3/06/2016

Addition reaction
FAU xxxx Organic Chemistry I Alkene
Alkyne
Benzene
Addition, reduction reactions

Ari Satia Nugraha PhD., Apt

Pharmaceutical Chemistry Department
University of Jember

Addition reaction: Alkene 1. Addition of Strong Brnsted Acids

Strong Brnsted acids such as HCl, HBr, HI & H2SO4
The most common chemical transformation of a carbon-carbon double bond is
Rapidly add to the C=C functional group of alkenes
the addition reaction.
Exothermic reaction

Weak Brnsted acids (i.e water (pKa = 15.7), acetic acid (pKa = 4.75)
Do not normally add to alkenes
The addition of a strong acid serves to catalyze the addition of water

CH2=CH2 + H3O(+) > HCH2CH2OH + H(+)

Markovnikov's Rule
Regioselectivity and the Markovnikov Rule
Markovnikov Rule predicts the regiochemistry of HX addition to
The Markovnikov Rule: When a Brnsted acid, HX, adds to an unsymmetrically
unsymmetrically substituted alkenes
substituted double bond, the acidic hydrogen of the acid bonds to that carbon of
The halide component of HX bonds preferentially at the more highly
the double bond that has the greater number of hydrogen atoms already
substituted carbon, whereas the hydrogen prefers the carbon which already
attached to it.
contains more hydrogens.

(CH3)2C=CHCH3 + H-Cl (CH3)2CHCHClCH3 or (CH3)2CClCHHCH3

2-chloro-3- 2-chloro-2-
2-methyl-2-butene
methylbutane methylbutane Anti-Markovnikov

Some reactions do not follow Markovnikov's Rule, and anti-Markovnikov

products are isolated. This is a feature for example of radical induced additions
of HX and ofHydroboration.

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Markovnikov's Rule
First Step: H2C=CH2 + HCl HH2CCH2(+) + Cl()
Markovnikov Rule predicts the regiochemistry of HX addition to
unsymmetrically substituted alkenes Second Step: HH2CCH2(+) + Cl() HH2CCH2Cl
The halide component of HX bonds preferentially at the more highly
substituted carbon, whereas the hydrogen prefers the carbon which already
contains more hydrogens.

Anti-Markovnikov

Some reactions do not follow Markovnikov's Rule, and anti-Markovnikov

products are isolated. This is a feature for example of radical induced additions
of HX and ofHydroboration.

Carb
ocati
CH2=CH (CH3)
on CH3(+) < CH3CH2(+) < (CH3)2CH(+) < C6H5CH2(+)
-CH2(+) 3C
(+)
Stabi
lity

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2. Rearrangement of Carbocations

3. Addition of Lewis Acids (Electrophilic Reagents)

R2C=CR2 + X2 > R2CX-CR2X

(CH3)2C=CH2 + HOBr > (CH3)2COH-CH2Br
(CH3)2C=CH2 + C6H5SCl > (CH3)2CCl-CH2SC6H5

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3. Hydroboration
Brown Hydroboration

The syn-addition of hydroboranes to alkenes occurs with predictable

selectivity, wherein the boron adds preferentially to the least hindered
carbon. This selectivity is enhanced if sterically demanding boranes are
used.

Coupling the hydroboration with a subsequent oxidation of the new

formed borane yields anti-Markovnikov alcohols. The
hydroboration/oxidation sequence constitutes a powerful method for the
regio- and stereoselective synthesis of alcohols.

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Stereoselectivity in Addition Reactions to Double Bonds 1. Brnsted Acid Additions

The stereoselectivity of Brnsted acid addition is sensitive to experimental
They may bond from the same side, conditions such as temperature and reagent concentration. The selectivity is
They may bond from opposite sides, or often anti, but reports of syn selectivity and non-selectivity are not
They may bond randomly from both sides. uncommon. Of all the reagents discussed here, these strong acid additions (E =
H in the following equation) come closest to proceeding by the proposed two-
The first two possibilities are examples ofstereoselectivity, the first being
step mechanism in which a discrete carbocation intermediate is generated in
termed syn-addition, and the second anti-addition.
the first step. Such reactions are most prone to rearrangement when this is
favored by the alkene structure.

Reagent HX X2 HOX RSCl Hg(OAc)2 BH3

Stereoselectivity mixed anti anti anti anti syn

2. Addition Reactions Initiated by Electrophilic Halogen

The halogens chlorine and bromine add rapidly to a wide variety of alkenes
without inducing the kinds of structural rearrangements noted for strong acids
(first example below). The stereoselectivity of these additions is strongly anti,
as shown in many of the following examples.

3. Hydrogenation

Alkene Isomer (CH3)2CHCH=C CH2=C(CH3)CH (CH3)2C=CHCH

H2 2CH3 3
3-methyl-1- 2-methyl-1- 2-methyl-2-
butene butene butene
Heat of
30.3 28.5 26.9
Reaction
kcal/mole kcal/mole kcal/mole
( H )

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Dienes
1. Properties of Dienes

2. Addition Reactions of Dienes

CH2=CH(CH2)2CH= BrCH2CHBr(CH2)2 BrCH2CHBr(CH2)2 CH2=CH(CH2)2CH=

CH2 + Br2 CH=CH2 + CHBrCH2Br + CH2

5,6-dibromo-1- 1,2,5,6- 1,5-hexadiene

hexene tetrabromohexan
e

3. Diels-Alder Cycloaddition

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Problems
The essential characteristics of the Diels-Alder cycloaddition
reaction may be summarized as follows:
The reaction always creates a new six-membered ring. When
intramolecular, another ring may also be formed
The diene component must be able to assume a s-cis
conformation
Electron withdrawing groups on the dienophile facilitate reaction
Electron donating groups on the diene facilitate reaction.
Steric hindrance at the bonding sites may inhibit or prevent
reaction.
The reaction is stereospecific with respect to substituent
configuration in both the dienophile and the diene.

Addition Reactions of Alkynes

1. Catalytic Hydrogenation

Alkynes are thermodynamically less stable

than alkenes to a greater degree than alkenes
are less stable than alkanes.

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2. Addition by Electrophilic Reagents

HCC-CH2-CH=CH2 + Br2 > HCC-CH2-CHBrCH2Br

Benzene: Addition

HCCH + HCl + HgCl2 (on carbon) > H2C=CHCl vinyl chloride

HCCCH2Cl + HCl + HgCl2 > H2C=CClCH2Cl 2,3-dichloropropene
HCCH + CH3CO2H + HgSO4 > H2C=CHOCOCH3 vinyl acetate
HCCH + HCN + Cu2Cl2 > H2C=CHCN acryonitrile

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