Reaktionen cyclischer Oxalylverbindungen, 34. Mitt.: Synthese von Dibenzoylacet-N-carboxyalkylamiden und semiempirische Rechnungen zur Keto-Enol Tautomerie

Summary 4-Benzoyl-5-phenylfuran-2,3-dione (1) and the urethanes2 combine under loss of carbon monoxide yielding the open chain dibenzoylacetic acid derivatives3 and4. 3a, b only can be cyclized to the oxazinone5. The keto-enole tautomerism3 4 is further investigated with aid of semiempirical quantum chemical calculations, based upon the molecular geometry of3a, deduced from an X-ray study.

Frau Univ. Prof. Dr. Helga Wittmann mit den besten Wünschen zum 70. Geburtstag gewidmet.     

Efficient syntheses of (±)-hydrangenol, (±)-phyllodulcin and (±)-macrophyllol

In this paper we report on a efficient and flexible synthetic route towards the total syntheses of the dihydrocoumarine derivatives hydrangenol (1), phyllodulcin (1a) and macrophyllol (6b). The syntheses started with a readily available phosphonium salt 2 and suitable modified benzaldehydes 3/3a/3b resulting in 46 to 61% overall yields in three to four-steps sequences. The racemic products could be separated by chiral HPLC. The evidence of the (R)-enantiomer for sweetness could be demonstrated for 1a.     

Manganese(III) acetate mediated synthesis of 3-trifluoroacetyl-4,5-dihydrofurans and 3-(dihydrofuran-2(3H)-ylidene)-1,1,1-trifluoroacetones by free radical cyclization. Part 1

2-Trifluoroacetyl-4,5-dihydrofurans were obtained by manganese(III) acetate mediated radical cyclization of trifluoromethyl-1,3-dicarbonyl compounds (1a-c) with conjugated alkenes (2a-h). The reaction of 1,1,1-trifluoropentane-2,4-dione (1a) with propenylbenzene and 1,1-diphenyl-1-butene surprisingly yielded 3-(dihydrofuran-2(3H)-ylidene)-1,1,1-trifluoroacetones besides 3-trifluoroacetyl-4,5-dihydrofurans.     

Alcohol-soluble functional vic-dioxime bearing alcoholhexylsulfanyl moieties: preparation, spectroscopy and electrochemistry

A new alcohol soluble functionalized vic-dioxime, bis-[(1-hydroxyhexyl)-(8,9-hydroxyimino)-7,10-dithiahexacosane (LH₂), and its alcohol-soluble mono and dinuclear complexes (Ni^II, Cu^II, Co^II, Mn^II, Pd^II and UO ₂ ^II ) have been prepared from 6-mercapto-1-hexanol and (E,E)-dichloroglyoxime under high dilution basic conditions. Reactive polyalcohol moieties appended at the periphery of the oxime containing two different heteroatoms (S-, O-), serve as a weak exocyclic binding sites for Pd^II and Ag^I metal ions and also provide solubility for the vic-dioxime complexes in low molecular-weight alcohols. Both mono-nuclear (LH)₂M and homodinuclear (LH)₂(UO₂)₂(OH)₂ and heterotrinuclear (LH)₂MM ₂ ^′ Xn, where M = Co^II M′ = Pd^II, X = Cl⁻, n = 4 and Ag^I X = NO ₃ ⁻ , n = 2) complexes have been obtained with a 1:2, 2:2, 3:2 metal/ligand ratio, respectively. Electronic spectra of the modified vic-dioximes exhibit monitorable changes in UV. All mono and dinuclear-complexes are soluble in common organic solvents. The elemental analysis, ¹H-n.m.r, i.r., u.v–vis, and f.a.b.–m.s data and by cyclic and differential pulse voltammetry measurements are presented.     

Variational approximations for renormalization group transformations

Approximate recursion relations which give upper and lower bounds on the free energy are described. Optimal calculations of the free energy can then be obtained by treating parameters within the renormalization equations variationally. As an example, a particularly simple lower bound approximation which preserves the symmetry of the Hamiltonian (the one-hypercube approximation) is described. The approximation is applied to both the Ising model and the Wilson-Fisher model. At the fixed point a parameter is set variationally and critical indices are calculated. For the Ising model the agreement with the exact results atd = 2 is surprisingly good, 0.1%, and is good atd=3 and evend=4. For the Wilson-Fisher model the recursion relation is reduced to a one-dimensional integral equation which can be solved numerically givingv=0.652 atd=3, or by expansion in agreement with the results of Wilson and Fisher to leading order in . The method is also used to calculate thermodynamic functions for thed = 2 Ising model; excellent agreement with the Onsager solution is found.Supported in part by the National Science Foundation under Grants Nos. MPS73-04886A01 and GH-41512 and by the Brown University Materials Research Laboratory supported by the National Science Foundation. M.C.Y. was supported by a grant from the Scientific and Technical Research Council of Turkey.     

A New Entropy Function to Analyze Isentropic Processes of Ideal Gases with Variable Specific Heats

A new entropy function s⁺ is defined in terms of the existing entropy function s° and temperature as s⁺ = s° − R lnT to facilitate the analysis of isentropic processes of ideal gases with variable specific heats. The function s⁺ also makes it possible to calculate the entropy changes of ideal gases during processes when volume information is available instead of pressure information and the variation of specific heats with temperature is to be accounted for. The introduction of the function s⁺ eliminates the need to use the dimensionless isentropic functions relative pressure P_r and relative specific volume v_r of ideal gases and to tabulate their values. The P_r and v_r data are often confused with pressure and specific volume, with an adverse effect on the study of the second law of thermodynamics. The new s⁺ function nicely complements the existing s° function in entropy change calculations: the former is conveniently used when volume information is given while the latter is used when pressure information is available. Therefore, the introduction of the new entropy function s⁺ is expected to make a significant contribution to the thermodynamics education and research by streamlining entropy analysis of ideal gases.     

Electroinitiated Polymerization of N-Vinylcarbazole by Direct Electron Transfer

Electroinitiated polymerization of N-vinylcarbazole has been accomplished by constant potential electrolysis. It was found that direct electron transfer from the monomer to the anode initiates the polymerization even at a potential as low as +0.95 V versus Ag^?/ Ag⁺. Dichloromethane was used as the solvent, and the electrolyte was tetrabutylammonium fluoroborate. Conversions as high as 86% were reached even when a microelectrode was used. Effects of electrode area, temperature, and electrode potential on polymerization were studied. Percent conversion was followed by cyclic voltammetry.     

A novel amperometric hydrogen peroxide biosensor based on pyrrole-PAMAM dendrimer modified gold electrode

Horseradish peroxidase (HRP) was immobilized into an electrochemically prepared copolymer of pyrrole–PAMAM (PAMAM; polyamidoamine) dendrimers for the construction of amperometric hydrogen peroxide biosensor. First, second, and third generation amidoamine–pyrrole dendrons having branched amine periphery and focal pyrrole functionality were synthesized via divergent pathway. Pyrrole dendrimers were covalently attached onto the electrode surface and polymerized by electrochemical copolymerization with pyrrole monomer. The synthesized dendrimers and copolymers have been characterized by FTIR-ATR and NMR. These copolymers have been utilized as conducting films for amperometric hydrogen peroxide sensing. The HRP retains its bioactivity after immobilization into the dendronized pyrrole-copolymers. Amperometric response was measured as a function of concentration of hydrogen peroxide, at fixed potential of +0.35 V vs. Ag/AgCl in a phosphate buffered saline (pH 7.5). The effect of pH and temperature of the medium, storage, and reusability properties were investigated. The results indicate an efficient immobilization of enzyme onto the PAMAM type dendrimer modified surface containing pyrrole monomer, which leads to high enzyme loading, and increased lifetime stability of the electrode.