SO42-/Zr-ZSM-5 超强酸催化剂的制备和表征

以硅溶胶和氧氯化锆为硅源和锆源，采用水热合成的方法制得具有ZSM-5结构的Zr-Si分子筛；用0.5mol/L的硫酸处理该分子筛，并在550℃焙烧，制得具有ZSM-5结构的SO4^2-/ZrO2-SiO2分子筛型的固体超强酸。采用XRD、SEM、TG、IR、NH3-PHD和指示剂法对其结构和酸性进行表征。结果表明，该SO4^2-/ZrO2-SiO2具有ZSM-5结构和超强酸性，其酸强度大于-13.75，且具有良好的热稳定性。     

Stereochemie von Metallocenen, 40. Mitt.

Starting from optically active methylferrocene-- and--carboxylic acids (1 a and1 b) of known absolute configuration and enantiomeric purity about 15 chiral ferrocenes (of each isomeric series— and ) were obtained by suitable ligand transformations. Thereby (almost) all possible chiral combinations of the ligands CH₃, COOH (COO^–), COOCH₃, CN and NH₂ (NH₃ ⁺) were accessible which are necessary for a potential test of approximations of chirality functions for compounds with basic symmetry C_5v. The chiroptical properties of these disubstituted ferrocenes are recorded.Preliminary tests using a shortened Ansatz revealed large discrepancies between calculated () and found [M]_D-values. Possible reasons for this failure are discussed.

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61. Mitt. über Ferrocenderivate

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39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).

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60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975).     

A Safe Way of Performing Some Dangerous Experiments. II. Construction of a Safety Dropper

Due to the high safety risks, chemistry instructors avoid demonstrating many remarkable experiments based on the addition of a liquid to a solid. Well-known examples of such demonstrations are various pyrotechnic mixtures of potassium chlorate and sugar (sucrose), which are usually activated with a drop of concentrated sulfuric acid. Other attractive demonstrations are the addition of water to freshly prepared magnesium phosphide and addition of water to burning magnesium. In all of these demonstrations the reaction that takes place immediately is very vigorous and can be hazardous for the instructor. Because chemistry teachers and instructors usually try to avoid performing experiments that include a hazard, a number of highly attractive experiments may remain unknown to the public. Using a simple homemade device called a safety dropper, one can perform all of these experiments with complete safety, both for the audience and the demonstrator. Details for performing some of these experiments as well as for the construction of the safety dropper are given in this paper. Video clips of demonstrations are included as an aid for inexperienced instructors.     

Radiation-induced polymerization of cyclohexene sulfide in the solid state

Radiation-induced solid-state polymerization of cyclohexene sulfide has been investigated. Differential thermal analysis shows that this compound has a phase transition point at ?74°C and behaves as a plastic crystal in the temperature range from ?74 to ?20°C (melting point). By rapid cooling, this plastic crystal was easily supercooled, and below ?166°C a glassy crystal, i.e., a supercooled nonequilibrium state of plastic crystal, was obtained. In-source polymerization proceeded in the plastic crystalline state. Postpolymerization of glassy crystalline monomer irradiated at ?196°C occurred above ?166°C (glass transition point) during subsequent heating.     

Qualitative analysis of motion properties of semistate models of large-scale systems

This paper studies the behavior of motions of large-scale (LS) semistate systems (SSS) governed byP _i (t)x _i =M _i (t,x _i )x _i +f _i (t)+h _i (t, x), i=1,2,...,s, =(x ₁ ^T x ₂ ^T x _s ^T )^T, where matricesP _i (t) are singular. Using Lyapunov's approach and the tools for LS system analysis, a variant of attractivity and ultimate boundedness of appropriate time-variable sets are investigated. The results are based on a specific choice of the aggregate functions. It is assumed that the reduction of equations to a normal form of lower order is inconvenient. The aggregation-decomposition approach used in this paper reduces the dimensionality of an aggregate matrix of the system to the number of its systems. Motion properties of LS systems are deduced from the properties of its isolated subsystems, the character of interconnections, and the conditions imposed on the system aggregate matrix. Sufficient algebraic conditions for the above-mentioned motion properties are developed.     

First-order transitions in spherical models: Finite-size scaling

Finite-size behavior near the first-order phase boundary of ferromagnetic spherical models is investigated for block- and cylinder-shaped systems ind dimensions. The bulk thermodynamic singularities are rounded and, asymptotically for large size, obey appropriate scaling laws. Both short-range interactions and long-range couplings, decaying like 1/r^d+ with >0, are analyzed: the short-range results agree precisely with a recently developed scaling theory forO(n) symmetric systems in the limitn. More generally, the scaling functions are universal, depending only on . Explicit aspects of the shape and interactions enter only in the spin wave or Goldstone mode contributions which appear, technically, as corrections to scaling. An appendix analyzes the truncation error in the approximation, by many-fold sums, of multivariate integrals with integrands diverging like [_ja_{j j} ² ]^- as 0.     

Mechanism of the cyclization of dimethyl diethynyl silane with selenium tetrabromide: Computational and structural studies, and monitoring

The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr₄ to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr₄ conversion into bimolecular complex Br₂?SeBr₂, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using ¹H NMR method.     

Synthesis and anion binding properties of 2,5-diamidothiophene polypyrrole Schiff base macrocycles

[reaction: see text] Two easy-to-synthesize polypyrrolic 2,5-diamidothiophene Schiff base macrocycles are reported, along with their anion binding properties as determined via UV-vis spectroscopic titrations carried out in dichloroethane. There is a striking difference between the interactions with anions of the two macrocycles, a finding ascribed to differences in their rigidity. For example, the more flexible dipyrromethane-derived macrocycle displays a 1.2:1 hydrogen sulfate versus nitrate selectivity, while its more rigid bipyrrole-derived congener shows a 7.4:1 selectivity in favor to hydrogen sulfate.     

Structure and photochemistry of 18-diazo-1,4,7,10,13,16-hexaoxacyclononadeca-17,19-dione and its sodium and potassium complexes. Control of the ground-state conformation of 2-diazo-1,3-dicarbonyl fragment via host-guest complexation

[reaction: see text] The macrocyclic 18-diazo-1,4,7,10,13,16-hexaoxacyclononadeca-17,19-dione (3-diazo-2,4-dioxo-19-crown-6, 1) readily forms complexes with potassium (2, stability constant in methanol is K(K+) = 229 +/- 25 M(-1)) and sodium ions (3, K(Na+) = 84.2 +/- 7.9 M(-1) in methanol). According to B3LYP/6-31G+(d,p) calculations and temperature-dependent 1H NMR spectroscopy, the predominant conformation of 1 has a Z,Z arrangement of the diazo and carbonyl groups. The X-ray crystal structure analysis showed that the potassium complex (2) has the same Z,Z arrangement, while the sodium analogue (2) exists in conformation with Z,E geometry of the diazodicarbonyl moiety. Direct 254 nm photolysis of diazo compounds 1-3 in methanol results in the formation of 3-methoxy-2,4-dioxo-19-crown-6 (5), the product of the insertion of corresponding alpha,alpha'-dicarbonylcarbene into the O-H bond of the solvent. The triplet-sensitized photolysis of diazomalonates 1-3 produces 2,4-dioxo-19-crown-6 (6), which is apparently formed via the triplet state of the intervening carbene.