Conformation of ring A in triterpenoid ketones. Carbon-13 chemical shifts and spin-lattice relaxation times of lupane and 18α-oleanane derivatives

1989 ◽  
Vol 54 (7) ◽  
pp. 1928-1939 ◽  
Author(s):  
Miloš Buděšínský ◽  
Jiří Klinot
Keyword(s):  
Chemical Shifts ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Chair Conformation ◽  
Spin Lattice Relaxation ◽  
Spin Lattice ◽  
Structural Assignment ◽  
Boat Form ◽  
The One ◽  
C Nmr

13C NMR spectra of sixteen lupane and 19β,28-epoxy-18α-oleanane triterpenoids I-XVI were measured and a complete structural assignment of chemical shifts was made. For most compounds also the carbon spin-lattice relaxation times T1 were obtained. Characteristic differences in chemical shifts of some carbon atom signals were found between 2α-methyl-3-oxo and 2α-methyl-1-oxo derivatives II, V and VIII with chair conformation of the ring A on the one hand and their 2β-isomers III, VI and IX (boat form) on the other. Using these 2-methyl ketones as models, the chair-boat population in allobetulone (I), 3-oxo-28-lupanenitrile (IV) and 1-oxo derivative VII was determined. The results agree well with the data obtained by other physical methods.

The conformational equilibrium in [13C-1-methyl]-cis-1,4-dimethylcyclohexane

1980 ◽  
Vol 58 (23) ◽  
pp. 2709-2713 ◽  
Author(s):  
Harold Booth ◽  
Jeremy Ramsey Everett
Keyword(s):  
Conformational Equilibrium ◽  
Chemical Shifts ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Coupling Constants ◽  
Spin Lattice Relaxation ◽  
Spin Lattice ◽  
Nuclear Overhauser ◽  
In Cis ◽  
C Nmr

The conformational equilibrium in [13C-1-methyl]-cis-1,4-dimethylcyclohexane has been assessed by (a) direct integration of signals due to equatorial and axial methyl carbons in the 13C nmr spectrum at 172 K and (b) by measurement of the 13C chemical shifts of C-1 and C-4 in the spectrum at 300 K. It is concluded that a 13C isotope effect on the position of the degenerate equilibrium in cis-1,4-dimethylcyclohexane is either nonexistent, or is too small to be detected by methods of analyses employed. The 13C nmr data incidental to the study (chemical shifts, coupling constants, spin–lattice relaxation times, nuclear Overhauser enhancements, and 1-bond isotope shifts) are recorded for the title compound and its trans-isomer.

Keto-Enol Tautomerism of Dimedone Studied by Dynamic NMR

1996 ◽  
Vol 50 (11) ◽  
pp. 1408-1412 ◽  
Author(s):  
Antonio Martínez-Richa ◽  
Guillermo Mendoza-Díaz ◽  
Pedro Joseph-Nathan
Keyword(s):  
High Resolution ◽  
Chemical Shifts ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Tautomeric Equilibrium ◽  
Spin Lattice Relaxation ◽  
Exponential Factor ◽  
Spin Lattice ◽  
C Nmr ◽  
Coalescence Temperature

The keto-enol tautomeric equilibrium of dimedone has been investigated by high-resolution 13C NMR spectroscopy. Kinetic information of the solution keto-enol tautomerism for dimedone in DMSO, in the temperature range of 25–85 °C, was derived from line shape measurements in a 75-MHz spectrometer. A value of 3.43 Kcal/mol was found for the Arrhenius activation energy Ea and of 1.07 × 106 s−1 for the pre-exponential factor A. With the use of the observed chemical shifts in the high-resolution 13C-NMR spectra of dimedone in the solid state, an estimate coalescence temperature of 240 K for dimedone in DMSO was obtained by extrapolation of the experimental curve. The estimated free energy of activation at the coalescence temperature, Δ Gc≠, is 10.8 Kcal/mol. Finally, the 13C spin-lattice relaxation times, T1(13C), in solid dimedone were measured as a function of temperature in the range of 25 to 90 °C. The data are discussed in terms of the different motional environments that result from the geometric restrictions imposed by hydrogen bonding in the crystal structure.

A 35CL NQR Spin-Lattice Relaxation Study on the Motion of D4h Anions in [C(NH2)3]2PdCl4, [C(NH2)3]2PtCl4, and [C(NH2)3]AuCl4

1986 ◽  
Vol 41 (1-2) ◽  
pp. 416-420
Author(s):  
Yoshihiro Furukawa ◽  
Daiyu Nakamura
Keyword(s):  
Relaxation Times ◽  
Sharp Decrease ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Temperature Dependent ◽  
Spin Lattice ◽  
35Cl Nqr ◽  
The One ◽  
Increasing Temperature ◽  
Complex Anions

The temperature dependence of 35Cl NQR spin-lattice relaxation times T1ClQ was observed for the crystal of the title complexes. For the Pd(II) and Pt(II) complexes, the log T1ClQ vs. 103 T-1 curves having gentle positive gradients at lower temperatures decreased sharply with increasing temperature from ca. 150 and ca. 130 K, respectively. This sharp decrease of T1ClQ can be explained by the C4 reorientation of the D4h complex anions with the activation energy Ea of 34 kJ mol-1 for the former and 29 kJ mol-1 for the latter complex. These values agree well with those estimated from 1H T1 showing temperature dependent dipolar-quadrupolar cross relaxation. For the Au(III) salt, two of four 35Cl NQR lines showed a sharp decrease in T1ClQ from ca. 270 K, suggesting the onset of the C4 reorientation of the one kind crystallographically equivalent anions with Ea of 67 kJ mol-1.

Germanium-73 chemical shifts and spin-lattice relaxation times of some tetrasubstituted germanes

1984 ◽  
Vol 23 (23) ◽  
pp. 3835-3836 ◽  
Author(s):  
Yoshito Takeuchi ◽  
Toshie Harazono ◽  
Norihiro Kakimoto
Keyword(s):  
Chemical Shifts ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Spin Lattice

Solitons, polarons and their dynamics in mixed-valence halogen-bridged MX-chains

2007 ◽  
Vol 366 (1862) ◽  
pp. 93-100 ◽  
Author(s):  
Shinya Takaishi ◽  
Masahiro Yamashita
Keyword(s):  
Mixed Valence ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Relaxation Processes ◽  
Spin Lattice ◽  
H Nmr ◽  
Spin Resonance ◽  
1D Chain ◽  
The One

This article describes the photo-generation processes of elementary excitations such as solitons and polarons, and their dynamics in the one-dimensional (1D) halogen-bridged Pt compound [Pt(en) 2 Br](ClO 4 ) 2 . Spin-solitons were photo-generated via relaxation processes of CT excitons and self-trapped excitons, made evident by photo-induced absorption and photo-induced electron spin resonance spectra. Polarons were not generated from CT excitons. Diffusion of spin-solitons on the 1D chain was studied quantitatively by analysing 1 H NMR spin-lattice relaxation times ( T 1 ).

13C Fourier transform nuclear magnetic resonance. XII. Structure of the phytol–lecithin bilayer. Application of electric field effects

1976 ◽  
Vol 54 (13) ◽  
pp. 2059-2067 ◽  
Author(s):  
Robert J. Cushley ◽  
Bruce J. Forrest
Keyword(s):  
Electric Field ◽  
Chemical Shifts ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Hydrocarbon Chain ◽  
Spin Lattice Relaxation ◽  
Head Group ◽  
Electric Field Effect ◽  
Spin Lattice ◽  
Lipid Head Group

Phytol has been incorporated into lecithin bilayers. 13C spin–lattice relaxation times, which have been measured for both components of the model membrane, indicate a marked destabilization of the bilayer due to intercalated phytol. The disruption of normal phospholipid packing is due to the highly branched nature of the phytyl hydrocarbon chain. In addition, the position of phytol in the bilayer has been determined by means of a linear electric field effect of the polar lipid head group upon the 13C chemical shifts of the phytol olefinic carbons.

Activation Energies for Fluxional Behavior in Aryl(pentachlorocyclopentadienyl)mercurials, η1 -C5Cl5 HgR, from 35Cl NQR Relaxation Times

1990 ◽  
Vol 45 (3-4) ◽  
pp. 503-510 ◽  
Author(s):  
Norbert Weiden ◽  
Alarich Weiss ◽  
Gary Wulfsberg ◽  
William Ilsley ◽  
William Ilsley ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Lattice Relaxation Time ◽  
Activation Energies ◽  
Spin Lattice Relaxation ◽  
Spin Lattice ◽  
35Cl Nqr ◽  
C Nmr ◽  
Phenyl Mercury

Abstract Solid-state activation energies for fluxional behavior in three aryl-subsituted (pentachlorocyclo-pentadienyl)phenylmercury compounds RHgC5 Cl5 : (pentachlorocyclopentadienyl)(pentamethyl-phenyl)mercury (I, R = C6 (CH3)5 , Eact = 19.3 kJ mol-1); (pentachlorocyclopentadienyl)(2,4,6-tris-(terf-butyl)phenyl)mercury (II, R = 2,4,6-C 6 H 2 (C(CH3)3)3 , Eact = 59.5 kJ mol-1); and (pentachloro-cyclopentadienyl)(phenyl)mercury (III, R = C6H5 , E act = 62.8 kJ mol-1) have beeb obtained from 35Cl NQR spin-lattice relaxation-time measurements. II has also been shown to be fluxional in solution by 13C NMR spectra. II was prepared by an exchange reaction between Hg(C5Cl5)2 and Hg(2,4,6-C6H2(C(CH3)3)3)2 , which reacted readily despite the great steric hindrance present in the latter reagent.

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