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1.
Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline‐2,3‐diyl)s
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Johannes Scholz Michael Reggelin 《Journal of polymer science. Part A, Polymer chemistry》2015,53(11):1320-1329
The development of synthetic routes which lead to five new diisocyanide monomers with one or two phenolic groups is described. Their polymerization behavior is studied with Pd‐ and Ni‐based initiators, as well as under microwave irradiation. The polymerizability is mainly dominated by steric effects as is concluded from experiments using different protecting groups. Chiroptical properties of these new polymers are studied by CD‐spectroscopy. After deprotection, helically chiral poly(quinoxalin‐2,3‐diyl)s are obtained which display a Brønsted function attached to a stereolabile biaryl axis whose configuration should be influenced by the chiral polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1320–1329 相似文献
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Stulz E Scott SM Ng YF Bond AD Teat SJ Darling SL Feeder N Sanders JK 《Inorganic chemistry》2003,42(20):6564-6574
The synthesis of linear multiporphyrin arrays with mono- and bisphosphine-substituted porphyrins as ligand donors and ruthenium(II) or rhodium(III) porphyrins as ligand acceptors is described. With appropriate amounts of the building blocks mixed, linear dimeric and trimeric arrays have been synthesized and analyzed by (1)H NMR and (31)P NMR spectroscopy. The Ru/Rh acceptor porphyrins can be located either at the periphery or in the center of the array. Likewise, the monophosphine porphyrins can be positioned at the periphery, thus allowing a high degree of freedom in the overall composition of the arrays. This way, both donor and acceptor porphyrins can act as chain extenders or terminators. One of the trimeric complexes with two nickel and one ruthenium porphyrin has also been analyzed by X-ray crystallography. Attempts have also been made to synthesize higher order arrays by mixing appropriate amounts of the porphyrins; however, from the NMR data it cannot be concluded if monodisperse five, seven, or nine porphyrin arrays are present or if the solutions are composed of a statistical mixture of smaller and larger arrays. 相似文献
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Preliminary results leading towards the total synthesis of Brefeldin A are presented. 相似文献
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S. G. Wang Y.X. Qiu E. Neumann H. J. Deiseroth W. H. Eugen Schwarz 《无机化学与普通化学杂志》2003,629(10):1718-1730
About 60 molecular species composed of up to 10 mercury atoms and of oxygen atoms and/or of some other elements or groups (such as halogen, OH2, OH, H, alkali, NO3) have been investigated quantum chemically. Different density functional approaches and the ab initio SCF‐MP2 method were applied, comparing different basis sets and different atomic core sizes. It is important not to treat the Hg 5s, p, d as inactive core shells, and to use sufficiently many polarization functions. The shape of the 〉O‐Hg‐Hg‐O〈 units is not favorable concerning the formation of lattices composed of HgI, O and OH only. Despite its bulkiness, the OHgHgO units can easily come into contact with each other and then disproportionate. This is prevented in the so‐called ternary M‐HgI oxides by the embedded oxometallate (oxoacidic) anions. Furthermore, the HgI and HgII oxide bond energies are less favorable towards the stability of HgI oxo compounds, as compared to Hg halidic or oxoacidic compounds. Both points are not promising concerning the search for HgI oxides/hydroxides, although the preparation of such compounds, including spacer groups, by topochemical reactions can still not be excluded. So far, experimental efforts towards the synthesis of such a new class of compounds have only demonstrated that HgII is strictly preferred over HgI in the formation of solids of binary Hg‐O or ternary A‐Hg‐O composition (A = electropositive metal such as alkali, in contrast to M = transition or semi‐metal). This is so even if compounds containing ‘electron rich Hgδ— atoms’ (i.e. A‐Hg amalgams) are oxidized under mild conditions. 相似文献