Nitrogen-15 n.m.r. studies of 13C, 15N labeled arginine

¹⁵N n.m.r. spectra of [¹³C-2, 3-¹⁵N₂-guanidino]arginine and [¹³C, ¹⁵N₂] urea were obtained in D₂O and H₂O at a variety of pH values both with and without proton decoupling. The effects of the proton exchange rate are readily observable in the proton coupled ¹⁵N spectra. When the guanidino group is deprotonated (pK = 12.5), the terminal nitrogens give a single resonance 6.6 ppm downfield of the protonated species, indicating a rapid tautomeric exchange. The observed NH and CN couplings are compared with calculated values, and good agreement is found for ¹J(CN) using a Blizzard–Santry type calculation. The ramifications of the proton exchange on ¹⁵N n.m.r. spectra of amino acids and peptides are discussed.     

Carbon-13 n.m.r. studies of methylquinolines and methylisoquinolines

Spectra are reported for all seven methylquinolines, nine dimethylquinolines, six methylisoquinolines and one dimethylisoquinoline. Substituent effects for the α, ortho, meta, para, vinylogous para and peri positions are reported for the monomethylcompounds. Additivity of these substituent effects is demonstrated for the dimethyl compounds which also exhibit a vicinal dimethyl steric effect.     

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.     

N.m.r. studies on aromatic compounds. I—13C n.m.r. spectra of some mono- and disulpho-substituted hydroxycarboxylic acids

Carbon-13 n.m.r. spectra of 3-hydroxy-4-sulpho-2-naphthoic, 3-hydroxy-5-sulpho-2-naphthoic, 3-hydroxy-7-sulpho-2-naphthoic, 5-sulphosalicylic, 3-hydroxy-5,7-disulpho-2-naphthoic, 1-hydroxy-4,7-disulpho-2-naphthoic, and 3,5-disulphosalicylic acids were recorded with and without proton noise-decoupling. Analyses of the spectra were carried out for all compounds except 3-hydroxy-5-sulpho-2-naphthoic acid which dimerized. The fine splitting caused by long-range coupling was used in identifying the lines of the ¹³C n.m.r. spectra.     

Nuclear magnetic resonance studies: VII—13C and 15N n.m.r. of diazo compounds

The ¹³C and ¹⁵N n.m.r. results for a series of diazo compounds are reported. It is found that the diazo carbon is shielded by an extraordinary amount compared with normal sp² hybridized carbons. The ¹⁵N chemical shifts reveal that the terminal nitrogen is deshielded relative to the central one. This is contrary to that expected from charge effects but support is found for this phenomenon in other systems. One-bond ¹³C? ¹⁴N coupling in diazomethane is also reported for the first time. INDO MO calculations of the charges and finite perturbation calculations of ¹³C? ¹⁴N and C? H couplings are compared with the experimental results.     

N.m.r. studies in the heterocyclic series: XVI—determination of the structure of 3-azidoindazole by 1H and 13C n.m.r. spectroscopy

The 1-NH structure for 3-azidoindazole has been demonstrated by the observation of ¹H? ¹H and ¹³C? ¹H couplings involving the hydrogen atom attached to nitrogen. A comparison between 3-azidoindazole and indazole shows that both compounds have the same tautomeric structure.     

Carbon-13 n.m.r. studies of substituted bisalkylamino-s-triazines in acidic media

The carbon-13 n.m.r. spectra of six substituted bisalkylamino-s-triazines are reported. The site of protonation of 2-methoxy-s-triazines is shown to be at N-1 or N-3. The effect of trifluoroacetic acid on 2-chloro-s-triazines is also discussed.     

15N and 13C n.m.r. study of azimines and azoxybenzenes

¹⁵N chemical shifts, ¹J(NN), ¹J(NC) and ²J(NC) coupling constants have been used to prove the open chain structure and configuration of cis- and trans-2,3-diphenyl-1-phthalimidoazimines. For comparison, the corresponding data of the iso-π-electronic cis- and trans-azoxybenzenes are also reported and discussed.     

13C n.m.r. studies of some phenanthrene and fluorene derivatives

The ¹H and ¹³C spectra of fluorene, fluorenone, phenanthrene and their 4-methyl and 4,5-dimethyl derivatives have been examined. To complete the analyses for fluorenone and 4-methylfluorenone, ¹H spectra were recorded at 270 MHz. The results from the ¹H spectra permitted unequivocal assignments for the protonated aryl carbons by selective proton decoupling. A consistent set of assignments for the quaternary carbons was obtained through consideration of the dominant relaxation processes operative at these centres. This series of compounds was examined to investigate the shielding effects produced by the close approach of methyl groups separated by five bonds for comparison with the contrasting trends found for methyl carbons separated by three and four bonds. The results indicate that the relative orientation of the methyl groups is an extremely critical factor governing their shieldings and those of neighboring centres.     

15N n.m.r.: Substituent effects on nitrogen chemical shifts in anilinium ions

¹⁵N chemical shifts were measured in a series of anilinium fluorosulfonate salts and compared with chemical shift data from a comparable series of ¹⁵N-enriched aniline derivatives. A smaller overall range of nitrogen chemical shifts was observed for the protonated aniline series compared with that for the unprotonated anilines and is attributed to the elimination of nitrogen lone pair delocalization in the former series. Further-more, it was found that the range of nitrogen chemical shifts in the protonated anilines is determined primarily by substituent electronic effects from the ortho ring position with almost negligible contributions from the para position.     

Carbon-13 n.m.r. studies of some saturated 1,2-oxazepine derivatives

The influence of incorporating an group, an oxygen atom and the fragment in a saturated 7-membered ring system on carbon-13 n.m.r. chemical shifts is examined, and also, the influence of the dioxolane ring moiety on the ¹³C chemical shifts in these ring systems. Substituent effects are generally additive except in cases where the ring is heavily substituted with methyl groups. A large upfield steric shift (γ effect) of 7–8 ppm is observed in two of the derivatives. An example of long range nonequivalence is also observed. Assignments of the ¹³C n.m.r. spectra have been made by comparison with model compounds, and from proton coupled ¹³C n.m.r. spectra. The synthesis of several new compounds is described.     

N.m.r. studies of the keto–enol tautomerism of acylthioacetamides

Acetylthioacetamides exist as different keto and enol isomers in chloroform solutions. The keto form with intramolecular hydrogen bonding between the NH and the carbonyl group is the dominant keto isomer. On the other hand the enol forms with intramolecular hydrogen bonding between the OH and the thioketo group are the dominant enol isomers in the temperature range 60°C to ?60°C. The thermodynamic data of the keto-enol equilibria were obtained by measuring the intensities of appropriate high resolution proton signals as a function of temperature. At low temperatures all lines characteristic of the enol forms are doubled in the N-phenyl-substituted derivatives because the rotation of the NH? C₆H₅ group around the C? N bond becomes slow and the chemical shifts characteristic of the E and Z isomers are different. We estimated approximate thermodynamic data of the E/Z equilibrium in some of the compounds. The changes of the line shape as well as the chemical shifts as a function of temperature indicate the presence of various additional exchange processes. In order to obtain further information we performed curve fittings of the chemical shifts of one acetylthioacetanilide and of a series of monothio-β-diketones (studied in another paper) assuming a fast two site exchange process. On the basis of the results obtained a reaction scheme for N-substituted acylthioacetanilides in solution is proposed.     

Synthesis and phosphorus 31 n.m.r studies of neutral and cationic compounds with platinum-mercury bonds

Summary The preparation and properties of the following neutral and cationic compounds containing Pt-Hg bonds is described: [(PPh₃)₂ClPt-HgR] (R=2,4,6-C₆H₂Cl₃; 2,3,4,6- and 2,3,5,6-C₆HCl₄ and C₆Cl₅), and [(PPh₃)₂LPt-Hg(C₆Cl₅)]ClO₄ (L=pyridine, , and -picoline; 2,4-lutidine and -colidine). All the compounds have been characterized by³¹P n.m.r. spectroscopy. The dependence of P, J(³¹P-¹⁹⁵Pt) and²J(³¹P-¹⁹⁹Hg) on the slight changes of the electronic properties of the ligands L and R has been studied.     

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).     

Carbon-13 n.m.r. studies: 68—diastereomeric nonequivalence and the characterization of some bisnorbornylpinacols

The sodium-ammonia reduction of racemic norcamphor, exo-3-methylnorcamphor and 3,3-dimethyl-norcamphor (camphenilone) leads to substantial yields (60–90%) of the corresponding 2,2′-bisnorbornyl-2,2′-diols as diastereomeric mixtures. A combination of their ¹H, ¹³C and infrared spectra together with the results of periodic acid and lead tetraacetate oxidations permits stereochemical assignments for these six pinacols.     

Carbon-13 n.m.r. characterization of indenyllithium in solution

¹³C N.m.r. chemical shifts obtained for indenyl- and cyclopentadienyllithium in several, mostly ethereal, solvents are presented. The chemical shift changes induced by varying the solvent are assumed to probe the actual π-electron density distribution, thus providing an insight into the structure of the ion-pair. The increase in the estimated π-electron densities obtained for the protonated aromatic carbons of indenyllithium by increasing the coordinating ability of the solvent gives evidence of a change of the ion-pair equilibrium towards solvent-separated species. The average chemical shifts for indenyl- and cyclopentadienyllithium were independent of the choice of solvent, a fact which supports the ion-pair model in all studied media.     

N.m.r. studies in the heterocyclic series: XVII—carbon-13 spectra of indazole derivatives

The ¹³C chemical shifts of 17 indazole derivatives are discussed as a function of substituent effects and the N-1—H or N-2—H structure of indazole. The presence in solution of the N-1—H tautomer is confirmed.     

1H n.m.r. studies on intramolecular hydrogen bonding in anilides of 6-methylpicolinic acid N-oxide

The ¹H n.m.r. spectra of eleven anilides of 6-methyl-picolinic acid N-oxide in chloroform were obtained. The influence of temperature, concentration and substituents on the chemical shifts of the N? H protons was investigated. The structure of the anilides is discussed.