sigma-Ferrier rearrangement of carbohydrate derived vinylcyclopropanes: a facile approach to oxepane analogs

This article presents our work on the sigma-Ferrier ring-expansion of carbohydrate derived vinylcyclopropanes (VCPs) under electrophilic conditions mediated by chloramine-T and a phase-transfer catalyst. The present work serves as the first example on the studies of the reactivity of carbohydrate VCPs towards the synthesis of densely functionalized oxepane analogues. The work elaborates on a reasonable mechanism for the product formation and our observations on the diastereoselectivity based on control experiments and gas-phase calculations. (C) 2014 Elsevier Ltd. All rights reserved.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

The extent of the rearrangement of material in Neuwerk/Scharhom flat [Translation from: Hamburger Kuestenforschung 33, 1-24 [p23 only], 1975]

Investigations of the rearrangement of material in Neuwerk/Scharhom flat showed that with the exception of the western border/edge and the parts of the Elbe and Oste shores/banks which lie most seawards, the entire mudflat area is only infrequently exposed to strong hydraulic forces. Only in extreme conditions, which on average occur rarely more than once a year, would the mudflats be severely affected. This partial translation provides the summary of the original article only.

Bicyclo[3.2.0]hepta-1,4,6-triene: synthesis, thermal rearrangement, and anion formation

In order to determine the properties of the bicycloheptatrienyl anion (Ia) (predicted to be conjugatively stabilized by Hückel Molecular Orbital Theory) the neutral precursor, bicyclo[3. 2. 0] hepta-1, 4, 6-triene (I) was prepared by the following route.

Reaction of I with potassium-t-butoxide, potassium, or lithium dicyclohexylamide gave anion Ia in very low yield. Reprotonation of I was found to occur solely at the 1 or 5 position to give triene II, isolated as to its dimers.

A study of the acidity of I and of other conjugated hydrocarbons by means of ion cyclotron resonance spectroscopy resulted in determination of the following order of relative acidities:

H₂S ˃ C₅H₆ ˃ CH₃NO₂ ˃ 1, 4- C₅H₈ ˃ I ˃ C₂H₅OH ˃ H₂O; cyclo-C₇H₈ ˃ C₂ H₅OH; фCH₃ ˃ CH₃OH

In addition, limits for the proton affinities of the conjugate bases were determined:

350 kcal/mole ˂ PA(C₅ H₅^-) ˂ 360 kcal/mole

362 kcal/mole ˂ PA(C₅H₇^-, Ia, cyclo-C₇H₇^-) ˂ 377 kcal/mole PA(фCH₂^-) ˂ 385 kcal/mole

Gas phase kinetics of the trans-XVIII to I transformation gave the following activation parameters: E_a = 43.0 kcal/mole, log A = 15.53 and ∆S^ǂ (220°) = 9.6 cu. The results were interpreted as indicating initial 1,2 bond cleavage to give the 1,3-diradical which closed to I. Similar studies on cis-XVIII gave results consistent with a surface component to the reaction (E_a = 22.7 kcal/mole; log A = 9.23, ∆S^ǂ (119°) = -18.9 eu).

The low pressure (0.01 to 1 torr) pyrolysis of trans-XVIII gave in addition to I, fulvenallene (LV), ethynylcyclopentadiene (LVI) and heptafulvalene (LVII). The relative ratios of the C₇H₆ isomers were found to be dependent upon temperature and pressure, higher relative pressure and lower temperatures favoring formation of I. The results were found to be consistent with the intermediacy of vibrationally excited I and subsequent reaction to give LV and LVI.

A method for VVER-1000 fuel rearrangement optimization taking into account both fuel cladding durability and burnup

A method for VVER-1000 fuel rearrangement optimization that takes into account both cladding durability and fuel burnup and which is suitable for any regime of normal reactor operation has been established. The main stages involved in solving the problem of fuel rearrangement optimization are discussed in detail. Using the proposed fuel rearrangement efficiency criterion, a simple example VVER-1000 fuel rearrangement optimization problem is solved under deterministic and uncertain conditions. It is shown that the deterministic and robust (in the face of uncertainty) solutions of the rearrangement optimization problem are similar in principle, but the robust solution is, as might be anticipated, more conservative. © 2013 Elsevier B.V.

Single particle properties in asymmetric nuclear matter and TBF rearrangement effect

We have developed the formula and the numerical code for calculating the rearrangement contribution to the single particle (s.p.) properties in asymmetric nuclear matter induced by three-body forces within the framework of the Brueckner theory extended to include a microscopic three-body force (TBF). We have investigated systematically the TBF-induced rearrangement effect on the s.p. properties and their isospin-behavior in neutron-rich nuclear medium. It is shown that the TBF induces a repulsive rearrangement contribution to the s.p. potential in nuclear medium. The repulsion of the TBF rearrangement contribution increases rapidly as a function of density and nucleon momentum. It reduces largely the attraction of the BHF s.p. potential and enhances strongly the momentum dependence of the s.p. potential at large densities and high-momenta. The TBF rearrangement effect on symmetry potential is to enhances its repulsion (attraction) on neutrons (protons) in dense asymmetric nuclear matter.

Isospin dependence of three-body force rearrangement contribution

Within the isospin-dependent Brueckner framework, we investigate the contribution of three-body force ( TBF) rearrangement to isospin symmetry potential as well as its momentum and density dependence. In particular, we investigate the TBF rearrangement effects on the isospin splitting of neutron and proton effective masses in neutron-rich nuclear matter. We show that the rearrangement contribution of TBF to neutron and proton single-particle potentials is repulsive and increases rapidly with increasing density and momentum. At low densities, the influence of the TBF rearrangement on symmetry potential is rather small, and the TBF rearrangement effect becomes more and more pronounced as the density rises. At high densities, the contribution of TBF rearrangement increases considerably the symmetry potential and modifies remarkably the momentum dependence of the symmetry potential. In both cases with and without including the TBF rearrangement contribution, the predicted neutron effective mass in neutron-rich matter is greater than the proton effective mass. The TBF rearrangement effect is to decrease remarkably both the proton and neutron effective masses, and reduce the magnitude of neutron-proton effective mass splitting in neutron-rich matter at high densities.

Three-body force rearrangement contribution to single nucleon potential in nuclear matter

Within the framework of microscopic Brueckner-Hatree-Fock, the contribution of the three-body force (TBF) rearrangement to the. single nucleon potential is calculated. The TBF rearrangement effects on the momentum and the density dependence of the single nucleon potential are investigated. The influence of the TBF rearrangement on the effective mass of nucleon is also discussed. It is shown that the rearrangement contribution of TBF is repulsive and momentum-dependent. The TBF rearrangement effect and its momentum dependence increase rapidly as increasing density and momentum. At high densities and high momenta, the repulsive rearrangement contribution reduces strongly the attraction of the single nucleon potential and enhances considerably the momentum dependence of the single nucleon potential.

Three-body force rearrangement effect on single particle properties in neutron-rich nuclear matter

We extend the Brueckner-Hartree-Fock (BHF) approach to include the three-body force (TBF) rearrangement contribution in calculating the neutron and proton single particle (s.p.) properties in isospin asymmetric nuclear matter. We investigate the TBF rearrangement effect on the momentum-dependence of neutron and proton s.p. potentials, the isospin splitting and especially its density dependence of the neutron and proton effective masses, and the isospin symmetry potential in neutron-rich nuclear matter by adopting the realistic Argonne V-18 two-body nucleon-nucleon interaction supplemented with a microscopic TBF. We find that at low densities, the TBF rearrangement effect is fairly weak, whereas the TBF induces a significant rearrangement effect on the s.p. properties at high densities and large momenta. The TBF rearrangement contribution to s.p. potential is shown to be repulsive, and it reduces considerably the attraction of the BHF s.p. potential. The repulsion from the TBF rearrangement turns out to be strongly momentum dependent at high densities and high momenta. As a consequence, it enhances remarkably the momentum dependence of the proton and neutron s.p. potentials and reduces the neutron and proton effective masses. At low densities, the TBF rearrangement effect on symmetry potential is almost negligible, while at high densities, it enlarges sizably the symmetry potential. At high enough densities, it may even change the high-momentum behavior of symmetry potential. In both cases, with and without including the TBF rearrangement contribution, the predicted neutron effective mass is larger than the proton one in neutron-rich matter within the BHF framework; i.e., the predicted isospin splitting of the proton and neutron effective masses in neutron-rich matter is such that m(n)(*)>= m(p)(*), in agreement with the recent Dirac-BHF predictions. The TBF rearrangement contribution reduces remarkably the magnitude of the proton-neutron effective mass splitting at high densities. At high enough densities, inclusion of the TBF rearrangement contribution even suppresses almost completely the effective mass splitting.

Effect of block sequence and block length on the stimuli-responsive behavior of polyampholyte brushes: hydrogen bonding and electrostatic interaction as the driving force for surface rearrangement

Diblock polyampholyte brushes with different block sequences (Si/SiO2/poly(acrylic acid)-b-poly (2-vinylpyridine) (PAA-b-P2VP) brushes and Si/SiO2/P2VP-b-PAA brushes) and different block lengths were synthesized by sequent surface-initiated atom transfer radical polymerization (ATRP). The PAA block was obtained through hydrolysis from the corresponding poly(tert-butyl acrylate). The polyampholyte brushes demonstrated unique pH-responsive behavior. In the intermediate pH region, the brushes exhibited a less hydrophilic wetting behavior and a rougher surface morphology due to the formation of polyelectrolyte complex through electrostatic interaction between oppositely charged blocks. In the low pH and high pH regions, the rearrangement of polyampholyte brushes showed great dependence on the block sequence and block length. The polyampholyte brushes with P2VP-b-PAA sequence underwent rearrangement during alternative treatment by acidic aqueous solution (low pH value) and basic aqueous solution (high pH value).

Vapor phase beckmann rearrangement of cyclohexanone oxime over rare earth pyrophosphates

A new application of rare earth pyrophosphates in vapor phase Beckmann rearrangement of cyclohexanone oxime was investigated. The rare earth phosphates were characterized by means of XRD, FT-IR, NH3-TPD and water contact angle measurement. It was found that the weak surface acidity and appropriate surface hydrophobicity should be two key factors in the excellent performance of these catalysts.