Highly Efficient One-Pot Synthesis of 2-Arylmethyl N-Substituted Anilines via Yb（OTf）3 Catalyzed Three-Component Reaction

An efficient method has been developed for one-pot three-component coupling reactions of various aldehydes, 1-cyclohexen-2-one, and primary or secondary amines in the presence of a catalytic amount of Yb（OTf）3 under mild conditions to afford the corresponding 2-arylmethyl N-substituted anilines in good yields. In addition, the catalyst was easily recovered and could be reused for at least four cycles without any loss of activity.     

Towards EPC-syntheses of the structural class of cochleamycins and macquarimicins. Part 3: EPC-syntheses of the β-keto lactone subunits and first attempts towards the syntheses of the pentacyclic antibiotics of this group

Practical EPC-syntheses of δ-substituted-β-keto δ-lactones, subunits of the cochleamycins and macquarimicins, are presented. In consequence Tietze's tandem reaction is employed to combine δ-allyl-β-keto δ-lactone with a hydrindene derivative, the second subunit of these acetogenic antibiotics. Model reactions for the final oxidative radical tandem cyclization reveal that the electrophilic radical cyclizes exclusively in exo-trig fashion. However, with the intended precursor of macquarimicin C allylic hydrogen abstraction thwarted the oxidative radical tandem cyclization.     

Yb2O3对TiO2/(O''+β'')-Sialon复相陶瓷中TiO2相变的影响

以纳米锐钛矿型TiO2粉和（O＇＋β＇）-Sialon粉为原料制备出了TiO2／（O＇＋β＇）-Sialon复相陶瓷，研究了Yb2O3添加剂对材料中锐钛矿型TiO2相变的影响，对其影响机制进行了探讨。采用XRD对材料进行物相组成和晶格参数表征。结果表明，Yb2O3对锐钛矿相变开始温度无明显影响，但对相变有显著的促进作用，随添加量的增加，其作用逐渐减弱。添加的Yb2O3同时以两种形式存在：一部分进入TiO2晶格，一部分堆积在TiO2晶粒表面。Yb^n＋进入TiO2晶格置换Ti^4＋和Yb^3＋与TiO2发生氧化还原反应促进相变，而存在于TiO2表面的Yb^3＋与TiO2相互作用形成Ti-O-Yb键而抑制相变。Yb2O3对锐钛矿相变的影响是这两方面机制共同作用的结果。     

免疫亲和柱净化/柱前衍生化-高效液相色谱荧光检测法测定粮谷中的T-2毒素

建立了免疫亲和柱净化/柱前衍生化-高效液相色谱荧光检测器测定粮谷中T-2毒素含量的方法。样品经甲醇-水(体积比为80∶20)混合溶剂提取,通过免疫亲和柱(IAC)净化,以氰酸蒽(1-AN)为衍生化试剂、4-二甲基氨基吡啶(DMAP)为催化剂进行衍生,以ZORBAX Eclipse XDB-C18 柱为分离柱,乙腈-水(体积比为80∶20)为流动相进行高效液相色谱分离及荧光检测，荧光检测的激发波长为381 nm，发射波长为470 nm。T-2毒素的质量浓度为0.01~1.5 mg/L时与峰高呈良好的线性,相关系数为0.9985。在0.01~1.5 μg/g添加水平下，回收率为79.7%~94.5%,相对标准偏差小于7%；检出限（S/N＝3）为0.01 μg/g。该方法净化效果好,灵敏度高,操作简便快速。     

Crystal Structure and Biological Activities of （R）-N′-[2-（4-Methoxy-6-chloro）-pyrimidinyl]- N-[3-methyl-2-（4-chlorophenyl）butyryl]-urea

1 INTRODUCTION The acyl ureas are a kind of high biological acti- vity compounds with low toxicity to mammals, birds, fish, amphibians, etc., and significant organic synthe- sis intermediates working extensively as insecticides, pesticides, fungicides and herbicides in agrochemi- cal industry[1～7]. While pyrimidinyl derivatives show excellent biological activities in the development of pesticide, and are used to develop high effective and high select herbicides. For example, pyrimidiny su…     

Tl2S: Re-Determination of Crystal Structure and Stereochemical Discussion

The crystal structure of synthetic carlinite, Tl₂S, was re-determined by single crystal and powder X-ray diffraction methods. The cell parameters obtained from Rietveld refinement are a=12.150(2) Å, c=18.190(4) Å, V=2325.5(7) ų. A single crystal data refinement proved Tl₂S crystallizing in the trigonal space group R3 with M=440.8gmol⁻¹, Z=27, R=0.076, and wR=0.145. The atomic arrangement found is that of a strongly deformed anti-CdI₂ type, but the deformation is clearly different from that given by previous workers. In the five crystallographically different STl₆ octahedra the S-Tl distances vary between 2.82 and 3.09Å, the Tl-Tl edges between 3.52 and 4.58Å. The common features of these octahedra are (i) each one with a definitely smaller vs larger Tl₃ face in trans-position, both faces parallel or sub-parallel (00.1), and (ii) each three shorter and longer S-Tl distances to the atoms of the larger and smaller Tl₃ faces, respectively. The Tl-Tl contacts between different Tl₂S sheets are on the average definitely shorter than the ones within the sheet and they can be smaller than the Tl-Tl contacts in the small Tl₃ faces of the STl₆ octahedra. The atomic arrangement indicates that the single electron pairs of the monovalent Tl atoms are not arranged all parallel to the z-axis, as one would expect for Tl₂S with an ideal anti-CdI₂ structure. The surrounding of the S atoms resembles that of one-third of the Cl atoms in yellow InCl. The absorbance of Tl₂S is very low at wave numbers approximately <9000 cm⁻¹.     

极性非质子溶剂与甲醇或1,2-二氯乙烷的汽液平衡

使用双沸点仪测定了丙酮、乙酸乙酯、对二氧六环、乙腈或三乙胺与甲醇或1,2→二氯乙烷以及二者混合物等十一组二元体系在99.3 kPa下的汽液平衡数据(T,x,p), 计算了有关体系的过量吉布斯自由能。结果表明, 六种非质子溶剂与甲醇组成的二元系GE>0; 乙腈或三乙胺与1,2-二氯乙烷组成的二元系GE>0, 而丙酮、乙酸乙酯或对二氧六环与1,2-二氯乙烷的二元混合物GE<0。从同种分子间或不同种分子间的缔合作用对上述结果进行了讨论。本文还在固定极性非质子溶剂(第三组分)物质的量浓度的条件下, 测定了非质子溶剂+1,2-二氯乙烷+甲醇三元混合物的汽液平衡数据, 考察了非质子溶剂的加入对甲醇+1,2-二氯乙烷二元系GE的影响。     

Cross-metathesis of vinyl aromatic heterocycles with 1-octene in the presence of a Schrock catalyst

Metathesis of 2-vinyl aromatic heterocycles such as furan, thiophene, pyrrole and pyridine in the presence of a molybdenum-based Schrock catalyst has been investigated from a synthetic point of view. The self-metathesis of 2-vinyl aromatic heterocycles was not successful. However, in cross-metathesis of thiophene, furan and styrene with 1-octene, the cross-metathesis product, heterodimer, was readily obtained selectively, together with only small amounts of the two corresponding self-metathesis products. The origin of the surprisingly high selectivity of heterodimer formation was elucidated through metallacyclobutane intermediate mechanism, observations of carbenes by in situ ¹H NMR, and reaction products.     

ansa-Metallocene derivatives XXXIII. 2-Dimethylamino-substituted bis-indenyl zirconium dichloride complexes with and without a dimethylsilyl bridge: syntheses, crystal structures and properties in propene polymerization catalysis

Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH₃)₂N-C₉H₆)₂ZrCl₂, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH₃)₂Si(2-(CH₃)₂N-C₉H₅)₂ZrCl₂, were prepared by reaction of the corresponding ligand lithium salts with ZrCl₄ in toluene. Diffractometric structure determinations reveal C₂-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH₃)₂Si(2-(CH₃)₂N-C₉H₅)₂ZrCl₂ catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me₂Si-bridged bis(indenyl)ZrCl₂ complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species.     

Preparation of Y2Ba4Cu7O15-δ Superconductor without High Oxygen Pressure

The synthesis of bulk Y₂Ba₄Cu₇O_15-δ superconductor at atmospheric oxygen pressure via solid state sintering is reported. Temperature ranging from 860 to 890 °C as well as time interval over 2 to 15 days were used to investigate the formation of the Y₂Ba₄Cu₇O_15-δ phase. A time-temperature profile characterizing the conditions for the preparation of Y₂Ba₄Cu₇O_15-δ phase suggests the optimal condition to be sintering at 890 °C for over 10 days. Detailed results of X-ray diffraction, electrical resistivity, iodometric titration and magnetization measurements are described.