A nitrogen-15 nuclear magnetic resonance study of the tetracycline antibiotics

1991 ◽  
Vol 69 (5) ◽  
pp. 834-838 ◽  
Author(s):  
Ronald D. Curtis ◽  
Roderick E. Wasylishen
Keyword(s):  
Solid State ◽  
Conformational Changes ◽  
Structural Integrity ◽  
Chemical Shifts ◽  
Nuclear Magnetic Resonance Study ◽  
Keto Form ◽  
Tetracycline Antibiotics ◽  
Key Words Antibiotics ◽  
High Frequency Shift ◽  
First Time

Natural abundance 15N NMR has been used to study several tetracycline antibiotics in the solid state and in solution. In the solid state, the 15N chemical shifts of the tetracycline free bases are sensitive to the site of protonation in the "A" ring. A high frequency shift of 14 ppm is observed for the keto form of oxytetracycline (N protonated) relative to the enol form of oxytetracycline (O protonated). Comparison of 15N chemical shifts in the solid and solution states indicates for the first time that the structural integrity (site of protonation and hence conformation) of the tetracyclines is maintained in (CD3)2SO solutions. In addition, the solid state 15N CP/MAS NMR spectra are sensitive to subtle conformational changes of the "A" ring amide substituent. Key words: antibiotics, tetracyclines, 15N NMR, molecular structure.

A carbon-13 CP/MAS nuclear magnetic resonance study of several 1,4-disubstituted benzenes in the solid state

1989 ◽  
Vol 67 (3) ◽  
pp. 525-534 ◽  
Author(s):  
Glenn H. Penner ◽  
Roderick E. Wasylishen
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Solid State ◽  
Magnetic Resonance ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
Nuclear Magnetic Resonance Study ◽  
Solution Studies ◽  
Temperature Solution ◽  
Cp Mas Nmr ◽  
Nuclear Magnetic

The carbon-13 chemical shifts of several 1,4-disubstituted benzenes in the solid state are reported. At least one of the substituents is unsymmetrical and in most cases this leads to different 13C chemical shifts of C-2 and C-6 and in some cases to different shifts for C-3 and C-5. The 13C chemical shifts observed in the solid state are compared with those measured in solution and, where possible, with those obtained in low temperature solution studies where internal rotation of the unsymmetrical substituent is slow on the 13C chemical shift time scale. Agreement between the chemical shifts observed in the solid state and solution is excellent. The potential application of CP/MAS nuclear magnetic resonance in deducing the conformation of benzene derivatives with two unsymmetrical substituents is discussed. Keywords: carbon-13 CP/MAS NMR, 13C NMR chemical shifts, substituent effects.

Lupin alkaloids 6. Stereochemistry of bis-quinolizidine alkaloids with γ-oxo-α,β-enamine system

1994 ◽  
Vol 72 (1) ◽  
pp. 193-199 ◽  
Author(s):  
Tadeusz Brukwicki ◽  
Waleria Wysocka ◽  
Barbara Nowak-Wydra
Keyword(s):  
Conformational Changes ◽  
Chemical Shifts ◽  
Molecular Geometry ◽  
Coupling Constants ◽  
Hydroxyl Group ◽  
Coupling Constant ◽  
H Nmr ◽  
Time Signals ◽  
Low Sensitivity ◽  
First Time

1H nmr, 1H,1H and 1H,13C COSY, and 2D J-resolved spectra of multiflorine (1) and 13α-hydroxymultiflorine (2) in CDCl3 were taken. Some erroneously determined chemical shifts in 1 were corrected and for the first time signals in 2 were assigned. Most of the coupling constants in 1 and 2 were established. A coupling constant of H7–H17β and chemical shifts for H17β, C14, and C8 were used to define the conformational equilibrium of boat or chair forms in the C rings, in 1 and 2 in solution. The results obtained confirm the previous findings based on chemical shifts of C12: ca. 75 and 70% of the "boat" conformer in 1 and 2, respectively, at room temperature. Of all the criteria used, the H7–H17β coupling constant seems to be least sensitive to the influence of substituents at rings A and D. From the Haasnoot equation, torsion angles of HCCH in regions of molecular geometry featuring low sensitivity to conformational changes were calculated. The hydroxyl group at position 13α has a slight influence on the geometry of ring D.

A carbon-13 nuclear magnetic resonance study of solid tetracyclines

1987 ◽  
Vol 65 (2) ◽  
pp. 357-362 ◽  
Author(s):  
Sandra Mooibroek ◽  
Roderick E. Wasylishen
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Solid State ◽  
Magnetic Resonance ◽  
Pulse Sequence ◽  
Chemical Shifts ◽  
Nuclear Magnetic Resonance Study ◽  
Magic Angle ◽  
X Ray Diffraction ◽  
Magic Angle Sample Spinning ◽  
Nuclear Magnetic

Magic angle sample spinning and proton/carbon-13 cross-polarization techniques have been used to obtain high resolution solid state 13C nuclear magnetic resonance spectra of several tetracycline antibiotics. Carbon-13 resonances in the solid state are assigned by measuring the extent of dipolar broadening due to neighbouring quadrupolar nuclei and by using a pulse sequence that suppresses non-quaternary carbon resonances. The observed 13C chemical shifts are discussed in light of the known solid state structures derived from X-ray diffraction, and are compared with those in solution. It is shown that the solid state nuclear magnetic reosnance technique is capable of clearly distinguishing between the neutral and zwitterionic forms of the tetracycline free bases.

Solid-state nuclear magnetic resonance study of the structure of lanthanum phosphate crystals and glasses

2000 ◽  
Vol 15 (11) ◽  
pp. 2463-2467 ◽  
Author(s):  
Nancy E. Rashid ◽  
Brian L. Phillips ◽  
Subhash H. Risbud
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Solid State ◽  
Magnetic Resonance ◽  
Chemical Shifts ◽  
Nuclear Magnetic Resonance Study ◽  
Phosphate Glasses ◽  
Resonance Spectroscopy ◽  
X Ray Diffraction ◽  
Lanthanum Phosphate ◽  
Nuclear Magnetic

Lanthanum phosphate glasses were synthesized by melt quenching and characterized by x-ray diffraction, electron microprobe analysis, and solid-state nuclear magnetic resonance spectroscopy. A range of compositions near the metaphosphate composition (75 mol% P2O5) was examined. Comparison of 31P chemical shifts and shielding anisotropies of glasses with those of the crystalline phases of La(PO3)3 (metaphosphate) and LaP5O14 (pentaphosphate) were consistent with the presence of primarily chainlike Q2 phosphate groups.

Bis(1-phenyl-1-propyne) complexes of tungsten(II): crystal structures of [WI2(CO)(NCR)(η2-MeC2Ph)2] (R = Me, Et, or Ph)

2001 ◽  
Vol 79 (3) ◽  
pp. 263-271
Author(s):  
Paul K Baker ◽  
Michael GB Drew ◽  
Deborah S Evans
Keyword(s):  
Carbon Monoxide ◽  
Solid State ◽  
Crystal Structures ◽  
Octahedral Geometry ◽  
X Ray ◽  
X Ray Crystallography ◽  
Alkyne Complexes ◽  
First Time

Reaction of [WI2(CO)3(NCMe)2] with two equivalents of 1-phenyl-1-propyne (MeC2Ph) in CH2Cl2, and in the absence of light, gave the bis(1-phenyl-1-propyne) complex [WI2(CO)(NCMe)(η2-MeC2Ph)2] (1) in 77% yield. Treatment of equimolar quantities of 1 and NCR (R = Et, i-Pr, t-Bu, Ph) in CH2Cl2 afforded the nitrile-exchanged products, [WI2(CO)(NCR)(η2-MeC2Ph)2] (2-5) (R = Et (2), i-Pr (3), t-Bu (4), Ph (5)). Complexes 1, 2, and 5 were structurally characterized by X-ray crystallography. All three structures have the same pseudo-octahedral geometry, with the equatorial sites being occupied by cis and parallel alkyne groups, which are trans to the cis-iodo groups. The trans carbon monoxide and acetonitrile ligands occupy the axial sites. In structures 1 and 2, the methyl and phenyl substituents of the 1-phenyl-1-propyne ligands are cis to each other, whereas for the bulkier NCPh complex (5), the methyl and phenyl groups are trans to one another. This is the first time that this arrangement has been observed in the solid state in bis(alkyne) complexes of this type.Key words: bis(1-phenyl-1-propyne), carbonyl, nitrile, diiodo, tungsten(II), crystal structures.

Complexation of 7-azaindole by the methylmercury(II) cation

1992 ◽  
Vol 70 (12) ◽  
pp. 2914-2921 ◽  
Author(s):  
Nathalie Dufour ◽  
Anne-Marie Lebuis ◽  
Marie-Claude Corbeil ◽  
André L. Beauchamp ◽  
Pascal Dufour ◽  
...  
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Pyridine Ring ◽  
Coordination Mode ◽  
Pyrrole Ring ◽  
Chemical Shifts ◽  
Lone Pair ◽  
Major Influence ◽  
Large Displacements ◽  
Dmso Solution

Complexes of the types [CH3Hg(aza)], [CH3Hg(Haza)]X, and [(CH3Hg)2(aza)]X are obtained by reacting CH3HgOH and/or CH3HgX (X = NO3, ClO4) with 7-azaindole (Haza). The weakly acidic N1-H proton on the pyrrole ring is displaced by the hydroxide, whereas the perchlorate and nitrate salts lead to CH3Hg+ coordination to the N7 lone pair on the pyridine ring. Detailed analysis of the infrared spectra of the complexes and their N-deuterated derivatives provides diagnostic regions for eventual prediction of the coordination mode in other systems. All compounds are characterized by means of 1H, 13C, and 199Hg NMR spectra in DMSO solution and solid-state CP-MAS 13C spectra. Comparison of the solution and solid-state 13C spectra show that the species present in the solids remain undissociated in DMSO. Each type of complex can be identified from a characteristic pattern of large displacements of the ligand 13C signals. The 1H spectra are less informative because substitution of the N1-H proton by CH3Hg+ induces only minor shifts. Metal solvation appears to have a major influence on the 13C and 199Hg chemical shifts of the CH3Hg+ groups.

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