Alkyl group effect on the conformational isomerism of trans-2-bromoalkoxycyclohexanes analyzed by nmr spectroscopy and theoretical calculations

Suitable (3)J(H,H) coupling constants and theoretical calculations were used to define the conformational preferences of trans-2-bromoalkoxycyclohexanes (alkoxy = OMe, OEt, O(i)Pr, and O(t)Bu) for the isolated molecule and as a function of the medium. The diaxial conformer was preponderant, or at least similarly populated to the diequatorial form, for the tert-butoxy derivative only, while the diequatorial conformer was prevalent for the remaining alkoxy derivatives (except for the OMe derivative in CCl(4) solution). The conformational behavior of these compounds was analyzed on the basis of classical steric effects and attractive electron delocalizations, by means of natural bond orbital analysis.     

The temperature dependence of quantum mechanical tunneling effects in the nmr spectrum of a methyl group

NMR line shapes have been obtained for CH₃CD₂I in CD₃CD₂I from 4.2 to 127°K. At 4.2°K tunneling is evident, at 87°K neither tunneling nor classical rotation can be detected, and at 127°K there is rapid, thermally activated rotation. The apparent tunneling frequency is found to decrease with increasing temperature.     

Structural assignment of n3-acylated uridine derivatives by means of 13c nmr spectroscopy

Diisopropylethylamine was effective as a base for acylation of 2′,3′,5′-tri-O-acetyluridine with various acid chlorides. The ¹³C NMR spectra of the products and related compounds showed clearly that the acyl groups intoduced to the uracil moiety are attached to the N³-nitrogen.     

Investigation of electronic structure of allenyl ethers by means of photoelectron and UV spectroscopy

A study of the photoelectron spectra of alkyl allenyl ethers has demonstrated their similarity to spectra of alkyl vinyl ethers, with the exception of a band in the 10.0–10.3 eV interval due to ionization of the -orbital of the allenyl fragment C=C. According to data obtained by photoelectron spectroscopy and MNDO quantum-chemical calculations, alkyl allenyl ethers with straightchain substituents exist primarily in the s-cis conformation. The stable conformation of allenyl tert-butyl ether is the s-trans form. The long-wave absorption bands in the UV spectra of alkyl allenyl ethers at 255–275 and 208–213 nm are assigned to electronic transitions of the ^* and ^{* *} types; these are quite insensitive to s-cis/s-trans isomerism.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 81–88, January, 1990.The authors are extremely grateful to V. K. Turchaninov for assistance in interpreting the spectra.     

Pseudooctahedral complexes of vanadium(III): electronic structure investigation by magnetic and electronic spectroscopy

A variety of physical methods has been used to probe the non-Kramers, S = 1, V(III) ion in two types of pseudooctahedral complexes: V(acac)(3), where acac = anion of 2,4-pentanedione, and VX(3)(thf)(3), where thf = tetrahydrofuran and X = Cl and Br. These methods include tunable frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy (using frequencies of approximately 95-700 GHz and fields up to 25 T) in conjunction with electronic absorption, magnetic circular dichroism (MCD), and variable-temperature variable-field MCD (VTVH-MCD) spectroscopies. Variable-temperature magnetic susceptibility and field-dependent magnetization measurements were also performed. All measurements were conducted on complexes in the solid state (powder or mull samples). The field versus sub-THz wave quantum energy dependence of observed HFEPR resonances yielded the following spin Hamiltonian parameters for V(acac)(3): D = +7.470(1) cm(-1); E = +1.916(1) cm(-1); g(x) = 1.833(4); g(y) = 1.72(2); g(z) = 2.03(2). For VCl(3)(thf)(3), HFEPR detected a single zero-field transition at 15.8 cm(-1) (474 GHz), which was insufficient to determine the complete set of spin Hamiltonian parameters. For VBr(3)(thf)(3), however, a particularly rich data set was obtained using tunable-frequency HFEPR, and analysis of this data set gave the folowing: D = -16.162(6) cm(-1); E = -3.694(4) cm(-1); g(x) = 1.86(1); g(y) = 1.90(1); g(z) = 1.710(4). Analysis of the VTVH-MCD data gave spin Hamiltonian parameters in good agreement with those determined by HFEPR for both V(acac)(3) and VBr(3)(thf)(3) and in rough agreement with the estimate for VCl(3)(thf)(3) (D approximately 10 cm(-1), |E/D| approximately 0.18), together with the finding that the value of D is negative for both thf complexes. The electronic structures of these V(III) complexes are discussed in terms of their molecular structures and the electronic transitions observed by electronic absorption and MCD spectroscopies.     

Conformational analysis by UV spectroscopy: the decisive contribution of environment-induced electronic Stark effects

UV chromophores are frequently used as probes of the molecular structure. In particular, they are sensitive to the electric field generated by the molecular environment, resulting in the observation of Stark effects on UV spectra. While these environment-induced electronic Stark effects (EI-ESE) are already used for conformational analysis in the condensed phase, this work explores the potential of such an approach when performed at much higher conformational resolution in the gas phase. By investigating model alkali benzylacetate and 4-phenylbutyrate ion pairs, where the electric field applied to the phenyl ring is chemically tuned by changing the nature of the alkali cation, this work demonstrates that precise conformational assignments can be proposed based on the correlation between the conformation-dependent calculated electric fields and the frequency of the electronic transitions observed in the experimental UV spectra. Remarkably, the sole analysis of Stark effects and fragmentation patterns in mass-selected UV spectra provided an accurate and complete conformational analysis, where spectral differences as small as a few cm⁻¹ between electronic transitions were rationalized. This case study illustrates that the identification of EI-ESE together with their interpretation at the modest cost of a ground state electric field calculation qualify UV spectroscopy as a powerful tool for conformational analysis.

The correlation between experimental electronic transitions and calculated electric fields leads to precise conformational assignments and opens up the possibility of interpreting electronic spectra in a quantitative manner at the wavenumber scale.     

On the feasibility of investigation of some defect and porous systems by means of positron annihilation spectroscopy

It was shown that positron annihilation spectroscopy is an effective technique for the determination of the size of nanodefects (vacancies, vacancy clusters); the free volumes of pores, cavities, and voids; and their concentration and chemical composition at the site of annihilation in some defect and porous systems. Experimental studies of nanodefects in porous silicon, proton-irradiated monolithic silicon and quartz single crystals, and quartz powders are briefly surveyed.     

Configurational assignment of epimeric 22,23-epoxides of steroids by carbon-13 nmr spectroscopy

The ¹³C-NMR spectra of epimeric 22,23-epoxides of steroids were recorded and the signals assigned. Based on these assignments information regarding the stereochemistry of the oxirane ring and conformations of the side chains of the steroids under study was obtained.     

Chirality,diastereotopism and structure of α-metallocenylcarbenium ions investigated by nmr spectroscopy

1-Metallocenyl-2-methylpropyl cations are found to be chiral using nuclei diastereotopism. The positive charge distribution over the cations and the effect of a central metal atom (iron, ruthenium, osmium) are discussed.     

The VUV electronic spectroscopy of acetone studied by synchrotron radiation

The electronic state spectroscopy of acetone (CH3)2CO has been investigated using high-resolution VUV photoabsorption spectroscopy in the energy range 3.7-10.8 eV. New vibronic structure has been observed, notably in the low energy absorption band assigned to the 1(1)A(1) --> 1(1)A2 (ny --> pi*) transition. The local absorption maximum at 7.85 eV has been tentatively attributed to the 4(1)A1 (pi --> pi*) transition. Six Rydberg series converging to the lowest ionisation energy (9.708 eV) have been assigned as well as a newly-resolved ns Rydberg series converging to the first ionic excited state (12.590 eV). Rydberg orbitals of each series have been classified according to the magnitude of the quantum defect (delta) and are extended to higher quantum numbers than in the previous analyses.     

Orientation effects in the pechmann reaction : Synthesis of 5,6-dimethylcoumarin and an examination of ortho-proximity effects in 13c nmr spectroscopy

In the Pechmann reaction with malic acid, m-cresol and 3,4-xylenol give mixtures of alkylcoumarins containing about 10% of the 5- and 5,6-isomers respectively. 7-Alkylcoumarins only are obtained from the reaction with ethylacetoacetate. A study of ortho-proximity effects on the ¹³C NMR of dimethylcoumarins is reported, and the results have been correlated with similar effects in other aromatic and heteroaromatic systems.     

The group identification of organic compounds by means of thin-layer chromatography

The group identification method was presented based on the constant differences ΔR_f and ΔR_M, calculated from the chromatographic parameters obtained in two different mobile phases. The applicability of this method was proved with higher aliphatic alcohols, acids, and esters.     

Alignment effects on high resolution nmr spectra,induced by the magnetic field

Molecules with an anisotropic susceptibility tend to be aligned by a magnetic field. Alignments of this type in liquids are extremely small, but may nevertheless induce detectable line splittings in high resolution NMR spectra. The splittings are proportional to the square of the magnetic field. High-field experiments on organic molecules are described in which these effects have been recorded.