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1.
An extended hexagonal molecule that has high symmetry and rigidity was designed and synthesized by a cobalt-catalyzed cyclotrimerization reaction. The ligand possesses six benzoic acids at its periphery, which were connected to a central hexakis(2,5-dodesyloxyphenyl)hexaphenylbenzene core with a maximum intramolecular carboxyl group distance of approximately 3.5 nm. 相似文献
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Marchesan D Coriani S Forzato C Nitti P Pitacco G Ruud K 《The journal of physical chemistry. A》2005,109(7):1449-1453
The absolute configuration of (S)-(-)-paraconic acid is correctly assigned on the basis of ab initio calculations of the specific optical rotation (OR) at the sodium D line, carried out both in vacuum and in methanol. Density functional theory (DFT) and M?ller-Plesset second-order perturbation theory (MP2) are used to determine the most stable conformational structures, whose OR values are then calculated using DFT linear response theory and London atomic orbitals. The total OR is obtained by averaging these values using the population fractions determined from Boltzmann's statistics. The total OR of the MP2 structures has the correct sign both in vacuum and in solution, whereas only the solvent-relaxed DFT structures correctly reproduce the experimental sign. The strong solvent effect on the total OR is shown to arise primarily due to the variations in the relative energies of the various conformations. 相似文献
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A series of transformations of cytochalasin D ( 1 ; zygosporin A) was carried out. After treatment of the diol 7 with mesyl chloride and pyridine, and subsequent chromatography on silica gel, the 17-acetyl derivatives 12 and 13 , the first members of the hitherto unknown [10]cytochalasans, were obtained. The alcohol 8 was converted to the chlorosulfinate 18 under the same conditions. Replacement of pyridine by triethylamine in the mesylation reaction led to the cyclohepta[4,5]benz[1,2-d]isoindole derivative 20 , also representing a novel ring system. 相似文献
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The bridge-substituted calix[4]arene carboxylic acid, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetramethoxy-calix[4]arene-2-carboxylic acid (1), can be readily converted to various esters 2-4 and reduced to the alcohol 5, which reacts with methyl iodide to give the ether 6. The alcohol can be dansylated to give 7, the fluorescence of which is selectively quenched by Cu(II) in acetonitrile. An attempt to convert the acid 1 to an amide resulted unexpectedly in the formation of a lactone 8. The conformational characteristics of 1-8 have been studied in solution and, in the cases of 2 and 4, in the solid state by determination of their single-crystal X-ray structures. With the exception of 8, in all these compounds the bridge substituent adopts an equatorial (lateral) orientation. 相似文献
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Abdulhamid Hamza 《Structural chemistry》2010,21(4):787-793
The conformations and exciton couplings in 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene (THDC) have been studied using resonance-enhanced two-photon ionization spectroscopy in a supersonic jet expansion. It has been estimated from the spectral analysis that 90% of THDC exists in the twist-boat (TB) conformation; the chair (C) conformer constitutes the remaining 10%. Most of the vibronic activity in the spectrum of THDC is associated with the symmetric flapping of the aromatic rings of the TB conformer. The observed S1/S2 exciton splitting of the TB conformer is 100 cm?1. The S1/S2 transition of the C conformer is found to be forbidden. The exciton splittings of the C and TB conformers were estimated by the spectral analysis of two deuterated isotopomers of THDC. The estimated exciton splittings of the C and TB conformers are 14.7 and 101.9 cm?1, respectively. The supramolecular model of bichromophores with identical chromophores at the CIS/6-31+G(d)//HF/6-31+G(d) level of theory predicted electronic coupling energies that are very close to the experimental exciton coupling energies. 相似文献
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-Various halides were used to alkylate at both nitrogen atoms of [4.3.3]propell-3-ene-bis-imidi 相似文献
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Two novel symmetrical triads of triphenylene-calix[4]arene-triphenylene bridged by aromatic amido or hydrazone spacers were synthesized with stepwise procedures in yields of 67% and 68%, respectively. They exhibited interesting mesomorphic behavior of triphenylene column with calix[4]arene units on ancillary lateral sides. 相似文献
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A simple model of self-avoiding chains of specific-sequence copolymers of H (hydrophobic) and P (polar) monomers on lattices gives many of the properties of proteins, including their tertiary structural symmetries. 相似文献
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An empirical model for calculating the torsional angles for flexible 6-membered rings is presented in terms of three independent parameters, two geometrical and one pseudorotation angle. The rings are classified according to four estimators, the fit of the model depending upon their values. Equations are given for defining any conformation by a point in a 2-dimensional pathway. Some examples have been examined in the light of this model. 相似文献
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Spectra, recorded in the manner of conventional absorption spectra, of polycrystalline samples of cyclohexane doped with anisole guest molecules at 10−4 M/M, exhibit a surprising behavior as a function of temperature, absorption features at high temperatures appearing inverted at low temperature. An analogous inversion is observed for spectral holes burned into these spectra. It is proposed that this unexpected phenomenon is an intriguing artifact, caused by strong elastic light scattering that attenuates the incident beam to such an extent that fluorescence and phosphorescence emission dominates the detected signal at low temperatures. 相似文献
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Kamlakar Avasthi Sangeeta Aswal Prakas R. Maulik 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(11):1324-1325
In the crystal structure of 1,1′-(1,3-propanediyl)bis(5-ethyl-6-methylthio-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-4-one), C19H24N8O2S2, the pairs of pyrazolo[3,4-d]pyrimidine rings of the molecule stack between the heterocyclic rings, due to intramolecular π–π interactions. The substituted ethyl and methyl groups are comparable as far as intramolecular stacking is concerned. 相似文献
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Furer VL Borisoglebskaya EI Kovalenko VI 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(1-2):355-359
The experimental IR and Far IR spectra of the calix[4]arene, p-tert-butylcalix[4]arene, thialcalix[4]arene and p-tert-butylthiacalix[4]arene were examined at different temperatures and interpreted. The band frequencies and intensities in the IR spectra of the calix[4]arene and thialcalix[4]arene were calculated. The absorption curves of the four possible calix[4]arene conformations: cone, partial cone, 1,2- and 1,3-alternate were computed. The bands characteristic for each conformation are defined and assigned. The obtained spectra-structure correlation can be used for the characteristic of calixarenes conformation. 相似文献
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Bachrach SM 《The journal of physical chemistry. A》2011,115(11):2396-2401
The three smallest symmetrical paracyclophanes, having tethers with two, three, or four methylene groups, have been examined with four density functional methods (B3LYP, M06-2x, B97-D, ωB97X-D). The geometries predicted by functionals accounting for medium-range correlation or long-range exchange and/or dispersion are in close agreement with experiment. In addition, these methods provide similar estimates of the strain energy of the paracylcophanes, which decrease with increasing tether length. [4.4]Paracyclophane is nearly strain-free, reflecting the small out-of-plane distortion of its phenyl rings. Lastly, the barrier for interconversion of the conformers of [3.3]paracylcophane is computed in close agreement with experiment, and an estimate for phenyl rotation in [4.4]paracyclophane of about 19 kcal mol(-1) is predicted by the DFT methods employed. 相似文献
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S. Carboni A. Da Settimo D. Bertini P. L. Ferrarini O. Livi I. Tonetti 《Journal of heterocyclic chemistry》1975,12(4):743-747
The boron trifluoride-catalyzed rearrangement of the epoxide derived from 3-benzylidene- 7-methyl-2,3-dihydro-1,8-naphthyridin-4-(1H)one (II) is described. The structure of the obtained 8-methyl-4-phenyl-1,2,3,4-tetrahydro-5H-pyrido[2,3,-b]-azepin-3, azepin-3,5-dione (X) has been elucidated with aid of chemical and spectral evidence. 相似文献
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No K Lee JH Yang SH Yu SH Cho MH Kim MJ Kim JS 《The Journal of organic chemistry》2002,67(9):3165-3168
A series of tetrahomodioxacalix[4]arene tetraamides and tetrathioamides with four p-phenyl groups on their upper rim were synthesized. From the (1)H and (13)C NMR and crystal structure, N-butylamido homooxacalix[4]arene (4) was found to be in the 1,3-alternate conformation and has intramolecular hydrogen bonding between N-H and facing oxygen atoms of the carbonyl O=C group. This hydrogen bonding decreased the metal ion complex ability. Transformation of the 1,3-alternate N-butylamido (4) into N-butylthioamido homooxacalix[4]arene (5) using Lawesson's reagent gave a conformational change to the C-1,2-alternate. 相似文献