Preparation and Conformational Study of 19β,28-Epoxy-18α-olean-5-ene Derivatives

2006 ◽  
Vol 71 (3) ◽  
pp. 387-410 ◽  
Author(s):  
Martin Dračínský ◽  
Václav Richtr ◽  
Václav Křeček ◽  
Jan Sejbal ◽  
Jiří Klinot ◽  
...  
Keyword(s):  
Double Bond ◽  
Coupling Constants ◽  
Conformational Study ◽  
Hydrogen Atoms ◽  
Vicinal Coupling Constants ◽  
Starting Compound ◽  
New Type ◽  
Type 3

New oleanane type triterpenoids with the 5(6) double bond were prepared using partial demethylation on carbon C-4. The starting compound was 23-hydroxybetulin (1b) and the key reaction was the methylation of 19β,28-epoxy-24-nor-18α-olean-4-en-3-one (3b). The 5(6) double bond was used in preparation of new derivatives with an epoxy or oxo substituent in ring B. The conformation of ring A of new type 3-oxo oleanane derivatives with a double bond or a substituent on ring B was elucidated from vicinal coupling constants of hydrogen atoms in positions 1 and 2.

Preparation and Conformational Study of B-Ring Substituted Lupane Derivatives

2006 ◽  
Vol 71 (8) ◽  
pp. 1131-1160 ◽  
Author(s):  
Martin Dračínský ◽  
Simona Hybelbauerová ◽  
Jan Sejbal ◽  
Miloš Buděšínský
Keyword(s):  
Double Bond ◽  
Hydroxy Group ◽  
Molecular Modelling ◽  
Nmr Spectra ◽  
Hydroxy Derivative ◽  
Secondary Hydroxy Group ◽  
Conformational Study ◽  
Primary Hydroxy Group ◽  
Type 3 ◽  
C Nmr

New lupane-type triterpenoids with 5(6) double bond were prepared using the method of partial demethylation on carbon C-4. Hydroboration of the double bond led to 6α-hydroxy derivative. By the oxidation and following reduction of 6α-hydroxy derivative the 6-oxo and 6β-hydroxy derivatives were prepared. A new method for selective oxidation of secondary hydroxy group in the presence of primary hydroxy group was performed. The conformation of ring A of new lupane-type 3-oxo derivatives with a substituent on ring B was elucidated on the bases of 1H and 13C NMR spectra and molecular modelling.

Conformational analysis of acyclic compounds with oxygen–sulphur interactions. Part VI. Some 1-thioderivatives of 2-propanol and its acetates

1979 ◽  
Vol 57 (18) ◽  
pp. 2426-2433 ◽  
Author(s):  
Felipe Alcudia ◽  
José L. García Ruano ◽  
Jesús Rodríguez ◽  
Félix Sánchez
Keyword(s):  
Conformational Analysis ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
Conformational Study ◽  
Conformational Preference ◽  
Methyl Group ◽  
Opposite Charge ◽  
H Nmr ◽  
Vicinal Coupling Constants

A conformational study of 1-X-2-propanol (X = SH, SMe, SOMe, SO2Me, +SMe2) and their O-acetyl derivatives (X = SMe, SOMe, SO2Me, and +SMe2) is reported. From the relative values of the vicinal coupling constants in 1H nmr spectra it has been possible to establish the conformational preference. When a density of opposite charge is supported by heteratoms, polar factors determined a great predominance of that conformation in which the sulphur function has an anti-relationship with respect to the methyl group. In thiol and thioethers the conformational preference is not so marked.

Molecular asymmetry in sugar derivatives

1975 ◽  
Vol 28 (3) ◽  
pp. 687 ◽  
Author(s):  
RE Gall ◽  
L Tarasoff
Keyword(s):  
Coupling Constants ◽  
Hydrogen Atoms ◽  
Vicinal Coupling Constants ◽  
Molecular Asymmetry ◽  
Sugar Derivatives ◽  
Derivatives Of

The N.M.R. spectra of a series of derivatives of the four trihydroxyglutaric acids (1)-(4) have shown non-equivalence of the hydrogen atoms attached to C 2 and C 4 in the D- and L-arabino series (3) and(4) which is not observed in the derivatives of symmetrical D- ribo and D-xylo acids (1) and (2). Vicinal coupling constants have led to predictions regarding the major conformations.

Gradient-Enhanced Inverse-Detected NMR Techniquesfor Determination of 1H-15N Coupling Constants in 2,2-Dimethylpenta-3,4-dienal Derivatives

1997 ◽  
Vol 62 (11) ◽  
pp. 1747-1753 ◽  
Author(s):  
Radek Marek
Keyword(s):  
Double Bond ◽  
Chemical Shifts ◽  
Multiple Bond ◽  
Coupling Constants ◽  
Single Quantum ◽  
Nmr Techniques ◽  
Phase Sensitive ◽  
Heteronuclear Coupling

Determination of 15N chemical shifts and heteronuclear coupling constants of substituted 2,2-dimethylpenta-3,4-dienal hydrazones is presented. The chemical shifts were determined by gradient-enhanced inverse-detected NMR techniques and 1H-15N coupling constants were extracted from phase-sensitive gradient-enhanced single-quantum multiple bond correlation experiments. Stereospecific behaviour of the coupling constants 2J(1H,15N) and 1J(1H,13C) has been used to determine the configuration on a C=N double bond. The above-mentioned compounds exist predominantly as E isomers in deuteriochloroform.

15N, 13C, and 1H NMR Spectra of Azo and Hydrazo Compounds Derived from 1,3,3-Trimethyl-2-methylidene-2,3-dihydroindole (Fischer Base)

1998 ◽  
Vol 63 (7) ◽  
pp. 1012-1020 ◽  
Author(s):  
Antonín Lyčka ◽  
Josef Jirman ◽  
Alois Koloničný
Keyword(s):  
Double Bond ◽  
Hydrochloric Acid ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
Azo Compounds ◽  
Passive Component ◽  
Geometric Isomers ◽  
H Nmr ◽  
Fischer Base ◽  
Hydrazone Form

The 15N, 13C, and 1H NMR spectra were measured for azo and hydrazo compounds derived from 1,3,3-trimethyl-2-methylidene-2,3-dihydroindole (Fischer base), which is a passive component with a terminal methylidene group. Products prepared by coupling in hydrochloric acid exist in the corresponding hydrazone form as the E-isomers. Neutralization gives a mixture of two isomeric azo compounds which differ in the arrangement at the C(2)=C(10) double bond. This mixture was alkylated with methyl iodide to obtain the =N-N(CH3)- hydrazone derivatives. The geometric isomers were resolved based on the NOESY approach and the stereospecific behaviour of the 2J(15N,13C) coupling constants was studied for the 15N-labelled compounds.

Conformational Studies on 1,3-Dioxepanes. Part IV. Applications of Geminal Coupling Constants to Conformational Analysis of 1,3-Dioxepanes

1974 ◽  
Vol 52 (24) ◽  
pp. 4062-4071 ◽  
Author(s):  
T. Bruce Grindley ◽  
Walter A. Szarek
Keyword(s):  
Conformational Analysis ◽  
Coupling Constants ◽  
Conformational Studies ◽  
Vicinal Coupling Constants ◽  
Geminal Coupling ◽  
Derivatives Of ◽  
Acetal Carbon

The magnitude of —OCH2O— group geminal H,H coupling contants, the size of the vicinal coupling constants, and the tenets of conformational analysis were used to establish that in solution the conformation of the 1,3-dioxepane rings in derivatives of 1,3:2,5-di-O-methylenemannitol and 2,5-O-methylenemannitol is predominantly the twist-chair in which the C2 axis passes through the acetal carbon.

Structural trends of29Si-1H spin-spin coupling constants across double bond

2012 ◽  
Vol 50 (10) ◽  
pp. 665-671 ◽  
Author(s):  
Yury Yu. Rusakov ◽  
Leonid B. Krivdin ◽  
Valentina M. Nosova ◽  
Alexander V. Kisin ◽  
Valentin G. Lakhtin
Keyword(s):  
Double Bond ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling

Formation of H -Addition Radicals in Adenine Derivatives

1976 ◽  
Vol 31 (5-6) ◽  
pp. 225-231 ◽  
Author(s):  
H. Zehner ◽  
W. Flossmann ◽  
E. Westhof
Keyword(s):  
Esr Spectroscopy ◽  
Coupling Constants ◽  
Molecular Orbital Calculations ◽  
X Rays ◽  
Hydrogen Atoms ◽  
Indo Calculations ◽  
Differential Stability ◽  
Purine Ring ◽  
Bonding Scheme ◽  
Adenine Derivatives

The formation of H-aduition radicals in monocrystals of 9-methyl adenine, deoxyadenosine monohydrate, and adenosine hydrochloride by irradiation with X-rays has been studied using ESR spectroscopy. In 9-methyl adenine and adenosine-HCl, hydrogen atoms add exclusively to position C8 of the imidazole part of the purine ring. On the other hand, in deoxyadenosine · H2O crystals, H-addition radicals at position C2 of the pyrimidine part of the purine ring occur together with H-addition radicals at position C8. Both radicals could be isolated by using their differential stability under warming or illumination with light. The C8-addition radical is characterized by two equivalent β-protons of 38.0 ± 0.5 G and the C2-addition radical by two non-equivalent β-protons of 34.0 ±1.0 and 50.0 ± 1.0 G. The nitrogen splittings perpendicular to the purine ring are 27.0 and 6.6 G for the C2-addition radical and 20.5 and 9.2 G for the C2-addition radical. The coupling constants of both radicals are in agreement with INDO calculations. It is further shown that the added hydrogen atom comes partly from the hydrogen bonding scheme and partly from the non­exchangeable hydrogens for the C8-addition radical. Together with additional experiments on polycrystalline samples, these results lead to the conclusion that hydrogen atoms add non-selectively to C2 and C8 of the neutral molecules, whereas protons add predominantly to C8 of anion radicals. This is supported by Hückel molecular orbital calculations.

Sign in / Sign up

Export Citation Format

Share Document