结果表明该模型预测准确。重复性考察发现,[HSO₃-BMIM][HSO₄]/SiO₂在前三次使用时的X_HAc (t = 4 h)超过60%,经六次使用后有所下降。使用Sol-Gel法制备的固载ILs的催化活性和稳定性优于浸渍法,表明Sol-Gel法更适合用于制备固载ILs。     

Ionic liquid as reaction medium for the synthesis and crystallization of a metal-organic framework: (BMIM)2[Cd3(BDC)3Br2] (BMIM = 1-butyl-3-methylimidazolium, BDC = 1,4-benzenedicarboxylate)

An ionic liquid, 1-butyl-3-methylimidazolium bromide, is used as reaction medium for the synthesis and crystallization of a coordination polymer, (BMIM)₂[Cd₃(BDC)₃Br ₂] (1) (BMIM = 1-butyl-3-methylimidazolium, BDC =  1,4-benzenedicarboxylate), which forms an anionic two-dimensional framework with the imidazolium cations located between the layers. This compound is thermally stable up to ca. 340 °C and exhibits blue emission in solid state at room temperature. Other characterizations by IR and UV–visible spectra are also described.     

Ionothermal synthesis and characterization of a 3-D (4, 8)-connected porous anionic metal–organic framework entrapped with 1-D [K2(H2O)6] chains

A novel metal–organic coordination polymer, namely, {[K₂(H₂O)₆][Cd₃(1,2,4,5-BTC)₂]}_n (1) (1,2,4,5-BTC = 1,2,4,5-benzenetetracarboxylate), was synthesized in an ionothermal reaction by using an ionic liquid 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) as solvent. Complex 1 features a novel 3-D (4, 8)-connected porous anionic architecture constructed by linking trinuclear Cd subunits with 1,2,4,5-BTC⁴⁻ ligands, which are further filled with 1-D [K₂(H₂O)₆] cationic chains.     

离子液体[C4mim][PF6]与N, N-二甲基甲酰胺二元混合物在298.15 K～318.15 K的密度和粘度

Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate （[C4mim][PF6]） and N, N-dimethylformamide （DMF） binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. It is shown that the viscosities and densities decrease monotonously with temperature and the content of DMF. Various correlation methods including Arrhenius-like equation, Sedclon et al.＇s equation, Redlich-Kister equation with four parameters, and other empirical equations were applied to evaluate these experimental data. A model based on an equation of state Ior estimating the viscosity of mixtures containing ionic liquids were proposed by coupling with the excess Gibbs free energy model of viscosity, which can synchronously calculate the viscosity and the molar volume. The results show that the model gives a deviation of 8.29% for the viscosity, and a deviation of 1.05% for the molar volume when only one temperature-independent adjustable parameter is adopted. The correlation accuracy is further improved when two parameters or one temperature-dependent parameter is used.     

配合物[Ni(IDB)_2][C_6H_4(OH)COO]·ClO_4·CH_3CH_2OH·H_2O催化尿素水解的机理及其电化学性质

报道[Ni(H2O)6](ClO4)2·2H2O的合成、晶体结构,单核镍(Ⅱ)配合物[Ni(IDB)2][C6H4(OH)COO]·ClO4·CH3CH2OH·H2O[配体IDB为N,N 二(2 苯并咪唑亚甲基)胺]的电化学性质,探讨标题配合物催化尿素水解的机理。X射线单晶衍射表明,[Ni(H2O)6](ClO4)2·2H2O晶体属单斜晶系,P2(1)/C空间群,化学式:Cl2H16O16Ni,Mr=401.74,晶胞参数:a=0.62383(12)nm,b=1.2464(3)nm,c=0.91845(18)nm,α=90°,β=106.93(3)°,γ=90°,V=0.6832(2)nm3,Z=2,F(000)=412,S=1.079,DC=1.953g/cm3,μ=1.890mm-1。最终因子R[I>2σ(I)]:R1=0.0423,wR2=0.1155;R(全部数据)∶R1=0.0506,wR2=0.1180。结构分析表明,[Ni(H2O)6](ClO4)2·2H2O的镍(Ⅱ)分别与6个H2O配位形成对称的正八面体构型。循环伏安实验说明,标题配合物在DMF溶液中在E1/2=0.884V处经历了一个准可逆的一电子氧化还原过程。     

A kinetic study of ‘living’ coordination polymerization of propene with the soluble V(acac)3-Al(i-C4H9)2Cl system

The soluble V(acac)₃-Al(i-C₄H₉)₂Cl system initiated living polymerization of propene at ?78°C affording monodisperse polymers ($\text{M}\text{?}{}_{\mathrm{w}}\text{M}\text{?}{}_{\mathrm{n}}\text{= 1.15 ± 0.10}$). A kinetic study (of the living polymerization) was carried out to evaluate the rate coefficients for propagation. The equilibrium constant K_M for a propene monomer coordinated to an active vanadium and the rate constant k_p for a subsequent insertion of coordinated monomer into a living polymer chain were determined and compared with the values for the polymerization of propene with other soluble vanadium-based catalyst systems. The relation between K_M and k_p revealed that a strong interaction between vanadium and propene is unfavourable for the insertion of the coordinated propene into a living polymer chain. The mechanism of an initiation reaction involving alkylation and complexing of V(acac)₃ with Al(i-C₄H₉)₂Cl has been proposed.     

Enantioselective two-phase hydrogenation of α-amino acid precursors with water soluble rhodium complexes of the cationic ligand (S,S)-2,4-bis[bis-(p-N,N,N-trimethylammoniumphenyl)phosphino]pentane, [CH3CH(P(p-C6H4NMe3)2CH2CH(P(p-C6H4NMe3)2CH3]4+

Rhodium complexes of the chiral cationic phosphine, (S,S)-2,4-bis[bis-(p-N,N.N-trimethyl-ammoniumphenyl)phosphino]pentane show excellent enantioselectivity for the hydrogenation of the DOPA precursor. (Z)-3-OMe,4-OAcC₆H₃CHC(COOH)(NHCOCH₃), and dehydro-phenylalanineacetamide as slurries in water. The catalytic reactions may be done in either a two-phase system with the catalyst in the aqueous phase or as a slurry in water provided the substrates have some water solubility. Enantioselectivities of as high as 95% can be obtained.     

磁场对(C4H9NH3)2(CH3NH3)Pb2I7钙钛矿发光特性调控的研究

(C₄H₉NH₃)₂(CH₃NH₃)Pb₂I₇是一种Ruddlesden-Popper相钙钛矿材料,具有层状结构,层间通过van der Waals力结合,因此可以通过机械剥离的方法,获得其二维薄层。二维(C₄H₉NH₃)₂(CH₃NH₃)Pb₂I₇内束缚激子会自发复合从而表现出强的荧光,其圆极化率、峰位均受磁场调控。在外磁场中,荧光圆极化率与磁场呈线性关系,激子中电子和空穴之间的朗德因子差Δg约为0.43。束缚激子在磁场中受抗磁效应影响,致使其发光峰随磁场增加而红移。     

The synthesis and single-crystal X-ray structure of the first mononuclear iridium carbonyl hydride with two orthometallated phosphite ligands,cis-[IrHCO{P(O-o-tBuC6H3) (O-o-tBuC6H4)2}2]

[Ir(μ-OMe)(COD)]₂ reacts with tris-ortho-tert-butylphenylphosphite in the presence of carbon monoxide to give the first example of a mononuclear iridium carbonyl hydride complex with two orthometallated phosphite ligands cis-[IrHCO{P(O-o-^tBuC₆H₃) (O-o-^tBuC₆H₄)₂}₂]. The complex shows great stability even under high pressures of hydrogen and carbon monoxide.     

Copper‐Mediated Tandem C(sp2)–H Sulfenylation and Annulation of Arenes with 2‐Mercaptoimidazoles: Regio‐ and Site‐selective Access to Polycyclic Fused Imidazo[2,1‐b][1,3]thiazinones

An efficient copper‐mediated tandem C(sp²)–H sulfenylation and annulation of arenes with 2‐mercaptoimidazoles to provide polycyclic fused imidazo[2,1‐b][1,3]thiazinones has been developed. This tandem reaction is likely initiated by C(sp²)–H thiolation of benzamide with 2‐mercaptoimidazole followed by intramolecular nucleophilic substitution of the amide carbonyl group. A notable feature of this reaction is that it can afford rather complex products in a single synthesis step from easily accessible starting materials using amide‐oxazoline as a removable bidentate directing group. A variety of benzamides and 2‐mercaptoimidazoles bearing different substituents are compatible with this transformation.

     

Silica-modified magnetite Fe3O4 nanoparticles grafted with sulfamic acid functional groups: an efficient heterogeneous catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-one and tetrahydrobenzo[b]pyran derivatives

Silica-modified magnetite-polyoxometalates functionalized with sulfamic acid groups as hybrid nanoparticles were prepared by sulfonation of diamine-functionalized propyl group grafted on the magnetic silica-coated Fe₃O₄ nanoparticles. This heterogeneous nanocatalyst was explored to present high catalytic performance for the synthesis of 3,4-dihydropyrimidinones and tetrahydrobenzo[b]pyrans under mild reaction conditions. The properties of this nanocatalyst were characterized by FT- infrared, energy-dispersive X-ray spectrum, scanning electron microscope, X-ray diffraction, X-ray fluorescence and elemental analysis. Easy separation of the nanocatalyst by using an external magnet, recyclability, non-toxicity, versatility and high stability of the catalyst combined with low reaction times and excellent yields make the present protocol very useful and attractive for the synthesis of the titled products.     

Mechanistic in situ High‐Pressure NMR Studies of Benzene Hydrogenation by Supramolecular Cluster Catalysis with [(η6‐C6H6)(η6‐C6Me6)2Ru3(μ3‐O)(μ2‐OH)(μ2‐H)2][BF4]

In situ high‐pressure NMR spectroscopy of the hydrogenation of benzene to give cyclohexane, catalysed by the cluster cation [(η⁶‐C₆H₆) (η⁶‐C₆Me₆)₂Ru₃(μ₃‐O)(μ₂‐OH)(μ₂‐H)₂]⁺ 2 , supports a mechanism involving a supramolecular host‐guest complex of the substrate molecule in the hydrophobic pocket of the intact cluster molecule.     

Efficient Access to Conjugated Dienones and Diene‐diones from Propargylic Alcohols and Enolizable Ketones: A Tandem Isomerization/Condensation Process Catalyzed by the Sixteen‐Electron Allyl‐Ruthenium(II) Complex [Ru(η3‐2‐C3H4Me)(CO)(dppf)] [SbF6]

A large variety of conjugated dienones R¹R²CCHCHC(R³)C(O)R⁴ and diene‐diones R¹R²CCHCHC{C(O)R³}C(O)R⁴ have been synthesized in high yields by reacting terminal propargylic alcohols HCCCR¹R²(OH) with enolizable ketones R³CH₂C(O)R⁴ and β‐dicarbonyl compounds R³C(O)CH₂C(O)R⁴, respectively. The process, which is catalyzed by the 16e^‐ (η³‐allyl)‐ruthenium(II ) complex [Ru(η³‐2‐C₃H₄Me)(CO)(dppf)] [SbF₆] associated with CF₃CO₂H, involves the initial isomerization of the propargylic alcohol into the corresponding α,β‐unsaturated aldehyde R¹R²CCHCHO (Meyer–Schuster rearrangement) and subsequent aldol‐type condensation.