Recent developments in the chemistry of stable doubly bonded germanium compounds

During the last 10 years, several compounds of the type Ge=X (X = C, Ge, N, P, S) have been isolated as monomers. The stabilization of such derivatives, which are generally highly polymerizable, was achieved by using very bulky groups both on the germanium atom and on the heteroelement X. Conjugation (particularly in a few germenes and germaimines) and intramolecular or intermolecular coordination with oxygen or nitrogen, also contributes, in some cases, to the stabilization. The X-ray analyses of such compounds show a significant bond shortening of the double bond (8–10%) relative to the corresponding single bond and a planar or nearly planar germanium. These doubly bonded germanium derivatives are usually thermally stable but must be handled in an inert atmosphere because of their high sensitivity to oxygen and moisture; they are extremely reactive, much more than the corresponding carbon analogues. Nearly quantitative additions on the double bond have been observed with electrophiles and nucleophiles, and various types of cycloadditions also occur. Except in one case, a germylene behavior has not been observed, proving that such compounds retain their structural integrity in solution.     

End unit effect on the Tg of differentiated series of perfluoro-poly (oxymethylene-co-oxyethylene) oligomers

Twelve series of linear oligomers of four different degrees of polymerization (x_n = 8.77−41.55), having a common perfluorinated random copolymeric chain as molecular body and two equal foreign end units of one of the types listed in Table 1, have been synthesized by derivatization of base samples of one of them having a diolic---CH₂OH functionality. The glass transition temperature T_g of all the series was measured and thus examined as a function of x_n. A clear end unit effect is observed, dominantly determined in every series by chemical nature and structure of the end units, quantitatively expressed at any x_n by different positive or negative T_g deviations from the common asymptotic T_g∞ value. The results are also discussed in terms of copolymer end effect and of relation between T_g and end copolymeric composition.     

Total Syntheses of Two Self-polymerizable Carbocyclic Analogues of 2′-deoxyribonucleosides

A short regio- and stereoselective synthesis of two carbocyclic 3′-deoxynucleoside analogues is described, the key step of which consists in the photosensitized addition of MeOH to a cyclopent-2-enone derivative. As in both cases functional groups capable to react with each other are present in the same molecule, the synthetic compounds can form polymers similar to oligonucleotides.     

Large Water-Soluble Cyclophanes with Convergent Intracavity Functionality

New tricyclic spacers, readily available through fourfold Mannich reaction of substituted dibenzyl ketones, were introduced into a series of ten H₂O-soluble cyclophanes with spacious preorganized cavity binding sites. These spacers provide H₂O-solubility with amine or crown-ether functionality remote from the cyclophane cavity while directing functional groups such as keto or OH groups in a precise geometrical array inside the cavity. The cyclophanes were designed to include organic substrates via a combination of apolar and specific polar functional group interactions. The X-ray crystal-structure analysis of the tritopic receptor 18 with one potential neutral-molecule and two cation-binding sites showed a large rectangular open cavity with dimensions of roughly 9 × 14 Å and a spacing of 9.7 Å between the O-atoms of two convergent C?O groups. Despite the binding-site preorganization, cyclophanes incorporating two of the new spacers did not show any substrate binding in aqueous solutions. The failure of these systems to function as receptors is mainly due to steric hindrance to important cyclophane aromatic ring-guest interactions. Also, the favorable solvation of the intracavity functionality may prevent the formation of complexes. Hybrid receptors constructed from the novel spacers and diphenylmethane units were found to bind flat aromatic substrates as well as bulky [4.2]paracyclophanes. The observed large differences in stability (ΔΔG°> 2 kcal mol^?1) of the complexes formed by three structurally closely related hybrid receptors with convergent C?O, OH or CH₂ groups and 6-hydroxynaphthalene-2-carbonitrile as guest can be explained by a strong solvation effect of the convergent functional groups on apolar inclusion complexation.     

Synthesis of Benzazepine Analogues of Noscapine

The synthesis of benzazepine analogues of the opium alkaloid noscapine ( 1 ) is described. The benzazepines 2 and 3 were prepared starting from nornarceine ethyl ester ( 4 ; readily available from 1 ) in several steps. X-Ray analysis of compound 2 revealed that it is not a diastereosisomer mixture but a racemate of the threo-form and thus has the same configuration as 1 .     

Publication list

The helium atom in its ground state, subject to strong magnetic fields, is treated using a variational method. Trial functions consisting of Gaussians with nonlinear parameters variationally optimized are used. The form of these functions is a generalized s-symmetry-state properly modified to admit spatial deformation along the direction on which the magnetic field is applied. © 1994 John Wiley & Sons, Inc.     

Theory of relaxed density matrices: Application to second-order response properties

The evaluation of second derivatives of the electronic energy for nonvariational wave functions using an energy functional is discussed. It is shown that, in certain cases, the formation of the first-order relaxed density matrix leads to an efficient algorithm for the calculation of second-order response properties. Detailed formulas are given for second-order Møller–Plesset perturbation theory. © 1994 John Wiley & Sons, Inc.     

Density functionals for exchange and correlation energies: Exact conditions and comparison of approximations

A set of exact conditions is compiled for the purpose of developing and testing approximations for the exchange-correlation energy as a functional of the electron density. Special emphasis is placed upon recently developed density-scaling relationships. Commonly used generalized gradient approximations are compared against several of these conditions. A direct tabular comparison of these functionals (not of calculated properties) with one another is also made. © 1994 John Wiley & Sons, Inc.