ALKIL HALIDA

Reaksi Substitusi dan

Eliminasi
 Reactions of RX
• There are two common types of
nucleophilic substitution reactions:
– SN1 reactions
• substitution, nucleophilic, unimolecular
– 3o, allylic, benzylic halides
– weak nucleophiles

– SN2 reactions
• substitution, nucleophilic, bimolecular
– methyl and 1o halides
– strong nucleophiles
Reactions of RX
 Reactions of RX
• Common strong nucleophiles:
– hydroxide ion
– alkoxide ions
– many amines
– iodide and bromide ions
– cyanide ion

• Common weak nucleophiles:

– water
– alcohols
– fluoride ion
 SN2 Reactions
• The reaction between methyl iodide and hydroxide
ion is a concerted reaction that takes places via an
SN2 mechanism

H H
-
HO - + H C I HO C H + I
nucleophile H H
Leaving
product
substrate group

 Substrate:
 the compound attacked by a reagent

(nucleophile)
 SN2 Reactions
• Concerted reaction:
– a reaction that takes place in a single step
with bonds breaking and forming
simultaneously

• SN2:
– substitution, nucleophilic, bimolecular
– transition state of rate-determining step
involves collision of 2 molecules
• 2nd order overall rate law
– Rate = k[RX][Nuc]
 SN2 Reactions
H
• SN2 Mechanism: Nuc C
H X
– Nucleophile attacks the back side of the electrophilic
H
carbon, donating an e- pair to form a new bond

H H - H
- Nuc C -
Nuc C Nuc C X + X
H X H
HH H
– H
Since carbon can only have 8 valence electrons, the
C-X bond begins to break as the C-Nuc bond begins
to form
H
Nuc C + X
H
H
 H H
HO C I HO C
SN2 Reactions H
• H reaction of methyl
S 2 Mechanism for the H
N
H
iodide and hydroxide ion:
-
H H H
H H
-
HOHO C CI C
I HO
HOHOC CC I
H H
H H HHHH
H H

HH
H H
HO HOHOC CI CI I HO C + I
H -
H
HHHHH H
 SN2 Reactions
• Reaction Energy Diagram:
– large Ea due to 5-coordinate carbon atom
in transition state
• no intermediates
– exothermic
 SN2 Reactions
• SN2 reactions occur with inversion of
configuration at the electrophilic
carbon.
– The nucleophile attacks from the back
side (the side opposite the leaving
group).
– Back-side attack turns the tetrahedron
of the carbon atom inside out.
ersion of configuration (Walden inversion) in an SN2
ction is due to back side attack
 SN2 Reactions
• Inversion of configuration:
– a process in which the groups bonded to
a chiral carbon are changed to the
opposite spatial configuration:
•R S or S R
 SN2 Reactions
Example: Predict the product formed by the SN2
reaction between (S)-2-bromobutane and
hydroxide ion. Draw the mechanism for the
reaction.
 SN2 Reactions
• The SN2 displacement reaction is a
stereospecific reaction
– a reaction in which a specific
stereoisomer reacts to give a specific
diastereomer of the product

OH H OH
H H H
+ OH-
H
CH3 Br H CH3 H H CH3 H
H H Br
Br CH3 Br CH3 Br + Br -
 SN2 Reactions
• SN2 reactions occur under the following
conditions
– Nucleophile:
• strong, unhindered nucleophile
– OH- not H2O
– CH3O- not CH3OH
– CH3CH2O- not (CH3)3CO-

– Substrate:
• 1o or methyl alkyl halide (most favored)
• 2o alkyl halide (sometimes)
• 3o alkyl halides NEVER react via SN2
 SN2 Reactions
• The relative rate of reactivity of simple alkyl
halides in SN2 reactions is:
methyl > 1o > 2o >>>3o

• 3o alkyl halides do not react at all via an SN2

mechanism due to steric hinderance.
– The back side of the electrophilic carbon becomes
increasingly hindered as the number or size of its
substituents increases
 SN2 Reactions
• Steric hinderance at the electrophilic carbon: