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Unit 4-3 Addition Reaction (2)

Addition reactions involve compounds with π electrons, such as alkenes, alkynes, and carbonyls, resulting in products that contain all elements from the reactants. The mechanisms include AdE2 and AdE3, with AdE2 being bimolecular and AdE3 trimolecular, and they follow specific regioselectivity rules like Markovnikov's rule. Various types of addition reactions include hydrogenation, hydration, and Diels-Alder reactions, each with distinct mechanisms and outcomes.

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35 views21 pages

Unit 4-3 Addition Reaction (2)

Addition reactions involve compounds with π electrons, such as alkenes, alkynes, and carbonyls, resulting in products that contain all elements from the reactants. The mechanisms include AdE2 and AdE3, with AdE2 being bimolecular and AdE3 trimolecular, and they follow specific regioselectivity rules like Markovnikov's rule. Various types of addition reactions include hydrogenation, hydration, and Diels-Alder reactions, each with distinct mechanisms and outcomes.

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Organic Chemistry I

4.3 Addition Reactions

2/27/2025 8:02 PM 1
ü Addition reactions occur in compounds having  electrons in:
– carbon–carbon double (alkenes) or
– triple bonds (alkynes) or
– carbon–oxygen double bonds (aldehydes and ketones).
ü In an addition reaction, the product contains all of the
elements of the two reacting species.

+ - Addition
C C + C C
E Nu
Nu E
Alkene Reagent
Product
Mechanism and Reactivity
ü The two electrophilic addition mechanisms are designated
as the AdE2 and AdE3 mechanisms.
ü The AdE2 is bimolecular, or the reaction has two reagents
involved in the rate-determining step.
ü The AdE3 is trimolecular, or a reaction with three reagents
involved in the rate-determining step.
ü The AdE2 mechanism corresponds closely to the E1
mechanism, and the AdE3 mechanism corresponds closely
to the E2 mechanism.
The AdE2 Reaction Mechanism
• Step 1: Pi electrons attack the electrophile.

• Step 2: Nucleophile attacks the carbocation.

ü In the first step the electrophilic portion of the reagent adds to the
substrate to form a carbocation.
ü In the second step the nucleophile adds to the carbocation
intermediate to complete the addition reaction.
The AdE3 Mechanism

ü The AdE3 mechanism requires a simultaneous collision of three


reactive species.
ü These species include the substrate molecule containing the
double bond, the electrophile, and the nucleophile.
ü In an AdE3 mechanism the electrophile and the nucleophile come
from two separate molecules.
ü The addition of an unsymmetrical reagent to an unsymmetrical
alkene or alkyne can, in principle, take place in either of two
directions.
ü The electrophilic portion of the reagent could add to either of the
carbons involved in the double bond.
ü Then the remaining nucleophilic portion could add to the other
carbon.
Types of Addition Reactions
Markovnikove’s Rule
ü addition of unsym-metrical reagents, e.g. HX, H2O or ROH, to an
unsymmetrical alkene proceeds in a way that the hydrogen atom
adds to the carbon that already has the most hydrogen atoms.
ü The reaction is regioselective, a regioselective reaction is a
reaction that can potentially yield two or more constitutional
isomers, but actually produces only one isomer.
ü The modern Markovnikov rule states that, in the ionic addition of
an unsymmetrical reagent to a double bond, the positive portion
of the adding reagent adds to a carbon atom of the double bond to
yield the more stable carbocation as an intermediate.
Anti-Markovnikove (Radical) Addition
It is possible to obtain anti-Markovnikov products when HBr is added
to alkenes in the presence of free radical initiators, e.g. hydrogen
peroxide (HOOH) or alkyl peroxide (ROOR).
Michael Addition
When HX adds to a double bond conjugated with a carbonyl
group, the X ends up on the beta carbon.

Mechanism
Examples of Addition Reactions
1. Addition of Hydrogen to Alkenes and Alkynes
üPreparation of Alkanes
ü Addition of hydrogen atoms in the presence of a metal
catalyst (Pd-C, Pt-C, Reny Ni …) to double or triple
bonds is known as hydrogenation or catalytic
hydrogenation.
2. Addition of Water to Alkenes
ü Preparation of Alcohols
ü Addition of water is known as a hydration reaction
ü The hydration reaction occurs when alkenes are treated
with aqueous acids, most commonly H2SO4, to form
alcohols.
3. Oxymercuration–Reduction of Alkenes
Preparation of Alcohols

Mechanism
4. Hydroboration–Oxidation of Alkenes
ü Preparation of Alcohols
ü Addition of water to alkenes by hydroboration–oxidation gives
alcohols via anti-Markovnikov addition.

Mechanism
5. Addition of Sulphuric Acid to Alkenes
Preparation of Alcohols

6. Addition of Halides to Alkenes


Preparation of Alkyl dihalides
Other Reactions of Double Bonds
1. Ozonization
A most widely used method for the oxidative cleavage
of double bonds is ozonolysis.

Mechanism
2. Diels-Alder Reaction
ü the Diels–Alder reaction is a [4+2] cycloaddition of a
conjugated diene and a dienophile (an alkene or alkyne).
ü an electrocyclic reaction that involves the 4 π-electrons
of the diene and 2 π-electrons of the dienophile.
ü The driving force of the reaction is the formation of new
σ-bonds, which are energetically more stable than the
π-bonds.
Examples
O O
H
1
Benzene
O O
Heat
4
O H O
1,3-butadiene maleic anhydride Tetrahydrophthalic anhydride
A conjugated diene A dienophile 95

O
O
Heat OMe
+ OMe

Methyl acetylenecarboxylate
Methyl cis-3,6-dimethyl-
1,4-Dimethyl-1,3-butadiene 1,4-cyclohexadiene-1-carboxylate
3. Glycol Formation
ü A dihydroxylation reaction adds two OH groups to a double bond
to form a diol.
ü The reaction of an alkene with cold alkaline potassium
permanganate (KMnO4) or with osmium tetroxide (OsO4) in an
aqueous hydrogen peroxide solution

Examples
4. Addition Polymerization
A high-molecular-weight material comprising a large number of
monomer subunits is called a polymer.

Mechanism

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