Aromatic Substitution and Substituent Effects

Substituent Effects:

Substituents on a benzene ring influence the ring's reactivity in two main ways:

1. Inductive Effect (–I, +I)

This effect involves the movement of electrons through sigma (σ) bonds, influenced by
the electronegativity of the substituent.
2. Mesomeric Effect (–M, +M)
This effect involves electron movement through pi (π) bonds or lone pairs of electrons on
an adjacent atom.

1. Inductive Effect (σ Bond)

 –I (Electron-Withdrawing):
o Substituents pull electrons away from the ring.
o This reduces reactivity at all positions but more at ortho and para positions, leaving the
meta position relatively more reactive.
o Meta-directing groups: e.g., –COOH, –HSO₃, –NO₂, Halogens (F, Cl, Br, I), –CF₃, –
CCl₃.

 +I (Electron-Donating):
o Substituents push electrons towards the ring.
o This increases reactivity at ortho and para positions, making them more reactive than the
meta position.
o Ortho/para-directing groups: e.g., –O, –OH, –NH₂, Alkyl (CH₃, C₂H₅), –Benzyl
(C₆H₅).

2. Mesomeric Effect (π Bond)

 Definition:
o Polarity arises from interaction between two π bonds or between a π bond and a lone pair.

 –M (Electron-Withdrawing):
o These groups reduce electron density on the ring, deactivating all positions. However,
ortho and para positions are deactivated more than meta.
o Examples: –NO₂, Carbonyl groups (C=O), –C≡N, –COOH, –SO₃H.

 +M (Electron-Donating):
 o These groups increase electron density on the ring, activating all positions. Ortho and
para positions are affected more than meta.
o Examples: –OH, –OR, –SH, –SR, –NH₂, –NR₂.

Comparing Inductive and Mesomeric Effects:

1. Mesomeric Effects Dominate:

o Groups like –OH and –NH₂ withdraw electrons by inductive effect (–I) but donate
electrons by mesomeric effect (+M).
o Since +M is stronger, the overall effect is electron donation, making these compounds
more reactive than benzene.

2. Inductive Effects Dominate in Halogens:

o Halogens show a –I effect (withdrawing electrons through σ bonds) and a +R effect
(donating electrons via lone pairs).
o However, the –I effect is stronger, so halogens are net deactivating.

Key Points on Electron Donation/Withdrawal:

1. Inductive Effect:
o Controlled by electronegativity and bond polarity.
o Electron-withdrawing groups: Halogens, C=O, CN, NO₂.
o Electron-donating groups: Alkyl groups.

2. Mesomeric Effect:
o +M Effect (Electron Donating): Order: –O⁻ > –NH₂ > –OR > –NHCOR > –OCOR > –
Ph > –CH₃ > Halogens.
o –M Effect (Electron Withdrawing): Order: –NO₂ > –CN > –SO₃H > –CHO > –COR >
–COOR > –COOH > –CONH₂.

Sample Problem Approach:

How to classify substituents:

1. Look at the atom directly bonded to the benzene ring:

o Lone pairs (e.g., O, N) → Electron-donating (+M).
o Positive charge or high electronegativity (e.g., Halogens) → Electron-withdrawing (–I, –
M).
2. Visualize lone pairs and multiple bonds to decide.
 Nitration: Detailed Understanding

Definition of Nitration

 Nitration is the process of introducing one or more nitro groups (–NO₂) into a molecule.
 Types of nitration based on the atom the nitro group attaches to:
1. C-Nitration: Nitro group attaches to carbon, forming nitro aromatic or nitro paraffinic
compounds.
2. O-Nitration: Nitro group attaches to oxygen, forming nitrate esters.
3. N-Nitration: Nitro group attaches to nitrogen, forming nitramines.

In this context, we consider only C-Nitration, where the nitro group replaces a hydrogen atom
directly attached to carbon, as these reactions are technically significant.

Applications of Nitration Products

Aromatic nitro compounds are essential in organic chemistry due to their:

 Easy availability.
 Conversion into various functional groups.

They are widely used in the synthesis of:

 Dyes and intermediates: e.g., Naphthol-S yellow, Flavianic acid.

 Pharmaceuticals: e.g., Chloramphenicol, Azomycin.
 Perfumes: e.g., Musk xylene, Musk ketone.
 Explosives: e.g., TNT (trinitrotoluene), Nitroglycerin, Nitrocellulose.
 Solvents: e.g., Nitrobenzene, Nitroethane.

Nitrating Agents

A wide variety of nitrating agents are used for aromatic nitration:

1. Nitric Acid (HNO₃):

o Fuming nitric acid.
o Concentrated nitric acid.
o Aqueous nitric acid.
 2. Mixtures of Nitric Acid with:
o Sulfuric acid.
o Acetic acid or acetic anhydride.
o Phosphoric acid.
o Chloroform.
3. Other Nitrating Agents:
o Nitrogen pentoxide (N₂O₅).
o Nitrogen tetroxide (N₂O₄).

The choice of nitrating system depends on:

 The species present in the mixture.

 The mechanism of the reaction.

Role of Sulfuric Acid in Nitration

Sulfuric acid serves several purposes in nitration:

1. Dehydrating Agent: Removes water produced during the reaction.

2. Catalyst: Protonates nitric acid to generate nitronium ions (NO₂⁺).
3. Enhances Efficiency:
o Makes fuller use of nitric acid.
o Inhibits oxidation of organic compounds.

Formation of Nitronium Ions (NO₂⁺)

 Nitronium ion is the active electrophile in nitration.

 It is formed through reactions involving sulfuric acid:

The reaction mechanism involves:

1. Protonation of nitric acid by sulfuric acid.

2. Elimination of water as a leaving group.
3. Formation of the nitronium ion (NO₂⁺).
Mixed Acid for Nitration

A nitrating mixture (nitric acid + sulfuric acid) is widely used in aromatic nitration. Key
benefits:

 Sulfuric acid:
o Acts as a catalyst and dehydrating agent.
o Increases nitronium ion concentration by minimizing water in the mixture.
 Nitronium ion formation is rapid and equilibrium is maintained throughout the reaction.

Variables affecting nitronium ion concentration:

1. Composition of Acid Mixture:

o Higher water content reduces nitronium ions.
o Maximum nitronium ion concentration occurs when nitric acid and sulfuric acid are in
equal molar amounts.
o Above 90% sulfuric acid, hydrogen bonds form, reducing electron density and the
reaction rate.

2. Temperature:
o Higher temperatures decrease nitronium ion concentration.
o Optimal temperature (e.g., 20°C) ensures high nitronium ion availability and efficient
nitration.

Aromatic Nitration Reaction

General equation:

Mechanism:

1. Nitronium ion (NO2+) attacks the aromatic ring, forming a sigma complex.
2. Proton loss restores the aromaticity, yielding the nitrated product.

Substituent Effects:

 Substituents on the benzene ring influence the position of nitration:

o Ortho/Para directing: Substituents that increase electron density at these positions.
o Meta directing: Substituents that increase electron density at the meta position.
Thermodynamics of Nitration

 The nitration reaction is highly exothermic.

 Cooling systems are essential to control heat evolution and prevent hazards.
 The energy released (Q=−ΔHQ = -\Delta HQ=−ΔH) must be carefully managed.

Kinetics of Aromatic Nitration

Rate of reaction:

Key factors affecting reaction rate:

1. Degree of Agitation:
o Improves mass transfer between the organic and acid phases.
o Reduces droplet size, enhancing reactant diffusion.
2. Temperature:
o Increases reaction rate by improving solubility, reducing viscosity, and enhancing
mixing.
3. Acid Composition:
o Nitronium ion concentration increases with sulfuric acid strength up to ~90%.
o Higher sulfuric acid concentrations reduce reaction rates due to hydrogen bond
formation.

Process Equipment for Technical Nitration

Types of Nitration Processes

1. Batch Nitration:
o Involves processing in a single vessel with controlled addition of reactants and close
monitoring.
o Suitable for small to moderate-scale production.

2. Continuous Nitration:
o Reactants and products flow continuously, allowing large-scale production.
 o Automated processes for efficiency and consistency.

Batch Nitration

 Vessel Construction:
o Closed vessels made of cast iron, steel, or mild carbon steel are commonly used.
o Includes cooling coils, agitators, feed inlets, product outlets, and emergency dumping
lines.

 Temperature Control:
o Cooling is achieved using:
 Coils: Tubes circulate cold water or brine for cooling or steam for heating.
 Advantages: Compact, high coolant velocity.
 Disadvantages: Prone to fouling and scaling, difficult to clean.
 Wall Jackets: Effective for small vessels but insufficient for larger setups.

 Safety Measures:
o Emergency quick-dump lines are included to rapidly transfer the contents to a drowning
tub filled with water if the reaction becomes uncontrolled.

 Ventilation:
o Suction lines in the vapor space above the liquid remove acid fumes and nitrogen oxides.

 Key Factors:

1. Degree of Agitation: Ensures uniform mixing and reaction.

2. Temperature Control: Prevents overheating, ensuring safety and reaction efficiency.

Continuous Nitration

 Setup:
o Similar vessels to batch nitration but include:
 Overflow Pipes/Weir: For continuous withdrawal of products.
 Continuous Feed System: Automated delivery of reactants.

 Advantages:
o Automation ensures consistent quality and reduces manual intervention.
o Suitable for large-scale production with smaller equipment footprint compared to batch
processes.
 Types of Nitrators

1. Schmid Nitrator:
o Reactants are fed from the top.
o Fresh mixed acid enters from the bottom and is mixed with reactants using agitators and
baffles.
o Reaction mixture passes upward through brine-cooled tubes, and products are withdrawn
continuously.

2. Biazzi Nitrator:
o Uses a turbine-type agitator that forms a vortex for intensive mixing.
o Reactants fed from the top are drawn into the vortex and circulated through cooling coils.
o High velocity ensures efficient mixing and heat transfer.
o Vapors formed due to "hot body meets cold body" effect are removed via suction lines.

Mixed Acid Composition

Efficient nitration depends on:

1. Nitric Acid:
o Must be present in sufficient quantities to satisfy stoichiometric requirements.
o Often used in excess to maintain a fast overall reaction rate.
2. Sulfuric Acid:
o Acts as a dehydrating agent, catalyst, and reaction promoter.
o Increases efficiency by removing water formed during the reaction.

Key Ratios:

 D.V.S (Dehydrating Value of Sulfuric Acid):

 D.V.S (Dehydrating Value of Sulfuric Acid):

 Ratio of H₂SO₄ to H₂O in the reaction mixture.

 High D.V.S ensures stability and reaction completion.

 Nitric Ratio:

 Ratio of the weight of nitric acid to the weight of material being nitrated.

Relation Between D.V.S and Stability

 High D.V.S promotes safety by:

  Driving the reaction to completion.
 Reducing accumulation of partially nitrated materials that may cause oxidation.

 Low D.V.S increases hazards by allowing unstable intermediates to accumulate.

Preparation of Nitrobenzene

Batch Process:

1. Reaction Setup:
o Benzene is charged into the reactor.
o Nitrating acid mixture (H₂SO₄: 56-60%, HNO₃: 27-32%, H₂O: 8-17%) is added slowly
below the benzene surface.
2. Reaction Conditions:
o Temperature is raised to ~90°C toward the end to complete the reaction.
o Reaction time: 2-4 hours.
o Typical yield: 95-98%.
3. Material Requirements:
o Benzene: 650 kg.
o Sulfuric acid: 720 kg.
o Nitric acid: 520 kg.
o Water: 110 kg.
o Sodium carbonate: 10 kg.

Separation:

 Mixture is transferred to a conical tank for settling (4-24 hours).

 Spent acid is drawn off for recycling.
 Nitrobenzene can be distilled for higher purity.

Neutralization:

 Warm sodium carbonate solution is used to neutralize nitrobenzene.

 Final product is washed with warm water and stored.

Continuous Process:

1. Setup:
o Benzene and nitrating acid are continuously fed into the nitrator (stirred reactor with
cooling systems).
o Spent acid and crude nitrobenzene are separated using gravity settlers or centrifuges.

2. Process Types:
o Adiabatic:
 Heat of the reaction is used to boil off water and benzene.
Reaction temperature: 120-160°C.
Eliminates excessive cooling and integrates with sulfuric acid reconcentration.
o Isothermal:
 Uses 2-4 nitrators in series for large plants.
 Heat is controlled to maintain a stable temperature for consistent product quality.

3. Advantages of Continuous Process:

o Smaller equipment size for the same production capacity as batch processes.
o Faster reaction times: 0.5-7.5 minutes for adiabatic nitration.

Engineering Factors for Nitration

1. Temperature:
o Influences solubility, viscosity, and interfacial tension between organic and acid phases.
o Proper control ensures efficient reaction and safe operation.

2. Agitation:
o Promotes mixing and mass transfer between organic and acid phases.
o Higher impeller speeds enhance the reaction by reducing droplet size in the dispersed
phase.

3. Acid Composition:
o Higher sulfuric acid concentration increases nitronium ion availability and reaction rate.
o Beyond 90% sulfuric acid, hydrogen bonding reduces electron density in the aromatic
ring, slowing the reaction.