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41.
Adam W Bargon RM Bosio SG Schenk WA Stalke D 《The Journal of organic chemistry》2002,67(20):7037-7041
The direct molybdenum-catalyzed sulfuration of a variety of isonitriles with elemental sulfur or propene sulfide as sulfur donors affords the corresponding isothiocyanates in good yields and under mild reaction conditions. A catalytic cycle is suggested, in which the molybdenum oxo disulfur complex operates as the active sulfur-transferring species. A novel adduct between the isonitrile and the molybdenum complex has been characterized by X-ray analysis and its association constant determined by UV-vis spectroscopy, but this adduct appears not to be involved in the sulfur-transfer process. 相似文献
42.
Adam W García H Diedering M Martí V Olivucci M Palomares E 《Journal of the American Chemical Society》2002,124(41):12192-12199
The photochemical denitrogenation of the cyclopentene-annelated DBH-type azoalkanes 1 has been examined in solution as a function of bridgehead substitution and temperature. For all derivatives, namely, the unsubstituted 1a(H/H), monomethyl 1b(Me/H) dimethyl 1c(Me/Me), monophenyl 1d(Ph/H), and diphenyl 1e(Ph/Ph), the temperature-dependent ratio of syn and anti housanes 2 provides experimental support for a competition between the singlet (high temperature) and triplet (low temperature) reaction channels in the direct photolysis. The syn/anti ratio of the housanes 2 depends on the extent and type of bridgehead substitution; the amount of the anti diastereomer (retention) follows the order Ph > Me > H, and double substitution is more effective than single. This stereochemical memory is interpreted in terms of the mass effect (inertia) of the substituents and steric interaction (size) between the substituents at the bridgehead and the methylene bridge during the deazetation step of the transient diazenyl diradical conformations (1)DZ (exo-ax) and (1)DZ (exo-eq). These conformers are impulsively generated upon decay of the (1)(n,pi)-excited azoalkane, a trajectory assessed through computational work. The new mechanistic feature disclosed by the unprecedented anti stereoselectivity (retention) is the intervention of a puckered 1,3-cyclopentanediyl singlet diradical (1)DR as product bifurcation step, whose conformational relaxation to the planar species (loss of stereochemical memory) is encumbered by bridgehead substitution. 相似文献
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46.
The effect of irradiation on concentrations and relaxation behaviour of brain metabolites was studied by means of high-resolution 1H NMR in vitro. The studies were performed on rat brains irradiated with the doses of 20 Gy applied in fractions of 2 Gy. Standard procedures were used to obtain HClO4 extracts of rat brains. The 1H NMR studies of the extracts solutions in D2O were performed using a Varian Inova-300 NMR spectrometer. The integral intensities of the metabolite signals were found to change during the irradiation cycle and after it. These changes are accompanied by the variations in the T1 relaxation times. N-acetylaspartate, glycerophosphocholine, phosphocholine, choline, creatine and phosphocreatine, myoinositol and taurine were analysed as potential markers of irradiation injury. 相似文献
47.
The spin-state-dependent reactivity, singlet versus triplet, of the 2-spiroepoxy-1,3-cyclopentane-1,3-diyl DR2 has been assessed through alcohol-trapping reactions for which the effect of solvent acidity on the product distribution of the alcohol trapping products 2 versus 3 + 4 and stereochemical deuterium-labeling studies have been performed. The proposed mechanism for the solvent effect on the product ratio (2/3 + 4) reveals the importance of the hydrogen-bonded intermediates I1 and I2 in the trapping reactions; the stereochemical deuterium-labeling results clarify the dipole structure trapped by the alcohol. The dipoles DP1 and DP2, in which the configuration between the epoxide oxygen and the deuterium atoms is retained, are inferred for the direct photodenitrogenation reactions (singlet state), whereas for the benzophenone-sensitized photoreactions (triplet state), after ISC, the ring-opened dipole DP3 is implied as the intermediate that is trapped by the alcohol. 相似文献
48.
Adam W Krebs O Orfanopoulos M Stratakis M Vougioukalakis GC 《The Journal of organic chemistry》2003,68(6):2420-2425
The intramolecular and intermolecular kinetic isotope effects (KIE) have been determined for the nitrosoarene ene reaction with deuterium-stereolabeled 2,3-dimethyl-2-butenes (TME). trans-TME-d(6) (k(H)/k(D) = 3.0) and gem-TME-d(6) (k(H)/k(D) = 4.0) show large intramolecular primary isotope effects. In contrast, the intramolecular competition in cis-TME-d(6) (k(H)/k(D) = 1.5) and the intermolecular competition for the TME-d(0)/TME-d(12) pair (k(H)/k(D) = 1.98) show considerably smaller, but mechanistically significant kinetic isotope effects. The latter fact is rationalized in terms of reversible formation of a three-membered-ring intermediate, namely the aziridine N-oxide, or a similar unsymmetrical, polarized diradical in the first step of the reaction. Such reversibility has also been implied earlier for triazolinedione (TAD) and singlet oxygen ((1)O(2)) with deuterium-stereolabeled 2-butenes, but of the three enophiles, ArNO is the most sensitive toward reversibility, which is due to its moderate reactivity and its high steric demand. 相似文献
49.
We propose a simple abstract version of Calderón–Zygmund theory, which is applicable to spaces with exponential volume growth, and then show that important specific operators can be treated within this framework.
Both authors are part of the European TMR network entitled ``Harmonic Analysis'. The first author was partially supported by KBN grant 5 P03A 050 20 and by the TMR network. The second author was partially supported by his university and by the Italian M.U.R.S.T 相似文献
50.
A simple model of exciton–phonon interaction in a crystal with one molecule in the unit cell is used to simulate some peculiar features of the oligothiophene absorption spectra. The model is treated in the limit of weak vibronic coupling, and the configuration interaction between the intense zero-phonon Frenkel state and the one-phonon continuum is described in terms of the Fano formalism. The good agreement between the calculated curve and a part of the experimental absorption profile allows one to discriminate some features that are physically relevant but are not accounted for in the model. 相似文献