Nitro groups, electron withdrawing

In the examples shown below, notice that a nitro substituent (electron-withdrawing) increases the strength of the acid, while a methoxy substituent (electron-donating) decreases the acid strength. The nitro group has a larger effect in the ortho and para positions than in the meta position. 

The nitro group can withdraw electron density from the carboxyl group by an inductive effect at both the meta and para positions. However, a para-ri xxo group also withdraws electron density from the carboxyl from the ring by a resonance effect. Therefore, the para isomer is more acidic. 

This makes the nitro group a powerful electron withdrawing deactivating substituent and a meta director... 

Table 19 3 lists the ionization constants of some substituted benzoic acids The largest effects are observed when strongly electron withdrawing substituents are ortho to the carboxyl group An o nitro substituent for example increases the acidity of benzoic acid 100 fold Substituent effects are small at positions meta and para to the carboxyl group In those cases the values are clustered m the range 3 5-4 5... 

Electron releasing substituents attached to the ring have a negligible effect on the acidity of phenols Strongly electron withdrawing groups increase the acidity The compound 4 nitro 3 (tnfluoromethyl)phenol for example is 10 000 times more acidic than phenol... 

Nitro C—NO2 Aliphatic ca 1560 (s) 1385-1350 (s) The two bands are due to asymmetrical and symmetrical stretching of the N=0 bond. Electron-withdrawing substituents adjacent to nitro group increase the frequency of the asymmetrical band and decrease that of the symmetrical frequency. 

Nucleophilic Displacement Reactions. The strong electron-withdrawing effect of a trifluoromethyl group activates ortho and para halogen toward nucleophilic attack. Such chlorine labiUty is utili2ed in the manufacture of crop control chemicals containing trifluoromethyl and nitro groups. 

Hydroxybenzaldehydes readily react with compounds containing methyl or methylene groups bonded to one or two carboxyl, carbonyl, nitro, or similar strong electron-withdrawing groups. The products are usually P-substituted styrenes. 4-Hydroxybenzaldehyde, for example, reacts with 2-methylquinazolines (where R = H, Cl) to give compounds which have anti-inflammatory activity (59). 

Aromatic haUdes do not react easily with phenoxide ions to produce diaryl ethers unless the aromatic haUde is substituted with one or more electron-withdrawing groups, eg, nitro or carboxyl groups. The Ullmann reaction uses finely divided copper or copper salts to cataly2e the reaction of phenoxides with aromatic haUdes to give diaryl ethers. 

Much of the reactivity shown by the ring atoms and substituents of pyrimidine is akin to that of the corresponding parts of 1,3-dinitrobenzene and 3-nitropyridine. This arises from the quantitatively similar electron-withdrawing effects of doubly-bound ring nitrogen atoms and of nitro groups in reducing sharply the aromaticity of the cyclic system. 

Halogen atoms on benzazole rings can be activated toward nucleophilic displacement by electron-withdrawing groups. Thus azide ion displaces chlorine from 5-chloro-4-nitro- and 4-chloro-7-nitro-benzofuroxan (65JCS5958). 

When the benzenesulfinates were substituted with electron-withdrawing groups, e.g., p-nitro- and p-cyanobenzenesulfinate, the yields were slightly improved when the reaction time with cyanogen chloride was lengthened to 1 hour. 

---