Organic Lecture 3/5

Physical Properties and Reactivity of Phenols

  • 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.

Electrophilic Aromatic Substitution (EAS) Reactions

  • 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.

Sulfonation

  • 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.

Functional Group Tests

  • 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.

Acylation Reaction of Phenols

  • 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.

Diazotization and Azo Dye Formation

  • 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.

Hydroxycarbonyl Formation via Carboxylation

  • 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.

Reimer-Tiemann Reaction

  • Mechanism Overview:

    • Reagent: chloroform and NaOH; forms ortho-substituted phenols upon heating.

    • The EAS type mechanism yields carbonyl products that restore aromaticity.

Oxidation and Reduction of Phenols

  • 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.

Spectroscopic Analysis of Phenols

  • 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.

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