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  • 1985-1989  (5.130)
  • 1840-1849  (4.620)
  • Organic Chemistry  (8.112)
  • Computational Chemistry and Molecular Modeling  (1.638)
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Erscheinungszeitraum
Jahr
  • 101
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 629-647 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two approaches in treating the weak representability problem for density operators are studied. In the first approach this problem is reduced to the minimization of a certain distance function. The second approach is based on inductive generation of linear inequalities for diagonal elements of the second-order density operators. Generalization of Kuhn-Yoseloff's results is also discussed.
    Materialart: Digitale Medien
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  • 102
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 103
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 761-767 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The approximation of hyperpolarizabilities through the use of operator inequalities is sketched. Previously applied methods to ordinary polarizabilities are extended. They lead to expressions involving moments of oscillator strength distributions related through sum rules to ground state properties. Systematic applications of new formulae are suggested.
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  • 104
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 839-850 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A generalization of the Gibbs-Bogoliubov inequality F ≤ F0 + 〈H - H0〉0 for the free energy F is studied which leads to a variation principle for this quantity that may be of importance in certain computational applications to quantum systems. This approach is coupled with a study of the perturbation expansion of the free energy for a canonical ensemble with H = H0 + λV in the general case when H0 and V do not commute. The second- and high-order derivatives of the free energy with respect to the perturbation parameter λ are calculated. From the second-order term is finally obtained a second-order correction to the previous variational minimum for the free energy.
    Materialart: Digitale Medien
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  • 105
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 5-14 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The ab initio calculation has been performed with the addition pathways of HLi and its dimer to acetylene at the RHF/3-21G basis set. It shows that the reaction mechanisms of these two reactions are rather similar. In either of two reaction pathways, there is a meta-stable molecular complex near the isolated reactant state. This kind of addition can be treated approximately as the unimolecular reaction in which the molecular complex rearranges into the product. We have estimated the activation entropies and the statistical A factors of these two reactions by the use of RRKM theory. Frontier molecular orbital analysis of these two transition states reveals their HOMOS to be formed from both HOMO-LUMO and HOMO-HOMO interactions.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 106
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 67-91 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In order to apply the TDHF equations in the matrix form we established previously, we conceive a model for which the static Hartree-Fock equations are rigorously solved; so we study problems only linked to the TDHF method, independent of any further approximation (for example, of LCAO type). This model is made of a spherical box containing electrons subject to a particular potential. We solve, numerically, the TDHF equations at different orders, and we calculate the third order hyperpolarizability tensor. We then compare our results with the ones given by a variation-perturbation method.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 107
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 127-140 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A explicit expression for the unitary group Clebsch-Gordan coefficients, which couple two fully antisymmetric single-column states into the two-column Gel'fand-Tsetlin states, is given in terms of isoscalar factors for the canonical subgroup chain U(n) ⊃ U(n - 1) ⊃ … ⊃ U(1). The isoscalar factors are expressed through the step numbers labeling canonical basis states and enable a straightforward construction of Gel'fand-Tsetlin states in the Clifford algebra unitary group approach, without the use of the tables for the symmetric group outer-product reduction coefficients.
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  • 108
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 109
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 379-389 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In this article, the Hamiltonian for the scattering of the He + H2 system is given by using the interaction potential V(X, Y, Θ) determined by experiments and the semiclassical method. From this Hamiltonian we find a dynamical algebra h6. The statistical expectation of the energy and the transition probability of H2, Pn→m, are derived; therefore, selection rules have been found easily.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 110
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 427-427 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 111
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Recently we extended our strategy for MRD-CI (multireference double excitation-configuration interaction) calculations based on localized/local orbitals and an “effective” CI Hamiltonian for molecular decompositions of large molecules to breaking a chemical bond in a molecule in a crystal or other solid environment. Our technique involves solving a quantum chemical ab-initio SCF explicitly for a system of a reference molecule surrounded by a number of other molecules in the multipole environment of more distant neighbors. The resulting canonical molecular orbitals are then localized and the localized occupied and virtual orbitals in the region of interest are included explicitly in the MRD-CI with the remainder of the occupied localized orbitals being folded into an “effective” CI Hamiltonian. The MRD-CI calculations are carried out for breaking a bond in the reference molecule. This method is completely general. The space treated explicitly quantum chemically and the surrounding space can have voids, defects, deformations, dislocations, impurities, dopants, edges and surfaces, boundaries, etc. We previously applied this procedure successfully to the H3C—NO2 bond dissociation of nitromethane in a nitromethane crystal with extensive testing of the number of molecules that have to be included explicitly in the SCF and how many molecules have to be represented by more distant multipoles. The results indicated that it took more energy to dissociate the H3C—NO2 bond when the nitromethane molecule was in the crystal than it did to dissociate that bond in the free nitromethane molecule. In this present study we have investigated the effect of voids (both in the nitromethane molecules treated explicitly in the SCF and those in the environment represented by multipoles) on the calculated H3C—NO2 bond dissociation energies.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 112
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 417-425 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The magnetooptical properties (B terms) vibronically induced have been calculated for a series of carbonyl compounds in the region of the first absorption band. The rules deduced experimentally for the signs and sizes of the B terms induced by vibrations of different symmetry are generally confirmed by these calculations.
    Zusätzliches Material: 1 Ill.
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  • 113
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 429-453 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A particularly compact form of the orthogonally spin-adapted coupled-cluster equations involving all singly and doubly excited clusters is derived for the general case of a non-Hartree-Fock closed-shell reference determinant. The diagrammatic approach based on the graphical methods of spin algebras is applied. The relationship of different diagrammatic procedures for spin-adaptation, employing both bare and spin-adapted two-electron interaction vertices, is discussed. A comparison with the results obtained with algebraic spin-adaption approaches is also given.
    Zusätzliches Material: 12 Ill.
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  • 114
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 553-561 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electronic properties of a one-dimensional diatomic crystal have been analyzed by using the MO-LCAO method in the tight binding approximation, with mathematical techniques involved in setting up and solving difference equations. The approach gives the exact sets of analytic solutions for both localized and nonlocalized states. The theory of surface states is developed as a characteristic value problem. To illustrate the method the surface states for a semiinfinite crystal which contains a local imperfection at the surface were examined. It appears that this method has advantages over previous methods developed to solve surface problems in crystalline lattices.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 115
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 633-646 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Energy levels of I2 ⃛ X van der Waals (VDW) molecules, where X is a rare gas atom (X = He, Ne) are obtained in an approximate way by using cofocal elliptic coordinates and taking the I2 internuclear axis as a quantization axis. This is the starting point to study vibrational predissociation (VP) of larger I2 ⃛ Xn (n ≥ 2) clusters, where a good energetic description may provide accurate initial conditions from which trajectory calculations can be carried out.
    Zusätzliches Material: 5 Tab.
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  • 116
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 669-670 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 117
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 659-667 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Pariser-Parr-Pople Hartree-Fock crystal orbital calculations (both restricted and unrestricted versions) are performed for one-dimensional models of π-electron polymers. The π-electron band structures corresponding to symmetric and nonsymmetric solutions have been calculated. To investigate the influence of the form of the interelectronic interaction, the calculations were performed with the Mataga-Nishimoto (MN) formula and a modified Mataga-Nishimoto (MMN) formula for two-electron integrals. We have found that curves of the points of the minimum total energy per unit cell for the alternating models are very similar, but band structures and energy gaps are quite different when the MN formula was substituted with the MMN formula for two-electron integrals.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 118
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 673-688 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: When viewed as a square two-indexed matrix, the array of atomic orbital-based, two-electron integrals (ij|kl) is a positive semidefinite array. Beebe and Linderberg showed, in 1977, that actual or near linear dependencies often exist within the types of atomic orbital basis sets employed in conventional quantum chemical calculations. In fact, large (i.e., higher quality) bases were shown to be substantially more redundant than smaller or more spatially separated bases. In situations where there exists significant basis near redundancy, the rank (r) of the (ij|kl) ≡ Vl,J matrix of integrals will be significantly smaller than the matrix dimension M. When this occurs, it proves computationally tractable to decompose the M-dimensional matrix V into components L (V = LLT) which contain all of the information needed to form the full V matrix. The Cholesky algorithm allow such a decomposition to be carried out and forms the basis of the work described here. The method is found to be highly successful in reducing the number of integrals and integral derivatives that must actually be calculated. In particular, results on the C2 molecule indicate that the algorithm can be superior to traditional methods of integral derivative generation if the orbital basis is large enough to contain appreciable near redundancy. In contrast, results on benzene with a more spatially delocalized basis show that conventional methods are preferred whenever substantial basis (near) redundancy is not present.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 119
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 773-790 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An analysis of the pathways and intermediates for the epoxidation of olefins using a Ru(IV)-oxo model complex is presented. Simple bonding concepts, coupled with INDO/1 semiempirical MO calculations, provide a description of the metal-oxo/olefin interaction that agrees well with experimental facts. Concerted [1 + 2] and [2 + 2] pathways are investigated and found to lead to unfavorable orbital interactions as with organic analogues. Nonconcerted process (those in which one bond is formed before the second), which connect the two concerted pathways, are preferred. A nonconcerted [1 + 2] pathway is preferred over a nonconcerted [2 + 2] pathway on the basis of less steric repulsions between the olefin and the metal ligands. Also, all open structures (those with one C—O bond formed) investigated minimized to bound epoxides. In the most favorable pathway, a nonconcerted [1 + 2] pathway, radical cation character on the terminal carbon increases as the nonconcerted process is induced. Preference for the bound epoxide intermediate over the oxometallocycle is simply explained by partial charge considerations.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 120
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 701-701 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 121
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 709-710 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 122
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 735-743 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Since the overlap integral between two functions in position space is the same as the overlap integral between their counterparts in momentum space, there is an intimate connection between orthonormalization procedures in the two spaces. It is pointed out that in certain cases this situation can be used to simplify the orthogonalization.
    Materialart: Digitale Medien
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  • 123
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 769-778 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: After a brief review of the historical development of the concept “antiparticle,” some recent theoretical results on CP violation are reviewed.
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  • 124
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 813-825 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The ground (N) state and the 1B1u(V) excited state of planar ethylene have been studied at the CPF and MR-SDCI levels of theory, using an extended CGTO basis set of the ANO type. The investigation especially addresses the near-degeneracy problem in the ground state and the coupling between the diffuse character of the π* orbital and the amount of correlation included in the wave function of the V state. The MR-SDCI results yield a vertical excitation energy in the range 7.8-8.0 eV, whereas the CPF result is 7.9 eV. The best MR-SDCI result for 〈1π*‖z2‖1π*〉 is 7.8, whereas CPF calculations based on MR-SDCI INOS give the value 6.7. It is clear from the results that these numbers have not converged and that more extended calculations than was possible in the present work would yield an even more compact wave function.
    Zusätzliches Material: 9 Ill.
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  • 125
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 869-885 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Self-consistent-field (SCF) wave functions are used to calculate cross sections for the elastic and inelastic scattering of fast electrons and x-rays from CH4 and C2H2 molecules. The effects of basis set choice and free rotation on these cross sections are investigated. The utility of an approximate scheme to correct SCF inelastic cross sections for the effects of electron correlation is examined. The probability density for the interelectronic distance, or radial intracule density, is obtained and discussed.
    Zusätzliches Material: 9 Ill.
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  • 126
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 15-18 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The problem of the validity of the mass-velocity operator in computational quantum chemistry is discussed. The opinion that the mass-velocity operator is incorrect is shown not to be well founded.
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  • 127
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 35-48 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A spin-free polynomial representation of antisymmetrized geminal products is presented for several cases. In particular, products of identical geminals, which possess different spin multiplicity, are considered. The cases of singlet geminals, singlet geminals with one or two triplet geminals coupled to the lowest possible spin multiplet, and triplet geminals coupled to an arbitrary multiplet are considered in detail, and explicit polynomial representation is given.
    Zusätzliches Material: 1 Ill.
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  • 128
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 61-65 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The Riccati equation is shown to be suitable for obtaining implicit approximate analytic expressions for the eigenvalues of quantum-mechanical systems. The Hamiltonian operator H = (1/2)p2 - (Z/r) + λr2 is used as a test example, and the resulting formulae are modified to deal with the Zeeman effect in hydrogen.
    Zusätzliches Material: 2 Tab.
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  • 129
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 49-60 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A perturbative SCF CI treatment to obtain energy levels of coupled oscillator systems is proposed. The method uses the virtual SCF basis set, and the SCF equations are solved by means of a perturbative treatment that provides the diagonal matrix elements involved in the CI calculation. The off-diagonal matrix elements are calculated using a commutation relationship derived from exact quantum theorems. Numerical results for several systems are obtained and compared with those from others SCF, SCF CI, and variational treatments.
    Zusätzliches Material: 8 Tab.
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  • 130
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 179-186 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A recently proposed (semiclassical) classical path method for treating reactive scattering is reviewed. This method exploits properties of hyperspherical coordinates which allow a collision coordinate to be defined without reference to the arrangement of the particles. The coordinate space is divided into classical and quantal subspaces such that the description of the “arrangement” is quantal. Selected results are presented for the three-dimensional D + H2 → HD + H reaction.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 131
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 141-155 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We report here a theoretical formulation of the transport of excitation energy in a three-dimensional molecular crystal containing one impurity. The excitation is assumed to be localized in the jth site at time t, and the expression for the probability of finding the excitation at some other site j′ at a later time t′ is derived. The probability is given by the correlation function \documentclass{article}\pagestyle{empty}\begin{document}$ \left\langle {\hat P_j (t)\hat P_j (0)} \right\rangle $\end{document}, where \documentclass{article}\pagestyle{empty}\begin{document}$ \left\langle {\hat P_m } \right\rangle $\end{document} represents the site projection operator, |m〉 〈m|. In our derivation we neglect the interaction among excitons of different bands, account for the presence of the impurity by adding a small perturbation term to the pure crystal Hamiltonian, and calculate the exciton solutions through first order. We consider a general impurity; that is, the trap depth is nonvanishing and may even be complex. The exciton-phonon interaction is taken to be linear in lattice displacement vectors; we assume that the short time behavior of \documentclass{article}\pagestyle{empty}\begin{document}$ \left\langle {\hat X} \right\rangle _{{\rm phonon}} $\end{document} gives the dominant contribution to the physical property X being studied and solve the dynamical problem by using a time-dependent effective potential consisting of fluctuations around the equilibrium average exciton-phonon interaction. Several limiting cases are briefly discussed.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 132
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 169-178 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The use of a new time-dependent ket, variationally determined as a linear combination of Slater determinants associated with an electric field variant factor, provides an efficient technique for the calculation of dynamic polarizability tensors. Including electron correlation, the method is applied to the evaluation of the frequency-dependent polarizability of H2O and N2 and can be used even when the photon energy is near the excitation energy. With relatively small basis sets, calculated polarizabilities and resonance frequencies are in good agreement with experimental values for H2O but have to be improved for N2.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 133
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 134
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 189-190 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 135
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 213-223 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Configuration interaction (CI) calculations are carried out for He atom and H2, LiH, and BH molecules in order to obtain the value of the charge density at the nucleus by the use of the Hiller-Sucher-Feinberg (HSF) identity. The HSF density also can be calculated with the double perturbation theory based on the Møller-Plesset-type theory and also on the Epstein-Nesbet type. It is found that each value of the HSF density for these perturbative corrections is very similar to the corresponding value by the CI with single- and double-electron excitations. Especially for the He atom, the HSF density value by the full-CI wave function coincides with the exact value of the charge density in three significant figures. The electron correlation effects are found to be small but cannot be ignored in the HSF density. It can be shown that the superiority of the HSF density over the usual delta-function-type density is excellently confirmed.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
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  • 136
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 265-275 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Hyperfine coupling constants (HFCC) of the 19F and 35Cl atoms and the 19F2- and 35Cl2- radical anions have been calculated by the unrestricted Hartree-Fock (UHF) method using polarization and diffuse functions with contracted double-zeta as well as uncontracted basis sets. The Adip values are fairly insensitive to changes in the basis set and show good accordance with experimental and other theoretical studies. The isotropic HFCCS aN of 19F, 19F2-, and 35Cl2- show strong dependence on d functions and the state of contraction of the s, p set. Spin-projected UHF wave functions lead to better agreement with experiment.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
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  • 137
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 313-317 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The pi interaction in complexes of (S)-methyl N-(2-naphthyl)alaninate with (S)- and (R)-N-(3,5-dinitrobenzoyl)leucine n-propylamide was investigated with Hartree-Fock and second-order Møller-Plesset perturbation theory calculations using the STO-3G basis set. For each complex, the geometry of the model of the pi interaction (i.e., naphthalene and 1,3-dinitrobenzene) was derived directly from the complex geometry which was relaxed by the semiempirical quantum-mechanical AM1 method. At the level of treatment used herein, our results are in agreement with our earlier AM1 interaction energy calculations in which the pi interaction, one of the three primary interactions proposed in models of the aforementioned complexes, is attractive and of equal strength (ca. 0.8 kcal/mol) in both complexes.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 138
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 319-323 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The solitonic models of proton transfer in a molecular hydrogen-bonded chain have been examined with respect to the shape of protonic interaction potential. The kink-like excitations with quadratic, quartic, Morse, and Toda interactions are reported and analyzed.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 139
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 455-472 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Electronegativity χ and hardness η for 54 atoms and their positive and negative ions are calculated by means of self-interaction-corrected DFT including correlation terms. The exchange potential energy is treated by local spin density approximation corrected to account for self-interaction effects as suggested by Rae. The highest occupied orbital eigenvalues for ions are identified to the chemical potential μ± for positive and negative charged atoms depending upon the developing charge process. Values of χ±δ and η± for the different ionic species are given for several values of δ. Average values for 〈χ〉 and 〈η〉 in the sense of Mulliken finite formula for neutral atoms are also tabulated and compared with Mulliken values from experimental data. The agreement among them is almost quantitative.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 140
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 537-537 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 141
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 545-552 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Oxygen clusters of the equilateral ring types On and their negative ions On- are studied by the recently developed pictorial-topological quantum chemistry method, VIF (valency interaction formulas), of this author. The species are found to be of high energy relative to separated oxygen atoms, the cause being evident from the VIF pictures. The odd n rings should be at local minima but are not likely to have observable negative ions. The even n rings have distortional instabilities, yet their negative ions are more likely to be observed as transients in beam experiments.
    Materialart: Digitale Medien
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  • 142
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 587-598 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The possible conformational changes of L-serine phosphate due to the interaction with ammonia are investigated by means of ab initio MO-LCAO-SCF calculations, using a supermolecule approach and an STO-3G basis set. The most favorable conformation of a four-hydrated L-serine phosphate anion is found to be changed by the binding of an ammonium ion. Cointeraction of ammonia and NH4+ suggests another conformational change through the displacement of the bridging water molecule of the polyhydrated L-serine phosphate anion.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 143
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 671-672 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 144
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Preparation of Substituted 2-Aminooxazole-4-carbonitrilesDuring our synthetic programme to convert 4-isoxazolylthioureas 3 into the corresponding carbodiimides 5, a side reaction leading to the hitherto unknown 2-aminooxazole-4-carbonitriles 6 was observed. By selecting appropriate reaction conditions, it was possible to improve the yields of the carbodiimides 5 as well as of the novel oxazole-carbonitriles 6 at will, thus allowing the synthesis of 6 to be conducted in very good yields. To overcome the difficulty of isolating unstable carbodiimides, the synthesis of 6 is best carried out in a one-pot procedure. A limited mechanistic study showed that the formation of 6 proceeds via 5 as the only intermediate. The stability of the N=C=N bonds against base attack (depending strongly on both sterical hindrance and electronic-density factors) forms the only limitation of this new synthetic pathway to oxazole-4-carbonitriles.
    Notizen: No abstract.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 145
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The 8-substituted xanthines 1-21 (including compound S 9795), caffeine (22), and the three isomeric dimethyl-xanthines 23-25 (see Table 1), were examined for their lipophilic behaviour using a reversed-phase HPLC technique. A number of flexible compounds showed a smaller-than-expected lipophilicity which based on conformational and tautomeric calculations were ascribed to the predominance of folded forms. A QSAR analysis of the phosphodiesterase-inhibitory potency of several compounds showed favourable factors to be a low lipophilicity and the absence of a substituent on the N7 position.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 146
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We present the application of several homo- and heteronuclear 1D- and 2D-NMR techniques to assign the 1H-NMR chemical shifts of the dominant conformation of didemnin B (2; three different conformations in (D6)DMSO solution in the ratio 8:1:1) and its conformational analysis, as well as the solution conformation of didemnin A (1). The conformations were refined by restrained molecular-dynamics calculations using the GROMOS program and by MOMO, a novel personal-computer-based interactive molecular-graphics and molecular-mechanics package, using experimental distances (via a H…H pseudo potential function) as restraints. The solution structures of 1 and 2 obtained by GROMOS and MOMO calculations were compared with each other and related to the recently solved crystal structure of 2. Focusing on the main conformer, the two kinds of the distance-restrained conformational calculations for 2 yielded a ‘solution structure’ close to the crystal structure. Almost all of the 40 restrained H…H distances coincided (within the estimated standard deviations) with those observed in the crystal structure. One more hydrogen bond was detected in solution involving the lactoyl OH group (disordered in the crystal structure) and the dimethyltyrosine (Me2Tyr5) carbonyl O-atom. The macrocyclic ring system in the modeled solution structure of 1 exhibited a topology close to those of the solution and crystal structures of 2. The main difference between 1 and 2 could be traced back to a significant change in the Ψ angle of the N-methyl-D-leucine (MeLeu7) residue. In 1, the N-methyl moiety of MeLeu7 points inward within the macrocyclic ring toward the 1st and Hip region. We also tested the suitability of structures obtained from NMR data as ‘search fragments’ in the ‘Patterson search approach’ of crystal-structure analysis. It proved possible to resolve the crystal structure of 2 a posteriori with the Patterson search program PATSEE, in this way.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 147
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 570-593 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The transformations of 12 bicyclo[2.2.2]oct-5-en-2-ols (V or VI) to 3-(cyclohex-3-enyl)-2-alkanones (III or IV), via β-cleavage of their potassium alkoxides in HMPA, has been investigated (cf. Table 1). As an illustration of this synthetic methodology, a stereoselective synthesis of (±)-trichodiene ((±)-1) is described which involves the β-cleavage of the tricyclic potassium alkoxides 46a and 47a to cyclopentanone 4 (cf. Scheme 7).
    Zusätzliches Material: 1 Ill.
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  • 148
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 631-631 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract.
    Materialart: Digitale Medien
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  • 149
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 594-607 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: About 65 diverse phenyl benzoates incorporating a trans-1,4-disubstituted cyclohexane ring and at least one lateral substituent have been synthesised. The dependence of the liquid-crystal transition temperatures of these materials on various lateral substituents (F, Cl, CN, and Br) in different positions of the esters has been investigated systematically. The influence of up to four F-atoms in various positions of a standard ester has been thoroughly studied and the optimum combination for a broad smectic C mesomorphic range established. In consequence, three homologous series incorporating the 4-alkoxy-2,3-difluorobenzoic-acid moiety were prepared. An additional C=C bond was introduced into the alkyl chain attached to the cyclohexane ring of some of these esters and the resulting modifications of the transition temperatures determined. Three ester series incorporating a lateral substituent and the optically active (+)-(S)-(1-methylheptyl)oxy substituent have also been synthesised, and similar effects have been observed. These materials can be used as important components of commercial chiral smectic C mixtures for electro-optic display device applications.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 150
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 624-630 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: X-Ray Crystal-Structure Analysis of 2,4,6-Tri(tert-butyl)phenyllithium · N,N,N′,N′-Tetramethylpropane-1,2-diamine: a Monomeric Organolithium CompoundTri(tert-butyl)phenyllithium is an important reagent for the preparation of derivatives of main-group elements with low coordination state as well as a highly hindered base for the generation of amine-free Li-enolates. Its monomeric nature in solution was previously deduced from NMR measurements. While Et2O, THF, and N,N,N′,N′-tetramethylethylene-1,2-diamine (tmen) led to crystalline samples which were not suitable for structure analysis, the N,N,N′,N′-tetramethylpropane-1,2-diamine (tmpn) gave good single crystals of the title compound from Et2O/hexane (disorder along the two-fold crystallographic axis running through Li—C(1) and C(4) of the Ph ring. The structure (Fig. 1, Table 1) has some remarkable features: (i) it is one of the very few monomeric organolithium compounds so far, (η1-Li on aromatic ring); (ii) it has the rare trigonal-planar coordination of the Li-atom; iii) there are close contacts between the Li-atom arid one of the Me groups in each ortho-position (Fig. 3). The internal angle on the Ph-ring ipso-C-atom is 114°. This angle as well as those of the other known phenyllithium (Table 2), -magnesium, and -aluminum structures are included in a plot of ipso-angles against Pauling electronegativities (Fig. 2).
    Notizen: No abstract.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 151
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 632-633 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract.
    Materialart: Digitale Medien
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  • 152
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989) 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 153
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Evidence is presented for the first time that ‘naked’ Fe+ ions, complexed to the NH2 group of primary amines, are capable of intramolecularly activating C—C bonds in a highly specific mode without preceding C—H activation.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 154
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Application of a stereoselective Prins/retro-Prins rearrangement sequence from (-)-(R)-campholenyl acetate((-)-4) opens a new access to the naturally occurring (-)-(R, R)-β-necrodol ((-)-1) and its three stereoisomers with high optical purity.
    Materialart: Digitale Medien
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  • 155
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1169-1169 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 156
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1169-1169 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 157
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1164-1168 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Determination of Stability Constants in Ethanol for Li+-selective Ionophores by Differential Vapour Pressure OsmometryStability constants of some neutral carriers and their bridged isologues in interaction with Li+ and Na+ are determined by a differential vapour pressure osmometry method in ethanol utilizing Bjerrum formation curves. All ionophores studied induce high Li+ selectivity in solvent polymeric membranes.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 158
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1170-1172 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 159
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989) 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 160
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Halochromic Molecules. Synthesis and Acidobasic Properties of 3′-substituted 6,11-dihydrospiro[[1]benzopyrano[4,3-b]indol-6,9′-9′9′H-xanthenes]We have synthesized a series of 3′-substituted 6,11-ihydrospiro[6H-chromeno[4,3-b]indol-6,9′-9′H-xanthenes] and one of their respective aza analogues. 1H-MR data as well as the fragmentation in the mass spectra of starting and final products supported the postulated structures. With acid, the spiro compounds form ring-opened intensely coloured xanthylium salts. UV/VIS spectra of these salts are listed and discussed. The ∊pH* curves in buffered MeOH/H2O solutions and the pK* values are determined. The title compounds could possibly be used in ‘pressure sensitive papers’.
    Zusätzliches Material: 2 Tab.
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  • 161
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1199-1215 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Nitroso-arene dienophiles 1 react regiospecifically with the conjugated dienals 2 and 3a/3b, and lead thereby to the unstable Diels-Alder cycloadducts 4 and 5. These undergo two types of cascade reactions which give pyridinium betaines 6 and pyrrolo-indoles 8 as the major reaction products. The one-pot syntheses of pyrroloindoles 8 represent a new and easy access to the basic skeleton of mitomycins 10. The scope and limitations of the cascade reactions were investigated.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
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  • 162
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It is shown that the demosponge Corallistes sp. (Tetractinomorpha, Lithistida, Corallistidae) collected in the Coral Sea, contains corallistin A (1), the second example, of a free porphyrin from a living organism. The compound proved to be active against the Kb cell line. In contrast with the geoporphyrins which do not bear any O-atom corallistin A (1) carries two carboxylic groups.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 163
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Three chromonocoumarins ( =6H, 7H-[1]benzopyrano[4,3-b][1]benzopyran-6,7-diones) 1-3 have been isolated from the leaves and the root bark of polygala fruticosa BERG. (syn. Polygala oppositifolia L.; Polygalaceae). The structure of frutinone A (1) was established by X-ray diffraction analysis. The structures of the previously undescribed compounds frutinone B (2) and C (3) were deduced by spectroscopic methods (EI-MS, UV, IR, 1H-and 13C-NMR, including NOE and COSY) in comparison with 1. Chromonocoumarins 1-3 are the first representatives of a new type of naturally occurring compounds. Frutinone A shows strong fungicidal activity against Cladosporium cucumerinum.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 164
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In 7 steps, 6- or 9-hydroxylated or -methoxylated trans-octahydrobenzo[g]isoquinolines were efficiently synthesized starling from dimethoxynaphtbalenes (Scheme), as potential new selective ligands for serotonin receptors. The 6-substituted compounds had very little affinity to common neurotransmitter receptors, with the exception of adrenergic α2. The 9-substituted compounds, while showing interesting affinity for 5HT1a receptors, had comparable affinities for adrenergic α1 and β2, and in one case for dopamine D2 receptors.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 165
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1554-1582 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The Access to the Three Subunits of the Antitumor Antibiotic CC-1065 by Hetero-Cope Rearrangement of Vinyl N-Phenylhydroxamates.The use of the hetero-Cope rearrangement of vinyl N phenylhydroxamates to indoles for the preparation of the 1,2-dihydro-3H, 6H-benzo[1,2-b:4,3-b′]dipyrrole skeleton, the structural subunits characteristic of the antitu-mor antibiotic CC-1065 as well as the phosphodiesterase inhibitors PDE-I and PDE-II is described.
    Materialart: Digitale Medien
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  • 166
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1537-1553 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: By appropriate structural modification of known musk odorants, new strong musk odorants have been discovered. Incorporation of supplementary CH3 or CH2 groups into the basic musk skeleton of type G only slightly modifies the global shape of the molecule but leads to densely packed structures of enhanced lipophilicity. For the construction of these highly substituted 1,2,3,4-tetrahydronaphthalenes, new annulation sequences (intramolecular mono- and dialkylations; see Schemes 3,6, and 8) have been developed and, in certain cases, the design of the target molecules was dictated by both structure-activity-relationship and synthetic considerations (e.g. 46 and 47, Scheme 6). This work also presents an original solution to an analytical problem: the distinction between a C2- and a Cs-symmetrical aromatic hydrocarbon (viz. 71 and 72) by conversion into a [Cr(CO)3arene]complex.
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  • 167
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1817-1824 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The title compound 7 is obtained by reductive dehalogenation from 4-bromo-2,3-dihydro-2,2. -dimethyl-3-oxo-1H-pyrrole-1-carboxylate (8) in 90% yield, Aza-enone 7 undergoes [2 + 2] cycloaddition from the triplet state with both electron-rich and electron-deficient alkenes. The behaviour of 7 in light-induced reactions is compared to those of 2,2-dimethyl-3(2H)-furanone (1a) and of the corresponding thiophenone 1b. In the photodimerization and the cycloaddition to either 2,3-dimethylbut-2-ene or to dimethyl maleate of these ketonic five-membered heterocycles with one heteroatom, the overall efficiency increases in going from the furan 1a to the thiophene 1b and to the pyrrole 7.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 168
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: (1R,2S,4R)-2-Cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1S′)-camphanate (5) was transformed into (-)-methyl 2,5-anhydro-3,4,6-O-tris[(tert-butyl)dimethylsilyl]-D-allonate (2), (+)-1,3-diphenyl-2-{2′,3′,5′-O-tris[(tert-butyl)dimethylsilyl]-β-D-ribofuranosyl}imidazolidine (3), and the benzamide 20 of 1-amino-2,5-anhydro-1-deoxy-3,4,6-O-tris-[((tert-butyl)dimethylsily)]-D-allitol. Compound 2 was converted efficiently into optically active tiazofurin (1).
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  • 169
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Yeast reduction of rac-ethyl 2-methyl-6-oxocylohexanecarboxylate (rac-1) yielded selectively (+)-ethyl 2-hydroxy-6-methylcyclohexane carboxylate (+)-2 (Scheme 1) which has been alkylated with 5-iodo-2-methylbut-2-ene by (the dianion method to furnish the 4-methylbut-3-enyl derivat 3 (Scheme 3)). NaBH4 reduction of (+)-1 led to three hydroxy-carboxylates (-)-2, (+)-5, and (-)-6 (Scheme 4). Allylation of the dianion of (+)-5 afforded (+)-7.
    Materialart: Digitale Medien
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  • 170
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Methyl Jasmonate: A Short Synthesis of Naturally Occurring Methyl Jasmonate and its Unnatural Enantiomer via Enantiodivergent Alkylation of Cyclopent-2-ene-1,3-diol Derivatives by Palladium(0)-Induced ReactionsPalladium-catalyzed alkylation of cyclopent-2-ene-1,2-diol derivatives like 2 is a useful method for enantiodivergent functionalization, resulting in both enantiomeric series of chiral building blocks. The chiral building blocks 3 and 13 can be transformed to methyl jasmonate (1)and its unnatural enantiomer ent-1, recent statement [1b] that 1 has no odour at all and that ‘methyl jasmonate's’ fragrance is actually due to its cis-isomer ent-11 has been confirmed also for the enantiomeric series.
    Materialart: Digitale Medien
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  • 171
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The crude petroleum-ether extract of the aerial parts of Hypericum calycinum L. (Guttiferae) exhibited in vitro growth-inhibitory activity against the Co-115 human colon carcinoma cell line. Bioassay-guided fractionation of this extract allowed the isolation of the cyclohexadienone derivatives 1-5, four of which are previously undescribed compounds. The structures of the known chinesin II (1) and of 2 (hypercalin A) were established by 1H- and 13C-NMR spectroscopy and were confirmed by X-ray analysis of their crystalline mixture which revealed the complete relative configuration of both compounds. The structure of 3 (hypercalin B) was elucidated by means of extensive 1D- and 2D-NMR experiments, including DQ-COSY, HETCOR and LR-HETCOR. The structure of compound 4 (hypercalin C) was established by 1H- and 13C-NMR spectroscopy and confirmed by X-ray analysis to be the 3,5-dihydroxy-4-{[(1R*,2S*, 5S*)-2-hydroxy-2-methyl-5-(1-methylethenyl)cyclopentyl]methyl}-6,6-bis-(3-methylbut-2-enyl)-2-(2-methylpropanoyl)cyclohexa-2,4-dien-1-one. The structures of the higher isomeric homologues 5a/5b were deduced by comparison of their UV, 1H-, and 13C-NMR spectra with those of 4. The isolated compounds appeared to be related to chinesin I and II previously isolated from Hypericum chinense L. and were responsible for the growth-inhibitory activity of the extract against the Co-115 human carcinoma cell line. Moreover, 1/2 and 3 showed molluscicidal activity against the schistosomiasis-transmitting snail Biomphalaria glabrata.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 172
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 1925-1925 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 173
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and NMR-Spectroscopic Characterization of New Adenine- and 6-ThioxopurinecarboxamidinesAdenine (1) or 1H-purine-6(7H)-thione (4) react with carboximidoyl chlorides 2 to yield the adenine-9-carboxamidines 3 or the 6,7-dihydro-6-thioxo-1H-purine-7-carboxamidines 5 and 6,9-dihydro-6-thioxo-1H-purine-9-carboxamidine 6 a, respectively. The structures of the compounds were determined by 1H- and 13C-NMR spectroscopy.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 174
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 267-275 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We present a simple model for calculating the interatomic interaction energies in the electron gas approximation. We use a generalization of the supermolecular electronic density which includes a density overlap term. We present numerical calculations for the He-He interaction as an illustration of the method.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 175
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 315-324 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 9-Amino-1,2,3,4-tetrahydroacridine (THA), a potent cholinesterase inhibitor, was recently used in the treatment of Alzheimer's disease. On attempting to prepare a dihydropyridine ⇆ pyridinium salt-based redox chemical delivery system (CDS) to enhance brain delivery of THA, several of the practical synthetic challenges were examined by using a theoretical MO approach. The structures, reactivities and stability of THA, derivatives of THA and a model compound, 4-aminopyridine, a simple dibasic heterocyclic amine, were studied in the framework of the AM-1 approximation. The study included the possible protonated forms of THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine, consistent with experimental results. Electron delocalization is responsible for the remarkable stability of these molecules and for the observed lack of reactivity of the amino group, both in the basic and protonated forms. The site of N-alkylation of the 9-nicotinamide derivative of THA (an intermediate in the synthesis of THA-CDS) is controlled by electronic, thermodynamic, and steric factors.
    Zusätzliches Material: 2 Ill.
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  • 176
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 483-494 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Structural parameters of a set of five thiocarbonyl molecules in the lowest nπ* states are calculated by using a generalized orbital optimization algorithm (a variant of the orthogonal gradient method) in an INDO MCSCF framework. Transition energies, singlet-triplet splittings, planar inversion barriers, and dipole moments in nπ* states of different spin multiplicities are reported. Predicted structural features agree reasonably well with available experimental or theoretical data. Some interesting trends are noted in the computed inversion barrier heights, singlet-triplet splittings, and dipole moments in nπ* states.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 177
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 703-703 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 178
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 717-719 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 179
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 679-685 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The self-consistent multiple scattering Xα (MSXα) method is used to arrive at the electronic structure of a helium-trapped vacancy in aluminum using a cluster model. The calculated orbital energies, electron density, and charge distributions are compared with the available theoretical results. It is shown that helium trapping causes the reshuffling and upward movement of the cluster levels (with vacancy).
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 180
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 687-700 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We consider the Hückel approximation to the π-electron spectrum of molecules which are built by linking a number of identical fragments to a central atom in an identical manner. The Hückel matrix H of the composite molecule (or equivalently the adjacency matrix of the molecular graph) is simply related to the Hückel matrix h of the fragment and a vector \documentclass{article}\pagestyle{empty}\begin{document}$ vec{f} $\end{document} which encodes the bonding of a fragment to the central atom. The eigenvalues and eigenvectors of H are obtained from those of h. The orbitals of the composite molecule are of three types: (1) a molecular orbital of the fragment localized on one of the fragments, (2) a molecular orbital of the fragment spread over more than one fragment, and (3) orbitals spread over the entire molecule including the central atom. The orbital energies Λ of the first two types of orbitals are same as the orbital energies λ of the fragment. Energies of the third type of orbitals separate a subset of orbital energies of the fragment and, barring accidental degeneracy, they are distinct from all orbital energies of the fragment. It is only through the third type of orbitals that the composite molecule manifests itself as a new entity rather than an aggregate of noninteracting fragments. It is shown that the graph group of H fails to explain its degeneracy if any eigenvector of the subgraph, not orthogonal to the connection vector \documentclass{article}\pagestyle{empty}\begin{document}$ vec{f} $\end{document}, belongs to a degenerate manifold of h. This solves a long-standing puzzle regarding degeneracy in the Hückel spectrum of triphenylmethyl.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 181
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The bivariational Hartree-Fock scheme for a general many-body operator T is discussed with particular reference to the complex symmetric case: T† = T*. It shown that, even in the case when the complex symmetric operator T is real and hence also self-adjoint, the complex symmetric Hartree-Fock scheme does not reduce to the conventional real form, unless one introduces the constraint that the N-dimensional space spanned by the Hartree-Fock functions φ should be stable under complex conjugation, so that φ* = φα. If one omits this constraint, one gets a complex symmetric formulation of the Hartree-Fock scheme for a real N-electron Hamiltonian having the properties H = H* = H†, in which the effective Hamiltonian Heff (1) may have complex eigenvalues εk. By using the method of complex scaling, it is indicated that these complex eigenvalues - at least for certain systems - may be related to the existence of so-called physical resonance states, and a simple example is given. Full details will be given elsewhere.
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  • 182
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 157-167 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The simple semiquantitative approach to the calculation of the energy of surface states, proposed recently by the authors, is applied to high-symmetry surfaces of selected transition metal carbides, nitrides, and oxides. The results are compared with recent experimental and theoretical data. The necessity to include the changes in the potential at the crystal surface is indicated.
    Zusätzliches Material: 4 Tab.
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  • 183
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 341-351 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An alternative scheme for ab initio polymer band structure calculations based on a Filon-type quadrature is proposed. This scheme avoids the explicit calculation and the storage of the “troublesome” Fourier transforms of the LCAO density matrix elements and is a first step towards a better control of the convergence of the different lattice sums appearing in the configuration space LCAO-SCF-CO method. The potential of the proposed technique is illustrated by a minimal basis set calculations on an infinite chain of H atoms.
    Zusätzliches Material: 2 Tab.
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  • 184
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 705-726 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Linkage properties of the diagrammatic representation of the energies obtained in the multireference many-body perturbation calculations with respect to the incompleteness or completeness of the model space are discussed. The case of not completely degenerate model space is considered for which a comparison with the standard single-reference many-body perturbation expansion is possible. The Hose-Kaldor type of graphical representation of the perturbation expansion for the effective Hamiltonian is used in this comparison. It is shown that for an incomplete model space the perturbation expansion is not size-extensive. In this case, for a truncated expansion of the effective Hamiltonian, the energies obtained by diagonalization of the effective Hamiltonian matrix are represented by both linked and unlinked irreducible contributions. The unlinked ones do not appear when the complete model space is used.
    Zusätzliches Material: 11 Ill.
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  • 185
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 369-377 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Experimental works suggest the existence of an oscillating complex in the collisional quenching of Na with N2 molecules. Until now, however, few efforts have been dedicated to the study of these possible complexes. In this work, a diabatic and diabatic-configuration interaction method are proposed in order to investigate the existence of these quasibound levels. The results and their comparison with other available data are presented and discussed.
    Zusätzliches Material: 4 Tab.
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  • 186
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 187
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 36 (1989), S. 487-501 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A mathematically well-defined measure of localization is presented based on Mulliken's orbital populations. It is shown that this quantity equals 1 for core- and lone-pair orbitals, 2 for two-atomic bonds, 6 for benzene rings, etc., and it is applicable for delocalized canonical HF orbitals as well. The definition of this quantity is general in the sense that ab initio MOS with overlapping AO expansion, and semiempirical wave functions using the ZDO approximation as well, can be treated. The localization quantity is essentially “intrinsic,” i.e., no subdivision of the molecule is required. For N-electron wave functions, mean delocalization can be defined. This measure is not invariant to unitary transformations of the one-electron orbitals, characterizing in this way the localized or extended representation of the N-electron wave function. It can be proven, however, that for unitary transformed wave functions a maximum delocalization exists which depends only on the physical (N-electron) properties of the molecule. It is shown that inhomogeneous charge distribution can cause strong electron localization in molecular systems. The delocalization of the canonical Hartree-Fock orbitals, the Parr-Chen circulant orbitals, and the optimum delocalized orbitals is studied by numerical calculations in extended systems.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 188
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 189
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We start by pointing out relationships between production of information, global simulation, and supercomputing, thus placing our research activities in today's society context. Then we detail the evolution in hardware and software for 1CAP, our experimental supercomputer, which we claim to be especially well suited for supercomputing in science and engineering. A preliminary discussion of 1CAP/3090 (our latest experimental effort) is included. Many examples from different disciplines are provided to verify our assertions. We “prove” our point by presenting an example of global supercomputing. Starting with 3 nuclei and 10 electrons, building up to a single water molecule, then to a few hundred, we learn, for example, about Raman, infrared, and neutron scattering; we then move up to a few hundred thousand molecules to analyze particle flow and obstructions; finally we experiment, but only preliminarily, with a few million particles to learn more on nonequilibrium dynamics as in the Rayleigh-Benard systems. In this way, quantum mechanics is overlapped with statistical mechanics and expanded into microdynamics. The entire paper is finally reanalyzed from a different perspective, presenting rather systematically, even if most briefly, our ideas on “modern” computational chemistry, where quantum mechanics is as much needed as fluid dynamics and graphics. In this section the main computational techniques are analyzed in terms of computer programs and their associated flow diagrams to solve the basic equations using parallel supercomputers.
    Zusätzliches Material: 33 Ill.
    Materialart: Digitale Medien
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  • 190
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 153-165 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effects of a proximate condensed environment as the solvent and cellular structured patterns (biopolymers, membranes, etc.) play an important role in determination of the courses of molecular processes in biology. We present here the background of methods developed for such an environmental effects estimation combining the continuum and discrete models. Their applications within theoretical studies into the mechanisms of carcinogenic action of alkylating N-nitrosocompounds are shown. The results given cover four different areas, namely the quantitative structure-activity relationship, mechanistic studies into their metabolic activation reactions, interactions of the ultimate carcinogens with DNA, and finally their genetic consequences.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 191
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 193-203 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Nucleoside antibiotics, which result as a consequence of minor modifications in pyrimidine and purine nucleosides, exhibit a wide variety of antiviral, antibacterial, antitumor, and cancerostatic properties. The conformational properties of a number of these antibiotics have been investigated by using the quantummechanical PCILO method, and the results indicate that the nucleoside antibiotics and their parent nucleosides have very similar conformational preferences. This similarity is strikingly marked in the situations which prevail in an aqueous medium. As a result, these antibiotics easily get incorporated in growing chains of RNA and DNA by mimicking their parent nucleosides and then bring about the inhibition of protein, RNA, or DNA syntheses. The experimental observations corroborate these deductions, and thus a correlation has been obtained between the conformation and the biological activity of nucleoside antibiotics; it is the striking conformational similarity between the nucleoside antibiotics and their parent nucleosides which gives rise to their biological activity. The PCILO investigations carried out on two 3-deazapurine nucleosides demonstrate that the converse of the above correlation also holds true.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 192
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 255-255 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 193
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 277-282 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The idea of a Franck-Condon (FC) operator is introduced, and its normally ordered form is obtained through the newly developed technique of “integration within an ordered product of operators (IWOP).” It is shown that the FC operator leads to a new approach for the calculation of FC factors. The results of existing theories are viewed, and the connection between the FC operator and the “squeeze-operator” is pointed out.
    Materialart: Digitale Medien
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  • 194
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 305-313 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It is shown that infinite long polyacene chains may have three energetically close but structurally distinct isomers (a symmetrical, sym, form and two lower symmetry forms: one with double bonds in a trans and another isomer with double bonds in a cis pattern). The energetics is based on solid state MNDO theory. We discuss that the symmetrical form has a substantial energy gap Eg in the Hartree-Fock approach owing to exact exchange terms, which are nonlocal. Broken symmetry Hartree-Fock (HF) solutions for polyacene are also described. An angularly distorted structure suggested earlier on Jahn-Teller grounds is found to be energetically not favorable.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 195
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 339-358 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An extensive theoretical calculation of the tetraphenyldithiapyranylidene DIPSφ4 molecule by means of the MSXα method is presented. The results obtained permit one to interpret the optical spectrum and the XPS spectrum as well as the charge transfer between DIPSφ4 and planar molecular semiconductor compounds such as TCNQ. To our knowledge, this is the first theoretical determination to date of such a charge transfer ratio from separate parameter-free calculations on large-size molecules.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 196
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 373-383 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The Herndon-Simpson model for a particular catacondensed polyphene chain is considered as a nontrivial many-body Hamiltonian, defined on a space with a basis of orthonormal Kekulé structures. An Explicitly correlated cluster expanded resonance-theoretic wave function is described for this model, and its quality is judged by calculation of the standard deviation for the energy expectation. The quality is found to be high. Indeed, for a particular parameter ratio within the range of experimental interest, the wave function ansatz is found to be exact. This very accurate solution is then used to gauge the quality of the common ansatz with equally weighted Kekulé structures, and it is found to be reasonably good.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 197
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 668-674 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Activity-guided fractionation of the MeOH extract of the fruits of Tetrapleura tetraptera TAUB. (Mimosaceae) afforded 4 saponins 1-4, which exhibited strong molluscicidal properties against the schistosomiasis-transmitting snails Biomphalaria glabrata. Chemical, enzymatic, and spectral methods (DCI-MS, 1H-NMR, 13C-NMR) showed that they were N-acetylglycosides of oleanolic acid and of echinocystic acid. Apart from saponin 1 (aridanin), previously isolated from this plant, glycosides 2-4 are new naturally occurring compounds.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 198
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 744-755 
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Condensation reactions of the 5-amino-6-(subst. amino)-2,4-dithiouracils 12 and 13 with diacetyl or benzil led to the 6,7,8-trisubstituted 2,4-dithiolumazines 14-16. Methylation of these compounds affected both thio functions forming various types of 2,4-bis(methylthio)lumazine derivatives depending on the nature of the substituents at C(7) and N(8). The 6,7,8-trimethyl-2,4-dithiolumazine (14) was converted into 7,8-dihydro-6,8-dimethyl-7-methylidene-2,4-bis(methylthio)pteridine (17), whereas the 8-methyl-6,7-diphenyl-(15) and the 8-(2-hydroxyethyl)-6,7-diphenyl-2,4-dithiolumazine (16) yielded the corresponding covalent inter- or intramolecular 7,8-adducts 18-21. The unusual structures were proven by spectroscopic means and those of the alcohol adducts 20 and 21, furthermore, confirmed by X-ray analysis.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 199
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: (E)-5-Demethyl-4-oxo-β-ionone (2), (E)-4-oxo-β-ionone (3), (E)-4-oxo-β-irone (4), and the five-membered ring analogs 36-41 were synthesized by a novel, convergent route starting from 2-methylfuran (1). A recently discovered, intramolecular reaction of 2-(diazoacyl)furans, catalyzed by dirhodium tetraacetate, leading to dienediones served as key step, thereby testing its utility in natural-product synthesis for the first time.
    Materialart: Digitale Medien
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  • 200
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ethyl (1R, 2S)-2-hydroxycyclopentanecarboxylate and -cyclohexanecarboxylate (1a and 2a, respectively) obtained in 40 and 70% yield by reduction of 3-oxocyclopentanecarboxylate and cyclohexanecarboxylate, respectively (Scheme 2), with non-fermenting yeast, are converted to bicyclic dioxanone derivatives 3 and 4 with formaldehyde, isobutyraldehyde, and pivalaldehyde (Scheme 3). The Li-enolates of these dioxanones are alkylated (→5a-5i, 5j, 6a-6g), hydroxyalkylated (→51, m, 6d, e), acylated (→5k, 6c) and phenylselenenylated (→7-9) with usually high yields and excellent diastereoselectivities (Scheme 3, Tables and 2). All the major isomers formed under kinetic control are shown to have cis-fused bicyclic structures. Oxidation of the seleno compounds 7-9 leads to α, β-unsaturated carbonyl derivatives 10-13 (Scheme 3) of which the products 12a-c with the C=C bond in the carbocyclic ring (exocyclic on the dioxanone ring) are most readily isolated (70-80% from the saturated precursors). Michael addition of Cu(I)-containing reagents to 12a-c and subsequent alkylations afford dioxanones 14a-i and 16a-d with trans-fused cyclohoxane ring (Scheme 4). All enolate alkylations are carried out in the presence of the cyclic urea DMPU as a cosolvent. The configuration of the products is established by NMR measurements and chemical correlation. Some of the products are converted to single isomers of monocyclic hydroxycyclopentane (17-19) and cyclohexane derivatives (20-23; Scheme 5). Possible uses of the described reactions for EPC synthesis are outlined. The observed steric course of the reactions is discussed and compared with that of analogous transformations of monocyclic and acyclic derivatives.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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