Anda di halaman 1dari 26

Islamic University in Madinah

Department of Chemistry

Physical Organic Chemistry


CH-5
Addition & Rearrangement reactions
Prepared By
Dr. Khalid Ahmad Shadid
Addition to double bond

 Alkene double bond contain sigma and pi, the bond is more reactive thane in alkane.
 Can react through electrophilic addition.

 Electrophilic addition
 Bromine and chlorine can react with alkene, while Iodine doesn't react. Florin react very
fast but no product.
 General Mechanism:

R2C=CR2 + X2 ——> R2CX-CR2X


Brominating Mechanism
 Exclusively Trans Addition to alkene. Even when alkene contain bulky group
like tertiary butyl.
 Br+ adds to an alkene producing a cyclic ion
 Bromonium ion, bromine shares charge with carbon
 Gives trans addition
 Electrophilic addition of bromine to give a cation is followed by cyclization to give a
bromonium ion
 This bromonium ion is a reactive electrophile and bromide ion is a good nucleophile
 Stereospecific anti addition
Addition of strong Acids

 Addition of proton to a double bond (rate determining step), then fast


nucleophilic attack.
Addition of Hydrogen Halide to alkene
 Addition of HX to alkene. Can cause carbocation rearrangement.
 Carbocation rearrangement from secondary to more stable tertiary.
Addition of Hypohalous Acids to
Alkenes: Halohydrin Formation
 This is formally the addition of HO-X to an alkene to give a 1,2-halo alcohol, called a halohydrin
 The actual reagent is the dihalogen (Br2 or Cl2 in water in an organic solvent)
 (HO-X), X: CL or Br is electrophile, its less electronegative than Oxygen
Mechanism of Formation of a Bromohydrin

 Br2 forms bromonium ion, then water adds

Orientation toward stable C+ species

Aromatic rings do not react


Addition sulfonyl chloride
Here electrophile is a cation RS+ . Chlorine more electronegative than sulfur

(CH3)2C=CH2 + C6H5SCl ——> (CH3)2CCl-CH2SC6H5


Addition of Water to Alkenes

 Hydration of an alkene is the addition of H-OH to to give an alcohol

 Acid catalysts are used in high temperature industrial processes: ethylene is


converted to ethanol
Oxymercuration Intermediates
 For laboratory-scale hydration of an alkene
 Use mercuric acetate in THF followed by sodium borohydride
 Markovnikov orientation
via mercurinium ion
Addition of Water to Alkenes: Hydroboration
 Herbert Brown (HB) invented hydroboration (HB)

 Borane (BH3) is electron deficient and is a Lewis acid

 Borane adds to an alkene to give an organoborane


Orientation in Hydration via
Hydroboration
 Regiochemistry is opposite to Markovnikov orientation
 OH is added to carbon with most H’s
 H and OH add with syn stereochemistry, to the same face of the alkene (opposite of anti addition)
 STEREOSPECIFIC
Mechanism of Hydroboration

 Borane is a Lewis acid


 Alkene is Lewis base
 Transition state involves anionic development on B
 The components of BH3 are added across C=C
 More stable carbocation is also consistent with steric preferences
Halogen Addition
 Mixed Halogens are polarized: X+- X-
 more electronegative halogen will carry partial negative charge
 Rate of addition:
BrCl > Br2 > ICl > IBr > I2
 Morkovinikov addition
Oxidation of Alkenes: Epoxidation and Hydroxylation
 Oxidation is addition of O, or loss of H
 Epoxidation results in a cyclic ether with an oxygen atom
 Stereochemistry of addition is syn
 MCPBA in CH2Cl2 are the usual conditions
 Addition of acid results in a trans-1,2-diol

 Treatment of the epoxide with aqueous acid give a trans diol


Osmium Tetroxide Catalyzed Formation of Diols
 Hydroxylation - converts to syn-diol
 Osmium tetroxide, then sodium bisulfate
 Via cyclic osmate di-ester
 Osmium is toxic, so catalytic amount and NMO are used
What is Rearrangement Reactions?
 The term of “rearrangements” is used to describe organic reactions which involve the
migration of an H atom or of a larger molecular fragment.
 Nucleophilic Rearrangements
 Electrophilic rearrangements
 Radical rearrangements

1. Nucleophilic Rearrangements
1 1
R(H) R(H)
+
C C+ C C
1' 2' 1' 2'

 [1,2]-Rearrangements

1 1
R(H) R(H)
+ +
C N C N2'
1' 2' 1'
Wagner-Meerwein rearrangements
 Wagner-Meerwein Rearrangements are [1,2]-rearrangements of H atoms
or alkyl groups in carbenium ions that do not contain any heteroatoms
attached to the valence-unsaturated center C-1 or to the valence-
saturated center C-2.

1 1
R(H) R(H)
+
C C+ C C
1' 2' 1' 2'
CH3 + CH3
H
CH3 C CH2OH CH3 C CH2OH2
CH3 CH3 H2O

Cl- Cl
CH3 CH3 C CH2CH3
CH3 C CH2 CH3 C CH2CH3 CH3
CH3 CH3 H+ CH3C=CHCH3
CH3
Wagner-Meerwein rearrangements

Carbocation
CH3+ < CH3CH2+ < (CH3)2CH+ < CH2=CH-CH2+ < C6H5CH2+
Stability

 Carbenium ions: 1 °→2 °,1 °→3 °


2 °→3 °
 Reactions include Wagner-Meerwein rearrangement step:
1. Electrophilic additions of alkenes
2. Nucleophilic substitutions (SN1)
3. E1 elimination
4. Friedel-Crafts alkylation reactions, etc
 Example: Friedel-Crafts Alkylation
 1-Bromopropane isomerizes quantitatively to 2-bromopropane under Friedel-
Crafts conditions. The [1,2]-shift A→B involved in this reaction again is an H-
atom shift.

cat. AlCl3 in CH3 CH3


+
H + H H
H H - AlBr3 Br
H
Br H - H -
AlBr4 AlBr4

NO2 A B
 Example:

Wagner-Meerwein rearrangement as part of an isomerizing E1


elimination

+
OH conc. H SO OH2 H
2 4
+
_H O
2 H

Methyl shift

H H
+
_
H+
 Example: Nucleophilic Substitution

CH3 OH
HNO2
H3C CH2NH2 CH3 C CH2CH3
CH3 CH3

Methyl shift
Mechanism
CH3 HNO2 CH3 +
H3C CH2NH2 CH3 C CH2
CH3 CH3

+ OH
CH3 C CH2CH3 H2O CH3 C CH2CH3
CH3 H+ CH3
 Example: E1 and Nucleophilic Substitution
CH2NH2 CH2OH OH
HNO2
+ + +

Mechanism
CH2NH2 + CH
2 +
HNO2

CH2OH OH

+ +
GOOD LUCK