LIGHT ABSORPTION STUDIES: PART XII. ULTRAVIOLET ABSORPTION SPECTRA OF BENZALDEHYDES

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. 1305-1314 ◽  
Author(s):  
J. C. Dearden ◽  
W. F. Forbes

Anisoles, compared with phenols, possess similar spectral properties, except that properties determined mainly by the hydrogen atom of the hydroxy group are modified. In this way, comparison of the ultraviolet absorption spectra of phenols and anisoles permits, for example, the study of the spectral effects of hydrogen bonding and the study of steric interactions involving the hydroxy and methoxy groups.


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. 1350-1361 ◽  
Author(s):  
W. F. Forbes

The spectra of nitrobenzenes are discussed in terms of previously proposed hypotheses relating electronic interactions and ultraviolet absorption spectra.


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.


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.


1959 ◽  
Vol 37 (12) ◽  
pp. 1977-1985 ◽  
Author(s):  
W. F. Forbes

The ultraviolet absorption spectra of a series of fluorobenzenes are determined. It is found that as a first approximation a fluoro substituent does not appreciably affect the benzenoid absorption. The spectra are discussed on the assumption that the mesomeric effect of the fluorine atom is small.


1960 ◽  
Vol 38 (7) ◽  
pp. 1104-1112 ◽  
Author(s):  
W. F. Forbes

The ultraviolet absorption spectra of a series of chlorobenzenes are determined. The spectral data suggest that the apparent mesomeric effect of the chlorine atom is greater than that of the fluorine atom, that solvent–solute interactions are generally less important in chlorobenzenes than in fluorobenzenes, and that, as expected, the effective interference radius of the chlorine atom is large. Moreover, spectral changes in o-substituted chlorobenzenes are consistent with the assumption that maximum electronic interaction requires the chlorine atom to be in the same plane as the benzene ring. The conformations of o-chloroacetophenone and o-chlorophenol are briefly discussed.


1961 ◽  
Vol 39 (11) ◽  
pp. 2295-2305 ◽  
Author(s):  
W. F. Forbes

As a sequel to previous studies on the ultraviolet absorption spectra of halogen-substituted benzenes the spectra of iodobenzene in various solvents, and the spectra of a series of substituted iodobenzenes in cyclohexane solution, are reported. It is shown that these spectra can be rationalized qualitatively in terms of simple resonance theory, if the apparent mesomeric effect of the iodine atom is assumed to be greater for iodine than for the other halogen atoms.


1958 ◽  
Vol 36 (10) ◽  
pp. 1371-1380 ◽  
Author(s):  
W. F. Forbes ◽  
I. R. Leckie

A spectral analysis of benzene derivatives in terms of steric and electronic interactions is extended to ring-substituted anilines.


1961 ◽  
Vol 39 (12) ◽  
pp. 2452-2465 ◽  
Author(s):  
W. F. Forbes ◽  
J. J. J. Myron

The ultraviolet absorption spectra and infrared carbonyl bands of a number of substituted benzoyl chlorides are determined. It is found that as a first approximation the B-bands of the ultraviolet spectra are similar for benzoyl chlorides and for the corresponding benzaldehydes and acetophenones. The spectra are discussed in terms of previously stated hypotheses. In this way the order of the apparent negative mesomeric effect is deduced to be —NO2 > — COCl > —CHO > —COCH3, and the effective size of these substituents is confirmed to be in the order —NO2 > —COCH3 > —COCl > —CHO.The infrared carbonyl band occurs as a well-defined doublet in most of the ring-substituted benzoyl chlorides. The most probable explanation is that these doublets occur because of an intramolecular vibration.


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