Synthesis and Crystal Structure of 3，3－Diphenylnaphtho ［1，2－b］furan－2（3H）－one

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ３，３－Ｄｉｐｈｅｎｙｌｎａｐｈｔｈｏ［１，２－ｂ］ｆｕｒａｎ－２（３Ｈ）－ｏｎｅＭｅｎｇＪｉ－Ｂｅｎ；ＷｅｎＺｈｏｎｇ；ＷａｎｇＹｏｎｇ－Ｍｅｉ；ＷａｎｇＲｕ－Ｊｉ；ＷａｎｇＨｏｎｇ－Ｇｅ...     

Studies on the Synthesis and Crystal Structure of 5－（3＇－methylphenyl）－2H－tetrazol－2－ylacetic acid

ＳｔｕｄｉｅｓｏｎｔｈｅＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ５－（３＇－ｍｅｔｈｙｌｐｈｅｎｙｌ）－２Ｈ－ｔｅｔｒａｚｏｌ－２－ｙｌａｃｅｔｉｃａｃｉｄＺＨＡＮＧＺｉ－ｙｉａｎｄＺＯＵＮｉｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍ...     

Semisynthesis and Biological Evaluation of Taxayuntin 13－［N－Benzoyl－（2’R，3’S）－3’－phenylisoserinate］

ＳｅｍｉｓｙｎｔｈｅｓｉｓａｎｄＢｉｏｌｏｇｉｃａｌＥｖａｌｕａｔｉｏｎｏｆＴａｘａｙｕｎｔｉｎ１３－［Ｎ－Ｂｅｎｚｏｙｌ－（２’Ｒ，３’Ｓ）－３’－ｐｈｅｎｙｌｉｓｏｓｅｒｉｎａｔｅ］ＱｉｎＹＵＥ；ＱｉＣｈｅｎｇＦＡＮＧａｎｄＸｉａｏＴｉａｎＬＩＡ...     

Synthesis and Crystal Structure of Cd（tla）（NO_3）_2［TLA＝tris（6－methyl－2－pyridylmethyl） amine］

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＣｄ（ｔｌａ）（ＮＯ_３）_２［ＴＬＡ＝ｔｒｉｓ（６－ｍｅｔｈｙｌ－２－ｐｙｒｉｄｙｌｍｅｔｈｙｌ）ａｍｉｎｅ］ＢＵＸｉａｎ－Ｈｅ；ＺＨＡＮＧＺｈｉ－Ｈｕｉ；ＺＨＵＺｈｉ－Ａｎｇ；ＣＨＥＮＹｕ...     

Synthesis and Crystal Structure of △~6－4－Amino－5，6－diphenyl－5－hydroxy－1，2，4－triaza－cyclohexene－3－thione－monohydrate

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ△~６－４－Ａｍｉｎｏ－５，６－ｄｉｐｈｅｎｙｌ－５－ｈｙｄｒｏｘｙ－１，２，４－ｔｒｉａｚａ－ｃｙｃｌｏｈｅｘｅｎｅ－３－ｔｈｉｏｎｅ－ｍｏｎｏｈｙｄｒａｔｅ￥ＬｉｎＺｈｅｎ－Ｇｕａｎｇ；?..     

A New Approach for Stabilizing Organouranium Dichloride： Synthesis and X－ray Structure of （MeOCH_2CH_2C_5H_4）_2UCl_2

ＡＮｅｗＡｐｐｒｏａｃｈｆｏｒＳｔａｂｉｌｉｚｉｎｇＯｒｇａｎｏｕｒａｎｉｕｍＤｉｃｈｌｏｒｉｄｅ：ＳｙｎｔｈｅｓｉｓａｎｄＸ－ｒａｙＳｔｒｕｃｔｕｒｅｏｆ（ＭｅＯＣＨ_２ＣＨ_２Ｃ_５Ｈ_４）_２ＵＣｌ_２￥ＤａｏＬｉＤＥＮＧ；ＸｉａｏＦａｎＺＨＡＮＧ；...     

A Study on the Regioselectivity of the Cyclization Reaction of 5－Amino－1， 2， 4－triazole with Asym－l， 3－dicarbonyl Compound

ＡＳｔｕｄｙｏｎｔｈｅＲｅｇｉｏｓｅｌｅｃｔｉｖｉｔｙｏｆｔｈｅＣｙｃｌｉｚａｔｉｏｎＲｅａｃｔｉｏｎｏｆ５－Ａｍｉｎｏ－１，２，４－ｔｒｉａｚｏｌｅｗｉｔｈＡｓｙｍ－ｌ，３－ｄｉｃａｒｂｏｎｙｌＣｏｍｐｏｕｎｄ￥ＲｏｎｇＪｉａｎＬＵ；ＧａｏＦｅｎｇ...     

The Synthesis and Biological Activity of N－Arylamino Carbonyl Methylene 1，2－Benzothiazine 1，1－Dioxides

ＴｈｅＳｙｎｔｈｅｓｉｓａｎｄＢｉｏｌｏｇｉｃａｌＡｃｔｉｖｉｔｙｏｆＮ－ＡｒｙｌａｍｉｎｏＣａｒｂｏｎｙｌＭｅｔｈｙｌｅｎｅ１，２－Ｂｅｎｚｏｔｈｉａｚｉｎｅ１，１－Ｄｉｏｘｉｄｅｓ￥ＧｕｏＦｅｎｇＺＨＡＯ；ＨｕａＺｈｅｎｇＹＡＮＧ（Ｉｎｓｔｉｔｕ...     

SiO_2-SUPPORTED HRh(DPPE)_2 GATALYST

ＳｉＯ_２－ＳＵＰＰＯＲＴＥＤ ＨＲｈ（ＤＰＰＥ）_２ ＧＡＴＡＬＹＳＴ￥ＣｈａｎｇＰｉｎｇＳＨＡＯ；ＪｉｅＹｕＷＡＮＧａｎｄＨｅＦｕＧＵＯ（ＤａｌｉａｎＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ，ＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃ...     

Synthesis and Biological Evaluation of Substituted 3＇－N－Benzoyl Taxol Analogs

ＳｙｎｔｈｅｓｉｓａｎｄＢｉｏｌｏｇｉｃａｌＥｖａｌｕａｔｉｏｎｏｆＳｕｂｓｔｉｔｕｔｅｄ３＇－Ｎ－ＢｅｎｚｏｙｌＴａｘｏｌＡｎａｌｏｇｓＱｉｎＹＵＥ；Ｑｉ－ＣｈｅｎｇＦＡＮＧａｎｄＸｉａｏＴｉａｎＵＡＮＧ（ＩｎｓｉｔｉｔｕｔｅｏｆＭａｔｅｒｉａＭｅ...     

高比表面积Cr2O3-α-AIF3催化剂的制备和应用

采用炭硬模板法制备了高比表面积Cr2O3-α-AIF3催化剂.该催化剂的合成过程主要包括三步:(1)将一定浓度的蔗糖溶液浸渍到Cr203-y-Al2O3中,然后经过热处理,使得蔗糖分解为炭;(2)将含炭的Cr2O3-y-Al2O3固体在400℃用HF气体进行完全氟化;(3)在高温下利用燃烧法除去炭硬模板.对所制备的催化剂进行了X射线衍射(XRD),氮气吸脱附曲线,氨气程序升温脱附(NH3-TPD),透射电镜(TEM),扫描电镜(SEM)和X射线能量散射(EDX)技术表征.结果表明,氟化过程对Cr2O3-α-AIF3催化剂比表面积有重要影响,在最佳实验条件下,能够得到比表面积为115 m2·g-1的催化剂.此催化剂对催化裂解二氟乙烷(HFC-152a)制备氟乙烯(VF)的催化活性明显高于直接氟化制备的Cr2O3-α-AIF3催化剂,这是因为高比表面积的Cr2O3-α-AIF3催化剂具有较大的酸量.     

NaCl和B2O3在修饰FeOχ催化剂中的协同作用

应用连续催化反应，ＸＰＳ，ＸＲＤ，Ｈ２－ＴＰＲ，Ｏ２－ＴＰＤ和Ｉｎ－ｓｉｔｕ Ｍｏｓｓｂａｕｅｒ谱等方法表征了一系列组成不同的ＮａＣｌ／Ｂ２Ｏ３／Ｆｅ２Ｏ３催化剂。结果表明ＮａＣｌ与Ｂ２Ｏ３在修饰ＦｅＯｘ催化剂上存在明显的协同作用，Ｂ２Ｏ３调变了ＦｅＯｘ的还原能力，ＮａＣｌ修饰了Ｂ２Ｏ３／ＦｅＯｘ使之具有很高的还原速度与晶格氧气化速度。催化剂的催化性能同这种协同作用密切相关。     

Highly diastereoselective Barbier allylation and iminium cyclization: a simple entry to bicyclic and tricyclic piperazinones

Barbier allylation of 5,6-dihydropyrazin-2(1H)-ones leads to a single isomer of 3-allylpiperazin-2-ones in high yields. Further Pictet-Spengler-Grieco cyclization of 3-allylpiperazin-2-ones with aldehydes provides bicyclic and tricyclic piperazinones with high diastereoselectivity.     

Conjugate addition of amines to chiral 3-aziridin-2-yl-acrylates

Conjugate addition of benzylamine to chiral methyl cis-3-aziridin-2-yl-acrylates was successfully proceeded to yield 3-aziridin-2-yl-3-benzylaminopropionates in high yield with high stereoselectivity. The addition products were used for the asymmetric synthesis of vicinal diamine derivatives including 4-amino-5-methylpyrrolidin-2-one, 3,4-diaminopentanoate, and 5-chloromethyl-4-alkoxycarbonylmethylimidazolidin-2-one.     

Phosphine-catalyzed dearomative [3+2] annulation of 3-nitroindoles and allenoates

The efficient phosphine-catalyzed dearomative [3+2] annulation of 3-nitroindoles with allenoates has been successfully developed, providing a facile access to cyclopenta[b]indolines with good to excellent yields and high diastereoselectivities. This strategy features mild reaction conditions, high functional group tolerance, and scalability. Additionally, the 2-nitrobenzofuran and 2-nitrobenzothiophene were good dearomative [3+2] annulation partners.     

Development of catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium complexes

Catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium species prepared from calcium isopropoxide and chiral bisoxazoline ligands have been developed. Glycine Schiff bases reacted with acrylic esters to afford 1,4-addition products, glutamic acid derivatives, in high yields with high enantioselectivities. During the investigation of the 1,4-addition reactions, we unexpectedly found that a [3 + 2] cycloaddition occurred in the reactions with crotonate derivatives, affording substituted pyrrolidine derivatives in high yields with high enantioselectivities. On the basis of this finding, we investigated asymmetric [3 + 2] cycloadditions, and it was revealed that several kinds of optically active substituted pyrrolidine derivatives containing contiguous stereogenic tertiary and quaternary carbon centers were obtained with high diastereo- and enantioselectivities. In addition, optically active pyrrolidine cores of hepatitis C virus RNA-dependent polymerase inhibitors and potential effective antiviral agents have been synthesized using this [3 + 2] cycloaddition reaction. NMR spectroscopic analysis and observation of nonamplification of enantioselectivity in nonlinear effect experiments suggested that a monomeric calcium species with an anionic ligand was formed as an active catalyst. A stepwise mechanism of the [3 + 2] cycloaddition, consisting of 1,4-addition and successive intramolecular Mannich-type reaction was suggested. Furthermore, modification of the Schiff base structure resulted in a modification of the reaction course from a [3 + 2] cycloaddition to a 1,4-addition, affording 3-substituted glutamic acid derivatives with high diasterero- and enantioselectivities.     

HCO_3~-浓度对油气田中CO_2腐蚀的影响

应用动电位扫描和失重法研究HCO3-对油气田CO2腐蚀的影响.实验表明,当HCO3-浓度低于0.042 mol/L时,随着HCO3-浓度的增加,溶液pH升高,H+的还原速率(阴极电流密度)下降;HCO3-浓度增至0.126 mol/L时,溶液中的H2CO3、HCO3-的直接还原占主导地位,故阴极过程随HCO3-浓度的上升而加速,对阳极过程,在HCO3-浓度低于0.042 mol/L下,主要为活化过程,而且其阳极溶解电流(密度)随HCO3-浓度的增加而下降;HCO3-浓度增至0.126 mol/L时,阳极过程出现明显的活化-钝化行为.高温高压腐蚀试验显示,材料的腐蚀速率随介质HCO3-浓度的增加而下降.SEM、EDS、XRD分析表明,在较低的HCO3-浓度下,腐蚀产物膜的主要成分为FeCO3晶体,HCO3-浓度较高时,则腐蚀产物主要为Ca、Mg的化合物,并形成Ca(Fe,Mg)(CO3)2复盐.在高pH值下,Ca2+、Mg2+比Fe2+更容易沉积.     

双功能催化剂催化CO2加氢制低碳烯烃反应中In2O3的尺寸效应

CO2催化加氢转化成高附加值化学品如低碳烯烃(C2=–C4=)等是减少碳排放的有效途径之一.采用金属氧化物/分子筛双功能催化剂可以实现CO2加氢直接高选择性合成C2+碳氢化合物.通常认为,金属氧化物组分可以活化CO2转化为甲醇等含氧中间体,该中间体在分子筛孔道内进一步转化为各种烃.氧化铟(In2O3)/SAPO-34双功能催化剂由于具有出色的催化CO2加氢制低碳烯烃反应性能而备受关注,然而,仍需进一步提升催化剂的催化性能以推动该反应的工业应用.目前,氧化物的结构与双功能催化剂性能之间的关系还不明确,这不利于其催化性能的改善.现有关于金属氧化物纳米粒子的尺寸(特别是小于23 nm)效应及其对双功能催化CO2加氢反应的活性和产物分布的影响的报道较少,对此深入理解将有利于设计更高性能的催化剂.本文采用沉淀法,通过控制焙烧温度得到了一系列尺寸为7～28 nm的立方相In2O3,通过多种表征手段探究了In2O3的尺寸对其结构与表面化学性质的影响.结果表明,随着In2O3晶粒尺寸的减小,其氧空位数目、CO2、H2与NH3吸附量以及Lewis较强酸性位比例均逐渐增加.在350oC,3 Mpa,9000 mL·gcat–1·h–1和H2/CO2比为3的反应条件下,研究了In2O3/SAPO-34双功能催化剂中In2O3粒径对其催化CO2加氢制低碳烯烃反应性能的影响.结果表明,随着双功能催化剂中In2O3尺寸的增大,低碳烯烃(尤其是丙烯)选择性、收率及烯烃与烷烃比例均先升高后降低,在尺寸为19 nm的In2O3上达到最大值,分别为76.9％、12.3 mmol goxide–1 h–1和4.8.较小尺寸的In2O3虽然具有较大的比表面积和更多的氧空位,并为CO2和H2的活化提供了更多的活性位,但小于19 nm的颗粒更容易烧结;In2O3的尺寸还会影响其与SAPO-34的协同效应,进而影响双功能催化剂的催化活性.此外,相对于其它尺寸的In2O3,19 nm的In2O3更有利于甲醇中间体的生成.因而19 nm In2O3耦合SAPO-34的双功能催化剂性能最好,其催化CO2转化率最高,为14.1％.综上,适中尺寸的In2O3能够促进In2O3/SAPO-34上CO2加氢制低碳烯烃反应.这些结果为通过平衡结构稳定性和催化性能来设计更有效的催化CO2转化的复合催化剂提供了理论指导.     

Reactivity of Ar'GeGeAr' (Ar' = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) toward alkynes: isolation of a stable digermacyclobutadiene

The first reactions of the "digermyne" Ar'GeGeAr' (1, Ar' = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) with alkynes are reported. 1 reacts with 1 equiv of H5C6CCC6H5 to afford the 1,2-digermacyclobutadiene 2 in high yield, while it reacts with 2 equiv of the less hindered alkyne Me3SiCCH to yield an unexpected bicyclic compound 3. Molecular structures of 2 and 3 were determined by X-ray crystallography. A possible mechanism for the formation of 3 is discussed. The high reactivity of 1, even at room temperature, emphasizes the fundamental differences between the GeGe and CC multiple bonds.     

TiO2/Bi2O3纳米复合体的制备及可见光催化产氢性能

首先采用相分离的水解-溶剂热法制备了Bi₂O₃纳米粒子,然后利用简单的湿化学法在Bi₂O₃表面负载不同比例的TiO₂纳米颗粒,进而得到TiO₂/Bi₂O₃纳米复合体。通过气氛调控的表面光电压谱(SPS)等测试表明,表面负载适量的TiO₂后能够提高Bi₂O₃光生电荷分离。可见光催化产氢和降解污染物测试结果进一步证明,表面负载适量的TiO₂后可显著提高其可见光催化活性,其中Ti/Bi摩尔比为7%时具有最高的光催化活性。这主要归因于TiO₂具有较为合适的导带能级位置,可以接收Bi₂O₃在可见光激发下所产生的高能级电子,从而抑制光生电子-空穴对复合,并且维持了高能级电子较高的还原能力。