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.

Concerning the mechanism of in toluene and its derivatives

1983 ◽  
Vol 61 (12) ◽  
pp. 2785-2789 ◽  
Author(s):  
Ted Schaefer ◽  
Reino Laatikainen
Keyword(s):  
Coupling Constants ◽  
Spin Coupling ◽  
Similar Magnitude ◽  
Conformational Preference ◽  
Conformational Studies ◽  
Methyl Group ◽  
Ring Substituent ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Derivatives Of

On the basis of the observed five-bond spin–spin coupling constants between the α protons and the meta ring protons in the 2,6-difluoro derivatives of toluene, ethylbenzene, and cumene, it is argued that [Formula: see text] in toluene can be written as A[Formula: see text]. A and B are of the same sign and of very similar magnitude. In consequence, [Formula: see text] cannot be used to measure the conformational preference of the methyl group. However, [Formula: see text] and [Formula: see text] in α-substituted toluene derivatives will be useful in conformational studies. [Formula: see text] in toluene derivatives varies between 0.30 and 0.46 Hz and some patterns in its ring substituent dependence can be gleaned from some fifty precise values.

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.

Magnetic non-equivalence of fluorine atoms of a trifluoromethyl group

1982 ◽  
Vol 60 (19) ◽  
pp. 2451-2455 ◽  
Author(s):  
Mohsin A. Khan ◽  
Donald F. Tavares ◽  
Arvi Rauk
Keyword(s):  
Methoxy Group ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Trifluoromethyl Group ◽  
Single Bond ◽  
Hindered Rotation ◽  
Geminal Coupling ◽  
Coupling Pattern ◽  
Derivatives Of

The three fluorine atoms of N,N-dialkyl amide and chloride derivatives of 2-methoxy-2-phenyl-3,3,3-trifluoropropanoic acid are magnetically nonequivalent below –60 °C and exhibit a clear ABC coupling pattern from which chemical shifts and geminal coupling constants are readily derived. The chemical shifts span a range of about 10 ppm and the geminal coupling constants average about 110 Hz. A five bond coupling of about 5 Hz is observed between the hydrogens of the methoxy group and one of the nonequivalent fluorine atoms of the trifluoromethyl group. Barriers to the hindered rotation about the single bond to the trifluoromethyl group are in the range 36–46 kJ/mol.

Cyclononatrienes vs. dihydroanthracenes

1970 ◽  
Vol 48 (22) ◽  
pp. 3591-3592 ◽  
Author(s):  
Robert R. Fraser ◽  
Adel Juraydini
Keyword(s):  
Coupling Constants ◽  
Mass Spectral ◽  
Geminal Coupling ◽  
Derivatives Of

This paper provides evidence that three compounds previously assumed to be methoxyl derivatives of dihydroanthracenes (1) are actually cyclononatriene derivatives. The revised structural assignments, made on the basis of mass spectral and n.m.r. evidence, remove a previous inconsistency in their n.m.r. properties. The constancy of geminal coupling constants in all three cyclononatrienes is discussed.

Discussion on 13C nuclear magnetic resonance spectra of structurally rigid cyclonucleosides. Violation of Karplus relationship between 3JC,H and dihedral angles

1984 ◽  
Vol 62 (8) ◽  
pp. 1555-1557 ◽  
Author(s):  
Jun Uzawa ◽  
Kentaro Anzai
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Coupling Constants ◽  
Dihedral Angles ◽  
Vicinal Coupling Constants ◽  
Nuclear Magnetic Resonance Spectra ◽  
13C Nuclear Magnetic Resonance ◽  
Karplus Relationship ◽  
Derivatives Of ◽  
C Nmr

Using structurally rigid cyclonucleoside derivatives of adenosine, the effect of the oxygen functional groups on the vicinal coupling constants between carbon and hydrogen in, 13C nmr was investigated.

Derivatives of 1-Phenylphthalan, 2-Methyl-1-phenylisoindoline, and 5H-Dibenzo[a,d]cycloheptene Oxides; Synthesis and Conformational Aspects

1971 ◽  
Vol 49 (5) ◽  
pp. 746-754 ◽  
Author(s):  
Robert R. Fraser ◽  
Roger N. Renaud
Keyword(s):  
Chemical Shifts ◽  
Coupling Constants ◽  
Ring Systems ◽  
Geometrical Properties ◽  
Geminal Coupling ◽  
Derivatives Of ◽  
Substituted 1

For the purpose of correlation of chemical shifts and geminal coupling constants with stereochemistry a number of compounds of fixed geometry have been synthesized. These include seven 6-substituted 1-phenylphthalans, five 6-substituted 2-methyl-1-phenylisoindolines, and six 2-substituted 5H-dibenzo-[a,d]cycloheptene oxides. The geometrical properties of the three ring systems are discussed and arguments in favor of a quasi-equatorial epoxide substituent in the latter series are supported by n.O.e. measurements.

The Effect of Substituents on Geminal Proton–Proton Coupling Constants; a Conformational Dependence. II

1971 ◽  
Vol 49 (5) ◽  
pp. 755-760 ◽  
Author(s):  
Robert R. Fraser ◽  
Roger N. Renaud
Keyword(s):  
Conformational Analysis ◽  
Solvent Effects ◽  
Coupling Constants ◽  
Methylene Carbon ◽  
Proton Proton ◽  
Proton Coupling ◽  
Geminal Proton ◽  
Methylene Groups ◽  
Geminal Coupling ◽  
Methylene Group

The effect of para-substituents on the geminal coupling constants in benzylic methylene groups has been studied as a function of the conformation at the benzene—CH2 bond. The slopes of Hammett plots of Jgemvs. σ are large (−1.6 to −1.9) when the geometry permits a hyperconjugative interaction between the benzene ring and the methylene group but negligible (+ 0.2) when this interaction is geometrically restricted. The effect of a change in electronegativity of the group attached to the methylene carbon has also been investigated. The change in the slope, ρ, from −1.7 to −1.6 on protonation of the nitrogen attached to the methylene group in a series of isoindolines shows this effect to be extremely small. Solvent effects on ρ are also very small. The potential of this J − σ relation for conformational analysis of benzyl groups is discussed in comparison with existing methods.

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