BiCl3 promoted aza-Prins type cyclization: a rapid and efficient synthesis of 2,4-disubstituted piperidines

Several N-protected homoallyl amines and epoxides were subjected to an aza-Prins cyclization. A rapid and efficient BiCl₃ promoted stereoselective synthesis of trans-2,4-disubstituted piperidine derivatives was achieved.     

Facile catalyzed acylation of heteroatoms using BiCl3 generated in situ from the procatalyst BiOCl and acetyl chloride

Acylation of a variety of alcohols, phenols, aliphatic and aromatic amines, a thiol and a thiophenol proceeds efficiently using BiCl₃ generated in situ from the procatalyst BiOCl and acetyl chloride in a solvent or under solventless conditions, furnishing the corresponding acylated derivatives in very good to excellent yields.     

A facile high-yield solvothermal route to tin phosphide Sn4P3

An effective method of synthesis of tin phosphide Sn₄P₃ starting from metallic tin and amorphous red phosphorus by a low-temperature (200 °C) solvothermal reaction in ethylenediamine is offered. The key parameters of this process - duration, temperature, and the ratio of initial components (Sn/P) are studied. The structure, phase composition, and morphology of the products are investigated using powder X-ray diffraction and scanning electron microscopy. Different synthetic ways for tin phosphide are discussed and compared with the proposed one. The mechanism of solvothermal preparation of tin phosphide in ethylenediamine is discussed. It is shown that the proposed solvothermal method opens up the possibility of preparing other metal-rich phosphides.     

SnCl2-mediated carbonyl allylation in fully aqueous media

Systematic studies were performed on SnCl₂-mediated carbonyl allylation reaction between aldehydes and allyl halides in fully aqueous media. Totally three valuable reaction systems were discovered, which were SnCl₂/CuCl₂, SnCl₂/TiCl₃, and SnCl₂/PdCl₂. They all provided good to excellent yields in the allylation of aliphatic and aromatic aldehydes under very mild and convenient conditions. SnCl₂, by itself, was also found to be effective for the allylation reaction when allyl bromide was employed. However, the SnCl₂-only reaction could only tolerate very small amount of water as the solvent. The SnCl₂/CuCl₂, SnCl₂/TiCl₃, and SnCl₂/PdCl₂-mediated reactions exhibited good regioselectivity favoring the γ-adduct when cinnamyl halides were employed as the allylation reagent. The same reactions with cinnamyl halides also showed good diastereoselectivity favoring the anti-product. Mechanistic studies using proton NMR techniques suggested that the additive (i.e., CuCl₂, TiCl₃, PdCl₂) could accelerate the formation of allyltin intermediate, but this step was shown not to be the most important for the allylation. Thus we proposed that the Lewis acid catalysis effect exerted by the additive was the main reason for the observed reactivity enhancement.     

Highly stereoselective synthesis of peracylated α-aldopyranosyl chlorides from aldopyranose peracetates and thionyl chloride catalyzed by BiCl3 generated in situ from the procatalyst BiOCl

Aldopyranose peracetates react with thionyl chloride and BiCl₃, generated in situ from a substoichiometric amount of the procatalyst BiOCl, producing the corresponding peracylated aldopyranosyl chlorides in very good to excellent yields (82–97%) with exclusive α-anomeric selectivity.     

Synthesis of 3-methyl-2-cyclohexenones catalyzed by mercury(II) salts and their microwave assisted BiCl3 catalyzed aldol condensations

HgSO₄ catalyzed hydrative cyclization of 1,6-heptadiynes is present. This reaction proceeded smoothly under the mild condition for differently 4-sustituted 1,6-diynic substrates giving corresponding 3-methyl-2-cyclohexenones with high to excellent yield. The microwave assisted aldol condensation of cyclohexenones under the catalysis of BiCl₃ afforded 3-styryl-cyclohexenones with high regio- and stereo-selectivity.     

Ring opening of epoxides with alcohols using Fe(Cp)2BF4 as catalyst

Fe(Cp)₂BF₄ is an efficient catalyst for the alcoholysis of aromatic, aliphatic, and cyclic epoxides giving excellent yields of the corresponding β-alkoxy alcohols under ambient conditions. The methanolysis of styrene oxide using Fe(Cp)₂BF₄ as a catalyst (5 mol %) gave excellent yield of 2-methoxy-2-phenylethanol with complete regio-selectivity. The ring opening of cyclic epoxides gave 77–97% yields of trans-β-methoxy alcohols, in 0.5–6 h. The use of 1,2-epoxyhexane and 1,2-epoxydodecane as substrates gave both regioisomers in excellent yields. The first order rate of reaction with respect to catalyst was observed for the kinetics of ring opening of 1,2-epoxyhexane with methanol.     

A highly efficient protocol for regioselective ring-opening of epoxides with alcohols,water, acetic acid,and acetic anhydride catalyzed by SbF3

SbF₃ as an efficient catalyst has been used for regioselective alcoholysis, acetolysis and hydrolysis of epoxides to the corresponding β-alkoxy, β-acetoxy alcohols, and 1,2-diols in high to excellent yields. This study also represents a convenient synthesis of vic-diacetates from ring-opening of epoxides with acetic anhydride.     

Synthesis of Gd3PO7:Eu nanospheres via a facile combustion method and optical properties

Eu³⁺-doped Gd₃PO₇ nanospheres with an average diameter of ∼300 nm and a narrow size distribution have been prepared by a facile combustion method and structurally characterized by X-ray diffraction and field emission scanning electron microscopy. The luminescent properties were systemically studied by the measurement of excitation/emission spectra, and emission spectra under different temperatures, as well as by photostability. The strong red-emission intensity peaking at 614 nm originates the ⁵D₀→⁷F₂ transition and is observed under 254-nm irradiation, indicating that Eu³⁺ ions in Gd₃PO₇ mainly occupied non-centrosymmetry sites. The CIE1931 XY chromaticity coordinates of Gd₃PO₇:Eu³⁺ nanospheres are (x=0.654, y=0.345) in the red area, which is near the National Television Standard Committee standard chromaticity coordinates for red. Thus, Gd₃PO₇:Eu³⁺ nanospheres may be potential red-emitting phosphors for PDP and Xe-based mercury-free lamps.     

New chiral cobalt salen complexes containing Lewis acid BF3; a highly reactive and enantioselective catalyst for the hydrolytic kinetic resolution of epoxides

A new type of chiral cobalt salen complexes bearing BF₃ Lewis acid proved to be reactive and enantioselective in the hydrolytic resolution of terminal epoxides. The polymer type salen catalysts also showed a high enantioselectivity in the same reaction.     

BaPbO3与BaTiO3多晶态陶瓷缺陷结构对比

BaPbO，是具有类金属导电特性的钙钛矿结构导电陶瓷，其晶体结构由Ba2＋和O^2-离子紧密堆积形成，pb^4＋离子占据由O^2-离子形成的八面体空隙。BaTiO3同为钙钛矿结构的陶瓷材料，由Ba^2＋和O^2-离子紧密堆积形成，Ti^4＋离子占据由O^2-离子形成的八面体空隙。BaPbO3和BaTiO3的A位离子相同,B位离子都为可变价离子。     

Synthesis of enantiopure azetidines: a route to new β-amino alcohols

β-Amino alcohols possessing an E vinylsilane moiety were cyclized in the presence of N-bromosuccinimide to afford diastereoisomerically pure polyfunctional azetidines. These azetidines were then transformed into enantiopure β-amino alcohols with a Z vinylic bromide moiety.     

Electronic tuning cyclization of aryl-1,4-enediones: AlCl3-mediated Nazarov-type cyclization to synthesize polysubstituted-1-indanones

An electronic tuning Nazarov-type cyclization protocol was proposed for the synthesis of polysubstituted-1-indanones from the readily available starting materials 1,4-enediones. AlCl₃ was highlighted as the most efficient promoter for this reaction.     

An efficient synthesis of silyl ethers of primary alcohols, secondary alcohols, phenols and oximes with a hydrosilane using InBr3 as a catalyst

An efficient method for the preparation of silyl ethers by InBr₃ catalyzed silylation of primary alcohols, secondary alcohols, phenols and oxime with a hydrosilane is described.     

Photoluminescence properties of a novel phosphor, Na3La9O3(BO3)8:RE(RE=Eu,Tb)

The new oxyborate phosphors, Na₃La₉O₃(BO₃)₈:Eu³⁺ (NLBO:Eu) and Na₃La₉O₃(BO₃)₈:Tb³⁺ (NLBO:Tb) were prepared by solid-state reactions. The photoluminescence characteristics under UV excitation were investigated. The dominated emission of Eu³⁺ corresponding to the electric dipole transition ⁵D₀→⁷F₂ is located at 613 nm and bright green luminescence of NLBO:Tb attributed to the transition ⁵D₄→⁷F₅ is centered at 544 nm. The concentration dependence of the emission intensity showed that the optimum doping concentration of Eu and Tb is 30% and 10%, respectively.     

一维纳米Co_3O_4,Ag/Co_3O_4及CuO/Co_3O_4的合成与电催化性能(英文)

采用水热合成法制备了Co3O4及复合Ag/Co3O4、CuO/Co3O4一维纳米产品。用XRD,FE-SEM和TEM手段对产品进行了表征。采用循环伏安法研究了合成产品修饰的玻碳电极在碱性溶液中对对硝基苯酚的电催化还原性能。与裸玻碳电极相比,1mmol·L-1的对硝基苯酚在用Co3O4、特别是CuO/Co3O4修饰的玻碳电极上还原的峰电流明显增大,用Ag/Co3O4(Ag/Co原子比分别为1∶5和2∶5)修饰的玻碳电极催化还原对硝基苯酚时,尽管还原峰电流增大不是太大,但其峰电位明显降低(分别降低0.265和0.371V)。     

A facile,one-pot procedure for the formation of benzimidazoles from esters using DABAL-Me3, an air stable source of AlMe3

A convenient, single-step, efficient synthesis of benzimidazoles from esters and diamines is reported. The methodology uses an air stable form of trimethylaluminum referred to as DABAL-Me₃ and is compatible with a wide range of functional groups, including acid-sensitive protecting groups.     

A new promising phosphor, Na3La2(BO3)3:Ln (Ln=Eu, Tb)

We present an efficient way to search a host for ultraviolet (UV) phosphor from UV nonlinear optical (NLO) materials. With the guidance, Na₃La₂(BO₃)₃ (NLBO), as a promising NLO material with a broad transparency range and high damage threshold, was adopted as a host material for the first time. The lanthanide ions (Tb³⁺ and Eu³⁺)-doped NLBO phosphors have been synthesized by solid-state reaction. Luminescent properties of the Ln-doped (Ln=Tb³⁺, Eu³⁺) sodium lanthanum borate were investigated under UV ray excitation. The emission spectrum was employed to probe the local environments of Eu³⁺ ions in NLBO crystal. For red phosphor, NLBO:Eu, the measured dominating emission peak was at 613 nm, which is attributed to ⁵D₀-⁷F₂ transition of Eu³⁺. The luminescence indicates that the local symmetry of Eu³⁺ in NLBO crystal lattice has no inversion center. Optimum Eu³⁺ concentration of NLBO:Eu³⁺ under UV excitation with 395 nm wavelength is about 30 mol%. The green phosphor, NLBO:Tb, showed bright green emission at 543 with 252 nm excited light. The measured concentration quenching curve demonstrated that the maximum concentration of Tb³⁺ in NLBO was about 20%. The luminescence mechanism of Ln-doped NLBO (Tb³⁺ and Eu³⁺) was analyzed. The relative high quenching concentration was also discussed.     

Syntheses and characterization of two oxoborates, (Pb3O)2(BO3)2MO4 (M=Cr, Mo)

Two oxoborates, (Pb₃O)₂(BO₃)₂MO₄ (M=Cr, Mo), have been prepared by solid-state reactions below 700 °C. Single-crystal XRD analyses showed that the Cr compound crystallizes in the orthorhombic group Pnma with a=6.4160(13) Å, b=11.635(2) Å, c=18.164(4) Å, Z=4 and the Mo analog in the group Cmcm with a=18.446(4) Å, b=6.3557(13) Å, c=11.657(2) Å, Z=4. Both compounds are characterized by one-dimensional chains formed by corner-sharing OPb₄ tetrahedra. BO₃ and CrO₄ (MoO₄) groups are located around the chains to hold them together via Pb–O bonds. The IR spectra further confirmed the presence of BO₃ groups in both structures and UV–vis diffuse reflectance spectra showed band gaps of about 1.8 and 2.9 eV for the Cr and Mo compounds, respectively. Band structure calculations indicated that (Pb₃O)₂(BO₃)₂MoO₄ is a direct semiconductor with the calculated energy gap of about 2.4 eV.     

A fast synthesis for Zintl phase compounds of Na3SbTe3, NaSbTe2 and K3SbTe3 by microwave irradiation

The microwave irradiation technique was used to prepare three Zintl phase compounds Na₃SbTe₃, NaSbTe₂ and K₃SbTe₃. The as-prepared products were analyzed and characterized by XRD, EDX and SEM techniques. Higher microwave oven power and shorter irradiation time are required for the synthesis of Na₃SbTe₃, whereas lower oven power and longer irradiation time are needed for NaSbTe₂. Moderate microwave irradiation conditions facilitate the formation of pure K₃SbTe₃. Pure phase of Na₃SbTe₃ are directly obtained by this technique for the first time. Compared with the traditional high-temperature solid-state synthesis, the microwave reaction required a considerable shortened reaction time for the preparation of the three Zintl compounds. The initial driving force for these reactions originates from the interaction of microwave electric field with alkali metals (Na and K) and Sb powders.