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8,2'-O-环化-9β-D-腺呤阿拉伯糖苷是阿糖腺苷合成过程中的一个关键性中间体,该化合物的NMR数据只有1H-NMR谱的糖环1'位质子化学位移和偶合常数的报道,13C-NMR谱未曾报道。本文用2D-NMR、NOE-DIF等技术,对它的1H、13C-NMR谱进行归属,进一步明确了它的结构。 相似文献
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Although quite a few papers have been devoted to the 13C NMR study of pyrazoles, there is one problem that has not yet been satisfactorily solved, namely the assignment of the 2JCH and 3JCH coupling constants. In general, the 3C chemical shifts and 1JCH coupling constants can be easily attributed, but the assigment of the long-range 2JCH and 3JCH coupling constants is not straight forward. In N- substituted pyrazoles, where annular tautomerism is prevented, each carbon atom can have two long-range coupling constants with the ring protons. 相似文献
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The parameters of the nuclear magnetic resonance (NMR) spectrum – shielding constants and indirect spin–spin coupling constants – of three isomers of C20 are studied using density-functional theory. The performance of different exchange–correlation functionals is analysed by optimising the geometry for the ring, bowl and cage isomers, followed by a computation of the NMR constants at the optimised structure. The results are analysed and rationalised by performing comparisons of the three isomers with one another and with related systems such as polyynes (for the ring), o-benzyne (for the bowl) and C60 (for the cage). The shielding and spin–spin parameters calculated using the Perdew–Burke–Ernzerhof (PBE) exchange–correlation functional are sufficiently reliable to assist in future experimental NMR studies of C20 and, in particular, the identification of its isomers. 相似文献
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J. Dommen W. Caminati H. Hollenstein T.-K. Ha R. Meyer A. Bauder 《Journal of Molecular Spectroscopy》1996,180(2):369-388
The microwave spectra of 2,5-dihydropyrrole and 2,5-dihydropyrrole-1-d1have been measured with Stark and Fourier transform spectrometers in the range 10–39 GHz. Rotational constants, centrifugal distortion constants, and14N quadrupole coupling constants have been determined from the observed transition frequencies for the ground vibrational state. In addition, two satellites of the normal species and one satellite of the deuterated species have been identified and measured. Splittings of the rotational transitions due to amino group inversion tunneling have been observed and analyzed. Infrared transitions of the amino group inversion mode have been measured in the range 490–720 cm−1. The effect of ring puckering on the inversion motion of the amino group in 2,5-dihydropyrrole and 2,5-dihydropyrrole-N-d1has been investigated byab initiocalculations and two-dimensional flexible model calculations from the results of microwave and infrared spectroscopy. The observed molecular properties have been reproduced by a model which involved adjustable parameters for the potential energy surface and the structural relaxation of the CCC valence angles. Additional parameters have been transferred from theab initiocalculations. The adjustment of the model to the experimental data has yielded an equatorial equilibrium conformation with slightly larger CCC valence angle than in the most stable axial conformation. Excitation of the first ring puckering state has been found to enhance the inversion tunnel splittings. 相似文献
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Robert C. Loyd Serweshwer N. Mathur Marlin D. Harmony 《Journal of Molecular Spectroscopy》1978,72(3):359-371
The microwave spectra of the normal and two isotopic species of cyclopentyl chloride have been observed and analyzed. For the normal isotopic species the rotational constants (in MHz) are A = 4547.77 ± 0.01, B = 2290.22 ± 0.01, and C = 2073.34 ± 0.01. From the rotational constant data, it has been shown that the stable molecular conformation is the bent axial form. Quadrupole coupling constants have been measured for the 35Cl nucleus, the values being (in MHz) χaa = ?23.70 ± 0.10, χbb = 32.33 ± 0.36, and χcc = ?8.63 ± 0.37. When transformed to the CCl bond axis system, the coupling constants confirm the axial structure. Extensive vibrational satellite structure, presumably arising from the pseudorotational ring mode with a fundamental frequency of 52 ± 5 cm?1, has been observed and assigned. No spectral evidence has been observed for a second stable molecular conformer. 相似文献
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The conformations of three analogues of baclofen 1: phaclofen, saclofen, and hydroxy-saclofen 2–4, potent GABAB antagonists, in solution (D2O) are estimated from high-resolution (300 MHz) H NMR coupling data. Conformations and populations of conformers are calculated by means of a modified Karplus-like relationship for the vicinal coupling constants. H NMR spectral analysis evidences how 1–3 keep in solution the preferred a conformation around C3-C4 bond. A partial rotation is set up around C2–C3 bond (the conformations about C2–C3 are all highly populated in solution) particularly for 2 and 3 while 1 shows a relative preferred a conformation. This evidences the influence of the anionic moiety. 相似文献
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The present study uses 2D NMR to assign all resonance lines of pentagastrin completely. From 2D NOESY and coupling constants JHNα, interproton distance and torsion angle Φ restraints were obtained. Based on them, the model of conformation for pentagastrin was proposed by restrained molecular dynamics calculation. It is shown that the C-terminal part of pentagastrin forms a Δ turn with a weak H-bond between the CO of Met and the NH of Phe. A strong H-bond between indole NH of Trp and β-carboxyl group of Asp stablizes the folded form in DMSO, which may result in a significant increase in the population of a favorable conformation for interaction with receptor. 相似文献
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K. Jackowski 《Applied magnetic resonance》2003,24(3-4):379-385
Intermolecular interactions modify nuclear magnetic resonance (NMR) chemical shifts and spin-spin coupling constants. The intermolecular effects can be determined if the NMR parameters for an isolated molecule are known. Gas-phase NMR spectroscopy offers such methods which allow one to measure the shielding and spin-spin coupling constants at the zero-density limit where the NMR parameters are free from intermolecular contributions. It is also shown that at present the multinuclear NMR spectra can easily be obtained for gaseous samples containing several micrograms of a solute compound. 相似文献
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The twisting of the A-, B-, and D- rings of β-arteether were determined from dihedral angles derived from 3JHH coupling constants and a Karplus-type equation that takes into account heteroatom substitution. The angles obtained by NMR were also compared to the angles obtained by molecular modeling and to those obtained from the methyoxyl analog (artemether) using x-ray crystallography. The NMR results showed that the A-ring was a relatively undistorted chair conformation with the 14-methyl group in an equatorial position. The NMR data indicated that the B-ring was very distorted and the D-ring was twisted outward because of the steric interactions with the ethoxy group. Two-dimensional NOESY data was used to measure selected proton-proton distances for arteether in solution and these distances were also compared to those obtained by molecular modeling and from the x-ray data for artemether. The NOESY data also indicated that the conformation of the A-ring was fairly normal, the B-ring was twisted, and the ethoxy group was in an extended conformation (C11-C12-O-C16=+170°, and C12-O-C16-C17=+169°) 相似文献
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The solution and solid state conformation of (S)-4,5,6,7-tetrahydro-5-methylimidazo [4,5,1-jk][1,4]-benzodiazepin-2(1H)-one (R78362) have been investigated by low temperature NMR and x-ray diffraction studies. The 1H NMR spectrum of R78362 shows no evidence of the presence of multiple conformers in the temperature range 340K - 177K. Molecular mechanisms and semiempirical molecular orbital calculations suggest that the nitrogen and ring inversion barriers of R78362 are small and thus a time-averaged 1H NMR spectrum is probably occurring at 298K. The x-ray diffraction data indicated that there were two independent molecules in the asymmetric unit of the crystal. The two molecules had similar conformations with the benzoimidazole ring being planar and the diazepine ring in a “half-chair” conformation. 相似文献
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Temperature dependent NMR chemical shifts for hydrogen and oxygen, NMR quadrupole coupling constants for deuterium and vibrational frequencies for the OH bond of liquid ethanol are calculated for the temperature range 250 to 350 K using the ab initio quantum cluster equilibrium method and compared with experimental measurements. The calculated NMR chemical shifts, quadrupole coupling constants and infrared vibrational frequencies are in good agreement with experimental measurements. The results indicate that cyclic tetramer and pentamer structures rather than linear structures are the principal components of liquid ethanol. 相似文献
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1H NMR spectra of epoxy-fused cyclopentane derivatives have been computationally investigated with density functional calculations in order to unravel the shielding effect of the epoxy ring on the 1H NMR chemical shifts of N-substituted epoxy-fused cyclopentane-3, 5-diol derivatives. Both 1H NMR chemical shifts and spin–spin coupling constants have been calculated with the WP04/cc-pVTZ level of theory in solution. The WP04/cc-pVTZ// B3LYP/6-31+G(d) methodology has been found to reproduce the best experimental results on epoxy-fused cyclopentane derivatives. This study is expected to lead experimentalists in their endeavour to characterize epoxy-fused cyclic systems with ease. 相似文献
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Accurate measurements of small J coupling constants under inhomogeneous fields via intermolecular multiple-quantum coherences 总被引:1,自引:1,他引:0
Lin Y Chen Z Cai S Zhong J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2008,190(2):298-306
Two new NMR pulse sequences, based on intermolecular multiple-quantum coherences (iMQCs), were developed to obtain apparent J coupling constants with a scaling factor from one to infinity relative to the conventional J coupling constants. Here the apparent J coupling constants were defined as apparent peak separations in unit of Hz in a reconstructed spectrum for a coupled spin system. Except for the adjustable scaling factor for apparent J coupling constants, the sequences hold the advantage of high acquisition efficiency, and retain the spectral information such as chemical shifts, multiplet patterns, and relative peak areas under inhomogeneous fields. For spin systems with small scalar coupling constants, well-resolved J-spectra can be achieved by selecting a proper scaling factor. Theoretical predictions are in good agreement with simulation results and experimental observations. 相似文献
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The rotational spectrum of a hydrogen-bonded isoxazole-water complex has been measured between 6–18 GHz with a pulsed nozzle Fourier transform microwave spectrometer. In addition to isoxazole-H2O, the complexes with HDO and D2O as well as isoxazole-15 N-H2O have been investigated in order to determine the structure of the complex. Rotational constants, quartic centrifugal distortion constants and quadrupole coupling constants, where applicable, have been fitted to the measured transition frequencies of the isotopomers. Structural data, which have been deduced from the planar moments of inertia and the quadrupole coupling constants of the isotopomers, have established conclusively that water binds to nitrogen in the ring plane of isoxazole. Ab initio calculations have revealed that complexes with a hydrogen-bond to nitrogen or to oxygen are both stable. The complex with water attached to nitrogen has been found to be more strongly bound than that with water attached to oxygen. Small splittings of the rotational transitions of the two complexes with H2O have been interpreted as being the result of an internal rotation of water with respect to isoxazole. 相似文献