介绍了Kirk—Othmer Encyclopedia of Chemical Technology（化工技术百科全书）（第五版）电子图书网络版数据库，并对该数据库使用方法和检索途径作出了说明，且结合实例简单地介绍了该数据库的检索方法。

Kirk-Othmer Encyclopedia of Chemical Technology数据库介绍及实例

This Account reports the synthesis and characterization of dendrimer-encapsulated metal nanoparticles and their applications to catalysis. These materials are prepared by sequestering metal ions within dendrimers followed by chemical reduction to yield the corresponding zerovalent metal nanoparticle. The size of such particles depends on the number of metal ions initially loaded into the dendrimer. Intradendrimer hydrogenation and carbon−carbon coupling reactions in water, organic solvents, biphasic fluorous/organic solvents, and supercritical CO2 are also described.

http://rcrooks.cm.utexas.edu/research/resources/Publications/rmc113.pdf

Dendrimer-Encapsulated Metal Nanoparticles: Synthesis, Characterization, and Applications to Catalysis

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Organic Chemistry By Dr. I. L. Finar. Vol. 2: Stereochemistry and the Chemistry of Natural Products. Pp. xi + 733. (London and New York: Longmans, Green and Co., Ltd., 1956.) 40s. net.

Advanced Organic Chemistry

Metal-mediated reductive hydrodehalogenation of organic halides.

Selective oxidations by nitrous acid in aqueous sulfuric acid towards alkyl side chains of enolizable ketones are reported. The conversion reagents–products in different experimental conditions is explored and the reaction path of the compounds involved as intermediates is tested. Side-chain oxidations are particularly successful for substrates with one site or with equivalent sites of oxidation. Thus, 95% of benzoylformic acid from acetophenone and 60% of 1,2-cyclohexanedione from cyclohexanone are obtained at ∼78 and at ∼40% H 2 SO 4 , respectively. Kinetic ( k obs ) and thermodynamic ( k °) rate constants of acetophenone are also determined, the latter by using the acidity dependence of the rates, the equilibria involving the reacting species and the departure from the ideality of the catalytic acid system. Details of the process between enolizable ketones and electrophilic species in concentrated aqueous acid solutions are discussed.

/pdf/selective-oxidations-by-nitrosating-agents-part-1-oxidations-2hn9vlh1eh.pdf

Selective oxidations by nitrosating agents: Part 1: Oxidations of ketones in concentrated sulfuric acid

The [PdCl2(dppf)] complex efficiently catalyzes the terpolymerization of propene and ethene with carbon monoxide in HCOOH–H2O as a solvent, when H2O concentration ranges between 50 and 65 molar %. The productivity, the melting temperature and the viscosity average molecular weight of the terpolymer depend on the propene concentration and on the reaction time. The NMR analysis of the polymer composition indicates the presence along the chain mainly of ethene–CO units together with a low percent of propene–CO units. A reaction mechanism is proposed and discussed.

/pdf/terpolymerization-of-propene-and-ethene-with-carbon-monoxide-4h0q00kf0w.pdf

Terpolymerization of propene and ethene with carbon monoxide catalyzed by (PdCl2(dppf)) in HCOOH-H2O as a solvent (dppf = 1,1 -bis(diphenylphosphino)ferrocene)

The copolymerization of ethene with carbon monoxide catalyzed by [Pd(OAc)2(dppp)] in an aprotic solvent such as 1,4-dioxane or nitromethane is efficiently promoted both by H2O and HCOOH and yields a perfectly alternating polyketone (PK). The influence of the concentration of the promoters, pressure and temperature on the catalyst productivity and the limiting viscosity number (LVN) has been studied. The productivity increases with the increase of temperature and pressure. The LVN increases upon increasing the pressure and lowering the temperature. At 363 K and 9.0 MPa, in HCOOH/H2O/1-4,dioxane (2.7/1.35/1 molar ratio), the productivity is 37.50 kgPK (gPd h)−1 (LVN 2.77 dL g−1). LVN lowers upon increasing the concentration of the acid, suggesting that it is involved in the protonolysis chain-transfer process.

/pdf/influence-of-formic-acid-and-water-on-the-pd-oac-2-dppp-5kaha7dxog.pdf

Influence of formic acid and water on the (Pd(OAc)2(dppp)) catalyzed ethene-carbon monoxide copolymerization carried out in aprotic organic solvents

The reactivity of a nitrosating agent (N2O3) on oxidations of alcohols and the methyl group of acetophenone were tested. Active electrophylic surface nitrosonium ions (NO+) was detected on H2SO4/SiO2 catalysts by Raman spectroscopy, suggesting a surface ionic mechanism of oxidation in agreement with the one proposed in acid aqueous solutions. Alcohols are selectively oxidized to ketones and aldehydes in high yield, useful for synthetic applications, at 25 °C in 1,2-dichlorethane and using commercial sulfonated styrene divinyl benzene resins (Amberlyst 15®) as catalysts. In addition, nitrous acid ester has been observed as intermediates according to an ionic mechanism by surface NO+. Under the same reaction conditions, acetophenone is selectively oxidized to benzoyl cyanide in high yield and selectivity. The comparison with oxidation carried out in aqueous solution of HNO2, where benzoyl formic acid was obtained, suggests that the differences in the final products are likely due to the specific stabilizing effect of each solvent. Moreover, the reactivity of the intermediates isolated in aqueous systems implies that α-nitroso-acetophenone is a probable reaction intermediate also in aprotic heterogeneous systems.

/pdf/selective-oxidations-by-nitrosating-agents-part-2-oxidations-2op6k95iv2.pdf

Selective oxidations by nitrosating agents. Part 2: Oxidations of alcohols and ketones over solid acid catalysts

Indole and its derivatives are molecules which play important roles in different fields, from biology to pharmacology. Here we report a thorough investigation on the anharmonic force fields of indole as well as the ab initio determinations of its gas phase basicity and aqueous pKa value. For the geometry optimizations, the calculations have been performed using both density functional (DFT) and second-order Moller–Plesset (MP2) levels of theory employing different basis sets. Anharmonic force fields have been obtained employing both the B3LYP and the B97-1 functionals and an hybrid approach: the best agreement to the experimental data has been determined employing the B3LYP functional combined with the recently developed N07D basis set (mean unsigned error, MUE, of 5.1 cm–1 and a root-mean-square error, RMSE, of 7.2 cm–1). Gas phase basicity and proton affinity have been computed employing several computational schemes, namely the G3 and G4 Gaussian models, the complete basis set (CBS) extrapolation metho...

Lucio Ronchin

Papers

Selective oxidations by nitrosating agents: Part 1: Oxidations of ketones in concentrated sulfuric acid

Terpolymerization of propene and ethene with carbon monoxide catalyzed by (PdCl2(dppf)) in HCOOH-H2O as a solvent (dppf = 1,1 -bis(diphenylphosphino)ferrocene)

Influence of formic acid and water on the (Pd(OAc)2(dppp)) catalyzed ethene-carbon monoxide copolymerization carried out in aprotic organic solvents

Selective oxidations by nitrosating agents. Part 2: Oxidations of alcohols and ketones over solid acid catalysts

Quantum Chemical Investigation on Indole: Vibrational Force Field and Theoretical Determination of Its Aqueous pKa Value