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1.
Valentine P. Ananikov 《Central European Journal of Chemistry》2004,2(1):196-213
A convenient methodology was developed for a very accurate calculation of 13C NMR chemical shifts of the title compounds. GIAO calculations with density functional methods (B3LYP, B3PW91, PBE1PBE) and
6-311+G(2d,p) basis set predict experimental chemical shifts of 3-ethynylcyclopropene (1), 1-ethynylcyclopropane (2) and 1,1-diethynylcyclopropane (3) with high accuracy of 1–2 ppm. The present article describes in detail the effect of geometry choice, density functional
method, basis set and effect of solvent on the accuracy of GIAO calculations of 13C NMR chemical shifts. In addition, the particular dependencies of 13C chemical shifts on the geometry of cyclopropane ring were investigated. 相似文献
2.
Dionisia Sanz Rosa M. Claramunt M. Ángeles GarcíaIbon Alkorta José Elguero 《Tetrahedron》2011,67(25):4633-4639
Eighteen aliphatic linear amines, from methylamine to stearylamine, have been experimentally studied by NMR and theoretically calculated at the GIAO/B3LYP/6-311++G(d,p) level. A partial exploration of their conformation has been carried out, mainly to determine the effect on the chemical shifts. In solution and for neutral amines, 15N chemical shifts indicate a mixture of two conformations. In the solid state (CPMAS NMR) only the subset of solid amines has been studied (from C14 to C18). The 15N signals of the corresponding ammonium salts in the solid state depend on the counteranions, Cl− and CF3CO2−, a result that is theoretically proven. 相似文献
3.
Ricardo O. Silva Ricardo A. W. Neves Filho Rodrigo Azevedo Rajendra M. Srivastava Hugo Gallardo 《Structural chemistry》2010,21(3):485-494
In this article, we describe the complete 1H and 13C NMR signal assignments of four 1,2,4-oxadiazoles possessing light-emitting liquid crystal properties. These results were
obtained by using one- and two-dimensional NMR techniques as well as GIAO (PCM) calculations at B3LYP/6-311++G(d,p) level
for compounds 1 and 2a–d. The computed values are in good agreement with the ones obtained experimentally. In addition, some previously unexplained
thermotropic features of compounds 2a–d could be clarified with the help of the geometry optimization calculations carried out by us. 相似文献
4.
2,5-bis-(4-biphenyl)-yl-1,3,4-oxadiazole (1a), 2,5-bis-(4-(6,8-difluoro)-biphenyl)-yl-1,3,4-oxadiazole (1b) and 2,5-bis-(4-(spiro-fluorenyl)-phenyl)-yl-1,3,4-oxadiazole (1c) were designed, synthesized and characterized. 1a–c were easily obtained from Suzuki reactions between 2,5-bis-(4-bromo-phynyl)-[1,3,4]oxadiazole (2) and aromatic boronic acids (3). They were characterized by 1H-NMR, DSC, TGA, UV-Vis, photoluminescence (PL) spectrometry and CV. The melting temperatures (T
m
) of 1a–c are 237, 208 and 370 °C, respectively, much higher than that of 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD, T
m
= 136 °C). The oxidation potentials of 1a–c are 1.86, 1.94 and 1.18 V, and their reduction potentials are −2.31, −2.22 and −2.27 V, respectively, indicating that the
introduction of electronegative oxadiazole unit lowers the electron density in molecules and enhances their stabilities. The
LUMO/HOMO energy levels of 1a–c are as low as −2.39/−6.56, −2.48/−6.69 and −2.43/−5.88 eV, respectively. The good thermal stabilities and low orbital levels
of 1a–c make them promising electron-transporting or hole-blocking materials for organic optoelectronic devices. 相似文献
5.
Nessrine Salah Youssef Arfaoui Mohamed Bahri Mohamed Lotfi Efrit Azaiez Ben Akacha 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):609-622
Abstract The addition of hydrazine and its derivatives to cycloalkoxyphosphinallenes leads to β-(5,5-dialkyl-2-oxo-1,3,2-dioxaphosphoranyl)-hydrazones in good yields. The structure of the obtained compounds were elucidated by the NMR (1H, 13C, 31P) spectroscopy and density functional theory (DFT) calculations at B3LYP/6-311++G (2d, 2p) level of theory. 相似文献
6.
Solid-state nuclear magnetic resonance (NMR) parameters of 17O, 14N/15N, and 2H/1H nuclei were evaluated in two available neutron crystalline structures of N-methylacetamide (NMA) at 250 and 276 K, NMA-I and NMA-II, respectively. Density functional theory calculations were performed
by B3LYP method and 6-311++G** and IGLO-II type basis sets to calculate the electric field gradient (EFG) and chemical shielding
(CS) tensors at the sites of mentioned nuclei. In order to investigate hydrogen bonds (HBs) effects on NMR tensors, calculations
were performed on four-model systems of NMA: an optimized isolated gas-phase, crystalline monomers, crystalline dimers, and
crystalline trimers. Comparing the calculated results reveal the influence of N–H···O=C and C–H···O=C HB types on the NMR
tensors which are observable by the evaluated parameters including quadrupole coupling constant, C
Q, and isotropic CS, σ
iso. Furthermore, the results demonstrate more influence of HB on the EFG and CS tensors of NMA at 276 K rather than that of
250 K. 相似文献
7.
A computational investigation was carried out to characterize the 17O and 1H chemical shielding (CS) tensors in crystalline aspirin. It was found that O–H⋯O and C–H⋯O hydrogen bonds around the aspirin
molecule in the crystal lattice have a different influence on the calculated 17O and 1H CS eigenvalues and their orientations in the molecular frame of axes. The calculations were performed with the BLYP, B3LYP,
and M06 functionals employing 6-311++G(d,p) standard basis set. Calculated CS tensors were used to evaluate the 17O and 1H chemical shift isotropy (δiso) and anisotropy (Δσ) in crystalline aspirin, which are in reasonable agreement with available experimental data. The difference
between the calculated NMR parameters of the monomer and molecular clusters shows how much hydrogen-bonding interactions affect
the CS tensors of each nucleus. 相似文献
8.
A rather neglected family of heterocyclic compounds, the 3-pyrazolines or 2,3-dihydro-1H-pyrazoles, has been studied theoretically at the B3LYP/6–311++G(d,p) level to obtain geometries and energies and at the GIAO/B3LYP/6–311++G(d,p) level for NMR chemical shifts. The calculated barriers of inversion of the N-substituents reproduce adequately the scarce experimental data. The calculated 1H and 13C chemical shifts are consistent with those reported in the literature. A combination of both results, geometries, and 13C chemical shifts, shed light on the conformation of N-phenyl groups. 相似文献
9.
Esmail Vessally Ladan Edjlali Maryam Saber Soma Aryana 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2012,86(5):791-797
Geometrical structures, Hammett constants, 1H and 13C chemical shift values, molecular electrostatic potential maps, and several thermodynamic parameters of α-acyloxy carboxamide
derivatives (4a–o) were calculated using HF and DFT/B3LYP methods with 6-31G(d) basis set. The optimized structures were compared with analogous compound. The 1H and 13C NMR shielding tensors were computed with the Gauge-Independent Atomic Orbital (GIAO) method. Comparison of the experimental
1H and 13C NMR chemical shifts of 4a–o molecules with the theoretical data indicates good agreement. 相似文献
10.
Comparative quantum chemical calculations of structural parameters, chemical shifts of 11B NMR spectra, and atomic charges in 10-vertex boron hydride anions [1-CB9H10]− and [1-B10H9N2]− were performed using the restricted Hartree-Fock method with the 6-31++G(D,P) basis set.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1853–1855, September, 2007. 相似文献
11.
Nazariy T. Pokhodylo Roman D. Savka Olga Ya. Shyyka Mykola D. Obushak 《Journal of heterocyclic chemistry》2020,57(7):2969-2976
The one-pot CuAAC synthesis of (1H-1,2,3-triazol-1-yl)methyl-1,3,4-oxadiazole and (1H-1,2,3-triazol-1-yl)methyl-1,2,4-oxadiazole derivatives via three-component reaction of consequent nucleophilic substitution of chlorine, with azide, and its further “click” reaction, with alkynes, in the presence of CuI was studied. The utility of newly synthesized 2-(azidomethyl)-1,3,4/1,2,4-oxadiazoles and chloromethyl-1,3,4/1,2,4-oxadiazole derivatives was explored, and their limitations were determined. Novel 5-([4-aryl-1H-1,2,3-triazol-1-yl]methyl)-3-(aryl)-1,2,4-oxadiazoles, 2-([4-aryl-1H-1,2,3-triazol-1-yl]methyl)-5-(aryl)-1,3,4-oxadiazoles were obtained in good yields. 相似文献
12.
S. V. Fedorov Yu. Yu. Rusakov L. B. Krivdin 《Russian Journal of Organic Chemistry》2014,50(2):160-164
Calculation was carried out of chemical shifts in 13C NMR spectra for a series of fluoromethanes CH n F4?n (n = 0–4) by the methods of the electron density functional theory GIAO-DFT taking in consideration the solvent effect in the framework of the polarizable continuum model Tomasi IEF-PCM. The best results were obtained at the use of Keal-Tozer KT3 functional combined with Pople standard basis sets 6-311G(d,p) and 6-311++G(d,p), and also with Jensen special set pcS-2 containing tight p-functions. The optimum reference in the calculation of chemical shifts in 13C NMR spectra for the fluoromethanes series is TMS. 相似文献
13.
O. A. Ignatenko M. A. Kuznetsov S. I. Selivanov 《Russian Journal of Organic Chemistry》2007,43(7):1042-1047
Oxidation of N-aminophthalimide with lead tetraacetate in the presence of 2-[(E)-2-arylethenyl]-5-phenyl-1,3,4-oxadiazoles gives the corresponding 2-(3-aryl-1-phthalimidoaziridin-2-yl)-5-phenyl-1,3,4-oxadiazoles. From 2-phenyl-5-[(1E,3E)-4-phenylbuta-1,3-dien-1-yl]-1,3,4-oxadiazole only the addition product at both C=C bonds was obtained, while in the reaction with 2,5-bis[(E)-2-phenylethenyl]-1,3,4-oxadiazole both mono- and bis-adducts were isolated. 相似文献
14.
Ali Coruh Faruk Yilmaz Busra Sengez Mustafa Kurt Mehmet Cinar Mehmet Karabacak 《Structural chemistry》2011,22(1):45-56
This work presents the synthesis and characterization of a novel compound, 4-(thiophene-3-ylmethoxy)phthalonitrile (TMP).
The spectroscopic properties of the compound were examined by FT-IR, FT-Raman, NMR, and UV techniques. FT-IR and FT-Raman
spectra in solid state were observed in the region 4000–400 cm−1 and 3500–50 cm−1, respectively. The 1H and 13C NMR spectra were recorded in CDCl3 solution. The UV absorption spectrum of the compound that dissolved in THF was recorded in the range of 200–800 nm. The structural
and spectroscopic data of the molecule in the ground state were calculated using density functional theory (DFT) employing
B3LYP exchange correlation and the 6-311++G(d,p) basis set. The vibrational wavenumbers were calculated and scaled values
were compared with experimental FT-IR and FT-Raman spectra. The complete assignments were performed on the basis of the experimental
results and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method.
Isotropic chemical shifts (13C NMR and 1H NMR) were calculated using the gauge-invariant atomic orbital (GIAO) method. A study on the electronic properties, such
as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The HOMO and LUMO analyses have been used
to elucidate information regarding charge transfer within the molecule. Comparison of the calculated frequencies, NMR chemical
shifts, absorption wavelengths with the experimental values revealed that DFT method produces good results. 相似文献
15.
2,5-Bihydrazino-1,3,4-thiadiazole (2) was synthesized by condensation of 2,5-bimercapto-1,3,4-thiadiazole (1) with hydrazine hydrate, and compound 2 reacted with acyl chloride to give 2,5-biacylhydrazino-1,3,4-thiadiazole derivatives (3a–3e). Ring closure of compounds 3a–3e was achieved with POCl3 as the cyclization agent giving 3,6-bisubstituted phenyl-bi-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole derivatives (4a–4e), respectively. The novel compounds were identified by elemental analysis, and by infrared (IR), 1H-nuclear magnetic resonance
(NMR), and mass (MS) spectrometry. The mechanism of the cyclization is also discussed.
__________
Translated from Organic Chemistry, 2006, 26(12): 1720–1722 [译自: 有机化学] 相似文献
16.
The intramolecular dynamic behavior of the tetrahedrane-type cluster [Fe2(CO)6(μ-SNH)] 1 was studied by 13C NMR spectroscopy. The 57Fe chemical shift of 1 and the coupling constants 1
J(57Fe,13C) were measured. These NMR parameters, and also 1
J(57Fe,15N), were found to be in good agreement with data calculated by using density functional theory (DFT) methods (B3LYP), based on the geometry calculated at the 6-311+G(d,p) level of theory. The isolobal replacement of the Fe(CO)3 with BH fragments leads to the tetrahedranes [Fe(CO)3(BH)(μ-SNH)] 2 and [(HB)2(μ-SNH)] 3. Both were identified by calculations as minima on the respective potential energy surface (PES). However, the tetrahedrane-type structure of 3 is much higher in energy when compared with the planar cyclic isomers 3a and 3b. 相似文献
17.
Éva Bokor Attila Fekete Gergely Varga Béla Szőcs Katalin Czifrák István Komáromi László Somsák 《Tetrahedron》2013
Synthesis of O-perbenzoylated 3-(β-d-glucopyranosyl)-5-substituted-1,2,4-triazoles, precursors of potent inhibitors of glycogen phosphorylase, was studied by ring closures of N1-acyl-carboxamidrazone type intermediates. Reactions of C-(β-d-glucopyranosyl)formimidate or C-(β-d-glucopyranosyl)formamidine with acid hydrazides as well as acylation of C-(β-d-glucopyranosyl)formamidrazone by acid chlorides unexpectedly gave the corresponding 1,3,4-oxadiazoles instead of 1,2,4-triazoles. The desired triazoles were obtained in reactions of C-(β-d-glucopyranosyl)formamidine or C-(β-d-glucopyranosyl)formyl chloride with arenecarboxamidrazones, and also in acylations of N1-tosyl-C-(β-d-glucopyranosyl)formamidrazone with acid chlorides. Theoretical calculations (B3LYP and M06-2X DFT with the standard 6-31G(d,p) basis set) on simple model compounds with methyl and phenyl substituents to understand the bifurcation of the ring closure of N1-acyl-carboxamidrazones indicated that in general the reaction led to 1,2,4-triazoles. However, the probability of the 1,3,4-oxadiazole forming pathway was shown to be significantly higher with N1-benzoyl-acetamidrazones, which were closest analogues of the intermediates resulting in C-glucosyl-1,3,4-oxadiazoles. It was thereby demonstrated that the substitution pattern of the N1-acyl-carboxamidrazones played a fundamental role in determining the direction of the ring closing reaction. 相似文献
18.
Alison G. Pacheco Viviane C. Abreu Heitor A. De Abreu Dorila Piló-Veloso Antônio F. de C. Alcântara 《Structural chemistry》2012,23(3):703-710
Aristolactam AII (1) and aristolochic acid I (2) were employed as examples in choosing the most suitable theoretical methodology for computing carbon chemical shifts (Calc
δ
C) and for the structural elucidations of aristolactams and aristolochic acids. Geometries of 1 and 2 optimized using HF, BLYP, B3LYP, and PBE methods and 6-311++G** basis set were subjected to δC calculations and the calculated chemical shifts obtained were correlated with their 13C NMR data. Different possibilities were considered (in the gaseous phase, model PCM (DMSO), and for dimeric systems 1-1 and 2-2), and an explicit solvent (DMSO) model employing BLYP/6-31G* calculations was determined to be the most efficient (R
2 = 0.99631 and 0.97713, for 1 and 2, respectively). 相似文献
19.
K. F. Koehler H. Zaddach A. D. Kuntsevich V. N. Voznesenskii I. I. Chervin R. G. Kostyanovsky 《Russian Chemical Bulletin》1993,42(10):1757-1759
The1H and13C NMR spectral parameters of α-, β-, and y-lewisites1–5 were obtained and a new isomer,cis,trans,trans-γ-lewisite5, was isolated and identified on the basis of chemical shifts, relative intensities of the signals, and the intra-chain (3
J
hh
,3
J
ch
) and interchain (3
J
casch
) coupling constants.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1833–1835, October, 1993. 相似文献
20.
The (19)F NMR shieldings for 53 kinds of perfluoro compounds were calculated by the B3LYP-GIAO method using the 6-31G(d), 6-31+G(d), 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p), 6-311++G(d,p), 6-311G(2d,2p), 6-311++G(2d,2p), 6-311++G(2df,2p), 6-311++G(3d,2p), and 6-311++G(3df,2p) basis sets. The diffuse functions markedly reduce the difference between the calculated and experimental chemical shifts. The calculations using the 6-31++G(d,p) basis set give the chemical shifts within 10 ppm deviations from experimental values except for the fluorine nuclei attached to an oxygen atom, a four- and a six-coordinated sulfur atom, and FC(CF(3))(2) attached to a sulfur atom. 相似文献