Substituent effects on 33S NMR chemical shifts in sulphones

The ³³S NMR spectra of some selected sulphones demonstrate additive substituent-induced chemical shift (SCS) effects. In dimethyl sulphone (1), replacement of a methyl group by a vinyl or a phenyl group causes an SCS effect of ?7 to ?8.5 ppm or ?4 to ?5 ppm, respectively. The ³³S chemical shift in 1 is also sensitive to substitution of methyl protons. The ß-substituent effect for methyl and phenyl groups is in the range +7 to +8 ppm and +5.5 to +6 ppm, respectively.     

Furan derivatives—LXXVII : Synthesis and study of sulphides and sulphones of 5-nitrofuran series

Two series of 5-nitro-2-furfurylarylsulphides 4a–4f and 5-nitro-2-furfurylarylsulphones 5a–5g were prepared by the reaction of 5-nitrofurfurylbromide¹ with 4-substituted thiophenols 2a–2f and with 4-substituted benzenesulphinic acids 3a–3g, respectively. In these compounds the transmission of polar effects of the substituents by the -S- and SO₂ groups, respectively, was found to take place. pK Values of compounds studied has been determined spectroscopically.     

Dipole moments of aryl cis - and trans -styryl sulphides and sulphones

The dipole moments of thirteen aryl styryl sulphides and eleven aryl styryl sulphones have been determined. Among them are eightcis-trans isomeric pairs, four sulphides and four sulphones. The styryl group is found to conjugate with the sulphide function as an electron-withdrawing group. The angles which the styrylthio and styrylsulphonyl groups make with their axes of rotation are calculated. The observed dipole moments of the sulphides and sulphones are compared with the moments calculated by the vector addition of group moments. The dipole moments ofcis aryl styryl sulphides and sulphones are found to be generally lower than those of theirtrans isomers. An explanation is offered attributing the cause to sterically enhanced styryl-sulphur conjugation in thecis isomers.     

Sulphur-33 nuclear magnetic resonance studies of sulphur compounds with sharp resonance lines. 33S NMR spectra of some sulphones and sulphonic acids

³³S NMR spectra have been obtained in the FT mode for some sulphones and sulphonic acids. The investigated compounds show narrow resonance lines. In the case of sulphones, the range of ³³S chemical shifts is sufficiently wide, i.e. the effects due to changes in substituents are significant enough to allow further use of the ³³S NMR of sulphones for quantitative analysis in petroleum chemistry.     

Stark widths and shifts of SnI,HgII, HgIII and PbII spectral lines

Stark widths and shifts of neutral and ionized heavy atom spectral lines have been measured and calculated. The Stark parameters of three SnI (284.0, 286.3 and 303.4 nm), five HgII (226.2, 398.4, 222.5, 615.0 and 326.4 nm), two PbII (220.4 and 438.6 nm) and one HgIII (235.4 nm) spectral lines were measured for the first time except the Stark widths of one HgII (398.4 nm) and one PbII (438.6 nm) line. Stark width values for a number of corresponding transitions were calculated on the bases of semiclassical and semiempirical formulae.     

Determination of the sulphoxides and sulphones of three simple sulphides in rat urine: effects of phenobarbitone, beta-naphthoflavone and methimazole

In this investigation, the measurement and identification of the S-oxidation products of three simple sulphides-ethyl methyl sulphide (EMS), 4-chlorophenyl methyl sulphide (CPMS) and diphenyl sulphide (DPS)-in rat urine were carried out and a study of the effects of phenobarbitone (PB), beta-naphtho flavone (betaNF) and methimazole on the urinary levels of their metabolites was conducted. Male Wistar rats (n = 4) were pretreated with PB (80 mg/kg/day in saline, i.p.), betaNF (100 mg/kg/day in corn oil, i.p.), methimazole (50 mg/kg/day in saline, i.p.) or the vehicles alone (1 mL/kg) for three consecutive days. After pretreatment, EMS, CPMS or DPS (50 mg/kg in corn oil, 500 microL) was administered orally to the appropriate groups of rats. The animals were placed in metabolic cages and urine samples collected at 24 h intervals over 96 h. Chromatographic and spectroscopic techniques were used for the measurement and identification of the sulphoxides and sulphones of EMS, CPMS and DPS in rat urine. Although only a trace of ethyl methyl sulphoxide (EMSO) was present in rat urine after administration of EMS, ethyl methyl sulphone (EMSO(2)) accounted for about 16% of the administered dose in the urine of male rats given EMS. In addition, pretreatment of rats with methimazole significantly decreased the S-oxidation of EMS. 4-Chlorophenyl methyl sulphone (CPMSO(2)) was the main metabolite recovered in the urine of male rats treated with CPMS, accounting for about 10% of the dose. Pretreatment of rats with PB before administration of CPMS significantly increased the levels of CPMSO(2) excreted in the urine. Additionally, pretreatment of rats with methimazole significantly decreased the S-oxidation of CPMS in vivo. About 2.5% of diphenyl sulphoxide (DPSO) and 4% of diphenyl sulphone (DPSO(2)) were recovered in the urine of male rats given DPS. Pretreatment of rats with PB, betaNF or methimazole before administration of DPS decreased the levels of DPSO and DPSO(2) excreted in the urine, although this was not statistically significant. These results indicate that microsomal monooxygenases mediate the S-oxidation of EMS, CPMS and DPS to their corresponding sulphones via a transient sulphoxide in rats.     

A study of gaseous 3-membered ring oxonium and sulphonium ions

The 1-methyl-1-thionia cyclopropane 3 and 1-phenyl-1-thionia cyclopropane 4 ions are stable, with lifetimes greater than 10^?5 sec, and can be identified from their collisional activation spectra. Their metastable counterparts (lifetime window 10^?6–10^?5 sec) have undergone ring opening to the isomeric structures CH₃S⁺CHCH₃9 and C₆H₅S⁺CHCH₃11 prior to decomposition. The 1-methyl-1-oxonia cyclopropane 1 and 1-phenyl-1-oxonia cyclopropane 2 ions could not be generated: instead acyclic structures CH₃O⁺CHCH₃5 and C₆H₅O⁺CHCH₃7 were found for both metastable and long living species. Loss of a phenoxy radical from C₆H₅OCH₂CH₂OCH₃ is shown to be preceded by a reciprocal hydrogen transfer and is not due to a SN_i-type reaction.     

33S NMR shieldings and chemical bonding in compounds of sulfur

Sulfur nuclear magnetic resonance (NMR) chemical shieldings have been determined at the correlation-including density functional theory scaled B3LYP/6-311+G(nd,p)//B3LYP/6-311+G(d,p) and modified MP2/6-311+G(nd,p) estimated infinite order Møller-Plesset levels with n = 2 for sulfur. The calculations span the range of sulfur shieldings and show agreement with experiment of about 3% of the shielding range. The atoms-in-molecules delocalization index and a covalent bond order from specific localized orbitals in the DFT approach are used to characterize sulfur's bonding and to relate it, where possible, to the calculated shieldings. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:216–224, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20000     

Statistical methods in determining dissociation constants and chemical shifts for N-acylonium ions and ion pairs

A new approach is proposed for determining dissociation constants and chemical shifts for the ions and ion pairs of N-acylonium salts in water and nonaqueous media on the basis of the concentration dependence. Mathematical simulation methods are used.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 4, pp. 497–501, July–August 1987.     

15N chemical shifts and long-range 1H-15N coupling pathways of selected strychnos alkaloids

The Strychnos alkaloids have been the focal point of considerable synthetic and spectroscopic effort. We now report the ¹⁵N chemical shifts and long-range ¹H-¹⁵N coupling pathways of strychnine, brucine, and holstiine at natural abundance. Long-range coupling pathways were established using a gradient-enhanced HMQC sequence optimized for the observation of ¹H-¹⁵N long-range couplings.     

Pseudocontact contribution to the isotropic chemical shifts of protons in octahedral paramagnetic complex ions

Following the formalism of Kurland and McGarvey, it is shown that transferred spin densities onto ligands can give rise to pseudocontact shifts even for protons in octahedral complexes. In the case of ammonia as a ligand the pseudocontact shift of the protons originates from the spin density on the p orbitals of the nitrogen as well as spin density on the s orbitals on the neighboring hydrogen atoms. Using LCAO-MO wavefunctions for the Ru(NH₃)³⁺₆ ion the contact and pseudocontact shifts were estimated to contribute about 75% and 25% of the total shift of the amine protons respectively. Based on experimental paramagnetic NMR shifts, the covalency parameter in the Ru(NH₃)³⁺₆ ion was recalculated to be λ = 0.325.     

High resolution FTS studies of glow discharge spectra line profiles and line widths

High resolution studies using Fourier transform spectrometry of the spectra emitted in the visible and ultraviolet regions by a microwave boosted glow discharge source have shown that when the source is operated in the dc (unboosted) mode, two anomalous forms of line profile occur for some analyte elements. (1) Some Fe I lines appear to have a triangular base of half-width about five times greater than that of the line proper. (2) Some Fe II and Ti II lines exhibit satellites about 8 cm^-1 wide and an intensity of up to 2% of the peak value on either side of the main line. Both effects depend on the carrier gas and its pressure and are much less pronounced or even absent in the boosted mode. They could both affect the accuracy of analytical results, particularly for depth-profiling. Further studies are in progress.     

High resolution FTS studies of glow discharge spectra line profiles and line widths

High resolution studies using Fourier transform spectrometry of the spectra emitted in the visible and ultraviolet regions by a microwave boosted glow discharge source have shown that when the source is operated in the dc (unboosted) mode, two anomalous forms of line profile occur for some analyte elements. (1) Some Fe I lines appear to have a triangular base of half-width about five times greater than that of the line proper. (2) Some Fe II and Ti II lines exhibit satellites about 8 cm(-1) wide and an intensity of up to 2% of the peak value on either side of the main line. Both effects depend on the carrier gas and its pressure and are much less pronounced or even absent in the boosted mode. They could both affect the accuracy of analytical results, particularly for depth-profiling. Further studies are in progress.     

Nitrogen nuclear magnetic resonance spectroscopy. Nitrogen-15 and proton chemical shifts of methylanilines and methylanilinium ions

Nitrogen and carbon electron densities of the toluidines and xylidines have been recalculated by the INDO method; previously published errors have been corrected. Although the nitrogen-15 chemical shifts of these compounds still display the earlier suggested correlation with σ and total electron densities, the calculated inverse correlation with proton electron densities has been shown to be incorrect. Methyl proton chemical shifts of these compounds display no meaningful correlation with the nitrogen shifts. The nitrogen chemical shifts of the toluidinium and xylidinium ions correlate moderately well with the ¹³C chemical shifts of the analogous di- and tri-methylbenzenes.     

Substituent effects on 13C-15N spin couplings and 13C chemical shifts in benzenediazonium ions

Similar trends are observed for ¹J(¹³C-¹⁵N) values for a series of aryldiazonium tetrafluoroborates and comparable anilinium fluorosulfonates. Contributions from resonance structures involving double-bond character in the CN bond are judged to be relatively unimportant in the ground state structure of aryldiazonium ions.     

GIAO/DFT evaluation of 13C NMR chemical shifts of selected acetals based on DFT optimized geometries

DFT/B3LYP calculations of the ground-state conformation of eight cyclic and acyclic acetals are presented and compared with experimental data. Results of single-point GIAO/DFT calculations at five different levels of theory show that isotropic shieldings need to be empirically scaled to achieve agreement with experimental chemical shifts. Statistical evaluation of data indicates that the most accurate prediction of 13C chemical shifts is achieved at the MPW1PW91/6-311G** level of theory. An empirical equation describing the relationship between delta values and shielding constants is postulated. This equation has been applied to the non-chair ground-state conformation of the six-membered acetonide and to the conformationally flexible benzodioxonine derivative. The agreement observed between the experimental and predicted chemical shifts shows that calculations at the MPW1PW91/6-311G** level of theory are adequate for addressing questions of conformation.     

The effect of sulfate-delta18O upon on-line sulfate-delta34S analysis, and implications for measurements of delta33S and Delta33S

On-line delta34S analysis of sulfate using an elemental analyzer has a number of advantages vs. conventional off-line techniques, such as ease of operation, rapidity, and the requirement for small amounts of material. Although the analyses are performed by converting sulfate into SO2 gas, the effect of sulfate-delta18O composition upon the SO2-delta18O composition and the value of delta66 during elemental analysis, and ultimately the calculated sulfate-delta34S composition, has rarely been addressed. Three BaSO4 samples were prepared with known identical delta34S compositions, but with a wide range of delta18O compositions. delta18O values were shown to range over 40 per thousand, but conventional on-line delta34S analyses verified that the sulfate-delta34S compositions were identical. These results indicate that conventional on-line analysis of sulfate-delta34S is unaffected by the value of sulfate-delta18O, and suggest that sulfide-delta34S standards can be used to calibrate sulfate-delta34S analyses (and vice versa). Moreover, these results suggest that it may be possible to use on-line sulfur isotope analysis of SO2 to measure delta33S and Delta33S in addition to delta34S, as a faster and safer alternative to the SF6 technique currently utilized, and hence promote further study of mass-independent sulfur isotope fractionation effects.