13C, 13C coupling constants in anthracene, 9,10-dihydroanthracene and phthalic acid derivatives. Determination of signs by the symmetrical double labelling (SDL) method V

Carbon-13, carbon-13 one-bound and long-range coupling constants are determined for anthracene and 9,10-dihydroanthracene labelled in the 9,10-positions, and for thiophthalic anhydride and phthalimide, labelled in both carbonyl groups. Relative signs are determined by the SDL method. Signs in naphthalene, anthracene and pyrene derivatives are discussed. The general trends observed in many aromatic compounds, ³J|>|²J|>|⁴J| and ²J positive, ³J positive, ⁴J negative are mostly confirmed. However, evidence suggests that two-bond couplings between carbon atoms in the same ring in aromatic hydrocarbons are negative.     

The 13C,H coupling constants in structural and conformational analysis. III.. Long-range carbon–hydroxyl proton couplings as evidence of hydrogen bonding in some acylphloroglucinols

Proton coupled ¹³C NMR spectra have been recorded for some acylphloroglucinol derivatives. Significant couplings over two, three and four bonds were observed between the hydroxyl proton and aromatic carbons for those compounds where the hydroxyl group is hydrogen bonded strongly enough to the carbonyl carbon of the acyl side chain. Typical values were ²J = 4.8 Hz, and ³J = 5.6 Hz or 6.7 Hz corresponding to dihedral angles of c. 0° and c. 180°, respectively; the dihedral angle is defined as the angle between the O—H bond and the plane of the aromatic ring. A stereospecific ⁴J(COH) value of 1.2 Hz for a ‘W’ arrangement of coupled atoms was also found. An interesting example of ‘virtual’ J(CH) coupling was observed in the proton coupled spectrum of 1-butyrylphloroglucinol 2-monomethyl ether in acetone-d₆ caused by the accidentally equal chemical shifts of the two ring protons.     

The structural dependence of two-bond 13C?13C coupling constants

Two-bond ¹³C? ¹³C coupling constants are discussed on the basis of INDO-SCPT calculations. The dependence of ²J(CC) on bond angle variation and on methyl substitution is evaluated, and it is shown that ²J(CC) depends linearly on the bond orbital s-character product of the terminal carbon atoms, whereas no systematic relationship with the hybridization of the central carbon atom was obtained. Alkyl group substituent effects are found to be additive. The coupling constants of a number of cyclobutane derivatives are discussed on the basis of these structural relationships; it is shown that the experimental findings can be interpreted quite consistently by assuming a dual-pathway coupling mechanism.     

Substituent Conformational effects in vicinal 13C?13C spin–spin coupling constants

A series of 7-¹³C-labeled o-substituted toluene derivatives and carboxyl-¹³C-isocrotonic and crotonic acid were synthesized and studied by ¹³C NMR spectroscopy to obtain ¹³C? ¹³C spin-spin coupling constants involving the labeled carbon. The cis ³J(CC) values were different from those in previous studies in that these J(CC) values were relatively small and the usual dependence of ³J(CC) on the s-character of the terminal carbon was reversed. Further, a strong dependence of ³J(CC) on the conformational orientation of a terminal carbonyl group was shown to exist. Through-space interactions of the two coupling carbons were shown to contribute to these ‘anomalous’ results, and thus it was shown the cis carbon-carbon couplings may not be directly related to geometrically equivalent proton-proton couplings, as are other carbon-carbon couplings.     

High resolution 13C NMR spectroscopy. IV—stereochemical assignments in butenedioic acids and 3-pentene-2-ones

Vicinal ¹³C, H coupling constants ³J(CO, H) for butenedioic acids and ³J(CH₃, H) for 3-pentene-2-ones have been determined and are correlated with the configuration of the corresponding C?C double bond. For both types the relationship ³J(CH) trans > ³J(CH)cis holds; in the case of the CH₃, H couplings, however, the ³J(CH₃, H) trans values are reduced because of steric reasons, so that configurational assignments seem possible only when both isomers are present. Additionally, the coupling constants ³J(COC H₃,H ) and the chemical shifts δ have been evaluated for the pentenones and it is shown that these parameters give information about the predominating conformation of α, β-unsaturated methyl ketones.     

13C?13C coupling constants in derivatives of trans-stilbene and tetraphenylethylene. Determination of relative signs II

Magnitudes and signs of ¹³C? ¹³C coupling constants in compounds of the type Ph¹³CR¹R²? ¹³CR¹R²Ph have been determined and the results are discussed in a broader context. Two types of coupling constants, J(C-i, C-α) and J(C-i, C-β), between aromatic carbon atoms and the benzylic carbons, probably with different coupling mechanisms, are considered. Whereas ²J(C-2, C-α) are always found positive, ²J(C-1, C-β) in the present compounds are found to be negative or about zero. ³J(C-3, C-α) has the same sign as ²J(C-2, C-α). A ⁴J and a ⁵J were observed in trans-stilbene.     

1H and 13C NMR study of α-acetylenic PIII and PIV derivatives. Signs and magnitudes of J(P?C) and J(P?H)

All J(P? H) and J(P? C) values, including signs, have been obtained in acetylenic and propynylic phosphorus derivatives, R₂P(X)? C?C? H and R₂P(X)? C?C? CH₃ (X ? oxygen, lone pair and R ? C₆H₅, N(CH₃)₂, OC₂H₅, N(C₆H₅)₂, Cl) from ¹H and ¹³C NMR spectra. In P^IV derivatives the following signs are obtained: ¹J(P? C)+, ²J(P? C)+, ³J(P? C)+, ³J(P? H)+, ⁴J(P? H)? . Linear relations are observed between ¹J(P? C), ²J(P? C) and ³J(P? C) versus ³J(P? H), indicating that these coupling constants are mainly dependent on the Fermi contact term, though the other terms of the Ramsey theory do not seem to be negligible for ¹J(P? C) and ²J(P? C). In P^III derivatives these signs are: ¹J(P? C)- and +, ²J(P? C)+, ³J(P? C)-, ³J(P? H)-, ⁴J(P? H)+. Only ³J(P? C) and ³J(P? H) reflect a small contribution of the Fermi contact term while in ¹J(P? C) and ²J(P? C) this contribution seems to be negligible relative to the orbital and/or spin dipolar coupling mechanisms.     

Temperature dependences of J(C,H) and J(C,D) in 13CH4 and some of its deuterated isotopomers

The nuclear spin—spin coupling constants J(C,H) and J(C,D) have been measured over the temperature range 200–370 K for the methane isotopomers ¹³CH₄, ¹³CH₃D, ¹³CHD₃ and ¹³CD₄. The coupling constants increase with increasing temperature for any one isotopomer and decrease with increasing secondary deuterium substitution at any one temperature. The results are entirely attributable to intramolecular effects and the data have been fitted by a weighted least-squares regression analysis to a spin—spin coupling surface thereby yielding a value for ¹J_e(C,H), the coupling constant at equilibrium geometry, and values for the bond length derivatives of the coupling. We find that ¹J_e(C,H) = 120.78 (±0.05) Hz which is about 4.5 Hz smaller than the observed value in ¹³CH₄ gas at room temperature. Results are also reported for J(H,D) in ¹³CH₃D and ¹³CHD₃ for which no temperature dependence was detected.     

13C NMR: Substituent effects on one-bond 15N?13C coupling constants in anilines and anilinium ions

¹J(¹⁵N¹³C) values obtained from FT ¹³C NMR spectra were measured for a number of ¹⁵N-enriched aniline derivatives and are found to exhibit varying degrees of dependence on the nature of the ring substituent. Theoretical calculations of ¹J(¹⁵N¹³C) values for representative members of the systems examined were made using INDO parameters and a ‘sum-over-states’ perturbation approach. The calculated coupling constants are generally in fair agreement with experimental values when the integral products S_N²(o)S_C²(o) and (r^?3)_N(r^?3)_C have values of 34.437 au^?6 and 2.770 au^?6, respectively.     

13C NMR spectra of non-labelled and 15N-mono-labelled azo dyes

¹³C NMR spectra of four types of azo coupling products from benzenediazonium chloride have been measured and interpreted, viz. hydrazo compounds with an intramolecular hydrogen bond (3-methyl-1-phenylpyrazole-4,5-dione 4-phenylhydrazone), azo compounds without an intramolecular hydrogen bond (4-hydroxyazobenzene), azo compounds with an intramolecular hydrogen bond (2-hydroxy-5-tert-butylazobenzene) and an equilibrium mixture of both the tautomers of 1-phenylazo-2-naphthol. The absolute values of the J(¹⁵N¹³C) coupling constants have been determined by recording the spectra of the ¹⁵N isotopomers, and have been used, in some cases, for ¹³C signal assignment. A relationship has been found between the chemical shifts of the C-1′ to C-4′ carbons of the phenyl group (from the benzenediazonium ion) or the ¹J(¹⁵N¹³C) coupling constant, and the composition of the tautomeric mixture.     

The structural dependence of 13C, 13C coupling constants in cyclopropanes

The smallest one-bond carbon—carbon coupling constants of cyclopropane derivatives have been measured for [1-¹³C]cyclopropane-1,1-dicarboxylic acid and cyclopropanecarboxylic acid. The ¹³C, ¹³C coupling constants of cyclopropylcarbinol have also been determined. The dependence of ¹J(CC) of the three-membered ring on different substituents and hybridization effects is evaluated. The carbon—carbon coupling constant of the unsubstituted cyclopropane is discussed on the basis of self-consistent perturbation theory (SCPT) and s character calculations (localized bond orbitals), and the results are compared with the experimental finding. It is shown that the ¹J (CC) can be interpreted by assuming a dual-pathway coupling mechanism.     

Long-range nuclear spin-spin coupling between 11B and 13C, 29Si or 119Sn: a promising tool for structural assignment

The influence of unresolved long-range nuclear spin-spin coupling [ⁿJ(¹¹BX) (n > 1; X = ¹³C, ²⁹Si or ¹¹⁹Sn)] on X resonances has been studied for aminoboranes (1 and 2), haloboration (2 and 4), hydroboration (5) and organoboration products of alkynes (6 and 7). The differential broadening of X resonances in the X NMR spectra arising from ⁿJ(¹¹BX) (most obvious for X= ¹¹⁹Sn) shows a qualitatively useful pattern of various coupling pathways. |²J(¹³CN-¹¹B)| in 1 and 2 appears to be sensitive to the nature of the trans-ligand and to the ring rize. In many alkenylboranes (3, 4, 5b and d, 6 and 7) the magnitude of the coupling constants across the CC double bond follows the trend |²J(¹¹BX)| ∼ |³J(¹¹BX)|_cis < |³J(¹¹BX)|_trans. An increasing number of electropositive substituents at the CC double bond causes an increase in the magnitude of |³J(¹¹BX)|_cis,trans. If there are only organyl groups of hydrogen attached to the CC double bond, as in the hydroboration products of alkynes (5a and c) |ⁿJ(¹³C-¹¹B)| appears to be too small with respect to [T_Q(¹¹B)]⁻¹, and the differential broadening was neglibible under the experimental conditions used.     

Substituent effects on one-bond 15N?13C couplings in N,N-dimethylanilines and nitrobenzenes. Effect of steric inhibition of conjugation

The ¹J(¹⁵N¹³C) values for a series of ring-substituted N,N-dimethylaniline-¹⁵N derivatives and a series of nitrobenzene-¹⁵N derivatives were measured from the ¹³C spectra. In the nitrobenzenes, small changes in ¹J(¹⁵N¹³C) are attributed to the inductive effect of the substituents, since steric inhibition of conjugation has little effect on the magnitude of the coupling. In contrast, steric inhibition of nitrogen lone-pair delocalization in N,N-dimethylaniline derivatives markedly reduces the value of ¹J(¹⁵N¹³C). Theoretical calculations of ¹J(¹⁵N¹³C) values for the two series of compounds were made using standard INDO parameters and a ‘sum-over-states’ perturbation approach. Fair agreement between the calculated and experimental values is found.     

Substituenteneffekte auf die NMR-Spektren von Pentafulvenen. (13C, 13C)-NMR-Kopplungskonstanten (1J(C,C))

Substituent Effects on NMR Spectra of Pentafulvenes. ¹³C, ¹³C-NMR Coupling Constants (¹J(C, C)) ¹H- and ¹³C-NMR spectra of 6-monosubstituted pentafulvenes 1 – 8 have been analysed, and ¹J(C, C) coupling constants have been determined from ID-inadequate spectra of ¹³C satellites. It turns out that ¹³C,¹³C coupling constants of the ring C-atoms, and especially J(1,2)/J(3,4) and J(2,3), reflect the extent of π delocalisation in the fulvene ring. With increasing electron-donating capacity of the substituent R, J(1,2)/J(3,4) values are decreasing, while J(2,3) (and J(1,5)/J(4,5) as well) are increasing, and linear correlations of Hammett substituent constants σ⁺ and ¹J(C,C) values are obtained.     

Carbon-13 NMR studies of monohydroxylated and monochlorinated derivatives of Z- and E-p-menthanes

J(¹³C¹H) coupling constants for some methyl- and aminopyrimidines have been determined by ¹³C NMR. Both the one-bond and long-bond and long-range coupling constants follow general trends which can be summarized in a few simple rules. In particular, the ³J(C-i,H) coupling constants between a ring carbon C-i and the ring protons are larger than the ²J(C-i,H) coupling constants. The opposite is observed for the couplings between the ring carbons and the methyl protons: ³J(C,Me). These general rules are very useful for the assignment of resonances in complex ¹³C spectra of pyrimidines and seem to be valid for other 6-membered aromatic nitrogen heterocycles. Furthermore, the additivity of substituent effects on ¹J (CH) for monosubstituted pyrimidines allows the estimation of ¹J (CH) for polysubstituted pyrimidines with a very good accuracy.     

The effect of solvents on the 13C NMR chemical shifts of the carbonyl carbon and the rotational barriers of N,N-dimethylbenzamide

The ¹³C solvent induced chemical shifts (SICS) of the carbonyl carbon and the thermodynamic barriers to rotation about the C? N bond of N,N-dimethylbenzamide are linearly related to the solvent parameter, E_T(30). A multi-parametric solvent parameter approach indicates that the SICS are influenced equally by polar effects and hydrogen-bond donor effects. Rotational barriers for N,N-dimethylbenzamide may, in principle, be determined by measurement of the ¹³C chemical shift of the carbonyl carbon in a particular solvent.     

High resolution proton coupled 13C spectrum and structure of butadieneiron tricarbonyl

A complete analysis of the proton coupled ¹³C spectrum of butadieneiron tricarbonyl is presented. The structure of the diene ligand is discussed on the basis of vicinal C,H and H,H coupling constants as well as ²J(HH), ¹J(CH) and ¹J(CC) data. These data are interpreted in terms of a non-planar C,H skeleton in which C,C bond lengths are nearly equal and the terminal carbon atoms exhibit some rehybridization towards sp³. The results obtained from the complex in solution agree with a structural model from X-ray data of substituted butadieneiron tricarbonyl complexes.     

Carbon-13 NMR of some organophosphorus compounds. 2—chemical shifts and P?C coupling constants of diaryl-, dialkoxy- and diaryloxy-phosphine amines with general formula Y2PNRR'

Carbon-13 chemical shifts and ²J(POC), ³J(POCC), ²J(PNC) and ³J(PNC) coupling constants of 30 compounds containing the amine moiety, with the general formula Y₂PNRR' (Y ? C₆H₅, CH₃O, CH₃CH₂O, CH₂O; Y₂ ? 1,2-dioxybenzene) have been determined. J(PNC) values have been used to explain the preferred conformation around the P? N bond. A comparison between ²J(PNC) and ²J(PNH) was accomplished.     

NMR study of E/Z isomerism in N‐alkoxybenzoimidic acid derivatives

Well defined E/Z isomers of N‐methoxy‐p‐nitrobenzimidoyl chloride, N‐methoxybenzimidoyl chloride, methyl N‐methylbenzohydroximate and ethyl N‐hydroxybenzimidate were prepared in order to provide model data for studies of benzhydroximic acid derivatives and related compounds. NMR parameters [¹H, ¹³C and ¹⁵N chemical shifts and ¹J(¹³C, ¹³C) coupling constants] were determined. The results show that stereochemically most significant are the values of ¹J(¹³C, ¹³C) couplings between aromatic C_ipso and C?N carbons and that the relationship, |J_cis| > |J_trans|, known for this coupling from oximes, is not affected by electronegative substituents at the C?N carbon atom, but the values are. Copyright © 2002 John Wiley & Sons, Ltd.     

13C, 1H spin coupling constants of dimethylacetylene

¹³C, ¹H spin coupling constants of dimethylacetylene have been determined by the complete analysis of the proton coupled ¹³C NMR spectrum. For the methyl carbon ¹J(CH) = + 130.6₄ Hz and ⁴J(CH) = + 1.5₈ Hz, and for the acetylenic carbon ²J(CH) = ? 10.34 Hz and ³J(CH) = +4.30 Hz. The ⁵J(HH) long-range coupling constant (+2.79 Hz) between the methyl protons was also determined.