A Scope Study of Condensation of1,3-Diketones with Diethyl Acetonedicarboxylate

ＡＳｃｏｐｅＳｔｕｄｙｏｆＣｏｎｄｅｎｓａｔｉｏｎｏｆ１,３－ＤｉｋｅｔｏｎｅｓｗｉｔｈＤｉｅｔｈｙｌＡｃｅｔｏｎｅｄｉｃａｒｂｏｘｙｌａｔｅＺＨＯＮＧＺｈｅｎ－ｑｉ,ＴＡＮＧＨｕｉ－ｔｏｎｇ,ＺＨＡＮＧＰａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓ...     

STUDY ON SYNTHESIS，CHARACTERIZATION AND CATALYSIS OF PILLARED ANION CLAY（Ⅲ）──SYNTHESIS OF ZnAl－BW_（11）O_（39）Z（H_2）~（n－）

ＳＴＵＤＹＯＮＳＹＮＴＨＥＳＩＳ，ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＡＮＤＣＡＴＡＬＹＳＩＳＯＦＰＩＬＬＡＲＥＤＡＮＩＯＮＣＬＡＹ（Ⅲ）──ＳＹＮＴＨＥＳＩＳＯＦＺｎＡｌ－ＢＷ_（１１）Ｏ_（３９）Ｚ（Ｈ_２）~（ｎ－）ＴｈａｎｋｓｆｏｒｔｈｅｓｕｐｐｏｒｔｏｆＦｏｕｎｄａｔｉｏｎｏｆＣＥＣａｎｄｔｈｅｏｐｅｎｌａｂｏｆＨｙｄｒｏｔｈｅｒｍａｌＳｙｎｔｈｅｓｉｓｉｎＪｉｎｎＵｎｉｖｅｒｓｉｔｙｅｄｄｉｆｆｅｒｅｎｔｋｉｎｄｓｏｆｔｒｉｈｅｔｅｒｏｐｏｌｙｏｘｏｍｅｔａｌａｔｅ（ＴＨ＇ＰＯＭｓ）ｔｏｔｈｅＺｎＡＩｌａｙｅｒｅｄｃｌａｙｓ，ｕｓｉｎｇｔｈｅｅｓｔｅｒｉｆｉｃａｔｉｏｎｏｆｎ－ｂｕｔｙｌａｌｃｏｈｏｌａｎｄａｃｅｔｉｃａｃｉｄａｓｐｒｏｂｅｒｅａｃｔｉｏｎ．ａｎｄｆｏｕｎｄｔｈａｔｔｈｅｐｉｌｌａｒｅｄｃｏｍｐｏｕｎｄｓｗｅｒｅｍｏｒｅａｃｔｉｖｅａｎｄｓｅｌｅｃｔｉｖｅｔｈａｎｔｈｅｓｏｌｉｄａｃｉｄｃａｔａｌｙｓｔｓｓｕｃｈａｓａｃｉｄｉｃｉｏｎ－ｅｘｃｈａｎｇｅｒｅｓｉｎｓｌ４］．Ｏｎｔｈｅｂａｓｉｓｏｆｐｒｅｖｉｏｕｓｗｏｒｋ．ｗｅｎｏｗｅｎｃａｐｓｕｌａｔｅｔｒｉｈｅｔｅｒｏｐｏｌｙｏｘｏｍｅ     

Spectrophotometric Determination of Iron(Ⅱ) Diphosphine Carbonyl Compounds Using Charge-transfer Ban

ＳｐｅｃｔｒｏｐｈｏｔｏｍｅｔｒｉｃＤｅｔｅｒｍｉｎａｔｉｏｎｏｆＩｒｏｎ（Ⅱ）ＤｉｐｈｏｓｐｈｉｎｅＣａｒｂｏｎｙｌＣｏｍｐｏｕｎｄｓＵｓｉｎｇＣｈａｒｇｅ－ｔｒａｎｓｆｅｒＢａｎｄＬＩＳｏｎｇ－ｌａｎ,ＺＨＡＮＧＢａｏ－ｓｈｅｎ,ＷＡＮＧＺｈｉ－...     

SiO_2-SUPPORTED HRh(DPPE)_2 GATALYST

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

DIELS-ALDER REACTIONS CATALYZED BY MISCH-LANTHANIDE CHLORIDES

ＤＩＥＬＳ－ＡＬＤＥＲＲＥＡＣＴＩＯＮＳＣＡＴＡＬＹＺＥＤＢＹＭＩＳＣＨ－ＬＡＮＴＨＡＮＩＤＥＣＨＬＯＲＩＤＥＳ￥ＳｈｕＷｅｎＹＵ；ＳｈｉＪｉａｎＬＩＡＯａｎｄＤａｏＲｏｎｇＹＵ（ＤａｌｉａｎＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ，Ｃｈ...     

STUDIES ON MACROCYCLIC DITERPENOIDS（XI）──A Convergent and Stereoselective Synthesis of Cembrenene Precursor－4，10－Dimethyl－7－Isopropenyl－14－Oxo－3Z，5E，10E－Pentadecatrienal

ＳＴＵＤＩＥＳ　ＯＮ　ＭＡＣＲＯＣＹＣＬＩＣ　ＤＩＴＥＲＰＥＮＯＩＤＳ（ＸＩ）──Ａ　Ｃｏｎｖｅｒｇｅｎｔ　ａｎｄ　Ｓｔｅｒｅｏｓｅｌｅｃｔｉｖｅ　Ｓｙｎｔｈｅｓｉｓ　ｏｆ　Ｃｅｍｂｒｅｎｅｎｅ　Ｐｒｅｃｕｒｓｏｒ－４，１０－Ｄｉｍｅｔｈｙｌ－７－Ｉ...     

Isotopic Shifts of the infrared Spectra of Cholic Acid and Sodium Cholate

ＩｓｏｔｏｐｉｃＳｈｉｆｔｓｏｆｔｈｅｉｎｆｒａｒｅｄＳｐｅｃｔｒａｏｆＣｈｏｌｉｃＡｃｉｄａｎｄＳｏｄｉｕｍＣｈｏｌａｔｅＴＩＡＮＷｅｎ;ＷＥＮＧＳｈｉ－ｆｕ;ＷＵＪｉｎ－ｇｕａｎｇａｎｄＺＨＡＮＧＱｉｎｇ－ｌｉａｎ（Ｔ．Ｌ－ＣＨＡＮＧ）（Ｄｅｐａ...     

STUDIES ON MACROCYCLIC DITERPENOIDS（Ⅻ）──A Convergent and Stereoselective Synthesis of Sarcophytol－Q Precursor──（11S）－3，7，11，15－Tetramethyl－11－Hydroxy－14－Oxo－3E，7E，12E－Hexadecatrienal

ＳＴＵＤＩＥＳＯＮＭＡＣＲＯＣＹＣＬＩＣＤＩＴＥＲＰＥＮＯＩＤＳ（Ⅻ）──ＡＣｏｎｖｅｒｇｅｎｔａｎｄＳｔｅｒｅｏｓｅｌｅｃｔｉｖｅＳｙｎｔｈｅｓｉｓｏｆＳａｒｃｏｐｈｙｔｏｌ－ＱＰｒｅｃｕｒｓｏｒ──（１１Ｓ）－３，７，１１，１５－Ｔｅｔｒａｍｅｔ...     

Structure of Gadolinium Complex with Acetylene Dicarboxylate(ADC)

ＳｔｒｕｃｔｕｒｅｏｆＧａｄｏｌｉｎｉｕｍＣｏｍｐｌｅｘｗｉｔｈＡｃｅｔｙｌｅｎｅＤｉｃａｒｂｏｘｙｌａｔｅ（ＡＤＣ）ＸｉｎｇＹａｎ；ＪｉｎＺｈｏｎｇ－Ｓｈｅｎｇ；ＤｕａｎＺｈｉ－Ｂａｎｇ；ＮｉＪｉａ－Ｚｕａｎ（ＣｈａｎｇｃｈｕｎＩｎｓｔｉｔｕｔｅｏ...     

Synthesis of α-Oxoketene CyclicO,S and S,S Acetals

Ｓｙｎｔｈｅｓｉｓｏｆα－ＯｘｏｋｅｔｅｎｅＣｙｃｌｉｃＯ,ＳａｎｄＳ,ＳＡｃｅｔａｌｓＬＩＵＱｕｎ,ＸＵＢａｉ－ｌｉｎｇａｎｄＺＨＡＯＨｏｎｇ－ｗｕ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ,ＮｏｒｔｈｅａｓｔＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ,Ｃ...     

基于一氧化碳、二氧化碳和氧气分子吸附为探针的碳化钼、碳化钨、氮化钼和氮化钨的表面化学性质：密度泛函理论分析

作为具有吸引力的电极材料,过渡金属碳化物与氮化物被应用在许多电化学储能及能量转换领域. 本工作中,通过密度泛函理论计算,以及一氧化碳 （CO）, 二氧化碳（CO₂）和 氧气（O₂）分子的吸附来表征钼和钨的碳化物及氮化物,如碳化钼（Mo₂C）、碳化钨（W₂C）、氮化钼（Mo₂N）和氮化钨（Mo₂C）的表面化学性质. 这些探针分子可为研究钼和钨的碳化物及氮化物表面在酸性/碱性的氧化还原性质提供衡量方法. 计算结果表明,CO₂分子的吸附发生在路易斯碱位,其碱性降低顺序为α-W₂C(001) > α-W₂N(001) > β-Mo₂C(001) > γ-Mo₂N(100). 此外,CO和O₂分子吸附可用于评估上述碳化物及氮化物的还原能力,其还原性减小顺序为β-W₂C(100) > α-Mo₂C(100) > α-W₂N(001) > α-W₂C(001) > β-Mo₂C(001) > γ-Mo₂N(100). 由于还原本性,使得上述这些碳化物和氮化物成为在各种催化反应中有可能取代贵金属的良好候选材料.     

杂多三金属磷酸盐的合成与表征

早期合成的Keggin结构杂多酸均是同种齿顶原子,后来人们合成了一系列含两种齿顶原子的三元杂多酸~[1,2],我们曾制备了含3种齿顶原子的四元杂多酸~[3,4].随着齿顶原子种类的增多,杂多酸在水溶液中的稳定性降低.本文采用空缺杂多酸阴离子逐步与不同齿顶原子结合,最后用溶解度极小的(C_1H_9)_4N~+盐沉淀方法合成了未见报道的磷的四元杂多酸盐.     

原子簇化合物[Et4N]2[Mo2O2S2(S2)(S4)]的合成和结构

目前,Mo-S化合物的化学,特别是以多硫基为配体的铟硫化合物的化学是一个活跃的研究领域。这里我们报道含S₂^2-、S₄^2-两种多硫基的二核钼原子簇化合物〔Et₄N〕₂〔Mo₂O₂(S₂)(S₄)(u₃-S)₂]的合成和单晶结构。     

β-Mo_2C和Ni_3Mo_3N/β-Mo_2C的制备及其甲烷化反应性能研究

通过焙烧钼酸铵和六次甲基四胺(HMT)生成的络合物,制备β-Mo_2C。在此基础上加入Ni助剂制备了Ni_3Mo_3N/β-Mo_2C双金属碳化物催化剂。采用XRD、SEM、HRTEM、低温氮吸附、元素分析等方法对催化剂进行了表征,考察了其合成气甲烷化反应性能。结果表明,β-Mo_2C有较高的CO转化率,但CO转化率和CH_4选择性分别从第10h的75.93%和36.79%降低到了第100h的67.41%和33.54%。因此,β-Mo_2C活性不够稳定且CH_4选择性较低。而Ni助剂的加入显著提高了催化剂的甲烷化活性及稳定性,使CO转化率和CH_4选择性分别从第10h的83.15%和46.64%升高到了第100h的92.51%和57.23%。这是因为Ni助剂的加入有助于生成Ni_3Mo_3N,新生成的Ni_3Mo_3N有利于甲烷化反应。     

南蛇藤昆虫拒食成分的研究(I)

南蛇藤昆虫拒食成分的研究（Ｉ）王明安,陈馥衡（北京农业大学应用化学系,北京,１０００９４）关键词南蛇藤,倍半萜,结构分析南蛇藤（Ｃｅｌａｓｔｒｕｓｏｒｂｉｃｕｌａｔｕｓ）是我国传统的低毒杀虫植物,其主要化学成分为倍半萜［１］．Ｓｍｉｔｈ等［２,３］对...     

One-pot Synthesis of α,β-Dehydroamino Derivatives from β,β-Dicyanostyrene with 1,3-Dibromo-5,5-dimethylhydantoin Promoted by Mild Base

The reaction of β,β-dicyanostyrene derivatives(1) with 1,3-dibromo-5,5-dimethylhydantoin(DBDMH) was systematicly studied. The reaction could generate different products when promoted by different mild bases. When the reaction was promoted by NaOAc(100%, molar ratio to compound 1), β,β-dicyanostyrene derivatives could be directly converted into corresponding α,β-dehydroamino derivatives in good to excellent yields in one-pot. When the reaction was promoted by K₃PO₄(80%, molar ratio to compound 1), the corresponding α,β-dehydroamino and double-α,β-dehydroamino compounds were simultaneously obtained and the total conversion of β,β-dicyanostyrene derivatives was up to 90% or higher.     

Experimental Binary Phase Diagram of Bilayer Compounds [n-CnH2n+1N(CH3)3]2CoCl4

Compounds [n-C_nH_2n+1N(CH₃)₃]₂CoCl₄(n=16, C₁₆C₃Co; n=18, C₁₈C₃Co) containing lipid-like bilayers embedded in a crystalline matrix exist in solid-solid phase transition. The low-temperature bilayer structures of the two compounds were organized by neutralizing CoCl₄^2- with alkylammonium ions. Alkyl chains lay parallel to each other and slightly tilted with respect to the normal of the inorganic layers. The adjacent alkyl chains interacted with each other by van der Waals interaction. When the temperature increased, the two compounds underwent a reversible solid-solid phase transformation within 310―330 K. In such a case, the chains showed a large motional freedom, and a disordered phase appeared. The structures can alternatively be viewed as a double layer of alkylammonium ions between CoCl₄^2- sheets and be considered as crystalline models of lipid bilayers. The experimental subsolidus binary phase diagram of [n-C₁₆H₃₃N(CH₃)₃]₂CoCl₄-[n-C₁₈H₃₇N(CH₃)₃]₂CoCl₄ was constructed over the entire composition range by differential scanning calorimetry and X-ray diffraction technique. Experimental phase diagram indicates one stable intermediate phase [n-C₁₆H₃₃N(CH₃)₃][n-C₁₈H₃₇N(CH₃)₃]CoCl₄ at w_C16C3Co= 39.89% and two invariant three- phase equilibria, which shows two eutectoid temperatures: T_e1 at (316±1) K for w_C16C3Co= 27.35% and T_e2 at (313±1) K for w_C16C3Co=59.76%. These three noticeable solid-solution ranges are α-phase at the left, β-phase at the right, and γ-phase in the middle of the phase diagram.     

高氯酸铕的双亚砜配合物研究

本文报告了高氯酸铕的高、低熔点双(正-辛基亚砜)乙烷和双(苯基亚砜)乙烷的四个配合物:Eu(ClO₄)₃(α-BOSE)₃·2H₂O(Ⅰ)、Eu(ClO₄)₃(β-BOSE)₄·2H₂O(Ⅱ)、Eu(ClO₄)₃(α-BPhSE)₃(Ⅲ)和Eu(ClO₄)₃(β-BPhSE)₄·2H₂O(Ⅳ)的合成及性质。     

Hydrothermal Synthesis and Structure of [CH_3NH_3]_2[(V~ⅣO)_2(V~ⅤO_4)_2]: A New Layered Mixed-valence Vanadium Oxide Incorporated with Organic Cations

IntroductionLayered intercalation compounds haveattracted increasing research attention due to theirapplications in diverse areas,for instance,some ofthem are used as rechargeable batteries,heterogeneous catalysts,and an exchange[1— 12 ] . Inprevious literatures,several layered mixed- valencevanadium oxides were reported,such as VO2 · 1 /2 H2 O[13 ] ,[H2 N( CH2 ) 4 NH2 ]V4O9[14 ] ,NH4V3 O8[15] ,( C6H14 · N2 ) V6O14 · 1 / 2 H2 O[16] ,[HN( C2 H4) 3 NH]V6O14 [17] ,NMe4V6O14 [18]…     

齿叶橐吾中新吉马烷型倍半萜结构研究

菊科案吾属植物在我国约有100种,是民间广泛应用的中草药资源,具有清热解毒、抗菌消炎、化痰止咳、活血止痛等功效D‘．本文报道了通过反复柱层析（溶剂石油醚：丙酮体积比为10：1～3：I）和制备薄层层析（溶剂苯：丙酮体积比为5：1）从齿叶蠢吾（＊fggLggfgdentata）中分离得到的一新吉马烷型倍半储,命名为la,4卢,6a,10a一四羟基一3卢,sa,sa一三当归酸氧基吉马一11一烯一9一酮（1）．化合物1为无色胶体,卜」g＋3·2“（＊＊Q。,C几51）．其’H、”C＊＊R和＊＊＊T谱表明1中存在3个当归酸氧基,在FAB－MS谱中有连续失去463…