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Marc Halpern Yoel Sasson Itamar Willner Mordecai Rabinovitz 《Tetrahedron letters》1981,22(18):1719-1722
The effects of water molecules and quat structure are shown to be significant in determining the behavior of alkylation reactions of weakly acidic carbon acids under PTC/OH? conditions. 相似文献
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Sternfeld T Thilgen C Hoffman RE Del Rosario Colorado Heras M Diederich F Wudl F Scott LT Mack J Rabinovitz M 《Journal of the American Chemical Society》2002,124(20):5734-5738
Reduction of the two "closed" [6,6] methanofullerenes, [6,6]C(61)H(2) (1) and [6,6]C(71)H(2) (5), to the corresponding hexaanions with lithium metal causes the bridgehead-bridgehead bonds to open, at least partially, and this change gives rise to diamagnetic ring currents in the resulting homoconjugated six-membered rings (6-MRs). These new ring currents shield the overlying hydrogen atoms on the methylene bridge and induce upfield shifts of 1.60 and 0.11 ppm in their (1)H NMR resonances, respectively. Analogous reduction of the already "open" [5,6]methanofullerenes, [5,6]C(61)H(2) (2) and [5,6]C(71)H(2) (3 and 4), only slightly enhances the shielding of the hydrogen atoms over the homoconjugated 6-MRs (upfield shifts of 0.13, 0.68, and 0.14 ppm, respectively) but leads to exceptionally strong diamagnetic ring currents in the homoconjugated five- membered rings (5-MRs), as evidenced by dramatic shielding of the hydrogen atoms situated over them (upfield shift of 5.01, 6.78, and 1.63 ppm, respectively). The strongest shielding is seen for the hydrogen atom sitting over the 5-MR at the pole of C(71)H(2)(6)(-) (delta = -0.255 ppm) indicating that the excess charge density is concentrated at the poles. 相似文献
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We report the crystal and molecular structures of the complex of 18-C-6 with H3O+BF4− (I) and the complex of 18-C-6 with BF3OH2·H2O (II). The different modes of appearance of the “BF3” species as BF3, BF3OH2, BF3OH2·H2O and BF4−, as well as their structurally significant intermolecular and intramolecular interactions, are discussed. In complex I the oxonium ion is bound at the centre of the 18-C-6 macrocycle. The oxonium oxygen is located practically equidistant (2.68–2.73 Å) from the six macrocyclic ethereal oxygens. The BF4− counter-ion is positioned 7.3 Å away from the oxonium ion in the same general plane of the crown ether. This anion is not involved in any direct intermolecular contacts, a fact that may explain why it is spherically disordered. In complex II there is no guest molecule (or ion) present in the “cavity” of the macrocycle, but there are two hydrogen-bonded systems of BF3OH2·H2O that are interacting with the crown ether on either side of the general macrocyclic plane. Complex II features three types of hydrogen bonds—the O(water)-HO(crown) bonds (2.83 and 2.85 Å), the O(water)H-O(BF3) bond (2.49 Å) and the O(BF3)-HO(crown) bond (2.65 Å). The strong intermolecular O(crown)O(water)O(BF3) and O(crown)O(BF3) interactions stabilize the normally unstable BF3OH2·H2O species. 相似文献
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Roy E. Hoffman Noach Treitel Mordecai Rabinovitz 《Magnetic resonance in chemistry : MRC》2001,39(8):489-494
Isotope shifts are a well-established tool for structural analysis by NMR. The substitution of a protium with a deuterium is the most widely studied of these effects. However, such studies call for specific deuteration that requires complex synthetic techniques owing to the low natural abundance of deuterium. 13C occurs at a higher natural abundance and couples strongly with its attached proton. We have developed and refined a method to reliably observe these much smaller shifts without needing to resort to chemical synthesis. We show that carbon induced isotope shifts reflect structural features. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
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Sternfeld T Hoffman RE Saunders M Cross RJ Syamala MS Rabinovitz M 《Journal of the American Chemical Society》2002,124(30):8786-8787
A 3He NMR resonance of C606- containing He is assigned to He2@C606-, thus showing that C60 can also accommodate two helium atoms. The ratio of the di-helium compound relative to the mono- is 1:200, 10 times lower than the equivalent counterpart of C70. The 3He NMR chemical shift of He2@C606- is 0.093 ppm downfield from the already known resonance of He@C606-. In the reduced endohedral mono- and di-helium C70, the 3He NMR chemical shift of He2@C706- is 0.154 ppm upfield from the peak of He@C706-. 相似文献
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Doubly charged systems derived from fused benzenoid polycycles reveal an unquenched delocalization of 4 n π-electrons and hence are predicted to possess antiaromatic character. The magnitude of the paratropic 1H NMR chemical shifts, due solely to the paramagnetic secondary field sustained in these species, was found to depend linearly upon the magnitude of LUMO-HOMO energy gaps of the corresponding systems. The existence of such a correlation enables a comprehensive treatment of the various factors which determine the antiaromatic character and the subtle interrelations between those factors. This, in turn, leads to a deeper understanding of antiaromaticity. 相似文献
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Omar Elmalak Mordecai Rabinovitz Jochanan Blum 《Journal of heterocyclic chemistry》1993,30(1):291-292
K-Region oxides and imines of phenanthrene, chrysene benz[a]anthracene, and dibenz[a,h]anthracene react in tetrahydrofuran with lithium and sodium to give the parent hydrocarbons. In the presence of excessive metal, the latter are converted into dianions from which the parent compounds can be regenerated upon quenching with oxygen. Metalate derivatives of the oxides and imines are proposed to be the corresponding reaction intermediates in the deoxygenation and deamination processes. 相似文献