13C n.m.r. spectra of cyclopropenes

¹³C n.m.r. chemical shifts and one bond ¹³C, ¹H coupling constants for cyclopropene and its 1- and 3-methyl derivatives as well as for methyl cyclopropane have been measured. The data for cyclopropene are 108·9 ppm and 228·2 Hz, 2·3 ppm and 167·0 Hz in the olefinic and allylic position, respectively. Substituent effects for the methyl group are discussed.     

Formation of a carboxyl group satellite line in the n.m.r. spectra of solid carboxylic acids

The structural factors resulting in the formation of the carboxyl group satellite line on the low field side of the ¹H n.m.r. spectra of carboxylic acids in the solid state have been determined from the temperature dependences of the carboxyl proton chemical shifts of acetic, dimethylacetic, ethylacetic, phenylacetic, benzoic, o-methylbenzoic, p-methylbenzoic and adamantyl carboxylic acids. The carboxyl group low field satellite forms at temperatures near the melting point only in the case of carboxylic acids with bulky hydrocarbon radicals (o-methylbenzoic and adamantyl carboxylic acids).     

13C n.m.r. spectra of some polychloroalkenes

¹³C n.m.r. spectra have been measured for thirty-two polychloroalkenes including (i) monosubstituted compounds CH₂?CHCCl_nH_2?nX, where ? X stands for ? H, ? Cl, alkyl, and trisubstituted alkenes CCl₂?CHAlk, none of which form geometric isomers; (ii) disubstituted compounds RCH?CHR′; (iii) and (iv) trisubstituted compounds of the types RCCl?CHR′ and CHCl?CClR, respectively. Compounds (ii) to (iv) represent either individual isomers or mixtures of the Z and E forms. In the case of compounds (ii) and (iii), the ordering of chemical shifts is δ_E > δ_Z for the sp²-carbon atoms and δ_E < δ_z for the adjacent tetrahedral ones. On the contrary, the signals of the sp²-carbon atoms of compounds (iv) obey the rule δ_E < δ_z. The effect of vinyl and allyl groups as substituents on the ¹³C chemical shifts of chlorine-containing groups is discussed. The dependence of the sp²-carbon spin–spin coupling constants J(¹³C? ¹H) on the number of chlorinated substituents in the molecule is also considered.     

13C n.m.r. spectra of 2-substituted pyrimidines

¹³C n.m.r. chemical shifts and carbon-proton coupling constants of 2-substituted pyrimidines are reported. The carbon chemical shifts are correlated with π-electron densities. Substituents which cause deshielding at the directly bound carbon (e.g. NH₂, OCH₃ and F) exert a more powerful effect in the benzene series than in the pyridine or pyrimidine series. The carbon-proton coupling constants do not correlate with the electronegativity of the substituents. Carbon-proton coupling constants and proton-proton coupling constants over the same number of bonds do not obey the Karabatsos relationship. The changes in the carbon-proton coupling constants in 2(1H)-pyrimidinone and 2(1H)-pyrimidinethione which accompany anion and cation formation are reported.     

13C n.m.r. spectra of N,N-dialkylamides

Carbon-13 n.m.r. spectra of formic, acetic, propionic and butyric acid amides with N,N-di-n-alkyl substituents have been completely assigned with the aid of extensive double resonance experiments. The data obtained were used to study long range steric effects on chemical and solvent shifts.     

13C n.m.r. spectra of quercetin and rutin

The noise-decoupled and gated-decoupled ¹³C n.m.r. spectra of quercetin and rutin are studied and assignments are proposed. The previous assignments of carbons 2 and 4′, carbons 5 and 9, carbons 6 and 8 have been reversed.     

1H n.m.r. spectra of 6-acetoxy-2,4-cyclohexadienones

¹H n.m.r. spectra of 36 derivatives of 6-acetoxy-2,4-cyclohexadienones were analysed. All available evidence indicates that all members of the series have similar conformations which do not depart significantly from planarity. Substituent-induced chemical shifts and interproton coupling constants correlate well with those in the analogously substituted ethylene and benzene derivatives. In particular, it appears that a substituent on the central carbon atom exerts a similar influence on ⁴J(HH) across a ‘W’ path when the three intervening carbon atoms are a part of a benzene ring, an allylic system (i.e. sp³–sp²–sp²), a localized sp²–sp²–sp² system or a saturated (i.e. sp³–sp³–sp³) system.     

Automatic analysis of n.m.r. spectra; a practical application to the spectra of oriented 2,4-dichlorobenzaldehyde and 2-chlorobenzaldehyde

The capabilities of a novel computer program for the ‘automatic analysis of n.m.r. spectra’ [J. Magn. Reson. 19 , 67 (1975)] are demonstrated in the analysis of the experimental spectra of oriented 2,4-dichlorobenzaldehyde and 2-chlorobenzaldehyde. In both cases solutions are found by starting from parameters which do not allow a line assignment. The fitting procedure is described in detail and the conclusion is reached that the program is a typical search program which is able to find, fully automatically, parameters which are unknown in principle. However, for reasons of efficiency, a certain amount of interaction between the computer and the spectroscopist is desirable. The structural results indicate that in both molecules, which are assumed to be planar, the O-trans-configuration vastly predominates and that the benzene rings are considerably distorted.     

1H n.m.r. spectra of N-phenylmaleimide in isotropic and nematic phases

¹H n.m.r. spectra of N-phenylmaleimide have been investigated in isotropic as well as nematic phases; the chemical shifts, the direct dipolar and the indirect spin–spin coupling constants have been determined. The direct dipolar coupling constants are consistent with rapidly interconverting energetically equivalent twisted conformations of C₂ symmetry. Under the assumption that only two such conformers are predominantly present, the angle between the phenyl and the maleimide planes is determined as 52.9±0.9°.     

Diamagnetic contribution and substituent effects on 13C n.m.r. spectra

Correction of measured chemical shifts by subtracting the diamagnetic contributions caused by certain substituents on various carbons of a molecule leads to data that allow a reasonable interpretation of substituent effects on chemical shifts in ¹³C n.m.r. spectroscopy. It is shown that both paramagnetic and diamagnetic terms increase on all carbons of a molecule when the atomic number of a substituent increases down the same group of the periodic table. An explanation of α-, β-, and γ- effects for methyl substitution using the same procedure is attempted.     

13C n.m.r. spectra of some pyrylium salts and related compounds

The ¹³C chemical shifts of several alkyl and phenyl substituted pyrylium perchlorates, together with related pyridine and pyridinium salts, are reported. The shifts in the isoelectronic series benzene, pyridine, pyrylium cation correlate well with charge densities calculated by INDO MO theory. Charge densities also account for the shift changes found at C-3, C-4 and C-5 for protonation of pyridine and 2,4,6-trimethylpyridine. The shift changes observed on protonation for C-2 and C-6, along the series pyridine, 2,4,6-trimethylpyridine and 2,4,6-triphenylpyridine can only be rationalized by consideration of both charge density and π-bond order changes. The effects of alkyl substitution on the shifts of the pyrylium cations are not accounted for by charge density changes. Empirical correlations of these shifts with literature data for the alkylbenzenes and the shifts of the phenyl substituted 6-membered heterocycles are discussed.     

Carbon-13 n.m.r. spectra of branched carboxylic acids and their derivatives

¹³C n.m.r. spectra have been measured for 39 compounds with branched structures including carboxylic acids, their methyl and ethyl esters, nitriles and chlorinated esters. The results obtained indicate that the ¹³ C n.m.r. technique is applicable to structure assignment of acids and their derivatives containing various numbers of substituents on the chain. The dependence of the carboxylic carbon chemical shift on the number and structure of α-positioned substituents has been determined. Calculation of the chemical shifts for branched carboxylic acids, esters and nitriles from the corresponding increments using the additivity scheme is shown to be possible in principle.     

13C n.m.r. spectra of some thiobenzamides. Correlation between 13C and 1H n.m.r. spectra and signal assignments of syn and anti CH2 groups

¹³C n.m.r. spectra of a series of N,N-disubstituted thioamides have been recorded and signal assignments were performed. Separate signals are observed for methylene groups fixed on the nitrogen atom. Since the carbon atom syn to the thiocarbonyl sulfur resonates at higher field than the anti carbon, the syn-anti assignment in ¹H n.m.r. is easily obtained by selective double irradiation. This method, which is rapid and reliable, affords a rather general solution to the interesting problem of resonance assignments in tertiary amides and thioamides (and in analogous molecules such as oximes and nitrosamines).     

Substituent effect of the nitro group on alkanes in carbon-13 n.m.r. spectroscopy

Linear correlation coefficients were obtained for the substituent effect of the nitro group in primary nitroalkanes. The solvent effect of chloroform is also discussed, as well as the influence of the scalar relaxation on the half-width of α-carbons in ¹³C n.m.r. spectroscopy.     

Carbon-13 n.m.r. analysis of selected strychnos alkaloids

The carbon-13 chemical shifts of strychnine and ten closely related analogues have been assigned and confirmed in several cases using selective proton decoupling techniques. Where additivity relationships are used the importance of having data on an array of structural analogues is emphasized. Quaternization at N-19 exerts long range polarization effects throughout the molecular framework. The effects of N-oxide formation on the carbon-13 shifts of 5 to 9-membered ring heterocycles and strychnine are discussed as aids to structural assignment. A Zwitterionic structure for strychnic acid is deduced.     

100 MHz n.m.r. spectra and conformational analysis of some methyl and trimethyl derivatives of 1-tetralone

The 100 MHz spectra of 2-methyl-, 4-methyl-, 4,5,8-trimethyl- and 4,5,7-trimethyl-1-tetralones have been analysed as 8-spin systems using iterative computation. The monomethyl derivatives exist in inverting half-chair conformations, the 2-methyl group favouring the equatorial site and the 4-methyl group showing equal preference for both axial and equatorial environments. The 5-methyl substituent of the trimethyl derivatives constrains the 4-methyl group to the axial site of rings which adopt non-half-chair conformations. The n.m.r. spectrum of 3-methyl-1-tetralone is also discussed.     

Steric effects in 29Si and 13C n.m.r. spectra of trimethylsiloxy-substituted benzenes

²⁹Si and ¹³C NMR spectra of trimethylphenoxysilane and three bis(trimethylsiloxy)benzenes have been investigated. Crowding in the ortho derivative leads to a small but observable deshielding of both silicon and carbon nuclei of the trimethylsiloxy group. In comparison to analogous effects observed in trimethylsilyl-substituted benzenes the oxygen link appears to increase the susceptibility of silicon to this steric effect but to decrease that of the methyl carbons. It is suggested that the operative steric interaction might not be that between the terminal methyl groups but involves the oxygen atom.     

Computer-aided n.m.r. spectra interpretation: Part 1. An artificial intelligence system

Some desirable hardware and software features of an artificial intelligence system tailored to the needs of a modern computerized n.m.r. laboratory are discussed. A system corresponding to this idea is described.