Influence of Substituents:
The nitro group (NO2) has a significant effect on acidity and reactivity compared to other groups.
Groups like carboxylic acids may require removal of water for reactions to proceed efficiently.
Mechanism Overview:
Reactions are acid-catalyzed (e.g., sulfuric acid, H2SO4).
Water removal might be necessary to shift equilibrium to favor product formation.
Halogenation with Bromine Water:
Phenols easily react with bromine in water, demonstrating high reactivity as an activated benzene ring.
Reaction must be done in a polar solvent (like water) to stabilize the bromide ion (Br-).
Multiple additions can occur, confirming the presence of excess phenol.
Nitration:
Using concentrated nitric acid will lead to multiple substitutions; dilute nitric acid can limit this to one substitution.
The hydroxyl (-OH) group acts as a strong electron-donor, enhancing reactivity.
Position Dependence on Temperature:
At low temperatures, sulfonyl group (-SO3H) prefers ortho substitution.
At high temperatures, para substitution is favored.
Sulfonyl group acts as a meta director and deactivator due to positive charge on sulfur.
Regeneration and Removal:
Sulfonyl group can be removed using diluted sulfuric acid, demonstrating phenol's high reactivity.
Testing for Presence of Phenols:
Bromine water is a specific test for phenols, indicating their reactive nature in electrophilic substitution.
The reaction proceeds only in water, confirming phenol presence based on consistent reaction outcomes.
Mechanism of O-Acylation:
Acid halides or anhydrides react with phenols to form esters via O-acylation (similar to Fischer esterification).
Lewis acids can facilitate acylation, changing reaction mechanism to involve EAS type reaction for electrophilic substitutions.
Formation of Azo Compounds:
A diazonium ion reacts with phenol to form azo compounds, useful as dyes.
Modification of the phenolic structure allows tailoring of dye colors.
Azodyes are prevalent in commercial applications, though not as commonly used in textiles due to fading issues.
Phenoxide Ion Formation and CO2 Reaction:
Phenol is converted to phenoxide ion using NaOH.
Phenoxide ion then reacts with CO2 gas under pressure to form carboxylic acids.
Mechanism Overview:
Reagent: chloroform and NaOH; forms ortho-substituted phenols upon heating.
The EAS type mechanism yields carbonyl products that restore aromaticity.
Oxidation Resistance:
Phenols resist oxidation, but di-phenols can be oxidized to diketones under strong conditions.
Mild Reduction Techniques:
Sodium thiosulfate (Na2S2O4) serves as a mild reducing agent for phenols, utilized in applications such as photography.
Infrared (IR) Spectroscopy Peaks:
Key peaks around 3200 cm-1 indicate -OH stretch; distinguish from carboxylic acids (which show broader peaks).
Nuclear Magnetic Resonance (NMR) Peaks:
-OH protons show variable shifts due to hydrogen bonding; deuterium exchange can help confirm presence.
C-13 NMR indicates downfield shifts for carbons attached to oxygen due to deshielding effects.