1H, 13C and 15N NMR spectra of ciprofloxacin

1H NMR assignment, including the values of delta(H) and J(H,H) for the cyclopropane moiety, and 13C NMR and 15N NMR spectral data for ciprofloxacin are presented.     

13C and 15N NMR spectra of aminobenzimidazoles in solution and in the solid state

The ¹³C [hexadeutero‐dimethylsulfoxide (DMSO‐d₆), hexamethyl‐phosphoramide (HMPA)‐d₁₈and solid‐state] and ¹⁵N (solid‐state) NMR spectra of six C‐aminobenzimidazoles have been recorded. The tautomerism of 4(7)‐aminobenzimidazoles and 5(6)‐aminobenzimidazoles has been determined and compared with B3LYP/6‐311 + + G(d,p) calculations confirming the clear predominance of the 4‐amino tautomer and the slight preference for the 6‐amino tautomer. GIAO‐calculated absolute shieldings compare well with experimental chemical shifts. Copyright © 2008 John Wiley & Sons, Ltd.     

1H, 2H and 13C NMR spectra and molecular dynamics of some solid alkylene-aromatic polyesters

Molecular dynamics of some mesomorphic main–chain alkylene–aromatic polyesters have been investigated by means of NMR spectra of various nuclei over a wide temperature range. In solid polymers regions of different molecular mobilities coexist and their fractions are determined by the sample temperature and thermal history. The sample annealing leads to the growth of rigid fraction. It was found that below the glass transition temperature the only forms of large–scale mobility are the torsional vibrations and flips of para–phenylene groups, while spacer groups are virtually rigid. Above the glass temperature almost all phenylene rings undergo flipping motions and methylene groups of the spacer take part in complicated motions of both anisotropic and isotropic character.     

1H, 13C and 15N NMR assignments of phenazopyridine derivatives

Phenazopyridine hydrochloride (1), a drug in clinical use for many decades, and some derivatives were studied by one- and two-dimensional (1)H, (13)C and (15)N NMR methodology. The assignments, combined with DFT calculations, reveal that the preferred protonation site of the drug is the pyridine ring nitrogen atom. The chemoselective acetylation of phenazopyridine (2) and its influence on the polarization of the azo nitrogen atoms were evidenced by the (15)N NMR spectra. Molecular calculations of the phenazopyridines 2-4 show that the pyridine and phenyl groups are oriented in an antiperiplanar conformation with intramolecular hydrogen bonding between the N-b atom and the C-2 amino group preserving the E-azo stereochemistry.     

1H, 13C and 15N NMR spectra of [1,2-15N2]pyrazole derivatives

The chemical shifts and coupling constants of [1,2-¹⁵N₂]pyrazole, 2-(1-[1,2- ¹⁵N₂]pyrazolyl)-2-[l,3-²H₆]propanol, 1-nitro[1,2¹⁵N₂] and 3-nitro[1,2-¹⁵N₂]pyrazole are reported.     

A 1H, 13C and 15N NMR study in solution and in the solid state of six N-substituted pyrazoles and indazoles

Three N-substituted pyrazoles and three N-substituted indazoles [1-(4-nitrophenyl)-3,5-dimethylpyrazole (1), 1-(2,4-dinitrophenyl)-3,5-dimethylpyrazole (2), 1-tosyl-pyrazole (3), 1-p-chlorobenzoylindazole (4), 1-tosylinda-zole (5) and 2-(2-hydroxy-2-phenylethyl)-indazole (6)] have been studied by NMR spectroscopy in solution (1H, 13C, 15N) and in the solid state (13C, 15N). The chemical shifts have been compared with GIAO/DFT calculated absolute shieldings. Some discrepancies have been analyzed.     

Structure of N,N'-bis(amino acids) in the solid state and in solution. A 13C and 15N CPMAS NMR study

Three bis(amino acids) linked by the amino groups have been prepared and structurally characterized. We have named them Gly-Gly, Ala-Ala and Gly-Ala (or Ala-Gly). These compounds have been characterized by NMR both in solution and in the solid state. They exist as zwitterions with the ammonium group proximal to the carboxylate anion. In the case of Gly-Ala, a dynamic situation is observed by CPMAS NMR ((13)C and (15)N) corresponding to a double proton migration between two proximal tautomers.     

1H, 13C and 15N NMR spectroscopy and tautomerism of nitrobenzotriazoles

Benzotriazole nitro derivatives were prepared by nitration of the corresponding benzotriazoles and by methylation or cyclization of appropriate nitro‐1,2‐phenylenediamines. Structures and tautomerism of the nitrobenzotriazoles were studied by multinuclear ¹H, ¹³C, ¹⁵N, and 2D NMR spectroscopy and quantum chemistry. Copyright © 2008 John Wiley & Sons, Ltd.     

13C,15N]2-Acetamido-2-deoxy-D-aldohexoses and their methyl glycosides: synthesis and NMR investigations of J-couplings involving 1H, 13C, and 15N

[reaction: see text] A series of 2-amino-2-deoxy-D-[1-13C]aldohexoses and their methyl glycosides was prepared with use of a simplified cyanohydrin reduction route. Four d-aldopentosylamines (arabino, lyxo, ribo, xylo) were prepared from the corresponding D-aldopentoses by reaction with NH3(g) in MeOH solvent, isolated in solid form, and characterized by 13C and 1H NMR. Hydrolysis of beta-D-xylopyranosylamine was studied using 13C-labeled substrates to establish optimal solution conditions for cyanohydrin formation. Major hydrolytic intermediates were observed and identified by time-lapse 1D and 2D NMR analyses of reaction mixtures. The aldopentosylamines were subsequently employed in cyanohydrin reduction reactions with K13CN to yield C2-epimeric [1-13C]2-aminosugars, which were separated by chromatography on ion-exchange columns. N-Acetylation and methyl glycosidation followed by chromatography gave pure 2-acetamido-2-deoxy-D-[1-13C]aldohexopyranosides. J(CH) and J(CC) spin-spin coupling constants involving the labeled anomeric carbon were measured and compared to those observed previously in methyl D-[1-13C]aldohexopyranosides. In parallel studies, theoretical J-couplings were calculated in model N-acetylated aldopyranosides using density functional theory (DFT) to predict the effect of OH vs NHCOCH(3) substitution at C2 on J(CH) and J(CC) values in aldopyranosyl rings. The synthetic method was also modified to accommodate (15)N- and (13)C-labeling within the N-acetyl side-chain, and some J-couplings involving 1H, 13C, and 15N atoms in 2-[1,2-13C2;15N]acetamido-2-deoxy-D-[1-13C]glucose were measured and interpreted.     

1H, 13C,and 15N NMR spectra of some pyridazine derivatives

¹H, ¹³C, and ¹⁵N NMR chemical shifts for pyridazines 4–22 were measured using 1D and 2D NMR spectroscopic methods including ¹H? ¹H gDQCOSY, ¹H? ¹³C gHMQC, ¹H? ¹³C gHMBC, and ¹H? ¹⁵N CIGAR–HMBC experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

Conformations and 13C NMR chemical shifts of some polyamides in the solid state as studied by high-resolution 13C NMR spectroscopy

High-resolution ¹³Carbon nuclear magnetic resonance (NMR) spectra of Nylons 4, 6, and 66 in the solid state were measured over a wide range of temperature. From the results, it was found that resonance lines of crystalline and noncrystalline components were separable and their chemical shifts were determined. The ¹³C chemical shift behavior is closely related to their conformation. The origin of the conformational effects on the chemical shifts is discussed.     

1H, 13C and 15N NMR spectral assignments for new triazapentalene derivatives

Mesomeric heteropentalene betaines are conjugated fused polyheterocyclic structures that represent interesting intermediates for organic synthesis. Five such structures, containing at least four nitrogen atoms and various substituents, have been characterized by ¹H, ¹³C and ¹⁵N NMR. We report, apparently for the first time, nitrogen NMR data and coupling information on such systems. Inter‐ring long‐range correlations across five bonds with ¹⁵N (⁵J_HN) and up to seven bonds with ¹³C (⁶J_HC and ⁷J_HC) were observed in HSQC experiments. The incorporation of an electron‐withdrawing substituent such as NO₂ was observed to cause an increase in the magnitude of the remote couplings and deshielding of nearby protons, carbons and on all nitrogen atoms of the structure, including remote ones situated on other cycles. Copyright © 2009 John Wiley & Sons, Ltd.     

Intramolecular interactions in nitroamines studied by 1H, 13C, 15N and 17O NMR spectral and quantum chemical methods

¹H, ¹³C, ¹⁵N and ¹⁷O NMR chemical shifts are used for the characterization of the intramolecular interactions in several nitramines of the Me₂N-G-NO₂ type. The charge of lone electron pair of the amino group in N,N-dimethylnitramine, N,N-dimethyl-2-nitroethenamine, N,N-dimethyl-p-nitroaniline, 4-nitro-β-dimethylaminostyrene, 4-N,N-dimethylamino-β-nitrostyrene, 4-(N,N-dimethylamino)-4′-nitrobiphenyl, and 4-(N,N-dimethylamino)-4′-nitrostilbene is transferred not only to the nitro oxygens, but also to the vinylene and benzene carbons of the G spacer and to N-methyl carbons as well. Decreased nuclear shielding is found to be qualitatively related to the decreased atomic charge around a nucleus. This finding was further verified and quantified by comparison of the NMR data with those obtained by ab initio quantum chemical calculations. ¹⁷O NMR chemical shift changes seem to be more significant when the interacting NMe₂ and NO₂ groups are separated by a short spacer. On the other hand, ¹⁵N NMR chemical shifts suggest that a decrease of the charge at the amino nitrogen is not related to the length of the spacer alone. A lack of the linear dependence between the ¹⁷O_nitro and ¹⁵N_amino chemical shifts suggests that the charge lost by the amino nitrogen was only partially gained by the oxygens in the nitro group. The increased shieldings of the aryl carbons in 4-(N,N-dimethylamino)-4′-nitrobiphenyl indicate that atoms of the p,p-biphenylene spacer also gain some charge originating from the amino nitrogen. ³ J _H,H spin–spin coupling constant shows that among different vinylene compounds, the charge transfer to the nitro group is practically effective only in N,N-dimethyl-2-nitroethenamine where the bond between the vinylene carbons is significantly of low order by character. The calculated Natural Population Analysis (NPA) data confirms that except the nitro oxygens, other atoms that receive the negative charge lost by NMe₂ in the compounds studied are the aryl and N-methyl carbons.     

Structure of ultrahigh-molecular-weight polyethylene in the solid state as studied by variable-temperature 13C CP/MAS NMR spectroscopy

In order to obtain some insight into the structure of an ultrahigh-molecular-weight polyethylene sample, ¹³C CP/MAS NMR experiments have been carried out at temperatures from 23 to ?108°C. The peak for the crystalline component moves upfield with a decrease in temperature, which is contrary to what was reported previously for a melt-crystallized polyethylene sample. On the basis of x-ray diffraction results and quantum-chemical calculations, it is suggested that the methylene carbons are in the distorted orthorhombic form at low temperatures.     

Polymorphism of N,N'-diacetylbiuret studied by solid-state 13C and 15N NMR spectroscopy, DFT calculations, and X-ray diffraction

The molecular configuration and crystal structure of solid polycrystalline N,N′′‐diacetylbiuret (DAB), a potential nitrogen‐rich fertilizer, have been analyzed by a combination of solid‐ and liquid‐state NMR spectroscopy, X‐ray diffraction, and DFT calculations. Initially a pure NMR study (“NMR crystallography”) was performed as available single crystals of DAB were not suitable for X‐ray diffraction. Solid‐state ¹³C NMR spectra revealed the unexpected existence of two polymorphic modifications (α‐ and β‐DAB) obtained from different chemical procedures. Several NMR techniques were applied for a thorough characterization of the molecular system, revealing chemical shift anisotropy (CSA) tensors of selected nuclei in the solid state, chemical shifts in the liquid state, and molecular dynamics in the solid state. Dynamic NMR spectroscopy of DAB in solution revealed exchange between two different configurations, which raised the question, is there a correlation between the two different configurations found in solution and the two polymorphic modifications found in the solid state? By using this knowledge, a new crystallization protocol was devised which led to the growth of single crystals suitable for X‐ray diffraction. The X‐ray data showed that the same symmetric configuration is present in both polymorphic modifications, but the packing patterns in the crystals are different. In both cases hydrogen bonds lead to the formation of planes of DAB molecules. Additional symmetry elements, a two‐fold screw in the case of α‐DAB and a c‐glide plane in the case of β‐DAB, lead to a more symmetric (α‐DAB) or asymmetric (β‐DAB) intermolecular hydrogen‐bonding pattern for each molecule.     

13C and 15N NMR spectra of 2,3-substituted 2H-azirines

The ¹³C and ¹⁵N NMR spectra of a series of 2,3-substituted 2H-azirines have been studied. The ¹⁵N chemical shift for the nitrogen in the azirine ring is found at much higher field than in acyclic imines with a considerable electronic effect for the substituents on the double bond. Cooperative steric and electronic effects associated with substituents on the unsaturated carbon atom of the ring were found to influence the shielding of the ¹³C and ¹⁵N nuclei. Reaction constants have been calculated for 2-alkyl(aryl)-3-phenylazirines. It has been shown that the azirine ring has a powerful —I effect (when compared with the phenyl ring) that exceeds the analogous value for the cyano group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1181–1183, September, 1986.     

Derivatives of pyrazinecarboxylic acid: 1H, 13C and 15N NMR spectroscopic investigations

NMR spectroscopic studies are undertaken with derivatives of 2‐pyrazinecarboxylic acid. Complete and unambiguous assignment of chemical shifts (¹H, ¹³C, ¹⁵N) and coupling constants (¹H,¹H; ¹³C,¹H; ¹⁵N,¹H) is achieved by combined application of various 1D and 2D NMR spectroscopic techniques. Unequivocal mapping of ¹³C,¹H spin coupling constants is accomplished by 2D (δ,J) long‐range INEPT spectra with selective excitation. Phenomena such as the tautomerism of 3‐hydroxy‐2‐pyrazinecarboxylic acid are discussed. Copyright © 2009 John Wiley & Sons, Ltd.