LIGHT ABSORPTION STUDIES: PART IV. THE EFFECTS OF STERICALLY HINDERED CONFORMATIONS ON THE ELECTRONIC SPECTRA (B-BANDS) OF CONJUGATED SYSTEMS

1956 ◽  
Vol 34 (9) ◽  
pp. 1347-1355 ◽  
Author(s):  
W. F. Forbes ◽  
W. A. Mueller

The equation ε/ε0 = cos2(θ1 − θ2) recently proposed by Braude and co-workers is developed to account more rigorously for the spectra of unsymmetrical molecules. The results obtained from the revised equation, [Formula: see text] support the interference value of hydrogen obtained independently from spectral data, and suggest a re-examination of the reported theories accounting for the spectra of alicyclic enones and dienones, and for steric effects of type I.

1961 ◽  
Vol 39 (5) ◽  
pp. 1131-1142 ◽  
Author(s):  
W. F. Forbes

The ultraviolet absorption spectra of bromobenzene in various solvents, and the spectra of a series of substituted bromobenzenes in cyclohexane solution, are reported. The B-band spectral data confirm the hypotheses postulated for the B-band spectra of chlorobenzenes in the previous part of this series of papers. That is, the bromine atom usually gives rise to greater steric effects than the chlorine atom and the apparent mesomeric interaction as judged from these spectra increases with the size of the halogen substituent.Both bromobenzene and chlorobenzene C-band intensities are unusually small, and this is assumed to account for the frequent C-band similarity between the spectrum of a mono-substituted benzene derivative PhX, where X = OH, OCH3, NH2, and the spectrum of the corresponding chloro- or bromo-substituted PhX derivative.


1965 ◽  
Vol 43 (9) ◽  
pp. 2603-2609 ◽  
Author(s):  
A. Balasubramanian ◽  
J. C. Dearden ◽  
W. F. Forbes ◽  
N. F. Cheetham

Steric effects, previously reported by other workers in o- and o,o′-alkyl-substituted anisoles, were reinvestigated using compounds carefully purified by vapor phase chromatography. The ultraviolet spectral data indicate that the o-alkyl-substituted anisoles exist in one conformation, whereas the investigated o,o′-dialkyl-substituted anisoles exist in a different conformation. The conformations appear to be almost independent of the size of the substituent groups. Infrared, dipole moment, and other data are consistent with this interpretation.


1955 ◽  
Vol 33 (12) ◽  
pp. 1829-1839 ◽  
Author(s):  
W. F. Forbes ◽  
M. B. Sheratte

The spectra of a number of substituted benzoic acids, acetanilides, and phenyl benzoates are discussed in terms of the electronic and steric effects of substituents.


1958 ◽  
Vol 36 (10) ◽  
pp. 1362-1370 ◽  
Author(s):  
J. C. Dearden ◽  
W. F. Forbes

The electronic spectra of benzaldehydes in the region 220–360 mμ are recorded and discussed in terms of previously stated hypotheses. The formyl group is shown to endow benzene derivatives with spectral properties similar to those of the acetyl group in acetophenones, except that steric interactions are slightly modified.


1959 ◽  
Vol 37 (8) ◽  
pp. 1294-1304 ◽  
Author(s):  
J. C. Dearden ◽  
W. F. Forbes

A spectral analysis of benzene derivatives is extended to substituted phenols. The discussion emphasizes hydrogen bonding and steric effects which occur in phenols. Some of the phenolic absorption bands are ascribed to locally excited states.


1955 ◽  
Vol 33 (6) ◽  
pp. 1145-1154 ◽  
Author(s):  
W. F. Forbes ◽  
W. A. Mueller

The steric hindrance postulated by Arnold and co-workers to account for anomalous reaction rates of some substituted acetophenones has been verified by means of ultraviolet light absorption data. The spectra of a number of other substituted acetophenones have been discussed in terms of the electronic and steric effects of substituents.


1956 ◽  
Vol 34 (9) ◽  
pp. 1340-1346 ◽  
Author(s):  
W. F. Forbes ◽  
W. A. Mueller

The spectra of a number of trisubstituted benzene derivatives which have recently been described by Doub and Vandenbelt are discussed in terms of the electronic and steric effects. The assumption of Doub and Vandenbelt, that the steric effects are usually small in absorption spectra, is criticized.


ACS Photonics ◽  
2021 ◽  
Author(s):  
Hyemin Bae ◽  
Suk Hyun Kim ◽  
Seungmin Lee ◽  
Minji Noh ◽  
Ouri Karni ◽  
...  

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