Reaction

Intermediates
Organic Chemistry
August 2023
Definition
• The short-lived (10-6 seconds to a few seconds) and highly reactive
fragments are called reaction intermediates that result from
homolytic and heterolytic bond fission.
Types of reaction Intermediates

• Carbocations
• Carbanions
• Free Radicals
• Carbenes
• Nitrenes
• Benzyne
1. Carbocations
• A carbocation is a molecule in which a carbon atom has a
positive charge and three bonds. We can say that, basically,
they are carbon cations. Formerly, it was known as
carbonium ion.
• Carbocation is an even-electron cation with a significant
positive charge on the carbon atom.
• In carbocation, the hybridization of carbocation will be
sp2 and its shape is trigonal planar.
• It possesses a vacant p-orbital which indicates its electron-
deficient nature.
• The positively charged carbon has 6 electrons in its valence
(outermost) shell owing to which it acts as an electrophile.
 Carbocation structure

• Observed in nucleophilic and elimination as well as substitution reactions.

• Carbocations are of different types.
 Reactions Involving Carbocations
• Elimination reactions (E1 )to form alkenes from alkyl halides and
alcohols.
• Electrophilic addition reaction of alkenes, alkynes, and alkadienes.
• SN1 reactions of alkyl halides and diazonium salts
• Molecular pinacol-pinacolone rearrangement.
Types of Carbocations
On the basis of the number of alkyl groups bonded to the electron-
deficient carbon atom, the carbocations are classified as follows:
• Methyl Carbocation: Bonded to only H atoms and no alkyl group.
• Primary Carbocation: Bonded to only 1 alkyl group.
• Secondary carbocation: Bonded to 2 alkyl groups.
• Tertiary Carbocation: Bonded to 3 alkyl groups.
Types of Carbocations
There are other types of carbocations depending upon the nature of the
positively charged C atom or the vicinity of the positive C atom as discussed
below:
• if the carbon with the positive charge is attached to a double bond, the
carbocation is termed vinylic carbocation.
• If there is a carbon-carbon double bond next to the carbon with the positive
charge, it is termed allylic carbocation.
• When the carbon with a positive charge is part of a benzene ring, it forms
an aryl carbocation.
• If the carbon having a positive charge is immediately next to a benzene ring,
it is termed a benzylic carbocation.
 Stability of Carbocation
The stability of a carbocation is influenced by the following factors:

• Resonance: The stability of carbocations increases with the increasing number of resonating
structures due to an increase in the delocalization of the positive charge. The electron deficiency is
decreased due to the delocalization, thereby increasing the stability.
• Hyperconjugation: Increasing substitution increases the hyperconjugation, and thus it increases
stability. The more the hyperconjugation, the higher the stability of carbocation.
• Inductive effect: The +I effect stabilizes the carbocation.
• Electronegativity: The electronegativity of the carbon atom carrying the positive charge directly
affects the stability of the carbocation. So, as the electronegativity of the carbon atom increases, the
stability of the carbocation decreases.
• The dispersal of positive charge stabilizes the carbocation. The more
the number of alkyl groups bonded to the positively charged C atom,
the higher the dispersal of the positive charge, and hence more the
stability of the corresponding carbocation. Therefore, the order of
stability of carbocations is given below:
• Stability decreases with decrease in +I effect

• α-hydrogen with respect to carbocationic carbon has one or more

than one lone pair of electrons, then lone pair of electrons strongly
stabilizes a carbocation due to the delocalization of electrons.

• Areareareawertttaare more stable than tertiary carbocation.