Substitution Reaction

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What is Substitution Reaction?

The substitution reaction can be described as a reaction in having the functional group of one chemical compound substituted by another group. It is also defined as a reaction that involves the replacement of one molecule or an atom of a compound with another molecule or an atom.

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Substitution Reaction Example

These types of reactions are referred to the nucleophilic and possess major importance in the field of organic chemistry. Let us say, for example, when the CH3Cl compound is reacted with the hydroxyl ion (OH-), it leads to the formation of the original molecule, which is called methanol with that hydroxyl ion. The chemical reaction for this can be given as follows:

CH3Cl + (−OH) ————-CH3OH( methanol) + Cl-

Another example would be the Ethanol reaction with the hydrogen iodide, which produces iodoethane along with water. The chemical reaction for this can be given as follows:

CH3CH2OH + HI———— CH3CH2OI + H2O

Substitution Reaction Conditions

In order for the substitution reaction to take place, there are some conditions that have to be used. They are given below.

Maintaining low temperatures such as room temperature

  • The strong base like NaOH has to exist in the dilute form. For suppose, if the base is with a higher concentration, there are high chances of dehydrohalogenation occurring

  • The solution is required to be in an aqueous state like water

Types of Substitution Reactions 

Substitution Reactions are given as two types, which are named as nucleophilic reactions and the electrophilic reactions. These both reactions primarily differ in the kind of an atom, which is attached to its original molecule. And, in the nucleophilic reactions, the atom is referred to as electron-rich species. On the other hand, in the electrophilic reaction, the atom is said to be an electron-deficient species. A detailed explanation of these two types of reactions can be given below.

  1. Nucleophilic Substitution Reaction:

  1. What Are Nucleophiles?

Nucleophiles are defined as the species either in the form of a molecule or an ion, which are strongly attached to the positive charge region. These are known to be either fully charged or contain negative ions, present on a molecule. The common examples of these nucleophiles can be given as water, cyanide ions, ammonia and hydroxide ions.

  1. What is the Nucleophilic Substitution Reaction?

In organic chemistry, a Nucleophilic substitution reaction can be defined as a type of reaction, where a nucleophile gets attached either to the positive charged molecules or atoms of the other substance.

  1. The Nucleophilic Substitution Reaction Mechanism

Let us discuss the mechanism of nucleophilic substitution reaction(s), which are SN1 and SN2 reaction. Here, S represents the chemical substitution, N represents nucleophilic, and finally, the number is the kinetic order of a reaction.

SN2 Reaction – Mechanism of SN2 Reaction

In this particular reaction, the addition of the nucleophile and the elimination of the leaving group takes place simultaneously. Also, SN2 reaction occurs where the central carbon atom has easy access to the nucleophile.

In these SN2 reactions, the reaction rate is affected by some conditions. They can be listed as follows:

  • The numerical value two present in the SN2 states that there exist two concentrations of the substances which affect the rate of reaction, which are nucleophile and substrate.

  • The rate equation for the reaction given above can be written as

Rate = k [Sub][Nuc].

  • An aprotic solvent like DMSO, DMF, or acetone is suited best for the SN2 reaction because they do not add the H+ ions for the solution.

  • If in case, there are protons available, they react with the nucleophile to limit the rate of reaction critically. This is a one-step reaction, and the speed of reaction is driven by the steric effects. During this intermediate step, the position of the leaving group can be inverted, whereas the nucleophile is given as 180°.

  • Also, nucleophilicity affects the rate of reaction.

SN1 Reaction – Mechanism of SN1 Reaction

There are some factors that affect the SN1 reaction also. A few of them are discussed below:

  • Instead of two concentrations, only one concentration, that is, the substrate affects the rate of reaction.

  • The rate equation for the reaction, which is given above can be written as 

Rate = k[Sub].

  • The reaction rate can be defined by its slowest step. Thus, the leaving group leaves at a specific rate that helps in defining the reaction speed.

  • It can be considered that the weaker the conjugate base, the better is considered as the leaving group.

  • SN1 reactions are defined by the bulky groups which are attached to the carbocations.

  • The tertiary carbocation reaction is faster to that of the secondary carbocation, which is faster than the primary carbocation.

  • In the rate-determining step, the nucleophile is not needed.

Example of Nucleophilic Substitution Reaction:

One of the good examples of a nucleophilic substitution reaction is given as the hydrolysis of alkyl bromide (R-Br), under the basic conditions. Whereas, the nucleophile the base OH, and the leaving group is the Br. The reaction for this can be given as follows:

R-Br + OH ————– R-OH + Br

Nucleophilic reactions are the most important ones in the field of organic chemistry, and these are broadly divided as to take place at the position of a carbon atom of a saturated aliphatic carbon compound.

2. Electrophilic Substitution Reactions:

  1. What Are Electrophiles?

The electrophilic substitution reaction involves electrophiles. Electrophiles are the ones which donate an electron pair in the covalent bond formation. The Electrophilic reactions take place mostly with the aromatic compounds. And, these compounds contain up to about excess electrons which can be shared on the whole system of reaction.

  1. What is Meant by the Electrophilic Substitution Reaction?

Basically, the Electrophilic substitution reactions can be described as those chemical reactions, where the electrophile replaces the compound’s functional group, but not the hydrogen atom. A few examples of the electrophiles species include hydronium ion (H3O+), and the halides of hydrogen, like HBr, HCl, sulphur trioxide (SO3), HI, the nitronium ion (NO2+).

  1. Types of Electrophilic Substitution Reaction:

There exist two types of electrophilic substitution reactions. They are the aromatic electrophilic substitution reaction and the aliphatic electrophilic substitution reaction.

Electrophilic Aromatic Substitution reaction

In this electrophilic substitution type, an atom which is attached to the aromatic ring, mostly hydrogen is substituted by an electrophile. The reactions that take place are said as aromatic halogenation, aromatic acylation and sulfonation, and aromatic nitration. Also, it is further composed of alkylation and acylation.

Electrophilic Aliphatic Substitution

In this electrophilic substitution reaction type, an electrophile dislocates one of the functional groups. The four electrophilic aliphatic substitution reactions that are the same as to the counterparts of nucleophile SN1 and SN2 are given as – SE1, SE2, SE2 and SEi (which are called Substitution Electrophilic). During the SE1 reaction, the substrate ionizes to the carbanion briskly recombines with the electrophile. And, during the SE2 reaction, only a single transition state takes place, where the old and newly formed bonds are present.

Other types of substitution reactions are organometallic substitution reactions, radical reactions.

FAQ (Frequently Asked Questions)

1. Is hydrolysis given as a substitution reaction?

Hydrolysis is simply a heat substitute. This is achieved by the displacement of sn2 of a primary halogen by water, by the water-stabilized trapped carbon nucleophile reaction, or just by adding water through a double bond.

2. What takes place in a substitution reaction?

Substitution reaction is otherwise called a single replacement reaction or single displacement reaction, which is a chemical reaction during which one functional group can be replaced by the other functional group in a chemical compound. For this, halogenation is a good example.

3. Explain about Nucleophile substitution reaction.

Nucleophilic substitution is defined as a fundamental class of reactions in both organic and inorganic chemistry, where an electron-rich nucleophile selectively attacks or binds either the positive partial or positive charge of either an atom or group of atoms to replace the left group.

4. Explain what the substitution reactions used for.

The most important reactions of synthetic organic chemistry can be given as an electrophilic aromatic substitution. These reactions can be used to synthesize the important intermediates, used as precursors for agrochemical, pharmaceutical, and industrial products manufacturing.