Benzene rings spectrum

An electron-accepting group, such as NO2, and an electron-donating group, such as OH, situated ortho or para to each other tend to cancel each other out and provide a spectrum not very different from the monosubstituted benzene ring spectrum (Table 5.9). 

Carbon-hydrogen stretching vibrations with frequencies above 3000 cm are also found m arenes such as tert butylbenzene as shown m Figure 13 33 This spectrum also contains two intense bands at 760 and 700 cm which are characteristic of monosub stituted benzene rings Other substitution patterns some of which are listed m Table 13 4 give different combinations of peaks... 

Since two quaternary atoms and four CH atoms appear in the C NMR spectrum, the latter with a benzenoid coupling constant of 7-9 Hz, this is a disubstituted benzene ring, and the C signal with 5c = 162.2 fits a phenoxy C atom. The keto carbonyl (5c = 204.9) and methyl (5c = 26.6) resonances therefore point to an acetyl group as the only meaningful second substituent. Accordingly, it must be either o- or m-hydroxyacetophenone A or B the para isomer would show only four benzenoid C signals because of the molecular symmetry. 

Substituent effects calculated for structure B lead to values which are not perfect but which agree more closely than for A with the measured C shifts of the benzene ring carbon atoms. The dia-stereotopism of the NC//2 protons in the H NMR spectrum also points to B as the Newman projection C along the C/fj-ammonium-N bond shows ... 

The benzene rings A and B derived from the H NMR spectrum can be completed using Table 41.1. The way in which the enol ether is bonded is indicated by the correlation signal of the proton at Sh = 8.48. The structural fragment C results. Incorporating the C atom resonating at 5c = 123.3, which has not been accommodated in ring A or B and which is two bonds Jch) removed from the enol ether proton. 

First the five protons (integral) of the //NMR spectrum (Sfj = 7.50 - 7.94) in the chemical shift range appropriate for aromatics indicate a monosubstituted benzene ring with typical coupling constants 8.0 Hz for ortho protons, 1.5 Hz for meta protons.). The chemical shift values especially for the protons which are positioned ortho to the substituent Sn = 7.94) reflect a -M effect. Using the CH COLOC plot it can be established from the correlation signal hclS = 66.AI7.94 that it is a benzoyl group A. 

The NMR spectrum of the cyclophane shows three signals at 6 4.27, 6.97, and 7.24 (1 2 1 ratio) due to the benzene ring hydrogens. Examine cyclophane and identify which hydrogens are responsible for each signal. 

In Section 17.13 reference has been made to the influence of various substituents in the benzene ring on the absorption of ultraviolet radiation, and the purpose of this exercise is to examine the effect in the case of benzoic acid by comparing the absorption spectrum of benzoic acid with those given by 4-hydroxybenzoic acid and 4-aminobenzoic acid. 

Except in simple cases, it is very difficult to predict the infrared absorption spectrum of a polyatomic molecule, because each of the modes has its characteristic absorption frequency rather than just the single frequency of a diatomic molecule. However, certain groups, such as a benzene ring or a carbonyl group, have characteristic frequencies, and their presence can often be detected in a spectrum. Thus, an infrared spectrum can be used to identify the species present in a sample by looking for the characteristic absorption bands associated with various groups. An example and its analysis is shown in Fig. 3. 

Even the benzene ring can be forced out of planarity. In [5]paracycIophane (21) the presence of a short bridge (this is the shortest para bridge known for a benzene ring) forces the benzene ring to become boat shaped. The parent 21 has so far not proven stable enough for isolation, but a UV spectrum was obtained and... 

The complex contains 72 atoms with 244 valence electrons distributed in 226 valence atomic orbitals. In order to reduce the computational effort, and to assess the contribution of the ligand 7r-orbitals to the overall spectrum, we examined a "reduced" model, see Figure 2, in which the benzene rings of the ligands are replaced by -HC=CH- groups. This model compound consists of... 

Spectrum 5.3 A benzene ring bearing a single fairly neutral substituent. 

Spectrum 5.4 shows a typical pattern of a benzene ring monosubstituted with an electron donating group (in this case, it s -NH2). 

Spectrum 5.5 shows the effect of a single deshielding substituent (carboxylic acid) on the benzene ring. 

And finally, Structure 5.2 and Spectrum 5.8 show a classic example of a 1,2,4 tri-substituted benzene ring, (a well known anti-asthma drug, salbutamol). Obviously, the scope for variation in these systems is vast ... 

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