Strukturaufklärung eines Dimethylfulven-Trimeren. Hinweis auf eine [6 + 4]-Cycloaddition von 6, 6-Dimethylfulven

Structure Elucidation of a Dimethylfulvene-trimer. Evidence for a [6+ 4]-Dimerization of 6, 6-Dimethylfulvene Thermal reaction of pure 6, 6-dimethylfulvene ( 1c ) at 60° gives an oligomeric mixture consisting mainly of fulvene-trimers. The structure of the main product 3c is partially elucidated by ¹H-NMR. investigations at 400 MHz and definitely confirmed by X-ray analysis. The formation of 3c is explained in terms of a [6+4] dimerization, followed by a 1, 5-proton-shift and a final Diels-Alder reaction.     

Chloracylierung und Bromacylierung von Carbonylverbindungen. III. Lage des Gleichgewichts

Chloroacylation and Bromoacylation of Carbonyl Compounds III. Reactant/Product Equilibria Aliphatic, α, β-unsaturated and aromatic aldehydes 1 as well as aliphatic ketones react with acyl halides 2 to α-haloalkyl esters 3 . In the presence of Lewis acids there is an equilibrium between reactants and product. The position of the equilibrium depends on the nature of the carbonyl compound as well as that of the acyl halide: The products 3 are favoured in the case of aldehydes, cyclobutanone and cyclohexanone, and the equilibrium constant increases in the series F < Cl < Br < I. Low reaction temperature, nonpolar solvents as well as high reactant concentrations favour the product 3 .     

Wurtzitan (Tetracyclo[5.3.1.12,6.04,9]dodecan)

A new synthesis of wurtzitane (13) is described starting from 2-oxo-protoadamant-4-ene (2). The key intermediate ketone 7 was obtained by regiospecific ring expansion of the β-amino alcohol 6. Entry to the wurtzitane system involved solvolysis of the tricyclic unsaturated mesylate 10 (→11).     

The accuracy of the pseudo-fermion method

The pseudo-fermion method for dynamical fermions is studied using Monte Carlo techniques. Various approximations are tested by calculating the mass gap of the Schwinger model and by comparing it with results obtained with an exact algorithm. The mass found is consistent with that obtained from the exact algorithm, implying that the systematic errors are small. In addition, the mass is almost independent of the number of pseudo-sweeps used, implying that the statistical error inherent in the Monte Carlo of the pseudo-fermion field does not have a strong effect on the observable. Numerical evidence is presented to show that the algorithm gives the correct answer for even a single pseudo-sweep in the limit that the Metropolis hit size goes to zero.