Nucleophilic additions to fused bicyclic five-membered ring oxocarbenium ions: evidence for preferential attack on the inside face

Evidence is provided that nucleophilic attack on five-membered ring oxocarbenium ions occurs from the inside face of the envelope. An eight-five fused-bicyclic system in which two substituents are constrained to pseudoequatorial positions underwent nucleophilic addition with selectivity that was comparable to an unconstrained monocyclic system. On the other hand, a bicyclic six-five analogue underwent reaction with low selectivity. This observation indicates that minimization of eclipsing interactions by attacking inside the envelope is not enough to control selectivity, but that the changes in the overall three-dimensional structure of the ring must be favorable as well. In the bicyclic six-five series, the six-membered ring is accommodated in the cation, but it destabilizes the transition state structure leading to the first-formed product of inside attack.     

The hit problem for the Dickson algebra

Let the mod 2 Steenrod algebra, , and the general linear group, , act on with in the usual manner. We prove the conjecture of the first-named author in Spherical classes and the algebraic transfer, (Trans. Amer. Math Soc. 349 (1997), 3893-3910) stating that every element of positive degree in the Dickson algebra is -decomposable in for arbitrary 2$">. This conjecture was shown to be equivalent to a weak algebraic version of the classical conjecture on spherical classes, which states that the only spherical classes in are the elements of Hopf invariant one and those of Kervaire invariant one.

     

Study on the isomeric ratios of (γ,p) photonuclear reactions with isotopes 40 92 Zr and 74 183 W in the giant dipole resonance region

We have carried out the study on the isomeric ratios in (γ,p) photonuclear reactions with isotopes ₄₀ ⁹² Zr and ₇₄ ¹⁸³ W in the giant dipole resonance (GDR) region. The targets were irradiated with bremsstrahlungs produced by electron accelerator Microtron MT-25 of the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia. Spectra of the irradiated samples were measured with a spectroscopic system consisting of 8192-channel analyzer CANBERRA and high-energy resolution semiconductor detector CANBERRA. The results were discussed and compared with those of other authors. The text was submitted by the authors in English.     

Direct observation of the temperature field during ablation of materials by multiple femtosecond laser pulses

We report a direct observation of the temperature field on a steel specimen during ablation by multiple femtosecond laser pulses using an infrared thermography technique. From the experimental results and simulation study of the temperature field, we quantified the deposited thermal power into the specimen during the ablation process. We found that more than two thirds of the incident laser power was deposited in the steel specimen when ablated by multiple femtosecond laser pulses. This result provides further understanding of the heating effect in materials processing by ultrashort laser pulses.     

Line intensities in the 1.5-μm spectral region of acetylene

Line intensities are measured for 546 transitions belonging to 13 bands of the main isotopologue ¹²C₂H₂ of the acetylene molecule, in the 1.5-μm spectral domain. A multispectrum fitting procedure is used to retrieve line parameters from Fourier transform spectra. Prior to this work, line intensities were known for only 4 bands in this spectral region, from the work of El Hachtouki and Vander Auwera [Absolute line intensities in acetylene: the 1.5 μm region. J Mol Spectrosc 2002;216:355-62]. An excellent agreement is found with the results of these authors, showing that the accuracy of both results is likely better than 1% for the strong bands. However, the spectrum becomes very crowded when one wants to study weaker bands, so that the average accuracy of the intensities reported in the present work is 5%. From these data, vibrational transition dipole moments squared and Herman-Wallis coefficients have been determined for all the bands.     

Structural studies of the chemical constituents of Tithonia tagetiflora Desv. (Asteraceae)

Tithonia tagetiflora Desv. (Asteraceae) is a widespread plant in Vietnam, and the species of Tithonia are known as plants containing many biologically active compounds. However, T. tagetiflora's chemical composition remains mostly unknown. Therefore, we now report the structural elucidation of two new sesquiterpene lactones, 8‐angeloyloxy‐2,14‐epoxygermacra‐4,10(1),11(13)‐trien‐6,12‐olide (1) and 6‐angeloyloxy‐1‐hydroxy‐3,4‐epoxygermacra‐9,11(13)‐dien‐8,12‐olide (2), together with three known compounds, including two norisoprenoids, (6S,9S)‐vomifoliol or (6R,9R)‐vomifoliol (3) and (6S,9S)‐roseoside (4), and one glutinane type triterpene, epi‐glutinol (5), from the leaves of T. tagetiflora. Their structures are established by 1D and 2D NMR spectroscopy, as well as ESI‐MS analysis and comparison with literature data. Copyright © 2013 John Wiley & Sons, Ltd.     

A new minor butenolide from <Emphasis Type="Italic">Machilus odoratissima</Emphasis>

A new butenolide, designated odoratinolide (1), was isolated from the bark of the Vietnamese medicinal plant Machilus odoratissima. Its structure was determined by spectroscopic analyses.     

Synthesis of polynorbornene‐poly(tert‐butyl acrylate) nanoparticles with original morphologies by tandem ROMP and ATRP in microemulsion

Composite latex particles based on homopolymers and graft‐copolymers composed of polynorbornene (PNB) and poly(tert‐butyl acrylate) (PtBA) were synthesized in microemulsion conditions by simultaneous combination of two distinct methods of polymerization: Ring‐opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). Only one commercial compound (first generation Grubbs catalyst) was used to initiate the ROMP of norbornene (NB) and activate the ATRP of tert‐butyl acrylate (tBA). Well‐defined nanoparticles with hydrodynamic diameters smaller than 50 nm were prepared with original morphologies depending on the monomer compositions, the type of combination (polymer blend or graft‐copolymer), and the conditions of microemulsion polymerizations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Infrared investigation of benzene to 30 GPa transformation to a polymer

Abstract

After a pressure cycle to 30 GPa, benzene transforms to a white solid which can be recovered at ambient. Results obtained from infrared spectroscopy and other physico-chemical methods show that the recovered solid is a highly cross-linked polymer. The molecular structure of benzene is very likely completely altered by the transformation.