Freie Auflösungen äußerer Potenzen

Let R be a commutative noetherian ring with identity. To a finite free resolution F of an R-module M and every integer p1 we associate finite free complexes C _* ^p F. C _* ^p F is a free resolution of PM-the p-th exterior power of M if the degree of torsionfreeness of M is large enough. Using C _* ^p F we further study the degree of torsionfreeness of PM. As an application we prove a special case of a conjecture of P. Hackman concerning a connection between rank and torsionfreeness of a module.     

CCSD(T) expectation value calculations of first-order properties

An expectation value approach to calculations of first-order properties using the non-iterative, triple-excitation amplitudes in the coupled cluster wave function is exploited. Three methods are suggested and analysed using the many body perturbation theory (MBPT) expansion arguments. The first method, in which non-iterative triple-excitation amplitudes are used in the expression for the expectation values, makes the wave function accurate through the second order of MBPT. In the second method, which is an extension of the first, effects of triple-excitation amplitudes are coupled with single- and double-excitation amplitudes. The correlated density matrix equivalent through the fourth order to that obtained when CCSDT-la amplitudes are used is employed in the third method. The suggested methods are tested on dipole moment and polarizability calculations for several diatomic closed-shell molecules and are compared to other related approaches. Received: 15 May 1997 / Accepted: 5 June 1997     

Complex forming and extraction properties of oligo benzo-fused crown ethers

The complex forming properties with alkali metal and ammonium ions of a series of oligo benzo-condensed 18-crown-6 ethers1–8 having a different gradation of lipophilicity and of molecular rigidity are investigated by voltammetry at the interface of two immiscible electrolyte solutions (ITIES) and by a liquid-liquid extraction technique. The experimental results obtained in the two phase system H₂O/nitrobenzene are discussed in relation to the structure of the crown and the cation type. The stability constants for the 1 : 1 complexes of Na⁺, K⁺, Rb⁺, Cs⁺ and NH ₄ ⁺ in nitrobenzene have been determined and compared with the extraction constants for the 1: 1 complexes of Na⁺ and K⁺ and for the 1 : 1 and 1 : 2 complexes of Cs⁺, showing the effect of oligo benzo condensation for the 18-crown-6 system.     

On the formation of protonated acetic acid from ionized n-alkanoic acids in the gas phase

By means of collisional activation mass spectrometry and semi-empirical molecular orbital calculations (MNDO) it is shown that the [C₂H₅O₂]⁺ ions from metastable molecular ions of n-pentanoic and hexanoic acid have the structure of carbonyl protonated acetic acid [CH₃C(OH)₂]⁺. The MNDO calculated geometries of this ion and some other isomeric forms are given together with the ΔH_f⁰ values.     

Biologically active metabolites from fungi, 19: new isocoumarins and highly substituted benzoic acids from the endophytic fungus, Scytalidium sp

Six known metabolites, two new isocoumarins 4 and 8, and one new highly substituted benzoic acid derivative 9 were isolated from the ethyl acetate culture extract of a fungal endophyte, Scytalidium sp. In addition, another new benzoic acid 10 with an unusual 1,2-dicarbonyl side chain was indirectly identified from its methylated derivatives 10a-10d.     

Heats of formation of [2.2]paracyclophane-1-ene and [2.2]paracyclophane-1,9-diene - an experimental study

The enthalpies of formation [Delta(g)] of tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),10(14),11-heptaene (2, 1,2-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1-ene) and tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),8,10(14),11-octaene (3, 1,2,9,10-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1,9-diene) have been determined by measuring their heats of combustion in a microcalorimeter and their heats of sublimation by the transpiration method. Values of the strain energies (SE) [SE(2) = 34.7 kcal mol(-)(1), SE(3) = 42.0 kcal mol(-)(1)] have been derived from the gas-phase heats of formation and are compared with those from MM3 and PM3 calculations and with the corresponding value SE(1) = 30.1 kcal mol(-)(1) for the parent tricyclo[8.2.2.2(4,7)]hexadeca-1(13),4(16),5,7(15),10(14),11-hexaene (1, [2.2]paracyclophane). The higher strain energies of 2 and 3 (by 4.6 and 11.9 kcal mol(-)(1)) are in accord with the well-known increased reactivities of their aromatic rings as a consequence of their increased bending. As revealed by an X-ray crystal structure analysis, the bending in the monoene 2 corresponds to that of 1 and 3 at one of two bridging corners.     

Synthesis of optically active 2-benzyldihydrobenzopyrans for the hypoglycemic agent englitazone

Two syntheses of some optically active 2-benzyl-2,3-dihydro-4H-benzopyrans and benzopyran-4-ones are presented. An asymmetric synthesis starting from D- and L-phenylalanine was used to provide both enantiomers of 2-benzyl-6-(methoxycarbonyl)-2,3-dihydro-4H-benzopyran-4-one 19. Phenylalanine was diazotized in aqueous sulfuric acid to 2-hydroxy-3-phenylpropionic acid 6 which was converted in four steps to 1-bromo-2-(4-methoxycarbonylphenoxy)-3-phenylpropane 11. (4R,S)-Benzamido-2-benzyl-2,3-dihydro-6-(methoxycarbonyl)-4H-1-benzopyran-4-carboxylic acid 16 was prepared from 11 by amidoalkylation with α-hydroxyhippuric acid in methanesulfonic acid solution followed by spiroalkylation to (4R,S)-2-benzyl-2,3-dihydro-6-(methoxycarbonyl)spiro[4H-benzopyran-4,4′-2′-phenyloxazolidin]-5′-one 15. After the phenyloxazolidin-5-one 15 was hydrolyzed to the spirobenzamido carboxylic acid 16 , oxidative decarboxylation with sodium hypochlorite yielded optically active 2-benzyl-6-(methoxycarbonyl)-2,3-dihydro-4H-benzopyran-4-one 19. The ketone in 19 was reduced by hydrogenation over palladium on carbon to a methylene group and the ester was converted to the aldehyde to give both isomers of the desired intermediate 2-benzyl-6-(formyl)-2,3-dihydro-4H-benzopyran 25. The second synthesis relied on an enzymatic hydrolysis of ethyl 2,3-dihydrobenzopyran-2-carboxylate 27 with the lipase from P. fluorescens to provide the desired 2R-ester. The ester group in (R)- 27 was converted to the triflate (R)- 29. Displacement of the triflate group with phenylmagnesium bromide and cuprous bromide as catalyst gave 2R-benzyl-2,3-dihydro-4H-benzopyran (R)- 30. Formylation of (R)- 30 provided 2R-benzyl-6-(formyl)-2,3-dihydro-4H-benzopyran (R)- 25 identical with that from the first synthesis. These optically active intermediates are used in the preparation of the hypoglycemic agent englitazone.     

Neutrino oscillations in the sun and the205Tl solar neutrino experiment

Neutrino induced transition rates from²⁰⁵Tl to excited states in²⁰⁵Pb were calculated for neutrino fluxes from the different hydrogen burning reactions in the sun. Suppression factors for electron neutrinos due to flavor oscillations in the sun were obtained. The influence of neutrino oscillations on the neutrino capture rate of²⁰⁵Tl in dependence of the mixing angle and neutrino mass difference is discussed.Dedicated to Prof. Dr. P. Kienle on the occasion of his 60th birthday     

Dioxygen activation by a low-valent cobalt complex employing a flexible tripodal N-heterocyclic carbene ligand

The novel versatile cobalt(I) tris-carbene complex [(TIMEN(xyl))Co]Cl (1) (where TIMEN = (tris[2-(3-arylimidazol-2-ylidene)ethyl]amine) reacts with CO, one-electron oxidizers such as CH(2)Cl(2), and O(2) to yield the cobalt complexes [(TIMEN(xyl))Co(CO)]Cl (2), [(TIMEN(xyl))Co(Cl)]Cl (3), and peroxo species [(TIMEN(xyl))Co(O(2))](BPh(4)) (5). All new complexes were fully characterized by (1)H NMR, UV/vis, and IR spectroscopy as well as superconducting quantum interference device (SQUID) magnetization measurements and single-crystal X-ray crystallography. The nucleophilic character of the eta(2)-bound dioxygen ligand in 5 was confirmed by density functional theory (DFT) studies and allows for oxygen-transfer reactions with electron-deficient organic substrates, such as benzoyl chloride.