Reactions of alkenes-Introduction

Preparation of Alkenes
Dehydration of Alcohols
The dehydration of alcohols is acid catalyzed (H2SO4, H3PO4)

Regioselectivity in Alcohol Dehydration

NB: Reactions that from the standpoint of orientation give exclusively or nearly exclusive one of
several possible isomeric products are regioselctive

The Zaitsev Rule - When more than one alkene product is possible from an elimination reaction,
the most highly substituted (most stable) alkene is usually the major product.

Mechanism for the formation of 2-Butene as the chief product in the alcohol dehydration of n-
Butyl alcohol
Dehydrohalogenation of Alkyl Halides
 This is the loss of H and X from adjacent carbons of an alkyl halide to form an alkene.

The reaction follows Zaitsev's rule in that the most stable double bond product usually
predominates.
Reduction of alkynes

Pd= Lindlar catalyst

Ni-B = Nickel bromide catalyst
Reactions of Alkenes

Since σ-bonds are stronger than π-bonds, double bonds tend to react to convert the double bond
into π-bonds. This happens through addition reactions.

Markovnikov’s Rule: The addition of a proton acid to the double bond of an alkene results in a
product with the acid hydrogen bound to the carbon atom that already has the greater number of
hydrogens attached.

Addition of hydrogen halides.

NB: The presence of peroxides causes a reversal of orientation.

Addition of water. Hydration

Addition of sulfuric acid

Ozonolysis.
Halohydrin formation

Orientenation follows Markovnikov’s Rule with the positive halogen going to the same
carbon that the hydrogen would.

Preparation of Alkynes

Double dehydrohalogenation of dihaloalkanes

Reaction of metal acetylides with primary alkyl halides

NB: Li can also be used instead of Na

Hydroboration-oxidation
This is a way to obtain to obtain anti-Markovnikov oriented alcohols. Borane has only six
valence electrons and is very electron deficient. Borane is an electrophilic molecule, and reacts
with double bonds in a one-step process to generate an alkylborane.
Oxymercuration-demercuration
Alkenes react with mercuric acetate in the presence of water to give hydroxymercurial
compounds which on reduction yield alcohols.

Oxymercuration-demercuration is highly regiospecific, and gives alcohols corresponding to

Markovnikov addition of water to the carbon-carbon double bond.
Reactions of Alkynes
Like alkenes, alkynes undergo addition reactions
Addition of hydrogen halides

The regioselectivity of addition follows Markovnikov’s rule

Addition of Halogens

Addition of water. Hydration