A new approach to the synthesis of α-chlorocycloalkanones

α-Chlorocycloalkanones(Ⅳ) were synthesized from cycloalkanones via potassiumα-oxocycloalkylsulfonates(Ⅱ).A two-step mechanism was proposed to explain the formation ofⅣfromⅡ.     

Iron-catalyzed ketonization of 2-aryl-1,1-dibromoalkenes with KOAc:Synthesis of α-acetoxy aryl ketones via a Michael-like addition process

A novel and convenient iron-catalyzed ketonization of 2-aryl-1,1-dibromoalkenes with KOAc has been achieved.A series ofα-acetoxy aryl ketones were prepared with moderate yields via 2-carbon position functionalization of 2-aryl-1,1-dibromoalkenes.     

A three-component one-pot synthesis of 2-alkoxy-4-amino-N- arylthiazole-5-carboxamides

A facile and efficient protocol was developed to access 2-alkoxy-4-amino-N-arylthiazole-5-carboxamides through a three-component one-pot reaction, which involved potassium methyl cyanimidodithiocarbonate, 2-halo-N-arylacetamides and alcohols. The easy availability and the broad structural diversity of substrates make the reaction useful for the construction of libraries in drug discovery.     

Diastereoselective α—Alkylation of β—Amino Esters：Preparation of Novel α—Substituted β—Amino Esers from α—Amino Acids

Enantiomerically pure α-substituted β-amino esters were prepared from natural L-α-amino acids through Arndt-Eistert homologation and diastereoselective α-alkylation.     

KINETICS AND MECHANISM OF PHOTOINDUCED POLYMERIZATION BY α,α-DIMETHOXY-α-PHENYL ACETOPHENONE

α,α-dimethoxy-α-Phenyl acetophenone (DMPA) is an efficient and thermally stable photoinitiator. Here its spectral characteristics in the transient state were shown. The transient species were identified as a benzoyl radical and a dimethoxyi benzyl radical that played a primary initiation role in polymerization. The kinetics and mechanism of the bulk polymerization of MMA were investigated. The exponent of DMPA concentration and k_p/k_1~(1/2) value were found to be 0.5 and 0.066 mol(-1/2)l~(1/2)s~(-1/2), respectively. The existence of oxygen led to obtain the polymer with higher molecular weight, which can be attributed to the occurrence of the subsequent polymerization induced by active polymer end group. In the photocrosslinking reaction, the dependence of DMPA content on initial rate has been found. A principal reason is that the sample contained higher percentage of DMPA has higher light-absorbed efficiency. In solid film, higher concentration of DMPA is permitted to be used because there is little excited state self-quenching effect in the rigid medium.     

Chiral Phosphine Ligands Derived from Sugars8. Crystal and Molecular Structure of Diphenyl (methyl 4', 6'-O-benzylidene-2'-deoxy-α-D-altropyranoside-2-)phosphine Oxide

1INTRODUCTIONChiralphosphinesareusefulligandsinenantioselectivecatalysiswithtransitionmetalcomplexes"',someofthemderivedfromsugarsarealsoofPOtentialapplicationsinbiphasiccatalysis"'andmedicinet3i.Bythenucleophilicreplacementreaction,itisdifficulttolinkthephosphorusatomtothesecondarycarbonofpyrano--,orfurano--sugarderivativesbecauseofthecompetingeliminationreaction[4i.Wehavefoundaneffectivemethodtoincorporateaphosphorusintoapyranosering"',viaregioselectiveandstereospecificring--openingreac…     

高效液相色谱法测定啤酒花及其制品中的α-酸、β-酸和异α-酸

1引言a-酸、B-酸及异a-酸是啤酒苦味酸的主要成分,它们的分析是啤酒花及其制品质量评价及控制的主要内容,国内主要使用光度法和电导滴定法分析,这两种方法因存在许多问题而影响测定结果,因此,国外近年已逐渐用高效液相色谱法（HPIn）分析啤酒、啤酒花及各种啤酒花制品的a一酸、卢一酸及异o一酸。我们在研究啤酒花制品时需要同时分析a一酸、卢·酸及异a一酸,但是已有的HPIn法仅可以同时测定a·酸和公酸,而异a一酸是单独分析的,只有在梯度洗脱和较高的柱温时可以同时测定三者,这就限制了它的推广应用。本文建立了室温下同时测定它…     

The Sulfinatodehalogenation Reaction of α,α-Difluorobenzyl Halides with Sodium Dithionite

Since the discovery of the first sulfinatodehalogenation reaction in 1981 1, great efforts havebeen devoted to this useful reaction. The substrates have been expanded fromperfluoroalkyl iodide (R.I) to per- and poly-fluoroalkyl handes (R,X, X = Br, I, R,CCI,),and many sulfinatodehalogenating reagents such as NaZSZO4, HOCH,SO,Na,H,NC(=NH)SO,H and NaZSZO, have been developed=. Recently, thesulfinatodehalogenation of 2,2,2-trifluoroethyl handes was accomplished by Chen et al.'Howev…     

Ligand Steric Effects on Naphthyl-α-diimine Nickel Catalyzed α-Olefin Polymerization

Naphthyl-α-diimine nickel complexes with systematically varied ligand sterics, activated by modified methylaluminoxane(MMAO), were tested in the polymerization of higher α-olefin(1-hexene, 1-decene and 1-hexadecene) under suitable conditions. The polymerization results indicated the possibility of precise microstructure control, depending on catalyst structure, polymerization temperature, monomer concentration and types of monomers, which in turn strongly affects the resultant polymer properties. Naphthyl-α-diimine nickel complex bearing chiral bulky sec-phenethyl groups in the o-naphthyl position showed good catalytic activity, and resulted in branched polymers(42-88/1000 C) with high molecular weights(M_n:(4.3-15.2) × 10~4 g·mol~(-1)) and narrow molecular weight distribution(M_w/M_n = 1.13-1.29, RT), which suggested a living polymerization. The increasing steric hindrance of catalyst leads to enhance insertion for 2,1-insertion of α-olefin and the chain-walking reaction.     

Markovnikov addition of vinyl acetate with azoles catalyzed by potassium tert-butoxide

A simple and efficient methodology for Markovnikov addition of azoles with vinyl acetate catalyzed by potassium tert-butoxide is described.N-heterocyclic compounds are synthesized from simple and commercially available starting materials under mild conditions in high yields.     

α-Oxo Ketene Dithioacetals Chemistry-A Facile Route to the Synthesis of Fused Heterocyclic Compounds

Q-Oxo ketene dithioacetals and related compounds are versatile synthons in organicsynthesis'-'. The substitution reaction of or-oxo ketene dimethylthio acetals with diamineis one of the impel'tant applications for the synthesis of corresponding a-oxo ketenecyclic N, N-acetals. Junjappa and co-workers described this reaction ill a review'.However, since some kinds of ketene dimethylthio acetals are not easy to prepare, themethod melltioned above is limited. Zhu and co-workers had successfully…     

由SRN1反应生成的三种取代苯并咪唑的薄层定量研究

研究了光诱导自由基链式亲核取代（ＳＲＮＩ）反应生成Ｎ－（α－萘基）苯并咪唑，Ｎ－（β－萘基）苯并咪唑和Ｎ－（α－吡啶基）苯并咪唑的薄层光密度定量方法，并成功地应用于其反应机理的研究，该法简便，快速，准确，线性范围０～３．０μｇ平均回收率９９．８％～１００．５％相对标准偏差〈４．７％。     

A kinetic study of the electron-transfer in the reaction of tribenzylchlorotin with[CoW_(12)O_(40)]~(5-)

A kinetic study of the electron-transfer in the reaction of tribenzylchlorotin with potassium 12-tungsto cobalt(Ⅲ) ate ion, K_5[CoW_(12)O_(40)],abbreviated as Co(Ⅲ)W,has been performed in different solvents.The studies were carried out in methanol, ethanol,acetonitrile and acetic acid/water.The rate constants,reaction rates and activation parameters were calculated. Our findings show that the rate of disappearance of the Co(Ⅲ) is pseudo-first order.The kinetic data is strongly affected by used solvents.T...     

Efficient iodination of aromatic compounds using potassium ferrate supported on montmorillonite

Potassium ferrate impregnated on montmorillonite is a mild,cheap,and non-toxic reagent for the iodination of phenols, including naphthol,aromatic amines,and heterocyclic substrates in fair to excellent yields by a simple isolation procedure.     

Regioselective iodination of aromatic compounds with potassium iodide in the presence of benzyltriphenylphosphonium perchlorate

A simple and efficient method for the selective iodination of various aromatic compounds by using potassium iodide in the presence of benzyltnphenylphosphonium perchlorate,is reported.This method provides several advantages such as good selectivity between ortho and para positions of aromatic compounds and high yields of the products.     

Hierarchical Porous Carbon Nanotube Spheres for High-performance K-O2 Batteries

In view of the ever-growing pressure for green gas emissionreduction,there is an urgent need for renewable energysystems.Rechargeablealkali metal-oxygen batteries,especially lithium-oxygen(Li-o2)batteries,are deemed themost promising energy storage systems because of their highertheoretical energy density than that of current lithium-ionbatteries[1-5].     

Potassium iodide catalyzed reductive dehalogenation ofα-halo-ketones using Hantzsch ester diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate as reductant

<正>In the presence of diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate(DHP) and a catalytic amount of potassium iodide,severalα-halo ketones were easily reduced to the corresponding ketones in acetone media.The procedure presented here showed several merits such as short reaction time,practical experimental and isolated procedure,and excellent yields of products.     

Chemical investigation of potassium methyl siliconate as deacidification and strengthening agent for preservation of aged papers

Potassium methyl siliconate(PMS) was investigated as a simple physicochemical modification in aged paper using silane coupling technique. The PMS-based solution was shown to favor penetration in the cellulose fibers on the paper with suitable uptakes being achieved at low concentrations. The studies of the physicochemical properties of the treated paper(mechanical strength and alkalinity) demonstrated that, besides the required deacidification feature and high level of alkali reserves, the immersion treatment by PMS allowed the enhancement of the mechanical intensities of paper arising from the interaction between Si―OH generated in hydrolysis of PMS and C―OH of cellulose on the paper. Adding ethanol into PMS solution could significantly improve mechanical properties of the aged paper treated by the formula apart from modifying the flatness of the paper. Optimized treatment process was achieved by altering the ratio of ethanol to water in PMS-based solutions. Contact angle measurements indicated the occurrence of hydrophobic character of the papers in immersion treatment with PMS-based solutions. The easy availability of the materials and simplicity of the method rendered it convenient for treatment for aged paper documents.     

A New Approach to α—Bromochalcones

α-Bromo benzolymethylene triphenylphosphorane 3 has been synthesized by the reaction of benzoylmethylene triphenylphosphorane 1 with N-bromosuccinimide in the yield of 87% and can react with aromatic aldehydes 4 to give α-bromochalcones 5 in good yields.