Vilsmeier Reaction of Enaminones: Efficient Synthesis of Halogenated Pyridin-2(1H)-ones

A facile and efficient one-pot synthesis of halogenated pyridin-2(1H)-ones from a series of readily available enaminones under Vilsmeier conditions is described, and a mechanism involving sequential halogenation, formylation, and intramolecular nucleophilic cyclization is proposed.

Aza-annulation of enaminones with itaconic anhydride:kinetic preference for exocyclic enamide products

Enaminones react with itaconic anhydride in methylene chloride at room temperature to give exocyclic enamides sis the major products. These can be readily equilibrated to the thermodynamically more stable endocyclic enamides. In substrates where the exocyclic isomer could not be formed only intractable materials were produced from this reaction. An intermediate in this two step process was detected and identified by proton and C-13 NMR spectroscopy. In two cases chiral enaminones were employed and the relative stereochemistry at the new chiral centre in the product was established by a crystal structure of compound 27.

Asymmetric Diels-Alder Reactions of Chiral Acrylates of Cholic Acid Derivatives

New steroid-based chiral auxiliaries 6, 9, and 12 have been synthesized from readily available cholic acid. These new chiral auxiliaries place the reactive and the shielding sites in a 1,5 relationship to each other. Diels-Alder reaction of cyclopentadiene with corresponding acrylate esters (7, 10, and 13) have been examined. Acrylates 7 and 10 yielded cycloadducts with 29-88% diastereomeric excess with excellent endo selectivity in the presence of an excess of Lewis acids such as AlCl3, BF3.OEt(2), FeCl3, SnCl4, TiCl4, and ZnCl2. Treatment of acrylate 7 with cyclopentadiene in the presence of BF3.OEt(2) at -80 degrees C gave the endo adduct (>99%) with 88% de. Lewis acid catalyzed and uncatalyzed reactions of acrylates 7 and 10 with cyclopentadiene yielded cycloadducts with opposite stereochemistry. The chiral auxiliary was recovered in a nondestructive manner only via iodolactonization. Acrylate ester of alcohol 12 did not show any selectivity in either catalyzed and uncatalyzed reactions with cyclopentadiene. The presence of a flat aromatic surface at C-7 of the steroid was found to be essential to effect high diastereoselection.

Gas-phase ion-molecule reactions of C-60 with the plasma of methyl acrylate

The gas-phase ion-molecule reactions of C-60 with the plasma generated from methyl acrylate under self-chemical ionization conditions were studied by use of a triple-quadrupole mass spectrometer. The adduct cation [C60C3H3O](+) and protonated molecular ion [C60H](+) were observed as the major product ions. The former adduct ion is formed by electrophilic reaction of C-60 with the ion [CH2=CHCO](+), a main fragment ion resulting from the methyl acrylate molecular ion [CH2=CHCOOCH3](+) through alpha cleavage. The latter ion is generated by proton transfer from protonated methyl acrylate to C-60. Semi-empirical quantum chemical calculations have been performed for the eight possible isomers of [C60C3H3O](+) at the Hartree-Fock level by use of the AMI method. The results show three types of cycloadducts as the most stable structures among the possible isomers.

N-Substituent effect of maleimides on acrylate polymerization initiated by three-component systems

In this paper, the relative photopolymerization efficiency for polymerization of a difunctional acrylate initiated by various N-substituted maleimides in the presence of amine and benzophenone are compared on the basis of a photo-differential scanning calorimetry (photo-DSC) study. The trends in the polymerization rates were obtained from the photopolymerization profiles and expressed in terms of a photoinitiation index, I-p. An N-substituent index, I-s, which indicates whether each N-substituent plays either a positive (when I-s > 1) or a negative (when I-s < 1) role in the initiation process relative to MI (unsubstituted maleimide), was determined. (C) 2003 Society of Chemical Industry.

Numerical simulation for the 3D seepage flow with fractional derivatives in porous media

In this paper, the numerical simulation of the 3D seepage flow with fractional derivatives in porous media is considered under two special cases: non-continued seepage flow in uniform media (NCSFUM) and continued seepage flow in non-uniform media (CSF-NUM). A fractional alternating direction implicit scheme (FADIS) for the NCSF-UM and a modified Douglas scheme (MDS) for the CSF-NUM are proposed. The stability, consistency and convergence of both FADIS and MDS in a bounded domain are discussed. A method for improving the speed of convergence by Richardson extrapolation for the MDS is also presented. Finally, numerical results are presented to support our theoretical analysis.

Modified alternating direction methods for solving a two-dimensional non-continuous seepage flow with fractional derivatives

In this paper, a two-dimensional non-continuous seepage flow with fractional derivatives (2D-NCSF-FD) in uniform media is considered, which has modified the well known Darcy law. Using the relationship between Riemann-Liouville and Grunwald-Letnikov fractional derivatives, two modified alternating direction methods: a modified alternating direction implicit Euler method and a modified Peaceman-Rachford method, are proposed for solving the 2D-NCSF-FD in uniform media. The stability and consistency, thus convergence of the two methods in a bounded domain are discussed. Finally, numerical results are given.

Numerical methods for fractional partial differential equations with Riesz space fractional derivatives

In this paper, we consider the numerical solution of a fractional partial differential equation with Riesz space fractional derivatives (FPDE-RSFD) on a finite domain. Two types of FPDE-RSFD are considered: the Riesz fractional diffusion equation (RFDE) and the Riesz fractional advection–dispersion equation (RFADE). The RFDE is obtained from the standard diffusion equation by replacing the second-order space derivative with the Riesz fractional derivative of order αset membership, variant(1,2]. The RFADE is obtained from the standard advection–dispersion equation by replacing the first-order and second-order space derivatives with the Riesz fractional derivatives of order βset membership, variant(0,1) and of order αset membership, variant(1,2], respectively. Firstly, analytic solutions of both the RFDE and RFADE are derived. Secondly, three numerical methods are provided to deal with the Riesz space fractional derivatives, namely, the L1/L2-approximation method, the standard/shifted Grünwald method, and the matrix transform method (MTM). Thirdly, the RFDE and RFADE are transformed into a system of ordinary differential equations, which is then solved by the method of lines. Finally, numerical results are given, which demonstrate the effectiveness and convergence of the three numerical methods.

Do derivatives have a role in the risk-shifting behaviour of fund managers?

In this paper we examine the extent to which derivatives are used to affect the risk-shifting behaviour of Australian equity fund managers. We find, after periods of good and poor performance, the risk-shifting behaviour of fund managers is different between derivative users and non-users. Our results support the gaming and active competition hypotheses but there is little support for the cash flow hypothesis. The study also allows for a complex reporting environment by analysing data across three alternate time periods: the calendar year, financial year and quarterly frames. Given that our results are not consistent across time periods for users and non-users of derivatives, some caution in interpretation is required.