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51.
The lattice energies of a series of organic dihydrogenphosphate salts capable of second harmonic generation (SHG) have been calculated. These calculations, coupled with empirical data, indicate that a minimum of 20–25% of the lattice energy arises from hydrogen-bond interactions. Hydrogen bonding is shown to be a strong enough force to have a profound effect on the overall packing and crystal geometry of such ionic materials, and is thus an important factor to consider for crystal engineering. 相似文献
52.
2,3-Dihydro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one ( (Stegobinone), the sex pheromone of the drugstore beetle, was successfully prepared from 4,6-dimethyl-3,5,7-nonatrione () by a biogenetically plausible scheme. 相似文献
53.
The formalism developed in the first two papers of this series is applied to the investigation of a new weak-field model. This crystal-field model lies on the use of a symmetry-adapted weak-field basis and an effective Hamiltonian involving in a symmetrical way both spin- and orbit-dependent contributions. Some general properties of this Hamiltonian are studied and complete calculation of its matrix elements is conducted in a symmetry-adapted weak-field basis in the case of an arbitrary configuration nlN in any symmetry. The case of a configuration ndN in octahedral symmetry is fully explored. In this case, the proposed weak-field model is restricted to a 12-parameter model which accounts for isotropic and anisotropic Coulomb interactions, isotropic and anisotropic spin-orbit interactions, and crystal-field interactions. A comparison between this 12-parameter weak-field model and the 14-parameter strong-field model is established. Equivalence between the latter two models requires two constraint relations to be satisfied for some strong-field parameters. These two relations are examined with various viewpoints. 相似文献
54.
55.
We report the time courses of five solid-phase reactions obtained using single bead FTIR microspectroscopy. This time-resolved information aided in the determination of the required reaction time, the nature of the solid-phase reaction, and resin property, effectively assisting in the initial phase of our combinatorial chemistry efforts. Our results showed that solid-phase organic reactions proceed faster than generally speculated. In addition, we have shown that reactions on the surface and in the interior of the bead occur at the same rate for reactions studied. The reaction on the TentaGel resin was shown to be not faster than reactions on Wang resin, suggesting that the diffusion of the substrate into polystyrene bead copolymerized with 1% divinylbenzene is not rate-limiting. Finally, the capability of obtaining IR spectra from the partial surface of a single bead demonstrated the femtomolar detection limit of single bead FTIR microspectroscopy. 相似文献
56.
An efficient eight-step synthesis (53% overall) and the evaluation of 1,2,9,9a-tetrahydrocyclopropa[c]benz[e]-3-azaindol-4-one (CBA) and its derivatives containing an aza variant of the CC-1065/duocarmycin alkylation subunit are detailed. This unique deep-seated aza modification provided an unprecedented 2-aza-4,4-spirocyclopropacyclohexadienone that was characterized chemically and structurally (X-ray). CBA proved structurally identical with CBI, the carbon analogue, including the stereoelectronic alignment of the key cyclopropane, its bond lengths, and the bond length of the diagnostic C3a-N2 bond, reflecting the extent of vinylogous amide (amidine) conjugation. Despite these structural similarities, CBA and its derivatives were found to be much more reactive toward solvolysis and hydrolysis, much less effective DNA alkylating agents (1000-fold), and biologically much less potent (100- to 1000-fold) than the corresponding CBI derivatives. 相似文献
57.
The stereochemical course of cycloalkanone imine reductions by a variety of boron hydride reagents is described; very high stereoselectivity with substituted alkali metal borohydrides is reported. 相似文献
58.
Mhamed Lemhadri Touriya Zair Maurice Santelli 《Journal of organometallic chemistry》2007,692(11):2270-2281
The Heck reaction of aryl halides with functionalised alk-1-enes should be a powerful method for the synthesis of functionalised (E)-1-arylalk-1-ene derivatives. The major problem of this reaction is the palladium-catalysed migration of the carbon-carbon double bond along the alkyl chain when there are no substituents on the C3 carbon of the alk-1-enes. We observed that for the arylation of ethyl pent-4-enoate, ethyl 2-methylpent-4-enoate or dimethyl allylmalonate this migration could be partially or completely controlled using appropriate reaction conditions. The ramification on the alkyl chain and the substituents on the aryl halide have also an important influence on this migration. Moreover, the cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/1/2[PdCl(C3H5)]2 system catalyses this reaction with a wide range of aryl bromides using very high ratio substrate/catalyst in good yields. 相似文献
59.
60.
Pasquale A. Falcigno Stanley Jasne Maurice King 《Journal of polymer science. Part A, Polymer chemistry》1992,30(7):1433-1441
We have synthesized a novel dianhydride, 2,2′-dichloro-4,4′,5,5′-benzophenone tetracarboxylic dianhydride (DCBTDA). Polyimides were synthesized with DCBTDA or 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) and several relatively rigid meta- and para- substituted mononuclear diamines. The BTDA based systems were insoluble in dipolar, aprotic solvents whereas the DCBTDA based polymers displayed enhanced solubility in these solvents. The thermal stability of these polyimides was excellent as measured by 5% weight loss decomposition. The Tg's of the polymers were all above 290°C. 相似文献