CHAPTER 4

INTRODUCTION TO ORGANIC REACTIONS

GENERAL PRINCIPLES
• There are 4 general types of organic reactions which are addition, elimination, substitution and rearrangement. • Addition – two reactants add together to form a single new product.

• Elimination – opposite of addition. Single reactant splits into 2 products

• Substitution – two reactants exchange part to give 2 new products

• Rearrangement – a single reactant undergoes a reorganization of bonds and atoms to yield an isomeric product

Reaction Mechanism
• Describes in detail exactly how the chemical reaction occur • Bond breaking and bond making • Example:

Reaction Mechanism and Potential Energy diagrams
• Potential energy diagram is used to depict the energy changes during the reaction.

• Activation energy – the difference in E between starting materials and the transition state • Heat of reaction – the difference in energy between product & starting materials

Reaction Intermediates
• short-lived species • 3 types

• The formation of intermediates: homolytic or heterolytic cleavage • Homolytic cleavage - symmetrical cleavage of bonding electron resulting free radical species. • Example:

• Heterolytic cleavage – unsymmetrical cleavage of bonding electron resulting carbocation or carbanion

SITES OF ORGANIC REACTIONS
• Specific reaction sites tend to be atoms or groups in which there is special availability or deficiency of electrons. • Electrophile – an electron deficient species that accepts electrons from availability species. Positively charged or neutral. Example: H3O+, H+, Br+, Cl+, NO+, FeBr3, AlCl3 • Nucleophile – an electron availability species that donates electrons to electron deficient species. Positively charged or neutral Example: OH-, Br-, I-, H2O, NH3

• Multiple bonds: double and triple bonds.Their π bonds are more readily available to an attacking species. π bonds – high electrons density, very accessible to species seeking electrons

• Polar bonds – covalent bonds in which there is uneven sharing of electron pairs between atoms of different electronegativity. Example:

• Lewis acids and bases
Lewis acids -A substance that accepts an electron pair Lewis basesA substance that donates an electron pair

Donated electron pair is then shared between acid and lewis base to form covalent bonding Example: H―Cl lewis acid + H 2O lewis base H 3O+ + ClHydronium ion

Example:

• Combination of site types

HALOGENATION OF ALKANES
• Halogenation – substitution reaction in which a hydrogen on an alkane is replaced by a halogen in presence of heat or light.

Notes: alkane, C<2 all hidrogen atoms are subtituted, C≥2 only one hidrogen is substituted !!!!!!!!!!!!!!!!!!!

• Chlorination of Methane:

Control of halogenation reaction - an alkane is introduced in a large excess so that the halogen molecules have always a probability of reacting with the alkane than mono- halogenated product.

CH4(excess) + Cl2

uv

CHCl3 + HCl

Reaction of pentane with Cl2

PREPARATION OF ALKENES:
1)Dehydrohalogenation by the E2 Mechanism

Elimination reaction

3) Dehalogenation of Vicinal Dibromides

4) Dehydration Reaction of alcohol

• Exercise

PREPARATION Reaction

OF

ALKYNES:

Elimination