A carbon-13 NMR study of some sulfur-containing organic compounds

Carbon-13 NMR spectra have been obtained and analyzed for a series of saturated linear and cyclic sulfur-containing organic molecules. For the large cyclic polythiaethers whose proton spectra are broad and unresolved, it is found that carbon-13 spectra are sharp and well resolved. The resonances of all carbons fall within the expected chemical shift ranges. Based upon the comparative resolution in the spectra of large and small cyclic species, it is concluded that whatever conformational motion may exist within the rings must be occurring very rapidly on the NMR time scale.     

Conformational preferences of some substituted methyl groups in cyclohexanes as studied by carbon-13 nuclear magnetic resonance

Low temperature ¹³C NMR spectra of 80:20 mixtures of cis and trans-4? CH₃? CH₃? C₆H₁₀CH₂X, where ? C₆H₁₀-is 1, 4-disubtituted cyclohexyl and X=Br, CN, OH, OCH₃, Si(CH₃)₃, Sn(CH₃)₃, Pb(CH₃)₃ and HgOCOCH₃ have been recorded. The signals of the trans (e, e) components were assigned from the ambient temperature spectra of C₆H₁₁CH₂X and the established substituent effects of an equatorial methyl group in cyclohexane. Conformational equilibria of the cis (e, a?a, e) components were then computed from the intensities of the (remaining) signals (～180 K) of the two conformational isomers. From these equilibria A values of CH₂X were calculated, assuming additivity of conformational energies of CH₃ and CH₂X (the counter-poise approach). In general, these values are very similar to the value of the CH₃, although some trends do emerge. This study provides α, β, γ, and δ effects for a wide range of axial and equatorial ? CH₂X groups.     

Temperature effects on the carbon-13 NMR shifts of selected compounds

The effects of temperature on the ¹³C NMR shifts of benzene, cyclohexane, pyridine, cyclohexene, neopentane, hexane, and heptane have been determined from +10 to +70°C. In addition, the temperature shift of ²D in D₂O was found to be +10.4 × 10^?3 ppm/°C. All shifts appear to be linear functions of temperature within experimental error.     

Synthesis and carbon-13 NMR analysis of some organoselenium compounds

Carbon-13 chemical shift assignments are reported for a series of 10 organoselenium compounds of the type PhSeL.In the course of this study, hydroalumination and bromination of alkynylselenium compounds was performed for the first time, and compared with the rate of hydroalumination and bromination of the corresponding alkynylsilane.The phenyl carbon shifts reflect ground state electron density changes. The selenium atom transmits electronic effects when the selenium atom acts as a link or bridge between two conjugative groups. For alkynylphenyl selenide, a polarization of charge within the triple bond occurs.     

A carbon-13 nuclear magnetic resonance study of compounds substituted by a perfluoroalkyl chain

The ¹³C NMR spectra of alkanes, alkanones and cyclohexanones substituted by perfluoroalkyl groups, R_F, have been studied. The influence of the perfluoroalkyl group on the chemical shifts of other carbons of the molecules is the same regardless of the R_F chain length.     

A carbon-13 NMR study of some metal carbonyl compounds containing one-electron ligands

Carbon-13 NMR spectral data for complexes having the general formula CpM(CO)_nX (Cp = η⁵-C₅H₅; M = Mo or W, n = 3; M = Fe, n = 2; X = halogen, methyl or acetyl) and their phosphine and isocyanide substitution products are reported. For CpM(CO)₃X complexes two carbonyl resonances (1 : 2 ratio) are observed in all cases, consistent with the retention of the “piano-stool” geometries observed in the solid state. Substituted complexes CpM(CO)₂(L)X (M = Mo or W; L = PR₃ or cyclohexyl isocyanide) are unequivocally assigned cis or trans geometries on the basis of the number of observed carbonyl resonances and values of ²J(PC) for the phosphine substituted derivatives. Spectral data for [M(CO)₅X]^? (M = Cr, Mo or W; X = Cl, Br or I) and η⁷-C₇H₇Mo(CO)₂X and the halide derivatives above generally show an increase in the shielding for carbonyls adjacent to the halide ligand in the order Cl < Br < I. Carbonyl resonances are more shielded in isostructural complexes in the order Cr < Mo < W (triad effect).     

A carbon-13 NMR study of phenyl-substituted cyclophosphazenes

The ¹³C NMR spectra of the cyclotriphosphazenes N₃P₃CI_6?n Ph_n (n=2, 3, 4, 6) and the tetrameric derivatives 2,2,6,6-N₄P₄CI₄Ph₄ and N₄P₄Ph₈ have been recorded. The carbon chemical shifts can be largely explained on the basis of concomitant mesomeric electron release from the benzene ring and inductive electron withdrawal by phosphorus. The magnitude of ¹J(P, C-1) for the non-geminal compounds is ?40 Hz higher than that observed for the geminal compounds. Some aspects of the NMR data are also discussed with reference to the X-ray crystal structures of several phenyl-substituted cyclotri- and cyclotetra-phosphazenes.     

A carbon-13 NMR study of benzonorbornene isomers

The carbon-13 NMR spectra of a series of exo-and endo-epimers of 2-substituted benzonorbornene (2-substituent = OH, OCHO, Br, NH₂, NHMe or NMe₂) have been examined. The spectra are readily assigned by comparison with the coupled and off-resonance proton decoupled spectra as well as by the use of shift reagents. Interesting and diagnostic features of the spectra allow the distinction between epimers.     

Linear free energy relationships for carbon-13 NMR chemical shifts of substituted benzoic acids1

In order to examine ¹³C-SCS of substituted benzoic acids, chemical shifts of the acid form (I) and the dissociated form (II) have been obtained separately. Single substituent parameters, σ⁰ or σ⁺ are correlated with the shifts for the carboxyl (δ_co) or ipso carbons (δ_ipso), respectively. Among the available five equations which are developed for the analysis with dual (or divided) substituent parameters (DSP), the Swain-Lupton equation (eqn 3) and the Taft-Swain-Lupton equation (eqn 4) give much better correlations, not only for δ_co and δ_ipso but also for the results for ring carbons (C(2), C(5), C(6)), except for those attached to or neighboured by substituents. It is concluded that the SCS of aromatic compounds are best analyzed with substituent parameters derived from reactions or equilibria on the basis of linear free energy relationships.     

A carbon-13 NMR spectroscopic study of ferrocenylmethyl carbonium ions

The ¹³C NMR spectra of three ferrocenylmethyl carbonium ions and of the alcohols from which they were derived have been obtained. The chemical shifts and coupling constants of the carbonium ions are explicable in terms of a structure that has the positive charge extensively delocalized throughout the entire molecule, with a fulvenelike structure for the substituted cyclopentadienyl ring.     

1H NMR spectroscopic investigation of β-cyclodextrin inclusion compounds with parecoxib

The inclusion complexes of β-CD and parecoxib [PRB] in aqueous solution were investigated using ¹H NMR spectroscopic study revealed the existence of four different equilibria for 1:1 inclusion complexes in which both the aromatic rings of the guest are tightly held by the host cavity. The NMR spectra of the PRB studied in the presence of β-CD are fully assigned and interpreted by means of COSY spectrum for the unambiguous assignment of guest aromatic ring protons. The parallel interpretation of β-CD chemical shift changes and dipolar contacts, with the aid of 2D ROESY, allows the mode of binding to be established for four possible structures of 1:1 PRB-β-CD inclusion complexes.     

Theoretic heat sink simulation and experimental investigation of the pyrolysis of substituted cyclohexanes

Reaxgen program for the pyrolysis mechanism of cycloalkanes was adopted to simulate the heat sink of substituted cyclohexanes. Thermal cracking of cyclohexanes was performed to examine the cracking performance, wherein the substituent effects were detailedly discussed under supercritical condition. It was found that Reaxgen program played a good part in the screening and optimization of cyclohexanes. A good agreement with the experimental data for the mono-substituted and bi-substituted cyclohexanes was demonstrated, however, some deviation for the tri-substituted cyclohexanes were observed. The experiment results indicated that the gaseous product yield increased sharply for monosubstituted cyclohexanes with short substituents containing no more than two carbons. Nevertheless, continuous increase in the alkyl chain depressed the gaseous product yield smoothly. The cyclic substituent dramatically inhibited the pyrolysis of cyclohexanes. All the substituents but cyclohexyl had no obvious effect on the yield of hydrogen and olefins(≤C4). For bi-substituted cyclohexanes, the more close the distance between the two substituents, the higher the gaseous product yield was obtained. However, opposite result on the selectivity to hydrogen and olefins(≤C4) was generally obtained except 1,3-dimethylcyclohexane. The position of tri-substituents acted little significance on the gaseous product yield, as well as the selectivity to hydrogen and olefins(≤C4).     

Raman-spectrum investigation of the equatorial and axial carbonyl groups of some substituted cyclohexanes

Summary In the determination of conformations in accordance with the largest substituents it is found that compound (IV) has the conformations trans-ee and trans-aa and compound (V) the conformations cis-ae and cis-ea; none of these conformations predominates substantially, as with neither of the two possible conformations of the compound (III).     

Characterization of cyclotriveratrylene inclusion compounds by means of solid state13C NMR

Solid inclusion compounds of cyclotriveratrylene (CTV) with benzene, toluene, acetone, tetrahydrofuran, acetic acid and chloroform, as well as two hydrated forms, were prepared and characterized by solid state¹³C NMR. The inclusion process for CTV appears to be quite selective, and in some instance depends critically on the presence or absence of water. A number of different structural types are indicated by the solid state¹³C NMR splitting paterns. For the guests listed above,¹H NMR in solution indicated a guest to host ratio close to 0.5, except for chloroform, for which the ratio is closer to 2.     

On the assignment of the carbon-13 NMR spectrum of bilirubin

An individual assignment of certain peaks in the proton and ¹³C NMR spectra of bilirubin and of bilirubin dimethyl ester is described. The assignment was achieved through the spectra of vinylneoxanthobilirubinic acid and by off-resonance decoupled ¹³C spectra of bilirubin dimethyl ester. The signals due to the endo and exo vinyl groups were separately assigned. This assignment allows a rational interpretation of previously obtained spin-lattice relaxation times of the vinyl carbon peaks. The two vinyl groups are found to differ considerably in their motional correlation time.     

13C NMR spectra of some N-aryl substituted sulphur–nitrogen compounds

The ¹³C n.m.r. spectra of four classes of N-aryl sulphur–nitrogen compounds are discussed. The para carbon shieldings of the N-phenyl derivatives reflect the substituents effects of the various nitrogen groups. These show large differences for the four classes of compounds due to differences in the electronic structure of the sulphur–nitrogen bond.     

Observation of steric hindrance in heteraferrocenophanes by carbon-13 NMR

The ¹³C NMR spectra of stereoisomeric trans- and cis-1,3-dimethyl-2-oxa[3](1, 1′)ferrocenophanes, 1,2,3-trithia[3](1, 1′)ferrocenophane and 1,3-dithia[3](1, 1′)ferrocenophane have been recorded and analysed. The presence of steric hindrance in some of these compounds was confirmed and the conformations of the molecules were determined.