固体超强酸SO4^2-／TiO2-SnO2的制备、表征及催化合成D，L-丙交酯

采用沉淀法在不同工艺条件下制备了稀土改性的新型固体超强酸SO4^2-／TiO,-SnO2催化剂,考察了其对D,L-乳酸合成D,L-丙交酯的催化活性,并通过Hammett指示剂法测定了催化剂的酸强度,用Fr—IR和FT-Raman技术考察了焙烧温度、硫酸浸渍液浓度和浸渍时间以及La2O3的负载量对该固体超强酸结构和性能的影响．研究结果表明：SnO2的存在促进了金红石相TiO2的形成,在600℃焙烧3h、3．0mol／LH2SO4溶液浸渍12h、n（Ti^4＋）：n（Sn^4＋）：n（La^3＋）=1：1：0．05条件下制备的SO4^2-／TiO2-一SnO2的酸强度最大,达-13．75以上,催化合成丙交酯的产率最高（78．4％）．并且考察了催化剂用量对D,L-丙交酯粗产率的影响和催化剂重复使用的性能．     

稀土固体超强酸SO2-4/TiO2/La3 +催化合成丙酸苄酯

采用浸渍法制备了稀土固体超强酸SO2-4/TiO2/La3+,并运用IR、XRD和Hammett指示剂法对其进行了表征.以制备的固体超强酸SO2-4/TiO23+为催化剂、丙酸和苯甲醇为原料合成了丙酸苄酯.考察了催化剂的制备条件及合成条件对酯化率的影响,结果显示催化剂最佳制备条件:钛前体氧化物的浸渍液为含0.07 mol·L-1 La3+的硫酸溶液,焙烧时间3 h,焙烧温度500℃.最佳反应条件:醇酸摩尔比为1:2、催化剂用量为苯甲醇用量的9.3%、反应时间3 h、反应温度120℃,酯化率达84.0%以上.用IR、1H-NMR等手段对产品进行了表征.     

稀土固体超强酸SO4^2-／TiO2／La^3＋催化合成丙酸苄酯

采用浸渍法制备了稀土固体超强酸SO2-4/TiO2/La3+,并运用IR、XRD和Hammett指示剂法对其进行了表征.以制备的固体超强酸SO2-4/TiO23+为催化剂、丙酸和苯甲醇为原料合成了丙酸苄酯.考察了催化剂的制备条件及合成条件对酯化率的影响,结果显示催化剂最佳制备条件钛前体氧化物的浸渍液为含0.07 mol·L-1 La3+的硫酸溶液,焙烧时间3 h,焙烧温度500℃.最佳反应条件醇酸摩尔比为12、催化剂用量为苯甲醇用量的9.3%、反应时间3 h、反应温度120℃,酯化率达84.0%以上.用IR、1H-NMR等手段对产品进行了表征.     

稀土固体超强酸SO_4~(2-)/TiO_2/La~(3+)催化合成丙酸苄酯

采用浸渍法制备了稀土固体超强酸SO2 -4/TiO2 /La3 + ,并运用IR、XRD和Hammett指示剂法对其进行了表征。以制备的固体超强酸SO2 -4/TiO2 3 + 为催化剂、丙酸和苯甲醇为原料合成了丙酸苄酯。考察了催化剂的制备条件及合成条件对酯化率的影响 ,结果显示催化剂最佳制备条件 :钛前体氧化物的浸渍液为含 0 0 7mol·L-1La3 + 的硫酸溶液 ,焙烧时间 3h ,焙烧温度 5 0 0℃。最佳反应条件 :醇酸摩尔比为 1∶2、催化剂用量为苯甲醇用量的 9 3%、反应时间 3h、反应温度 12 0℃ ,酯化率达 84 0 %以上。用IR、1H NMR等手段对产品进行了表征。     

镧改性固体超强酸SO42-/ZrO2-TiO2/La3+催化剂的制备及性能研究

将固体超强酸SO42-/ZrO2 TiO2负载镧制备新型催化剂SO42-/ZrO2 TiO2/La3+,以催化合成溴代正辛烷为模型反应,考察了不同制备条件对催化剂性能的影响,结果表明:以0.5mol·L-1H2SO4和5.0%的La(NO3)3混合溶液浸渍的锆钛前体氧化物,经110℃烘干后于550℃焙烧3h所得催化剂(LSZT5.0 3 550)活性较好,在n(HBr)∶n(辛醇)=5.12∶1.00、催化剂用量为反应物总质量的1.6%、反应时间为4h,反应温度约130℃的条件下,合成溴代正辛烷产率达75%以上。采用IR,XRD,DTA/TGA和Hammett指示剂法对催化剂进行表征显示:LSZT5.0 3 550具有较高的酸强度,且为无定型态。     

焙烧温度对纳米级SO2- 4/TiO2固体超强酸性能的影响

用锐钛型纳米TiO2制备了纳米级SO2- 4/TiO2固体超强酸,考查了焙烧温度对酸强度、比表面积、红外光谱及其催化活性的影响.结果显示该催化剂在450℃焙烧3 h,可以形成纳米级SO2-4/TiO2固体超强酸的结构.用该催化剂催化乙酸和丁醇酯化反应可使酯化率达到98.4%.     

SO_4~(2-)/TiO_2固体超强酸新制备方法及其对形成邻苯二甲酸二丁酯的催化活性

建立了用钛白粉制备固体超强酸SO42-/TiO2的新方法.考察了超强酸SO42-/TiO2的制备条件对催化邻苯二甲酸酐和正丁醇酯化反应的催化活性的影响.实验表明,以合成的超强酸为催化剂,在160℃反应4h,邻苯二甲酸二丁酯的产率大于99%.     

稀土固体超强酸SO_4~(2-)/TiO_2-La~(3+)催化合成尿囊素

尿囊素(1 脲基间二氮杂茂烷二酮—(2,4),allantoin)是一种两性化合物,可作为医药、化妆品、农业等化工原料中间体。通常用硝酸或过氧化氢氧化乙二醛生成乙醛酸后,再在酸催化下由乙醛酸与尿素缩合而成。但采用浓H2SO4、HNO3等作催化剂,产率偏低(<50%),选择性差,产品质量不好,同时设备腐蚀严重,污染环境。用SO2-4/MxOy型固体超强酸催化剂催化合成尿囊素[2 3],仍有产率偏低等不足之处。我们用La3+掺杂改性SO2-4/TiO2体系,合成了稀土固体超强酸催化剂SO2-4/TiO2 La3+,考察了合成尿囊素缩合反应的催化条件,在最适宜的反应条件下,催化…     

SO42-/ZrO2固体超强酸催化合成乙醛酸L-盖基酯

乙醛酸L-盖基酯是一种重要的手性试剂和手性中间体.本文以SO42-/ZrO2固体超强酸作催化剂,由乙醛酸与L-薄荷醇酯化合成乙醛酸L-盖基酯,通过正交实验探讨了反应温度、反应时间、催化剂用量、酸醇摩尔比4个因素对该酯化反应的影响,得到优化工艺条件,收率达78.5%,并对L-薄荷醇的套用及SO42-/ZrO2固体超强酸的重复使用进行了研究.     

SO42-/TiO2固体超强酸新制备方法及其对形成邻苯二甲酸二丁酯的催化活性

建立了用钛白粉制备固体超强酸SO4^2-/TiO2的新方法．考察了超强酸SO4^2-/TiO2的制备条件对催化邻苯二甲酸酐和正丁醇酯化反应的催化活性的影响．实验表明，以合成的超强酸为催化剂，在160℃反应4h，邻苯二甲酸二丁酯的产率大于99％．     

Homopolymerization of 2-alkyl- and 2-aryl-2-oxazolines

2-Aryl- and 2-alkyl-2-oxazolines have been polymerized to poly-(N-aroyl)aziridines and poly(N-acyl)aziridines, respectively, in the presence of boron trifluoride. The polymers obtained were glassy, light yellow resins with molecular weights ranging from 3500 to 7500 (35–50 oxazoline units per chain). The polymerization rates have been determined for several of these monomers. A polymerization mechanism is proposed.     

Synthesis and reactions of 2-chloro- and 2-tosyloxy-2'-deoxyinosine derivatives

Convenient syntheses of 2-chloro- and 2-tosyloxy-2'-deoxyinosine as their tert-butyldimethylsilyl ethers are described. Both compounds can be synthesized via a common route and rely on commercially available 2'-deoxyguanosine. The present method leading to the chloro nucleoside is operationally simpler compared to previously reported glycosylation techniques where isomeric products were obtained. Both electrophilic nucleosides can be used for the preparation of N-substituted 2'-deoxyguanosine analogues via displacement of the leaving groups, and a comparison of their reactivities shows the chloro analogue to be superior. Interestingly, a Pd catalyst-mediated, two-step, one-pot conversion of an allyl-protected chloro nucleoside intermediate to the final modified 2'-deoxyguanosine derivatives is also feasible. On the basis of these observations, initial assessments of Pd-catalyzed aryl amination as well as a C-C cross-coupling have also been performed with the chloro and tosyloxy nucleoside substrates. Results indicate a potentially high synthetic utility of 2-chloro-2'-deoxyinosine and in many instances this derivative can supplant the bromo and fluoro analogues that are more cumbersome to prepare or are not readily available.     

Structure and properties of single crystalline CaMg2Bi2, EuMg2Bi2, and YbMg2Bi2

Single crystals of CaMg(2)Bi(2), EuMg(2)Bi(2), and YbMg(2)Bi(2) were obtained from a Mg-Bi flux cooled to 650 °C. These materials crystallize in the CaAl(2)Si(2) structure-type (P ?3m1, No. 164), and crystal structures are reported from refinements of single crystal and powder X-ray diffraction data. EuMg(2)Bi(2) displays an antiferromagnetic transition near 7 K, which is observed via electrical resistivity, magnetization, and specific heat capacity measurements. Magnetization measurements on YbMg(2)Bi(2) reveal a weak diamagnetic moment consistent with divalent Yb. Despite charge-balanced empirical formulas, all three compounds are p-type conductors with Hall carrier concentrations of 2.0(3) × 10(19) cm(-3) for CaMg(2)Bi(2), 1.7(1) × 10(19) cm(-3) for EuMg(2)Bi(2), and 4.6(7) × 10(19) cm(-3) for YbMg(2)Bi(2), which are independent of temperature to 5 K. The electrical resistivity decreases with decreasing temperature and the resistivity ratios ρ(300 K)/ρ(10 K) ≤ 1.6 in all cases, indicating significant defect scattering.     

Substituted 2-methyl- and 2-methyleneindolines. 2. Nitro- and amino-substituted 2-methyl- and 2-methylene-indolines

From 5- and 6-aminotetramethylindolines, 2-methyleneindolines have been synthesized; these compounds can be condensed with other heterocyclic systems. The nitration of 1,2,3,3-tetramethylindoline under different conditions was studied.For communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–923, July, 1989.     

Electronic structure and spectrum of UO2 2+ and UO2Cl4 2-

A theoretical study is presented of the electronic spectra of the UO(2) (2+) and UO(2)Cl(4) (2-) ions, based on multiconfigurational perturbation theory (CASSCF/CASPT2), combined with a recently developed method to treat spin-orbit coupling [P.-A. Malmqvist et al., Chem. Phys. Lett. 357, 230 (2002); B. O. Roos and P.-A. Malmqvist, Phys. Chem. Chem. Phys. 6, 2919 (2004)]. The results are compared to the experimental spectroscopic data obtained for uranyl ions in Cs(2)UO(2)Cl(4) crystals from Denning [Struct. Bonding (Berlin) 79, 215 (1992)] and to previous theoretical calculations performed using a combined configuration-interaction spin-orbit treatment [Z. Zhang and R. M. Pitzer, J. Phys. Chem. A 103, 6880 (1999); S. Matsika and R. M. Pitzer, J. Phys. Chem. A. 105, 637 (2001)]. As opposed to the latter results, the calculations performed in this work point to a significant effect of the weakly bound equatorial chlorine ligands on the excitation energies.     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Rh2CO2/Al2O3上H2吸附及CO和H2共吸附

CO加氢反应机理一直是许多化学工作者感兴趣的课题．Rh催化剂因其优良的性能而被用于 CO加氢机理研     

Synthesis of fluorodinitromethane and 2-fluoro-2, 2-dinitroethanol

Conclusions The authors have obtained fluorodinitromethane and 2-fluoro-2, 2-dinitroethanol and studied some of their physiocochemical properties.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 912–914, April, 1968.     

Synthesis of 2-deamino- and 2-deamino-2-nitroactinomycin D

A single step synthesis of 2-deaminoactinomycin D ( 3a ) and 2-deamino-2-nitroactinomycin D ( 2a ) arising from actinomycin D ( 1a, AMD ) is reported. Structural confirmation was made by nmr, ir and chemical conversion to known materials.