Studies on the PMR Spectra of Oxetanes. VI 2-(3-Chlorophenyl)oxetane and 2-(2-Chlorophenyl)oxetane at 60 and 100 MHz

1974 ◽  
Vol 29 (12) ◽  
pp. 1902-1906 ◽  
Author(s):  
Jukka Jokisaari
Keyword(s):  
Long Range ◽  
Chemical Shifts ◽  
Methine Proton ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Proton Proton ◽  
Temperature Range ◽  
Proton Coupling ◽  
Phenyl Proton ◽  
Pmr Spectra

The 100 MHz spectra of the phenyl protons in 2-(3-chlorophenyl) oxetane and 2-(2-chlorophenyl) oxetane have been analysed. The 60 MHz PMR chemical shifts and proton-proton coupling constants have been studied in the temperature range from -20 C to +80 °C. The chemical shifts were sensitive to temperature, while the coupling constants were not, except the long range 5Jm coupling constant between the methine proton and the meta positioned phenyl proton in 2-(2-chlorophenyl) oxetane.

An 1H NMR conformational analysis of 3-phenylpentane in solution

1993 ◽  
Vol 71 (4) ◽  
pp. 520-525 ◽  
Author(s):  
Ted Schaefer ◽  
Lina B.-L. Lee
Keyword(s):  
Alkyl Chain ◽  
Chemical Shifts ◽  
Close Approach ◽  
Solvent Mixture ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Proton Proton ◽  
Vicinal Coupling Constants ◽  
Proton Coupling ◽  
Proton Chemical Shifts

Some 30 proton chemical shifts and proton–proton coupling constants are reported for a 4.7 mol% solution of 3-phenylpentane in a CS2/C6D12/TMS solvent mixture at 300 K. The long-range coupling constant over six formal bonds between the methine and para protons is used to deduce an apparent twofold barrier of 15.0 ± 0.3 kJ/mol to rotation about the Csp2—Csp3 bond, at least twice as large as that for isopropylbenzene in solution. AM1 computations agree with experiment in finding the conformation of lowest energy as that in which the methine C—H bond is situated in the phenyl plane, but predict a barrier height of only 13.9 kJ/mol. The vicinal coupling constants are consistent with a fractional population, 0.38(2), of the TT conformer, that in which all the carbon atoms of the alkyl chain lie in a plane. A doubly degenerate conformer, TG+(G−T), in which one methyl group is twisted away from the phenyl substituent, then has a fractional population of 0.62(2). The assumption that only these three conformers are present is tested with the signs and magnitudes of the four different coupling constants over four bonds. These coupling constants are consistent with the absence of significant proportions of the other six all-staggered conformers. These six are characterized by a close approach of the methyl groups (1,5 interactions) or by proximity of the methyl and phenyl moieties.

The relationship between carbon-13 substituent chemical shifts and proton coupling constants in aza-aromatic systems

1984 ◽  
Vol 37 (2) ◽  
pp. 311 ◽  
Author(s):  
IB Cook ◽  
S Pengprecha ◽  
B Ternai
Keyword(s):  
Experimental Data ◽  
Chemical Shift ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Proton Proton ◽  
Proton Coupling ◽  
Substituted Pyridines ◽  
Aromatic Systems ◽  
The Relationship

An equation which relates the ortho carbon-13 substituent chemical shift α-SCS in aza-aromatics to the ortho proton-proton coupling constant 3J(HH) in the corresponding carbocyclic compound is derived from experimental data. The implications for N-N bond fixation in diaza-aromatics are discussed. When the equation is applied to 2-substituted pyridines, an electronegativity parameter must be included to explain the results.

Long-range spin–spin coupling constants between ring protons and aldehydic protons in some para-substituted benzaldehydes

1969 ◽  
Vol 47 (21) ◽  
pp. 4005-4010 ◽  
Author(s):  
S. S. Danyluk ◽  
C. L. Bell ◽  
T. Schaefer
Keyword(s):  
Long Range ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Coupling Constant ◽  
Proton Proton ◽  
Proton Coupling ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Coupling Mechanisms ◽  
Benzaldehyde Derivatives

The long-range proton–proton coupling constants between the ring protons and the aldehydic proton are reported for a series of para-substituted benzaldehyde derivatives. It was found that JoH,CHO < 0 and JmH,CHO > 0. Furthermore, JoH,CHO increases in magnitude as the electron donating power of the sub-stituent increases. A similar trend is observed forJmH,CHO but the ratio of the increase to the magnitude of JmH,CHO is much less than for JoH,CHO. A good correlation is obtained between JoH,CHO and the sub-stituent parameters of Swain and Lupton.The coupling constant data are discussed in terms of σ and π coupling mechanisms and it is concluded that σ electron mechanisms are dominant for both JoH,CHO and JmH,CHO.

An Investigation of Long-range Proton–Proton Coupling Constants in Phenylacetylene Derivatives

1972 ◽  
Vol 50 (13) ◽  
pp. 2035-2040 ◽  
Author(s):  
C. J. MacDonald ◽  
G. K. Hamer ◽  
I. R. Peat ◽  
W. F. Reynolds
Keyword(s):  
Hyperfine Interaction ◽  
Long Range ◽  
Excellent Agreement ◽  
Quantitative Estimation ◽  
Theoretical Calculations ◽  
Experimental Results ◽  
Coupling Constants ◽  
Proton Proton ◽  
Proton Coupling

Signs and magnitudes of long-range coupling constants in three phenylacetylene derivatives have been determined. Values of the coupling constants are discussed in terms of the McConnell formulation and compared with results of MO–INDO–FPT calculations. Coupling constants are dominated by π contributions. Estimated values of hyperfine interaction constants for acetylene and methylacetylene groups are respectively QCC≡CH = −12 and QCC≡CCH = +12 G. The theoretical calculations are in excellent agreement with experimental results. Both approaches allow quantitative estimation of nine bond couplings in 4-vinylphenylacetylene.

Concerning the conformational distribution in isopropylcyclopropane

1982 ◽  
Vol 60 (7) ◽  
pp. 845-847 ◽  
Author(s):  
Ted Schaefer ◽  
Rudy Sebastian ◽  
Roderick E. Wasylishen
Keyword(s):  
Methine Proton ◽  
Coupling Constant ◽  
Nmr Spectrum ◽  
Proton Proton ◽  
H Nmr ◽  
Proton Coupling ◽  
Trans Conformer ◽  
Partial Analysis ◽  
Vicinal Proton ◽  
Conformational Distribution

A partial analysis of the 400 MHz 1H nmr spectrum of isopropylcyclopropane yields 8.6 ± 0.2 Hz for the vicinal proton–proton coupling constant between a cyclopropyl proton and the methine proton of the isopropyl group. The fractional population of the s-trans conformer is estimated as 0.65 ± 0.l0 at 300 K, in reasonable agreement with molecular mechanics and INDO MO computations of the energies of the gauche and trans forms.The conformational preference of this molecule is similar to that in n-butane and in vinylcyclopropane but contrasts with that in biisopropyl and bicyclopropyl.

An Investigation of Substituent Effects on Coupling Constants to Vinyl Protons in Styrene Derivatives

1974 ◽  
Vol 52 (19) ◽  
pp. 3415-3423 ◽  
Author(s):  
William F. Reynolds ◽  
Ian R. Peat ◽  
Gordon K. Hamer
Keyword(s):  
Long Range ◽  
Substituent Effects ◽  
Phenyl Group ◽  
Coupling Constants ◽  
Vinyl Proton ◽  
Model Compounds ◽  
Proton Coupling ◽  
Phenyl Proton ◽  
Styrene Derivatives ◽  
Induced Changes

Experimental long-range phenyl proton–vinyl proton coupling constants in 4-substituted styrenes are substituent independent. This is also predicted by INDO–finite perturbation theory calculations of these coupling constants. Comparison with calculated and experimental long-range coupling constants for 4-substituted benzaldehydes suggests that the previously reported substituent dependence for the latter coupling constants arises from substituent-induced changes in molecular geometry.Geminal vinyl coupling constants in 4-substituted styrenes, α-methylstyrenes, and α-t-butylstyrenes are substituent dependent with substituent effects increasing as phenyl and vinyl groups are twisted out of planarity. These trends are reproduced by INDO–FPT calculations. It is concluded that the substituent effects are primarily transmitted through space.Both experimental and calculated vinyl 13C–1H coupling constants show strong stereospecific substituent effects. From the pattern of results (particularly the greater field dependence for JC(β)H(9) than JC β)H(8)) it is concluded that these coupling constants.also reflect through-space substituent effects. This is supported by calculations on model compounds with no intervening phenyl group.

C13 SPLITTINGS IN SOME SUBSTITUTED BENZENES

1962 ◽  
Vol 40 (9) ◽  
pp. 1758-1762 ◽  
Author(s):  
H. M. Hutton ◽  
W. F. Reynolds ◽  
T. Schaefer
Keyword(s):  
Long Range ◽  
Electron Acceptors ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Substituted Benzenes ◽  
First Order ◽  
Proton Coupling

C13 sidebands in the proton spectra of some symmetrically substituted benzenes have been used to obtain carbon–hydrogen coupling constants as well as proton coupling constants.A long-range carbon–hydrogen coupling constant has also been found. Substituents which act as electron acceptors in an inductive manner are found to increase the C13H coupling constants by as much as 20 c.p.s. The patterns of the sidebands are discussed and possible errors in first-order analyses are indicated.

Substituent effects on geminal proton–proton coupling constants

1970 ◽  
Vol 48 (13) ◽  
pp. 2134-2138 ◽  
Author(s):  
Y. L. Chow ◽  
S. Black ◽  
J. E. Blier ◽  
M. M. Tracey
Keyword(s):  
Carbon Tetrachloride ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
Coupling Constants ◽  
Proton Proton ◽  
Proton Coupling ◽  
Geminal Proton ◽  
Geminal Coupling ◽  
Hammett Σ Constants

The geminal coupling constants between the non-equivalent benzylic protons of a series of para- and meta-substituted N-benzyl-2-methylpiperidines were shown to be proportional to the Hammett σ constants of the substituents with ρ −1.38 in carbon tetrachloride, −1.21 in benzene, and nearly 0 in 1 N DCl solutions. The ρ values were compared with those of other series and were discussed in terms of the possible conformations involved. The chemical shifts of the benzylic protons of the piperidine derivatives did not give a good correlation with the Hammett σ constants in these solvents.

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