Depending on the and alcohol, dehydration often alkenes; however predominates.

structure of the alkyl halide dehydrohalogenation and yield a mixture of isomeric only one isomer generally

(1841 1910), was a Russian chemist from Kazan. He worked on organic compounds and proposed Zaitsev's rule, which predicts the product composition of an elimination reaction.

In dehydrohalogenation and dehydration, the double bond of the alkene is formed predominantly towards the adjacent carbon atom having fewer hydrogen atoms.

CH3CH2CHCH3 Br
CH3CH=CHCH3 H H H H H C C=C C H H H Major product (disubstituted alkene) CH3CH2CH=CH2 H H H H H C C C =C H H H Minor product (monosubstituted alkene)

CH3 | CH3-C-CH2CH3 | OH
CH3 | CH3C=CHCH3 Major product CH3 | CH2=C-CH2CH3 Minor product

CH3 Cl | | H-C-C-CH3 | | CH3 H

CH3 | H-C=C-CH3 | | CH3 H NaOH

Major product

+H2O + Na Cl

CH3 | H-C-C=CH2 | | CH3 H

Minor product

Cl | CH3-CH3-C-CH3 | CH3

CH3-CH=C-CH3 | CH3

Major product

H2

O CH3-CH2-C-CH3 || CH2

+H3 O Cl

Minor product

+
Unsaturated Saturated organic hydrocarbon compound In an addition reaction, carbon-carbon double bonds become single bonds. This means that an unsaturated hydrocarbon becomes a saturated organic compound.

Why do alkenes undergo addition reactions?

Carbon-carbon double bonds in alkenes are reactive. readily undergoes addition reactions

Hydrogenation
Hydrogenation is the addition of hydrogen to the double bond.

Halogen Addition
This reaction involves the addition of Cl2 or Br2 (I2 is too unreactive) to the alkene, forming a vicinal dihalide.

Hydrohalogenation
Hydrohalogenation is the addition of gaseous hydrogen halide, HX, to an alkene, forming an alkyl halide. The order of reactivity of HX is HI> HBr > HCl. The order of reactivity of the HX reflects their ability to donate a proton.

Hydrohalogenation
For the type RCH=CHR, the hydrogen of HX may add to any of the doubly-bonded carbon atoms, forming only one product.

Hydrohalogenation
For unsymmetrical alkenes of the type R-CH=CH3, there is the possibility of obtaining two isomeric products during hydrohalogenation.

(1838 1904), was a Russian chemist. Markovnikov is best known for Markovnikov's rule, elucidated in 1869 to describe addition reactions of H-X to alkenes.

When a hydrogen halide adds to an unsymmetrical alkene, the hydrogen adds to the carbon that already holds the greater number of hydrogens, and the halogen adds to the carbon having fewer hydrogens.

Markovnikovs Rule

Markovnikovs Rule

Orientation of Addition of HBr

The addition of HBr was unpredictable in that sometimes addition occurred according to Markovnikovs rule and at other times, anti-Markovnikov addition was observed. Kharasch and Mayo discovered that anti-Markovnikov addition was promoted when peroxides were present during the reaction.

Orientation of Addition of HBr

Hydration
Hydration is the addition of water to the carbon-carbon double bond to yield an alcohol.

Hydroxylation
Hydroxylation is an oxidation reaction wherein alkenes are converted to 1,2 diols (dihydroxy alcahols containing the two OH groups on adjacent carbons). The most commonly used oxidizing agent is aqueous KMnO4 solution. The reaction amounts to an addition of two hydroxyl groups to the double bond.

Polymerization
Polymerization is the combining together of alkene molecules (monomers) to form one large molecule, called a polymer. Alkenes will polymerize in the presence of acid catalysts via a carbonium ion mechanism, or peroxide initiators via a free radical mechanism.

Polymerization

Polymerization

General Equation:
Reaction with ethene Hydrogenation (Addition of hydrogen) Reaction Conditions
Pt, Pd, Rh, or Ni catalyst

Example

H H C C H H H C H H C H H C H H C H

+ H2

H H H C C H H H H H C Cl H H C H H C H Cl H C Cl H

Halogen Addition Hydrohalogenation (Addition of hydrogen halide)

Room temperature

+ Cl2
+ HCl

Reaction with ethene

Reaction Conditions

Example

Hydration (Addition of steam)

H2SO4

H H C C H H H H C H

+ H2O
H H C C H H
KMnO4

H H H C C H H OH H H C C H OH OH H H C C H Cl

Hydroxylation

KMnO4

CH3

Polymerization

peroxide

H H nC C CL H H

Dehydrohalogenation of Alkyl Halides

For primary alkyl halides, the mechanism is a continuous one-step process.

The basic reagent directly abstracts a hydrogen ion on an adjacent carbon at the same time that the double bond is forming and the halide ion is leaving.

Dehydrohalogenation of Alkyl Halides

For secondary and tertiary alkyl halides, the mechanism involves two steps. Step 1: The alkyl halide undergoes slow heterolysis to form a carbonium ion and a halide ion.

Dehydrohalogenation of Alkyl Halides

Step 2: The carbonium ion rapidly loses a proton to the base. The electron pair left behind forms the pi bond between the carbon atoms.

Dehydrohalogenation of Alkyl Halides

Example

Dehydrohalogenation of Alkyl Halides

Example

Mechanism
CH3-CH2-CH-CH3 | Cl CH3-CH=CH-CH3
2 butene

Step 1 : Loss of Cl produces a 2 carbonium ion

CH3-CH2-CH-CH3 | Cl

Slow, E1 -Cl

CH3-CH=C+H-CH3

Mechanism
Step 2 : The carbonium ion rapidly loses a proton to the base. The electron pair left behind forms the pi bond between the carbon atoms.
Fast

CH3-CH2-C+H-CH3

-H+

CH3-CH=CH-CH3
2-butene

(from C2)

Fast -H+ (from C2)

CH3-CH2-CH=CH2
1-butene

Mechanism
Dehydration of alcohols. In dehydration reactions, a molecule of water is eliminated from an alcohol molecule by heating the alcohol in the presence of a strong mineral acid. A double bond forms between the adjacent carbon atoms that lost the hydrogen ion and hydroxide group.

CH3-CH2-OH + H2SO4

heat

CH2=CH2 + H2O

Mechanism
1. Protonation of the alcohol

CH3-CH2-O-H

heat

CH3-CH2-O+-H | H H | O S O

H+ | OS O

H | O O

-O

Mechanism
2. The protonated ethanol loses a water molecule to give a carbonium ion.

CH3-CH2-O+-H | H

CH3-C+H2

H 2O

Mechanism
3. The carbonium ion loses a proton forming the alkene.

CH2-C+H2 | H H | -O O S O O

CH2=CH2 H | O S O O H | O

When propylene polymerizes into polypropylene, the methyl groups appear regularly on alternate carbons of the main chain. + H nCH2=CH -CH2CH-CH2-CH-CH2-CHCH3 CH3 CH3 CH3

OR

(-CH2-CH-)n CH3

When a hydrogen halide adds to an unsymmetrical alkene, the hydrogen adds to the carbon that already holds the greater number of hydrogen, and the halogen adds to the carbon having fewer hydrogen.
CH3CH=CH2 + HCl CH3CHCH3 | Cl

Used in the production of margarine

200 C, nickel catalyst

Hydrogen + vegetable oil

Margarine

The greater the amount of hydrogen used, the saturated the fat and the more _________ solid more ___________ the margarine becomes.

CH3CH=CH2 + HCl

CH3CH-CH3 + CH3CH2-CH2Cl CH3C+H-CH3 + :ClCH3C2H-C+H2 + :ClCH3CHCH3 Cl CH3CH2CH2Cl

Step 1. The H+ electrophile protonates the pi bond

CH3CH=CH2 + H:Cl CH3CH=CH2 + H:Cl

Step 2. The carbocation reacts with the halide anion to form the product.

CH3C+H-CH3 + :ClCH3C2H-C+H2 + :Cl-

CH3 CH2=CHCH3 + HBr

2-Methylpropene A. Chain Initiating Steps

HOOH

CH3 | BrCH2CHCH3

B. Chain Propagating Steps

C. Chain Terminating Step

Br + Br

Br:Br