SN1 & SN2 Reactions

Complete NCERT Notes | Nucleophilic Substitution Reactions

Class 12 Chemistry | Haloalkanes and Haloarenes

1. Introduction to Nucleophilic Substitution

Nucleophilic substitution reactions are among the most important reactions of alkyl halides
(haloalkanes). In these reactions, a nucleophile replaces a leaving group (usually a halide) at a
saturated carbon atom.

General equation: R—X + Nu⁻ → R—Nu + X⁻

Where: R = alkyl group, X = halogen (leaving group), Nu⁻ = nucleophile

Key terms to know:

• Nucleophile: An electron-rich species that attacks electron-deficient carbon. Can be negatively
charged (CN⁻, OH⁻) or neutral with lone pair (NH₃, H₂O).
• Leaving Group (LG): The atom/group that departs with the bonding electrons. Good leaving
groups are weak bases: I⁻ > Br⁻ > Cl⁻ > F⁻ (in terms of leaving ability).
• Electrophilic Carbon: The carbon bearing the leaving group; it is electron-deficient due to the
C—X bond polarity (δ+).

Types of Nucleophilic Substitution:

SN1 → Substitution Nucleophilic Unimolecular (2-step, involves carbocation)

SN2 → Substitution Nucleophilic Bimolecular (1-step, concerted, back-side attack)

2. SN1 Reaction — Substitution Nucleophilic Unimolecular

2.1 Definition & Key Features
SN1 stands for Substitution Nucleophilic Unimolecular. The '1' in SN1 means only ONE molecule (the
substrate) is involved in the rate-determining step. The reaction proceeds in two distinct steps through
a carbocation intermediate.
 ★ NCERT Important Line: "The rate of SN1 reactions depends only on the concentration
of the alkyl halide and not on the concentration of the nucleophile."

2.2 Mechanism of SN1 (Two Steps)

Step 1 — Ionisation (SLOW, Rate-Determining Step)

The C—X bond breaks heterolytically. Both electrons go to X (the leaving group). A
planar, sp²-hybridised carbocation intermediate is formed.

(CH₃)₃C—Br ⟶ (CH₃)₃C⁺ + Br⁻

tert-butyl bromide → tert-butyl carbocation + bromide ion
Note: This step is SLOW because it requires breaking a bond (energy input). The
carbocation is planar (120° bond angles, sp² carbon).

Step 2 — Nucleophilic Attack (FAST)

The nucleophile attacks the planar carbocation from EITHER face (top or bottom) since
both faces are equally accessible. This leads to racemisation.

(CH₃)₃C⁺ + H₂O ⟶ (CH₃)₃C—OH + H⁺

Why racemisation? The sp² carbocation is flat. Attack from top gives one enantiomer;
attack from bottom gives the other. Equal probability → racemic mixture (50:50).

2.3 Rate Law of SN1

Rate = k [R—X]

Rate depends ONLY on the concentration of substrate (R—X). Doubling [Nu] has NO effect
on rate. This confirms only one molecule is in the transition state of the slow step.

2.4 Substrate — Effect of Structure on SN1

SN1 reactions are favoured by substrates that form stable carbocations. Order of reactivity:

3° > 2° > 1° > Methyl (for SN1)

 3° alkyl halide is best because it gives a 3° carbocation — stabilised by three alkyl groups
(hyperconjugation + inductive effect).
Methyl and 1° alkyl halides essentially do NOT undergo SN1 because the resulting
carbocation would be too unstable.

Stability Order of Carbocations:

3° > 2° > 1° > Methyl (most stable → least stable)
Reason: More alkyl groups → more hyperconjugation and +I (inductive) effect → more stabilisation of
positive charge on carbon.
Special cases: Allylic carbocations (C=C—C⁺) and benzylic carbocations (Ar—C⁺) are very stable
due to resonance, so they also readily undergo SN1.

2.5 Conditions Favouring SN1

• Solvent: Polar protic solvents — water (H₂O), ethanol (EtOH), methanol (MeOH). These
stabilise both the carbocation and the leaving group through solvation/hydrogen bonding.
• Nucleophile: Weak nucleophile is sufficient (H₂O, ROH, acetate). Since Nu is not involved in
the rate step, its strength does not matter.
• Temperature: Can work at room temperature, but higher temperature can shift products
toward E1 elimination (competing reaction).
• Substrate: 3° alkyl halides (also allylic and benzylic halides). Methyl and 1° substrates avoid
SN1.

2.6 Stereochemistry of SN1 — Racemisation

★ NCERT Important Line: "SN1 reactions lead to racemisation because the nucleophile
can attack the planar carbocation from either face, giving equal amounts of R and S
configurations — a racemic mixture."

If starting material is optically active (chiral, R or S), the SN1 product is a racemic mixture
(optically inactive, 50% R + 50% S).
In practice: SN1 gives slightly more inversion than retention (~60:40) because the leaving
group partially shields one face even after it departs. But in exam, SN1 = racemisation.

2.7 Carbocation Rearrangements in SN1

Since a free carbocation intermediate forms in SN1, rearrangements (hydride shifts and methyl shifts)
are possible if a more stable carbocation can form.

Example: Rearrangement in SN1

 When neopentyl bromide ((CH₃)₃C—CH₂Br, a 1° halide) is treated in SN1 conditions:

(CH₃)₃C—CH₂Br → (CH₃)₃C—CH₂⁺ → (CH₃)₂C⁺—CH₃ → (CH₃)₂C(OH)—CH₃

A hydride shift converts the 1° carbocation to a 3° carbocation → more stable → reaction

proceeds. Product is NOT what you'd expect from simple substitution.

2.8 Important Reactions via SN1 (NCERT Examples)

Reaction 1: tert-Butyl bromide + Water (Hydrolysis)

(CH₃)₃CBr + H₂O → (CH₃)₃COH + HBr

Conditions: Aqueous solvent (H₂O), no strong nucleophile needed. 3° substrate → stable
carbocation → SN1 proceeds readily.
Product: tert-Butanol + HBr (racemic if chiral centre present)

Reaction 2: Allylic/Benzylic Halides + Weak Nucleophile

C₆H₅—CH₂Cl + H₂O → C₆H₅—CH₂OH + HCl

Benzyl chloride reacts via SN1 because benzylic carbocation (C₆H₅—CH₂⁺) is resonance-
stabilised.

Reaction 3: Solvolysis — SN1 with Solvent as Nucleophile

(CH₃)₃CBr + EtOH → (CH₃)₃C—OEt + HBr

Here ethanol acts as both solvent AND nucleophile (solvolysis). Since it is present in large
excess, the reaction is still first-order (pseudo-unimolecular).

3. SN2 Reaction — Substitution Nucleophilic Bimolecular

3.1 Definition & Key Features
SN2 stands for Substitution Nucleophilic Bimolecular. Both the substrate and nucleophile are involved
in the single, concerted transition state. There is no intermediate — the bond breaking and bond
forming happen simultaneously.
 ★ NCERT Important Line: "In SN2 reactions, the nucleophile attacks from the back side
of the C—X bond, and the transition state has a trigonal bipyramidal geometry with the
carbon partially bonded to both the incoming nucleophile and the outgoing leaving group."

3.2 Mechanism of SN2 (One Step — Concerted)

Single Step — Back-Side Attack

The nucleophile approaches the substrate from the back (180° opposite to the leaving
group). As the nucleophile forms a new bond with carbon, the C—X bond simultaneously
breaks. The carbon passes through a trigonal bipyramidal transition state (like an
umbrella flipping).

Nu⁻ + R—X → [Nu···R···X]‡ → Nu—R + X⁻

(transition state: trigonal bipyramidal, ‡ symbol)
Walden Inversion: The three substituents on carbon flip like an umbrella in wind. If starting
material is (R), product is (S) and vice versa — always complete inversion of configuration.

3.3 Rate Law of SN2

Rate = k [R—X][Nu⁻]

Rate depends on concentration of BOTH substrate AND nucleophile. Doubling [Nu] doubles
the rate. Doubling [RX] also doubles the rate. This is second-order kinetics (first order in
each reactant).

3.4 Substrate — Effect of Structure on SN2

SN2 is extremely sensitive to steric hindrance at the carbon being attacked. Order of reactivity:

Methyl > 1° > 2° >> 3° (for SN2)

Methyl halide reacts fastest — no bulky groups to block approach of nucleophile.
1° alkyl halide reacts well — only one alkyl group, moderate hindrance.
2° alkyl halide reacts slowly — two alkyl groups crowd the back-side approach.
3° alkyl halide essentially does NOT undergo SN2 — three alkyl groups completely block
back-side attack.
 ★ NCERT Important Line: "The steric hindrance at the carbon atom bearing the leaving
group determines the rate of SN2 reaction. The more alkyl groups around the reaction
centre, the slower the SN2 reaction."

3.5 Nucleophile Strength in SN2

Since the nucleophile is involved in the rate step, its nucleophilicity directly affects the reaction rate.

Nucleophilicity Order (in polar protic solvents):

I⁻ > Br⁻ > Cl⁻ > F⁻ (halide ions: larger = better nucleophile in protic solvent)
RS⁻ > RO⁻ > OH⁻ > RCO₂⁻ > H₂O (oxygen nucleophiles)
R₃P > R₃N (phosphorus better than nitrogen)

Rule of thumb: More polarisable, less electronegative, larger atoms are better nucleophiles in protic
solvents.

3.6 Solvent Effect in SN2

• Polar aprotic solvents (DMSO, DMF, acetone, CH₃CN) strongly favour SN2. Why? They
dissolve ionic nucleophiles but do NOT solvate the anion (no N—H or O—H bonds), leaving the
nucleophile 'naked' and more reactive.
• Polar protic solvents (H₂O, ROH) solvate the nucleophile through hydrogen bonding →
reduce nucleophilicity → slows SN2.

Memory trick: Protic solvent = has H on O or N (can H-bond). Aprotic = NO such H.

Aprotic = better for SN2.

3.7 Stereochemistry of SN2 — Walden Inversion

★ NCERT Important Line: "SN2 reactions proceed with complete inversion of

configuration at the carbon atom. This is known as Walden inversion. The product has
opposite configuration (R→S or S→R) compared to the starting material."

If a chiral (R) compound reacts via SN2, the product is the (S) enantiomer. This is 100%
stereospecific — unlike SN1 which gives racemisation.
Why inversion? Back-side attack forces the three substituents to flip to the opposite side,
like an umbrella inverting in wind.
3.8 Important Reactions via SN2 (NCERT Examples)

Reaction 1: Methyl bromide + NaOH → Methanol

CH₃Br + NaOH(aq) → CH₃OH + NaBr

Methyl bromide (no steric hindrance) + strong nucleophile OH⁻ → SN2. Product: methanol.
Configuration inverted (not relevant for CH₃ as no chirality).

Reaction 2: n-Propyl bromide + KCN → Nitrile

CH₃CH₂CH₂Br + KCN → CH₃CH₂CH₂CN + KBr

Primary alkyl halide + CN⁻ (strong, excellent nucleophile for SN2) in polar aprotic solvent →
SN2. Carbon chain increases by one carbon (useful in synthesis).

Reaction 3: Ethyl bromide + NaI (in acetone) — Finkelstein Reaction

C₂H₅Br + NaI —(acetone)→ C₂H₅I + NaBr↓

The Finkelstein reaction uses acetone (polar aprotic). NaI is soluble in acetone; NaBr
precipitates → reaction driven to completion. I⁻ is better nucleophile than Br⁻ in protic
solvent but here aprotic solvent helps.

Reaction 4: Primary Alkyl Halide + NH₃ → Amine (SN2)

CH₃CH₂Br + NH₃(excess) → CH₃CH₂NH₂ + HBr

Ammonia acts as nucleophile via its lone pair. Primary alkyl halide + NH₃(excess) →
primary amine via SN2. Excess NH₃ prevents over-alkylation.

Reaction 5: Williamson Ether Synthesis (SN2)

C₂H₅ONa + CH₃I → C₂H₅—O—CH₃ + NaI

Sodium ethoxide (RO⁻, strong nucleophile) attacks methyl iodide (1°, no steric hindrance)
via SN2 → ether formed. Note: 3° alkyl halides must NOT be used (would give E2
elimination instead).

Reaction 6: Alkyl Halide + AgNO₃ — Diagnostic Test

R—Br + AgNO₃(alcoholic) → R—ONO₂ + AgBr↓

 3° > 2° > 1° in reactivity (forms AgX precipitate). 3° reacts immediately (SN1), 1° reacts
slowly or on heating (SN2). Used to distinguish degree of alkyl halide.

4. SN1 vs SN2 — Master Comparison Table

Parameter SN1 SN2

Mechanism 2 steps (Stepwise) 1 step (Concerted)

Rate / Kinetics Unimolecular rate = k[RX] Bimolecular rate = k[RX][Nu]
Intermediate Carbocation (stable, sp²) No intermediate — transition state
only
Best Substrate 3° alkyl halide (stable carbocation) 1° alkyl halide (least steric hindrance)
Nucleophile Weak nucleophile (H₂O, ROH, etc.) Strong nucleophile (CN⁻, RS⁻, I⁻,
N₃⁻)
Solvent Polar protic (H₂O, EtOH, MeOH) Polar aprotic (DMSO, DMF, acetone)
Stereochemistry Racemisation (attack on both faces) Complete inversion (Walden
inversion, 100%)
Rearrangements Possible (hydride/methyl shift) Not possible
Temperature Room temp; heat shifts toward E1 Room temp (competing E2 at high
elimination temp)
Order of reactivity 3° > 2° >> 1° (methyl = almost never) Methyl > 1° > 2° (3° = almost never)
Effect of conc. of Nu No effect on rate Rate increases with higher [Nu]
Product Substitution product (+ possible Substitution product (clean inversion)
elimination)

5. Factors Affecting SN1 and SN2 Reactions

5.1 Nature of Substrate
SN1 SUBSTRATE SN2 SUBSTRATE
• 3° alkyl halide — highly preferred • Methyl halide — fastest (no steric
• 2° alkyl halide — possible in polar block)
protic • 1° alkyl halide — very good
• Allylic / Benzylic halides — • 2° alkyl halide — slow
resonance stabilised carbocation
 • 1° and Methyl — essentially NO • 3° alkyl halide — essentially NO SN2
SN1

5.2 Nature of Nucleophile

• For SN1: Nucleophile strength does NOT matter. Even weak nucleophiles (H₂O, ROH) work
because they are not involved in the rate-determining step.
• For SN2: Strong nucleophile required. Nucleophilicity determines rate. Strong nucleophiles:
CN⁻, I⁻, RS⁻, N₃⁻, HO⁻, RO⁻.

5.3 Nature of Solvent

Polar Protic Solvent (H₂O, EtOH, MeOH):

• Stabilises carbocations and leaving group anions → FAVOURS SN1
◦ Solvates nucleophile by H-bonding → reduces nucleophilicity → DISFAVOURS
SN2

Polar Aprotic Solvent (DMSO, DMF, acetone, CH₃CN):

• Does NOT solvate nucleophile → nucleophile is 'naked' and very reactive →
FAVOURS SN2
◦ Does NOT stabilise carbocations well → DISFAVOURS SN1

5.4 Nature of Leaving Group

Both SN1 and SN2 require a good leaving group. Good leaving groups are stable after departure
(weak bases):
I⁻ > Br⁻ > Cl⁻ >> F⁻ (best → worst leaving group)
Tosylate (OTs), mesylate (OMs) are excellent leaving groups used in synthesis (even better than
iodide).

5.5 Effect of Temperature

• Higher temperature generally favours elimination (E1/E2) over substitution (SN1/SN2)
because elimination increases entropy (forms two molecules from one).
• For SN2 specifically: temperature increase slightly increases rate but too much heat shifts to
E2.
6. How to Decide SN1 or SN2 in Exam Questions

Step-by-Step Decision Method

1. Degree of substrate: 3° → lean toward SN1. 1° or Methyl → lean toward SN2. 2°

→ depends on other factors.
2. Nature of nucleophile: Weak Nu (H₂O, ROH) → SN1. Strong Nu (CN⁻, OH⁻, I⁻)
→ SN2.
3. Solvent: Polar protic (H₂O, EtOH) → SN1. Polar aprotic (DMSO, DMF) → SN2.
4. Check for carbocation stability: If stable carbocation possible (3°, allylic,
benzylic) → SN1 viable.
5. Stereochemistry in product: Racemisation → SN1. Inversion only → SN2.
6. Rate law: Rate independent of [Nu] → SN1. Rate depends on both [substrate] and
[Nu] → SN2.

Quick Trick — The EASY 3-Question Test:

Q1: Is the substrate 3°? YES → SN1. Is it 1° or methyl? YES → SN2.

Q2: Is the solvent protic? YES → SN1. Is it aprotic? YES → SN2.
Q3: Is the nucleophile weak? YES → SN1. Is it strong? YES → SN2.

If all three point the same way → very clear answer. If mixed → look for dominant factor
(substrate degree is usually most important).

7. Special Topics & NCERT Important Points

7.1 Competition Between SN1 and E1
SN1 and E1 always occur simultaneously because both go through the same carbocation intermediate.
Under identical conditions with a 3° substrate:
• Lower temperature → more substitution (SN1)
• Higher temperature → more elimination (E1)
• More concentrated/stronger base → shifts from SN1 to E1

7.2 Competition Between SN2 and E2

SN2 and E2 compete when strong nucleophile / strong base is used with a substrate that has β-
hydrogens.
 • Strong, small nucleophile (OH⁻, CN⁻) + 1° substrate → SN2 preferred
• Strong, bulky base (KOtBu) → E2 preferred (cannot approach carbon from back due to bulk)
• High temperature → always shifts toward elimination

7.3 Ambident Nucleophiles (NCERT Important)

★ NCERT Important Topic: Ambident nucleophiles have TWO possible attacking sites.

CN⁻ (cyanide): Can attack via C (gives nitrile R—CN) or via N (gives isonitrile R—NC). In
SN2, carbon attack preferred → R—CN.
NO₂⁻ (nitrite): Can attack via N (gives nitroalkane R—NO₂) or via O (gives nitrite ester R
—ONO). In SN2, N-attack often gives nitroalkane.
AgNO₂: Gives R—ONO (O-attack, nitrite ester) because Ag⁺ coordinates with N, forcing O
to attack.

7.4 Effect of Concentration on Reaction Pathway

★ NCERT Important Line: "In aqueous solution of alkyl halides, increasing the
concentration of nucleophile does not change the rate of SN1 but linearly increases the rate
of SN2 reaction."

7.5 Optical Activity and Substitution

• SN1: Chiral starting material → racemic product (optical rotation = 0). Product is optically
inactive.
• SN2: Chiral starting material → single enantiomer (opposite configuration). Product is optically
active but with opposite sign of rotation.
• Example (NCERT): (R)-2-bromobutane + OH⁻ via SN2 → (S)-2-butanol (100% inversion,
optically active)

8. Exam Tricks & Quick Memory Aids

Memory Trick 1 — SN1 = 'Two step, Flat, Racemate'

Two steps → flat carbocation → attack from both faces → racemisation.
'Flat carbocation = sp² = planar = both faces open = racemisation'
 Memory Trick 2 — SN2 = 'Back Attack, Inversion, Concerted'
Back side attack → umbrella inversion → one step → no carbocation → no rearrangement.
'Back-Attack Bob always Inverts' → SN2 always gives inversion

Memory Trick 3 — Solvent Memory

Protic has a Proton on O or N (alcohol, water). → Use for SN1.
Aprotic = no such proton (DMSO, DMF). → Use for SN2.

Memory Trick 4 — Substrate Reactivity

SN1: 3 > 2 > 1 (three is best, most stable carbocation = most fingers to hold +)
SN2: Methyl > 1 > 2 (smallest is best, least steric = easiest back-attack)
'3rd floor for SN1. Ground floor for SN2.'

Key Numbers for Exam

SN1 rate law: Rate = k[RX] — 1 molecule in rate step
SN2 rate law: Rate = k[RX][Nu] — 2 molecules in rate step
SN1 stereochemistry: Racemisation (50:50 R:S)
SN2 stereochemistry: 100% inversion (Walden inversion)
SN1 intermediate: Carbocation (sp², planar, 120°)
SN2 intermediate: NONE — transition state only (trigonal bipyramidal, sp³d-like)

9. NCERT-Style Practice Questions with Answers

Q1. Which of the following undergoes SN1 most readily?

(a) CH₃Cl (b) C₂H₅Cl (c) (CH₃)₂CHCl (d) (CH₃)₃CCl

Answer: (d) (CH₃)₃CCl — tert-butyl chloride (3° substrate → most stable carbocation →
SN1 fastest)

Q2. Which compound undergoes SN2 fastest with NaOH in DMSO?

 (a) (CH₃)₃CBr (b) (CH₃)₂CHBr (c) CH₃CH₂Br (d) CH₃Br

Answer: (d) CH₃Br — methyl bromide (methyl = no steric hindrance, fastest SN2)

Q3. What is the stereochemical outcome of SN2 on (R)-2-bromobutane?

Answer: (S)-2-butanol — complete inversion of configuration (Walden inversion). The OH⁻

attacks from back, all three groups flip, R → S.

Q4. Why does SN2 not occur on 3° alkyl halides?

Answer: Three bulky alkyl groups around the α-carbon cause severe steric hindrance,
physically blocking the nucleophile from approaching the back side of the C—X bond. The
transition state would be too crowded to form.

Q5. Why does polar aprotic solvent favour SN2?

Answer: Polar aprotic solvents (DMSO, DMF) dissolve ionic nucleophiles but do NOT
solvate the anion (no O—H or N—H bonds). The nucleophile remains 'naked' (unsolvated),
making it highly reactive and nucleophilic, thus favouring SN2.

Q6. Explain why allylic halides are reactive toward SN1.

Answer: Allylic halides (CH₂=CH—CH₂X) ionise to give allylic carbocations (CH₂=CH—

CH₂⁺), which are resonance-stabilised (delocalised over C1 and C3). This stability makes
ionisation favourable, promoting SN1.

10. Quick Summary — One-Page Revision

SN1
Full name: Substitution Nucleophilic Unimolecular
Steps: 2 (Ionisation → Nucleophilic attack)
Intermediate: Carbocation (sp², planar)
Rate: k[RX] — unimolecular, first order overall
Best substrate: 3° > 2° > 1° (3° always preferred)
Nucleophile: Weak nucleophile sufficient
Solvent: Polar protic (H₂O, EtOH, MeOH)
Stereochemistry: Racemisation (planar carbocation, attack from both faces)
Rearrangements: POSSIBLE (hydride/methyl shift)
Competing reaction: E1 (same carbocation intermediate)

SN2
Full name: Substitution Nucleophilic Bimolecular
Steps: 1 (Concerted — bond forming and breaking simultaneously)
Intermediate: NONE — only a trigonal bipyramidal transition state
Rate: k[RX][Nu] — bimolecular, second order overall
Best substrate: Methyl > 1° > 2° >> 3° (methyl always preferred)
Nucleophile: Strong nucleophile required (CN⁻, I⁻, OH⁻, RS⁻)
Solvent: Polar aprotic (DMSO, DMF, acetone, CH₃CN)
Stereochemistry: 100% Inversion (Walden inversion) — R→S or S→R
Rearrangements: NOT POSSIBLE (no carbocation formed)
Competing reaction: E2 (with strong, bulky base)

— End of Notes —