SN1 and SN2 Reactions and their Mechanisms for JEE

VSAT 2022

Nucleophilic Substitution Reaction

A nucleophile is defined as an atom or a molecule that contains a pair of electrons to donate to another atom or molecule. In simple terms, we can say that these are electron-rich species with unused electrons in their orbit. Nucleophiles can be anions or neutral anions that are negatively charged ions. For example, Hydroxide ion (OH-).

Neutral nucleophiles are molecules that contain a lone pair of electrons with zero charges on them. For example, Ammonia (NH3). Even though the molecule ammonia is neutral, the nitrogen atom contains a lone pair of electrons, which can be donated to electron-deficient species.

A substitution reaction is a type of chemical reaction, where the atom or the functional group of a molecule gets substituted by another atom or a functional group. Substitution reactions can be of two types: Electrophilic Substitution Reactions and Nucleophilic Substitution Reactions.

A nucleophilic substitution reaction is a reaction in which one nucleophile replaces the other nucleophile in a molecule. The molecule on which substitution occurs is known as the ‘substrate’, and the group that leaves is called ‘leaving group’. In this topic, we will learn about the types of nucleophilic substitution reactions along with their mechanisms. 


What are SN1 and SN2 Reactions?

SN1 and SN2 reaction mechanisms belong to nucleophilic substitution reactions. To understand these reaction mechanisms better, it is important to learn the basics of nucleophilic substitution reactions. SN2 reaction (substitution, nucleophilic, bimolecular ) is a one-step mechanism, following second-order kinetics whereas SN1 is a two-step mechanism, following first-order kinetics. In the SN1 mechanism, the product is formed via the formation of carbocation, whereas in the SN2 mechanism the reaction occurs through a transition state.


Mechanism of SN2 Reaction

Let us consider the reaction between methyl chloride and hydroxide ions to produce methanol and chloride ions. In the SN2 reaction, the rate of reaction depends on the concentration of both the reactant, i.e. methyl chloride and hydroxide ions. In other words, rate $=\mathrm{k}\left[\mathrm{CH}_{3} \mathrm{Cl}\right]\left[\mathrm{OH}^{-}\right]$.

Mechanism


Image: Mechanism of SN2 reaction


Hence, in this reaction both the alkyl halide and nucleophile simultaneously take part in the rate-determining step of the SN2 reaction. Thus, SN2 is a concerted reaction i.e. step reaction. SN2 reaction occurs through the transition state in which the carbon atoms are simultaneously bound to the incoming nucleophile OH- ion and the outgoing leaving group chloride ion.


Due to the instability of the transition state, it decomposes into product methanol and leaves a group of chloride ions. In the SN2 reaction, the attack of the nucleophile occurs from the back side where the leaving group leaves from the front side. It results in the inversion of the configuration which is also known as ‘Walden Inversion’.

 

Mechanism of SN1 Reaction:

Let us consider the reaction between tert-butyl bromide and the hydroxide ion to yield tert-butyl alcohol and chloride ion.

SN1 reaction follows first-order kinetics, that is, the rate of reaction depends on the concentration of only one reactant, which is tert-butyl bromide and is independent of the concentration of hydroxide ion. Rate $=k\left[\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CBr}\right]$. Hence, the reaction occurs in two steps.

Step 1: This step is slow, reversible and the rate-determining step. Here, tert-butyl bromide undergoes ionisation to produce tert-butyl carbocation and the bromide ions.

Formation


Step 1. Formation of carbocation


Step 2: Since the carbocation is very reactive, it is immediately attacked by the nucleophile, i.e, OH- to give the substitution, that is tert-butyl alcohol.

The step is fast and therefore, does not affect the rate of reaction.

Attack


Step 2. Attack of nucleophile


Stereochemistry of SN2 and SN1 

Stereochemistry of SN2 reaction: As we previously discussed, in an SN2 reaction, the attack of a nucleophile occurs to form the back side, that is, in the direction opposite to the one where the halogen leaves. As a result, SN2 is accompanied by inversion of configuration just the same way an umbrella turns inside out. This inversion of configuration is also called ‘Walden inversion’. Hence in SN2, there is a complete inversion of configuration.

Stereochemistry


Stereochemistry of SN2


Stereochemistry of SN1: In the SN1 reaction, if the alkyl halide is optically active, then the product is a racemic mixture. In the SN1 reaction, nucleophile attacks occur from both the backside and front side. However, backside attack is predominant. We can say that the nucleophile attack in SN1 carbocation can occur with equal ease from both the front and the backside. Given the racemic mixture of the product, the overall result is generally racemisation with some inversion i.e, partial racemisation occurs.

Stereochemistry


Stereochemistry of SN1


Distinguish Between SN1 and SNMechanism 

Point of Difference

SN1 Reaction Mechanism

SN2 Reaction Mechanism

Rate Law

follows first-order kinetics.

follows second-order kinetics.

Reactivity order 

the order of reactivity follows the sequence: $3^{\circ} > 3^{\circ} > 1^{\circ}$

the order of reactivity follows the sequence: $1^{\circ} > 2^{\circ} > 3^{\circ}$

Nucleophile

It is a weak nucleophile such as water or alcohol.

It is a strong nucleophile such as alkoxide. 


Stereochemistry of SN1 and SN2 reactions 

Racemisation with some inversion.

Complete inversion of configuration.

Solvents

Polar protic solvent of high dielectric constant.

Polar aprotic solvent i.e. acetone.

Intermediate

Carbocation is intermediate.

The reaction occurs through a transition state.


Conclusion

To sum it up, SN1 and SN2 are two types of nucleophilic substitution reactions explained by taking Sn1 and Sn2 reaction examples. A nucleophile is defined as an electron-rich atom or molecule. It can be in the form of an anion (negatively charged ion) or in the form of a compound that has one lone pair of electrons.

A nucleophilic substitution reaction involves the replacement of one functional group or atom with another anion or atom. 

FAQs on SN1 and SN2 Reactions and their Mechanisms for JEE

1. What is nucleophilicity and how does it differ from basicity?

In a substitution reaction, nucleophilicity refers to a nucleophile's capacity to displace a leaving group. This section discusses several nucleophilicity trends. There is a trend within a period, a trend within a group, a trend depending on the nucleophile's charge and a nucleophile's steric effect. Nucleophiles are also bases. In elimination reactions, they can abstract protons. Although nucleophilicity and basicity are both connected to the availability of the same electron pair, the reactions of a series of nucleophiles do not always follow the same pattern as the reactions of the same species as bases.

2. What is an optically active substance?

The substances which can rotate the plane of polarised light in either direction (left or right ) are called ‘optically active substances’ and the property of substances to rotate the plane of polarised light is called ‘optical activity’. Substances that rotate the plane of polarised light toward the right i.e. in the clockwise direction, are called ‘dextrorotatory’ and denoted by algebraic sign (+). Substances that rotate the plane of polarised right light toward the left i.e. in the anti-clockwise direction, are called ‘laevorotatory’ and are denoted by algebraic sign (-).

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