17O NMR: 2J(17O1H) coupling constants by line shape analysis

Two bond spin-spin coupling constants ²J(¹⁷O¹H) are determined for the oxygen in ether, aldehyde, acid, ester and amide groups by line shape analysis of the corresponding ¹⁷O NMR spectra.     

1H, 1 3C,and 1 5N Chemical shifts and 1H-1 5N and 1 3C-1 5N heteronuclear spin-spin coupling constants in the NMR spectra of 5-substituted furfural oximes

The ¹H, ¹³C, and ¹⁵N NMR spectra of ¹⁵N-enriched 5-substituted furfural oximes were investigated. It was shown that the chemical shifts of the ring atoms and the oxime group correlate satisfactorily with the F and R substituent constants, whereas their sensitivity to the effect of the substituents is lower than in monosubstituted furan derivatives. The constants of spin-spin coupling between the ring protons and the oxime group were determined. An analysis of the ¹H-¹H spin-spin coupling constants (SSCC) on the basis of their stereospecificity indicates that the E isomers have primarily an s-trans conformation in polar dimethyl sulfoxide, whereas the Z isomers, on the other hand, have an s-cis conformation. The signs of the direct and geminal ¹³C-¹⁵N SSCC were determined for 5-trimethylsilylfurfural oxime.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1172–1177, September, 1985.The authors thank N. O. Saldabol, L. M. Ignatovich, and N. P. Erchak for providing us with the investigated compounds.     

Complete prediction of the 1H NMR spectrum of organic molecules by DFT calculations of chemical shifts and spin-spin coupling constants

1H NMR chemical shifts and coupling constants for several aromatic and aliphatic organic molecules have been calculated with DFT methods. In some test cases (furan, o-dichlorobenzene and n-butyl chloride) the performance of several functionals and basis sets has been analyzed, and the various contributions to spin-spin coupling (Fermi-contact, diamagnetic and paramagnetic spin-orbit) have been evaluated. The latter two components cancel each other, so that the calculation of the contact term only is sufficient for an accurate evaluation of proton-proton couplings. Such calculated values are used to simulate the 1H NMR spectra of organic molecules with complicated spin systems (e.g. naphthalene, o-bromochlorobenzene), obtaining a generally very good agreement with experimental spectra with no prior knowledge of the involved parameters.     

Measurement of long‐range heteronuclear coupling constants using the peak intensity in classical 1D HMBC spectra

In this contribution, we show that the magnitude of heteronuclear long‐range coupling constants can be directly extracted from the classical 1D HMBC spectra, as all multiplet lines of a cross‐peak always and exclusively vanish for the condition Δ = k/ⁿJ_CH. To the best of our knowledge, this feature of the classical HMBC has not yet been noticed and exploited. This condition holds true, irrespective of the magnitude and numbers of additional active and passive homonuclear ⁿJ_HH′ couplings. Alternatively, the ⁿJ_CH value may also be evaluated by fitting the peak's intensity in the individual spectra to its simple sin(πⁿJ_CHΔ)exp(−Δ/T_2eff) dependence. Compared to the previously proposed J‐HMBC sequences that also use the variation of the cross‐peak's intensity for extracting the coupling constants, the classical HMBC pulse sequence is significantly more sensitive.     

IR, 1H NMR and 13C NMR spectra of isomeric 1-aryl-4-methyl-3- and-5-pyrazolecarboxylic esters

The IR, ¹H and ¹³C NMR spectra of six esters of 1-aryl-4-methyl-3- and 5-pyrazolecarboxylic acids are reported. On the basis of their spectra the 3- or 5-position of the substituent in such structural isomeric pairs can be established without recourse to the spectrum of the other member of the pair. The spectral data also give information on the conformation, which depends on the relative position and size of the hetero ring substituents.     

Determination of 31P,31P coupling constants in cyclotriphosphazenes and their influence on 1H and 13C NMR spectra of phosphorus substituents

¹H and ¹³C NMR spectra of symmetrically substituted cyclotriphosphazenes exhibit second‐order effects. The influence of the ³¹P,³¹P coupling constants between ring phosphorus atoms on these effects was studied. Some values of this coupling constant between phosphorus bearing identical substituents were measured using ¹³C satellites of the ³¹P signals or by introduction of a chiral substituent on the third phosphorus atom. Copyright © 2003 John Wiley & Sons, Ltd.     

Use of Eu(DPM)3 to study the long-range spin-spin coupling of1H-1H and1H-14N via the PMR spectra

Conclusions Employing heteronuclear double resonance and paramagnetic additives it was established that the additional broadening of the signals in the PMR spectrum of 1-vinylimidazole is caused by the¹H -¹⁴N spin-spin coupling, while in the spectrum of 1-vinylpyrazole it is caused, in addition, by the long-range¹H-¹H spin -spin coupling via six bonds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 200–201, January, 1977.     

Towards the automatic analysis of 1H NMR spectra: Part 4--additional requirements of flow-NMR

Flow-NMR allows more rapid and convenient acquisition of NMR spectra. Its main application area has therefore been in multiple parallel synthesis or combinatorial chemistry. At the same time, there is a significant need to automate the analysis of the resultant spectra. However, flow-NMR brings spectral imperfections, which compromise attempts to automate this analysis. This study proposes experimental and computational expedients to accommodate the effects of residual solvent peaks, 13C satellites, finite signal-to-noise ratio, impurities, presaturation on integral calculations, the 'silent' region and how multiplet areas can be scaled to numbers of protons in this environment.     

新试剂1-(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯与镉的显色反应及应用研究

研究了新试剂 1 -( 2 ,6 -二氯 -4 -硝基苯 ) -3 -( 4-硝基苯 ) -三氮烯与镉的显色反应。在 Triton X-1 0 0存在下 ,于 p H=9.8～ 1 1 .0的 Na2 B4 O7-Na OH缓冲溶液中 ,镉与试剂有高灵敏的显色反应 ,生成 1∶ 3型黄色配合物 ,最大吸收波长为 44 5nm。用双峰双波长法测定 ,其表观摩尔吸光系数为 2 .85× 1 0 5L·mol- 1·cm- 1。用拟定的方法测定了人发和废水中的镉含量 ,标准加入回收率分别为 1 0 4.5%和 1 0 5.8% ,相对标准偏差分别为 3 .2 %和 4.1 %。     

The complete analysis of the 1H NMR spectra of quinoline and two of its derivatives. sign determinations of inter-ring coupling constants by means of the INDOR technique

The complete ¹H NMR spectral analyses of quinoline and two of its derivatives (4,7-dichloroquinoline and 8-nitroquinoline) have been performed. All the long-range coupling constants were determined both in magnitude and sign. In determining the signs the INDOR technique was very useful and successful, allowing the resolution of transitions as close as a few hundredths of a Hz. The signs of the inter-ring coupling constants alternate with the number of intervening bonds, according to McConnell's rule, except the all-trans⁶J couplings. A linear relationship has been found between the ¹H?¹H and ¹⁹F?¹⁹F inter-ring coupling constants for which the spin polarization is transmitted almost exclusively via the π-electron system.     

Indirect NMR spin-spin coupling constants 3J(P,C) and 2J(P,H) across the P-O...H-C link can be used for structure determination of nucleic acids

Calculated indirect NMR spin-spin coupling constants (3)J(P,C) and (2)J(P,H) were correlated with the local structure of the P-O...H-C linkage between the nucleic acid (NA) backbone phosphate and the H-C group(s) of a nucleic acid base. The calculations were carried out for selected nucleotides from the large ribosomal subunit (Ban et al. Science 2000, 289, 905) with the aim of identifying NMR parameters suitable for detection of certain noncanonical RNA structures. As calculations in the model system, dimethyl-phosphate-guanine, suggest, the calculated indirect spin-spin couplings across the linkage are sensitive to the mutual orientation and distance between the phosphate and nucleic acid base. A short distance between the nucleic acid base and phosphate group and the angles C...P-O and P...C-H smaller than 50 degrees are prerequisites for a measurable spin-spin interaction of either coupling (|J| > 1 Hz). A less favorable arrangement of the P-O...H-C motif, e.g., in nucleotides of the canonical A-RNA, results in an effective dumping of both spin-spin interactions and insignificant values of the NMR coupling constants. The present work indicates that quantum chemical calculations of the indirect spin-spin couplings across the P-O...H-C motif can help detect some rare but important backbone topologies, as seen for example in the reverse kink-turn. Measuring of (3)J(P,C) and (2)J(P,H) couplings can therefore provide critical constraints on the NA base and phosphate geometry and help to determine the structure of NAs.     

NMR analysis of restricted internal rotation in 2-substituted-2,3-dihydro-3-o-tolyl(chlorophenyl)-4(1H)-quinazolinones

Steric interactions between aryl and heterocyclic moieties in 2-substituted-2,3-dihydro-3-o-tolyl(chlorophenyl)-4(1H)-quinazolinones 1a-j produce sufficient restriction to rotation about the aryl C? N bond that the presence of torsional isomers may be detected at room temperature. Diastereomeric population and free energy of activation for rotation have been calculated by ¹H nmr spectra. Probably due to a preferred axial position of R² substituent no dramatic variation both in A /B ratio and in ΔG≠ value has been observed for 1a-f . The comparison between 1a and 1j ΔG^≠ values allows to formulate a hypothesis on the structure of the transition state.     

Study of conjugation effects by NMR spectroscopy. XXIV. Determination of the conformational composition of alkyl phenyl ethers with branched alkyl radicals from the13C-1H and13C-13C spin-spin coupling constants

Conclusions During analysis of the¹³C-¹-H and¹³C-¹³C spin-spin coupling constants of the phenyl group in alkyl phenyl ethers it was established that the steric inhibition of the conjugation due to increase in the branching of the alkyl group partial in nature and is strongest in 2-methyl-2-phenoxypropane, whereas further increase in the effective volume of the alkyl group leads to some decrease in the population of the orthogonal conformer.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2463–2467, November, 1985.     

Towards the automatic analysis of 1H NMR spectra: Part 3. Confirmation of postulated chemical structure

A method is proposed which automatically compares experimental and predicted ¹H chemical shifts, integrals and scalar couplings and allows the structure on which the predictions are based to be confirmed or refuted. The method is comparatively insensitive to the variable presence of labile protons but is sensitive to the reliability of chemical shift prediction. Nonetheless, even with current commercially available ¹H chemical shift prediction, amongst a set of unrelated compounds the structure can be confirmed with 99% confidence. Where the compounds are closely related, the confidence decreases to approximately 60%, or 88% when labile protons are excluded. If closely related pairs are nominated explicitly, a specific criterion can be set for each pair, allowing every pair to be differentiated. Copyright © 2002 John Wiley & Sons, Ltd.     

Conformational analysis and diastereotopic assignments in the series of selenium-containing heterocycles by means of 77Se-1H spin-spin coupling constants: a combined theoretical and experimental study

A combined theoretical and experimental study on the stereochemical behavior of (77)Se-(1)H spin-spin coupling constants has been performed at the second-order polarization propagator approach level together with heteronuclear multiple-bond correlation technique in the series of selenium-containing four-, five- and six-membered heterocycles including the derivatives of thiaselenetane, selenasilole, thiaselenole, thiaselenolane and dihydrothiaselenine. Geminal and vicinal (77)Se-(1)H spin-spin couplings were shown to have the pronounced stereochemical dependences in respect with the topology of the coupling pathway, internal rotation of the side-chain substituents and ring inversion providing a straightforward tool for the conformational analysis and diastereotopic assignments in the chiral organoselenium compounds.     

Heteroorganic derivatives of furan. 65. Effect of substituents on shielding of 1H, 13C,and 29Si and 29Si-13C spin-spin coupling constants in NMR spectra of 2-substituted furans and 5-trimethylsilylfurans

The results of an investigation of 2-substituted furans and 5-trimethylsilylfurans by NMR spectroscopy and the CNDO/2 method showed that the chemical shifts of the different nuclei do not correlate sufficiently clearly with the calculated charges because of an additional change in the electron density under the influence of a -d interaction. The ¹³C-²⁹Si direct spin-spin coupling constants (SSCC) are less sensitive to this interaction, since they depend primarily on the inductive effects of the substituents.See [1] for Communication 64.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 588–596, May, 1990.