A correlation of substituent effects with proton chemical shifts in aromatic tetrazolic acids

The effect of substituents on the proton chemical shifts and spin–spin coupling constants in ortho-, meta- and para-substituted 5-phenyltetrazoles (tetrazolic acids) in DMSO–CH₃CN (1:1, v/v) was studied. With the meta- and para- substituted compounds the additivity rule of chemical shifts was obeyed, thereby enabling increments characterizing the effects of individual substituents in monosubstituted benzenes to be determined. By employing the Smith and Proulx equation, the chemical shifts of the aromatic protons were correlated with the F, R and Q substituent constants. The values of these constants are 1.02, ?0.004 and 5.49, respectively, for the tetrazolyl substituent.     

13C NMR spectra of substituted phenazines: Substituent effects on carbon-13 chemical shifts and the use of 13C?15N coupling constants for the assignment of the aromatic carbons

The ¹³C NMR spectra of 19 substituted phenazines have been measured. Substituent increments of the chemical shifts were calculated for methoxy, carbomethoxy and methyl derivatives. ¹⁵N-Enriched phenazines were synthesized and ⁿJ(¹³C¹⁵N) values were used for the assignment of the signals of the aromatic carbons.     

A new method for the determination of the absolute stereochemistry of aromatic and heteroaromatic alkanols using Mosher's esters

A list of the ¹H NMR chemical shifts of the methoxy group of α-methoxy-α-(trifluoromethyl)phenylacetic acid (Mosher's) esters of α- and β-(hetero)aromatic secondary alkanols has been compiled. Methoxy groups which are orientated syn to the (hetero)aromatic group in Mosher's conformational model have lower chemical shift values than those in the anti-orientation.     

Nuclear magnetic resonance studies of boron compounds : XVI. Carbon-13 studies of organoboranes: Phenylboranes and boron-substituted aromatic heterocycles

¹³C and ¹¹B NMR data of 29 phenylboranes and 9 boron-substituted aromatic heterocycles (thiophene, N-methylpyrrole and furan) are discussed. The observed ¹³C chemical shifts of the para-carbon atoms in phenylboranes and the corresponding carbon atoms in the aromatic heterocycles are consistent with mesomeric interactions of the boryl group with the aromatic system. The trend of δ(¹³C(para)) in phenylboranes corresponds to that observed for isoelectronic phenylcarbocations. Low temperature ¹³C NMR and/or ¹³C {¹¹B, ¹H} heterocuclear triple resonance experiments were employed to obtain the ¹³C chemical shifts of the boron-bonded carbon atoms.     

13C NMR chemical shifts of benzophenone azine as a benchmark for configurational assignment of azines with aromatic substituents

An analysis of the ¹³C NMR spectral data and quantum chemical calculations for benzophenone azine shows that the shielding constant of the C _ipso atom of its molecule is stereo-specific. The characteristic difference in chemical shifts of the C _ipso atoms of the phenyl rings in the cis- and trans-positions with respect to the lone pair of the neighboring nitrogen atom is 2–3 ppm. The stereospecificity observed for chemical shifts was proposed to be used for the configurational assignment of azines containing aromatic substituents.     

Model compounds and 13C NMR increments for the characterization of maleic anhydride-grafted polyolefins

A set of model compounds that mimic the graft sites of maleic anhydride (MA) functionalized polyolefins was synthesized and characterized with NMR spectroscopy. The acquired carbon nuclear magnetic resonance data were used to deduce chemical-shift increments for the prediction of ¹³C chemical shifts of MA functionalized polyolefins. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4368–4385, 1999     

Investigation of substituent effects on the 1H NMR spectra of chalcones

¹H NMR spectra of 26 substituted chalcones (3-aryl-1 phenyl-2-propene-1-ones and 1-aryl-3-phenyl-2-propene-1-ones) have been studied. The chemical shifts of the α and β protons to the carbonyl group were correlated with Hammett s? parameters. To gain information on the effect of the transmission of the resonance and inductive contributions of the substituents on the chemical shifts of H-α and H-β, two parameter correlations with ?? and ?? parameters were also perfomed. The chemical shifts of the aromatic protons of the para-disubstituted benzene ring correlated with the a_i substituent increments.     

Substituent increments for the 1H-NMR. Chemical shifts of the 18- and 19-methyl protons of steroids. Part I: 9beta, 10alpha(retro)-steroids

This paper reports 261 substituent increments for the ¹H? NMR. chemical shifts (solvent: CDCl₃) of the 18- and 19-methyl protons of 9β, 10α(retro)-steroids relative to 5β,9β,10α,-androstane. The increments were calculated by a least-squares procedure from 1334 spectra of 759 different steroids.     

Substituent increments for the 1H-NMR. Chemical shifts of the 18- and 19-methyl protons of steroids. Part II: 9alpha, 10beta(normal)-steroids

In Part II of this series we report 292 substituent increments for the ¹H-NMR. chemical shifts (solvent: CDCl₃) of the 18- and 19-methyl protons of 9α,10β(normal)-steroids relative to 5α,9α,10β,-androstane. The increments were calculated by a least-squares procedure from 988 spectra of 681 different steroids.     

17O NMR Investigation of cyclic aromatic ethers

A linear relationship between the C-O-C angle and the molecular dihedral angle in a series of phenoxathi-ins and azaphenoxathiins is reported. ¹⁷O nmr spectroscopic data (natural abundance in acetonitrile at 75°C) were obtained on eight cyclic aromatic ethers 1-8 , including phenoxathiins, and two model compounds, acyclic aromatic ethers 9 and 10. The chemical shifts of the cyclic aromatic ethers were very sensitive to structural variations and were dependent upon electonic and conformational effects; however, no quantitative relationship between ¹⁷O chemical shift and geometric parameters was found.     

The increment scheme for the prediction of13C NMR chemical shifts in polychlorinated dibenzo-p-dioxins

A topological method for the calculation of¹³C NMR chemical shifts was developed for polychlorinated dibenzo-p-dioxins (PCDD). Based on previous results for polychlorinated benzenes and polyhydroxybenzenes, the collective influence of the substituents on carbon chemical shifts is presented as the sum of two-particle increments. The increments only of two new monosubstituted graphs have to be added to those known for PCDD spectra: 1-Cl-DD and 2-Cl-DD. All structural situations in the¹³C NMR chemical shifts of the whole class of 75 PCDD can be covered with a few model compounds. The coefficients of the increment scheme are independent of the change of CDCl₃ for acetone-d₆, so it may be a new reliable criterion for recognizing PCDD by¹³C NMR, in spite of the close resemblance of NMR spectra of aromatic compounds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 280–284, February, 1995.     

Activation of chlorine and fluorine by a phenylazo group towards nucleophilic aromatic substitution. Regioselective preparation of polysubstituted anilines

A phenylazo group was used for selective activation of ortho fluorine and chlorine atoms towards nucleophilic aromatic substitution with the propanethiolate anion. This enabled a regioselective synthesis of three substituted 4-alkoxyanilines. The regioselectivity of substitution was confirmed by comparison of experimental NMR chemical shifts with empirically predicted values. The observed reactivity of the substrates is discussed in the context of the substituent effect.     

Spectrometric study of a-methylene aromatic araminenone and aminoketone

Thirteen α-methylene aromatic araminenone and four α-methylene aromatic aminoketones were prepared by modified Mannich reaction. On the basis of isotopic labeling, a plausible way of cleavage was proposed for the formation of the M^＋- 17 fragment peak in the MS of the α-methylene aromatic araminenone and aminoketones. The characteristic chemical shift of the olefinic protons in ^1H NMR is also discussed.     

1H NMR structural increments for alkyl substituted η3-allyl transition metal complexes

The ¹H NMR spectra of various alkyl substituted η³-allyl transition metal complexes (M?Ni, Ru) have been analysed. The chemical shifts of the η³-allyl protons can be calculated using additive increments; the values of the syn and anti vicinal proton-proton coupling constants approach each other on alkyl substitution of the η³-allyl group.     

H-N HMBC as a valuable tool for the identification and characterization of nitrones

¹H-¹⁵N HMBC has been evaluated as an efficient and high-speed method to determine ¹⁵N chemical shifts for nitrones, which can be used to identify aromatic nitrones and to extract structural information by comparison with reference data. Substituent effects have been measured on C and N aryl groups separately, showing up the influence of electronic effects on C-aryl groups rather than N-aryl groups on the ¹⁵N chemical shifts. Steric effects are remarkable in the case of C-aryl-N-alkyl nitrones. Depending on N or C substitution, chemical shift changes in such an additive way that it is possible to predict chemical shifts for unknown nitrones.     

Calculation of 13C NMR chemical shifts for aromatic carbons in polyalkylated benzenes

¹³C NMR spectra of a large number of polyalkylated benzenes with branched and linear aliphatic chains have been studied. This resulted in the development of a general procedure that can be used for the calculation of the aromatic chemical shifts in any polyalkylated benzene.     

On the photonics of aromatic azide molecules

Energies of electronically excited states of a number of aromatic azides have been calculated using ab initio quantum-chemical methods. It has been shown that the relative arrangement of the singlet and triplet states of the A′ and A″ types changes with an increase in the number of π electrons in the system. As in the case of other classes of heteroaromatic molecules, five relative locations of these states are possible. On this basis, the dependence of the luminescent and photochemical properties of molecules of aromatic azides on their chemical structure has been rationalized.     

内氢键对芳环~(13)C化学位移的影响

本文讨论水杨醛、邻——基苯乙酮及2——基雌甾化合物的分子内氢键对芳环~13C化学位移的影响。采用量子化学CNDO/2方法,计算取代芳烃各原子的净电荷,从碳原子的净电荷与化学位移的对应关系进一步论证了此种影响.首次得到形成内氢键的甲甲基、乙乙基及及基对所在碳的取代基增量的校正值,经校正后化学位移的计算值与实测值很好符合。     

Correlation of para substituent carbon-13 chemical shifts in aromatic compounds using polar (inductive) and resonance constants which are identical for aliphatic and aromatic compounds

A correlation of para substituted ¹³C chemical shifts in aromatic compounds with substituent polar (inductive) and resonance constants σ* and σ^r of aliphatic compounds has been studied. It has been shown that the precision of the correlations obtained corresponds to that of the Swain-Lupton and Taft two-parameter equations, but the correlation equation used in this work seems to permit a more exact separation of the substituent effects of aromatic compounds into inductive and resonance contributions. Thus, σ* and σ^r substituent constants are universal parameters which can be used in a correlation analysis of the properties of both aliphatic and aromatic compounds.     

A unified correlation of substituent effects with carbon,proton and fluorine chemical shifts in aromatic and olefinic systems

At the present time no completely satisfactory quantum mechanical calculations exist for carbon, proton or fluorine chemical shifts in various substituted aromatic or olefinic systems. However, the chemical shifts in such systems have been shown to be well correlated by a linear multiple regression analysis with the Swain and Lupton field and resonance para meters ? and ?, and the semiempirical parameter Q. The utility of Q in testing substituent stereochemistry has been exemplified previously. Here the applications of the complete regression analysis to a wide variety of different systems for the three nuclei are given. The correlation is also shown to apply to selenium in substituted selenophenes. The ¹³C chemical shifts for a series of ortho substituted toluenes are presented and comparisons made with other ortho disubstituted benzenes.