Carbon-13 chemical shifts of some propargyl alcohol derivatives

The natural abundance ¹³C chemical shifts of a range of propargyl alcohol derivatives have been determined and individual resonances assigned. The shielding effects of the triple bond and hydroxyl group on neigbouring carbons have been characterised. The observed for these compounds are compared to those of alkyl or allyl alcohols.     

Carbon-13 chemical shifts of substituted nortricyclenes

¹³C NMR spectra of a series of substituted nortricyclene derivatives have been measured, and the ¹³C chemical shifts interpreted in terms of α, β, γ and δ-effects. The nature of these substiuent shifts is discussed together with some analytical possibilities. The substituent shifts provide valuable data about the steric effects in strained molecules and can be used as increments for structural analysis, particularly for the determination of orientations of substituent groups.     

Carbon-13 chemical shifts of monosubstituted cyclohexanes

The carbon-13 chemical shifts of monosubstituted cyclohexane derivatives are compared with those of aliphatic compounds. The polar substituents exert a similar influence on the α-, β- and γ-carbons in both series of compounds. The δ-effect is shown to be characteristic mainly to the cyclic compounds, however. The appearance of a δ-effect is discussed as a possible consequence of electron delocalization in alicyclic molecules. A correlation of these δ-effects with inductive parameters of the substituents is presented.     

Carbon-13 chemical shifts of bicyclic compounds

¹³C NMR absorption spectra of 50 bicyclic hydrocarbons, alcohols and ketones have been measured, in addition to some terpenes. The ¹³C chemical shifts are approximately additive for similar compounds and can be used for the determination of molecular structure; they differ for endo- and exo-isomers, just as in proton spectra. These quite regular and predictable ¹³C shift differences are much larger and are caused by the 1,4-nonbonded interaction between atoms heavier than hydrogen, not by magnetic anisotropy effects.     

Carbon-13 chemical shifts of inverted carbon atoms

The inverted carbons in 2,4-methano-2,4-dehydroadamantane are shielded by 14.3 ppm relative to the corresponding carbons in 2,4-methanoadamantane. This was explained by the balance of the inverted carbon hybridization deshielding, the shielding effect of the cyclopropane rings formed, and the change in the influence of the neighbouring atoms.     

Carbon-13 chemical shifts and conformations of dimethylcyclohexanols

Carbon-13 chemical shifts of all twenty-two dimethylcyclohexanols, formed by the hydrogenation of isomeric xylenols, have been measured and assigned. Conformational peculiarities of dimethylcyclohexanols are discussed on the basis of their carbon-13 chemical shifts.     

Carbon-13 chemical shifts of some cholinergic neural transmission agents

Carbon-13 chemical shifts have been obtained in the pulse Fourier transform mode on the following cholinergic neural transmission agents: acetylcholine, β-methyl acetylcholine, carbamoyl choline, choline, tetramethylammonium, scopolamine, atropine, methyl atropine, tropine, tropic acid, nicotine, dimethyl phenylpiperazinium, arecoline, oxotremorine and pilocarpine. The effects of structural variations, asymmetric centers and steric interactions on the ¹³C shielding are considered. The observed chemical shifts do not appear to correlate simply with potencies in the cholinergic nervous system.     

Carbon-13 chemical shifts of some model carboxylic acids and esters

Selected model carboxylic acids and esters dissolved in deuteriochloroform have been studied by carbon-13 nuclear magnetic resonance under standardized conditions. Assignments of the chemical shifts have been made for all samples, and the spin–lattice relaxation times and nuclear Overhauser effects measured for a few selected esters. The results are intended to provide a practical aid for the analysis of carboxylic acids and esters of a more complex nature (e.g. polymers, natural products, etc.).     

Carbon-13 chemical shifts of bicyclo[3.2.1]octane and bicyclo[2.2.1]heptane derivatives

¹³C chemical shifts of more than fifty bicyclo[3.2.1]octane and bicyclo[2.2.1]heptane derivatives (hydrocarbons, alcohols, ketones and esters) have been determined. The usefulness of ethyl derivatives for the assignment of close ¹³C chemical shifts in bicyclic methyl derivatives is shown both for the bicyclo[3.2.1]octane and bicyclo[2.2.1]heptane series. Comparison of substituent effects on α-, β-, γ- and δ-carbons in both series of compounds shows remarkable differences in steric interactions. In contrast to the rigid bicyclo[2.2.1]heptane system, both chair and boat conformations can be predominant in the bicyclo[3.2.1]octane series with the conformationally flexible 6-membered ring.     

Carbon-13 NMR chemical shifts in some substituted 1,2,4-triazol-3-ones

Carbon-13 NMR data for 15 substituted 1,2,4-triazol-3-ones are presented and discussed with regard to enolization in the neutral molecules. The coupling constant and chemical shift data show that the proton at N-2 is not exchanging rapidly in the DMSO-d₆ solvent. Using D₂O? OD^? as a solvent, it is found that the C-3 and C-5 resonances are shifted downfield by nearly the same amount, suggesting that the proton at N-4 is being removed. Enolization in the neutral molecules does not occur to any significant extent.     

Carbon-13 chemical shifts and coupling constants in cis- and trans-1,2-di-tert-butylethylene

The spectral parameters of the title compounds were redetermined to resolve discrepancies between data reported in the literature.     

13C NMR chemical shifts of N-unsubstituted- and N-methyl-pyrazole derivatives

¹³C shielding data for 100 derivatives of pyrazole are reported. These include methyl, ethyl, n-propyl, tert-butyl, phenyl, hydroxymethyl, carboxyl, ethoxycarbonyl, cyano, amino, hydrazino, nitro, azido, chloro, bromo and iodo groups as substituents on the ring carbon atoms.     

Carbon-13 nuclear magnetic resonance chemical shifts and 13C-199Hg coupling constants for symmetrical dialkylmercurials

The carbon-13 chemical shifts and coupling constants (J[¹³C? ¹⁹⁹Hg]) have been determined for a series of eleven symmetrically substituted organomercurials. Empirical substituent parameters can be calculated which correlate observed and predicted chemical shifts for dialkylmercurials.     

Carbon-13 NMR studies of substituted naphthalenes. I—complete assignments of the 13C chemical shifts with the aid of deuterated derivatives

Proton-coupled as well as noise-decoupled ¹³C NMR spectra of several substituted naphthalenes have been studied. Complete assignments of the ¹³C signals based on selectively deuterated derivatives and on the ¹³C? ¹H coupling pattern have been made. For the methoxynaphthalenes, acetylnaphthalenes and naphthaldehydes the dominant conformations of the substituents have been deduced from the ¹³C chemical shifts.     

Carbon-13 chemical shift assignment of E-Hydroxyazastilbenes

The ¹³C NMR spectra of nine isomeric E-hydroxyazastilbenes (E-hydroxystyrylpyridines) have been fully assigned. The Ai and AiK empirical parameters of o-(m or p-)hydroxystyryl and 2-(3- or 4-)vinylpyridyl groups for the prediction, of chemical shifts of substituted styrylpyridines were calculated.     

Carbon-13 substituent chemical shifts of 4-substituted bicyclo[2.2.2]oct-1-yl cyanides

The carbon-13 substituent chemical shifts of 4-substituted bicyclo[2.2.2]oct-1-yl cyanides are a linear function of the substituent inductive parameters.     

Survey of structural regularities in molecular properties. I. Carbon-13 chemical shifts in alkanes

Many regularities in properties among structurally related compounds are known but a systematic approach to investigate all such cases is rare. A plan is outlined for a systematic study of structural regularities that is based on use of selected graph invariants as prime auxiliary quantities. In this paper carbon-13 chemical shifts in alkanes are examined. Since NMR spectra of paraffins are well understood, the example provides a useful illustration of the approach, introduces basic concepts, and illustrates the kind of the results that the graph-theoretical scheme generates. Differences and similarities between graph-theoretical viewing of the problem of structural regularities and customary direct use of additivities are discussed in some detail.     

Carbon-13 chemical shifts of 3-substituted thietanes,thietane 1-oxides and thietane 1,1-dioxides

Carbon-13 chemical shifts of the α- and β-carbon atoms for 12 thietane 1,1-dixides, 9 thietane 1-oxides and 7 thietanes with a variety of 3-substituents [H, CH(CO₂Et)₂, SEt, Br, SPh, Ph, Cl, NMe₂, OH, OSiMe₃, OAc, OEt] are correlated according to the nature of the sulfur atom (Y=sulfone, sulfoxide, sulfide) and the nature of the 3-substituent (X) by the equations δ_α= a_Y+b_X and δ_β=a_X+b_Y, where a and b are parameters characteristic of X and Y. One-bond coupling constants [J(CH)] are reported for 21 compounds. The chemical shifts for the α- and the β-carbon atoms of the sulfones show the ‘fore-membered ring sulfone effect’ (α-carbon unusually deshielded, β-carbon unusually shielded), but the α-carbon-hydrogen coupling constants are similar to those of the sulfoxides and sulfides; the β-carbon-hydrogen coupling constants are sensitive to the nature of the substituent (X) but no special β-effect is observed. Comparison of the chemical shifts of the α-methylene carbon atoms of 3-phenyl-, 3-(β-naphthyl)- and 3-(α-thienyl)-thietes with those of the coresponding sulfones also reveals the ‘four-membered ring sulfone effect’ cis- and trans-3-Substituted thietane 1-oxides may be distinguished by the greater downfield shift for the β-carbon atom in the trans-isomer.     

丁烷衍生物类木脂素13C NMR化学位移预测

借助原子电性作用矢量(AEIV)和原子杂化状态指数(AHSI),对39种丁烷衍生物类木脂素共计854个等价C原子进行表征,并建立用于模拟该类分子13C NMR化学位移的多元线性回归方程.所得定量结构波谱关系(QSSR)模型及留一法交互检验相关系数分别为r=0.981和q=0.962.进一步用从马尾松松针中分离所得新木脂素中20个13C NMR化学位移对模型进行外部验证,预测结果与实验值较接近.表明所建模型有良好稳定性和泛化力,可对丁烷衍生物类木脂素13C NMR谱学数据准确模拟.