ALKYL HALIDES

Objective
Apply the IUPAC rules of nomenclature to naming organo halogen,
alcohols, thiols,
Be able to write the mechanisms for both the SN1 and SN2 reaction types
Know the effect of the SN1 and SN2 reaction mechanisms on the
stereochemistry of reactions

Recognize how the structure of the substrate affects the outcome of

nucleophilic reactions
Understand the factors that affect the stability of carbocations

Understand how halide, oxygen, nitrogen, and carbon nucleophiles react with
various substrates
Recognize the factors that make good nucleophiles and good leaving groups
Know how a functional group adjacent to the site of a nucleophilic substitution
affects the course of reactions
Know how the solvent affects the outcome of nucleophilic substitution
reactions
 ALKYL HALIDES
a compound with a halogen atom bonded to
one of the sp3 hybrid carbon atoms of an alkyl
group
 R CX sp3-hybridized---
alkyl halide easily replaced by others
possible introducing a multiple bond

C C
sp2-hybridized---
X
their chemistry are quite
X different from alkyl halides

vinylic(or phenyl) halide

 FUNCTIONAL GROUP CHARACTERSITIC: RX

+
-
Size of X: ? F<Cl<Br<I
C X Electronegativity: ? F>Cl>Br>I
polarized
Bond Strength: ? R-F>R-Cl>R-Br>R-I
X:F,Cl,Br,I Bond Length: ? R-F<R-Cl<R-Br<R-I

Usage: important starting materials

 Reactions of RX

C X
+ -

Most reactions of alkyl halides involve breaking

the C-X bond.
Nucleophilic substitution
Elimination
Reactions of Alkyl Halides
REAKSI SUBSTITUSI (SN1, SN2)

REAKSI ELIMINATION (E1, E2)

 SN2
Reactions
 SN2 Reactions

hydroxide ion methyl iodide

H SN2 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
SN2 Mechanism: H
Nuc C
Nucleophile attacks the back side of the electrophilic
-
H X
carbon, donating an e pair to form a new bond H

H H - H
- -
Nuc C Nuc C X Nuc C + 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
 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]
 Energy Diagram of SN2 Reactions

large Ea due to 5-coordinate carbon atom in transition state

no intermediates
exothermic
 INVERSION OF CONFIGURATION
in SN2 Reactions
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.
 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

Walden inversion
 SN2 Reactions
Example:
Predict the product formed by the SN2 reaction
between S-2-bromobutane
H and
H hydroxide ion.
DrawHOthe mechanism
C for
HO the
C reaction.
CH3 CH3
CH2CH3 CH2CH3
H H -
H
- C Br HO C Br HO C
OH CH3 CH3
CH2CH3 CH3 CH CH CH2CH3
2 3
H
+ Br -
HO C Br
 SN2 Reactions
Example:
(CH3)2CHCH2CH2Cl + NH3 (xs)
Predict the product of the following reactions:

CH3CH2CH2CH2Cl + NaCN

(CH3)2CHCH2CH2Cl + NH3 (xs)

CH3CH2CH2CH2Cl + NaCN
 (CH3)2CHCH
S2CH
N22Cl + NH3 (xs)
Reactions
Example:
CH3CH2CH What
CHreagent
Cl + would you use to
NaCN
2 2
do the following reactions:
CH3CH2CH2Br + ? CH3CH2CH2OCH2CH3

CH3CH2I + ? CH3CH2C CH
 SN2 Reactions Application
SN2 reactions can be used to convert alkyl halides to
other functional groups:
RX + I - R-I
KNOW
RX + OH - R-OH THESE!
RX + RO- R-OR
RX + NH3 R-NH3+ X-
RX + xs NH3 R-NH2 Be able
RX + CN- R-CN to apply
RX + HS- R-SH these!
RX + RS- R-SR
RX + RCOO- RCO2R
The SN1
Reaction
Previously we learned that tertiary alkyl halides
react extremely slowly in SN2 reactions. But tert-butyl
bromide reacts with water 1,000,000 times faster than
methyl bromide.

Acetone

(CH3)3CBr + OH- (CH3)3COH + Br

H2O
 Tertiary alkyl halides react rapidly in protic solvents by a
mechanism that involves departure of the leaving group
prior to addition of the nucleophile Called an SN1

SN1 reaction occurs in two distinct steps while SN2

occurs with both events in same step

If nucleophile is present in reasonable concentration (or

it is the solvent), then ionization is the slowest step
 t-butyl chloride with hydroxide ion: SN1 Reaction

(CH3)3CCl + OH - Acetone
(CH3)3COH + Cl
H2O

the reaction rate: R=k[(CH3) 3CCl]

only t-butyl chloride is involved in the trasition state

the reaction be unimolecular SN1(substitution,

nucleophilic, unimolecular)
 Mechanism for the SN1 reaction
(CH3)3CCl + OH- (CH3)3COH + Cl

CH3 CH3
slow - + 3 carbocation
H3C C Cl
H2 O
Cl + H3 C C
CH3 (I) CH 3
Aided by polar solvent: heterolytic
cleavage of C-Cl bond (II) HO :
fast Lewis
H base
CH3
deprotonation CH3
+ H+ +
H3 O +H 3C C OH H 3C C OH Protonated
products
H2O as a lewis base (III)
proton acceptor CH3 fast CH3 H
 ENERGI DIAGRAM for the SN1 reaction

(I) a slow step,rate-determining step(endothermal)

(II) protonated, (III) proton transfer to lewis base

(I) (II) (III)

Free
energy

(CH3)3C+/Cl
-
/2 H2O

(CH3)3COH/
(CH3)3Cl/H2O +
(CH3)3CO H2/ Cl-/H3+O
Cl-/H2O
 Rate-Limiting Step
The overall rate of a reaction is controlled by the
rate of the slowest step
The rate depends on the concentration of the
species and the rate constant of the step
The highest energy transition state point on the
diagram is that for the rate determining step
(which is not always the highest barrier)
 Stereochemistry of SN1 Reaction
The planar
intermediate should
lead to loss of
chirality
A free carbocation
is achiral

Product should be
racemic
 C3 H7 C3 H7
Br - the carbocation
C Br C+ --a trigonal plane
slow ---achiral
H3 C C2 H5 H3 C C2 H5

C3 H7 ..
C3 H7
C3 H7
.. H H OH
**
C O+ C OH
C+ H
H3 C C2 H5 H3 C + H3O+
fast C2 H5
H3 C C2 H5
C3 H7 C3 H7
.. H ..
H OH
..
** H OH +O C HO C
** H C H3 C H3

attack from both front and C2 H5 C2 H5

back side with equal rates A mixture of two + H3O+
enantiomers
 SN1 in Reality
Carbocation is biased to react on side opposite
leaving group
Suggests reaction occurs with carbocation loosely
associated with leaving group during nucleophilic
addition
Alternative that SN2 is also occurring is unlikely
 Effects of Ion Pair Formation
If leaving group
remains associated,
then product has more
inversion than retention
Product is only partially
racemic with more
inversion than retention
Associated carbocation
and leaving group is an
ion pair
 How to predict which pathway
(SN1or SN2) following the
reaction of any alkyl halide with
any nucleophile under varing
condition ?
 Factors affecting SN1and SN2

1. The structure of the substrate

2. The concentration and reactivity of the
nucleophile (only for bimolecular
reactions)
3. The effect of the solvent
4. The nature of the leaving group
 The effect of the structure of the substrate

(1) Electronic effects

Methyl > primary > secondary >>tertiary (unreactive)

(the general order of reactivity in SN2 reactions for simple
alkyl haildes)
CH3

H3C C CH2 X
(2) Steric effects
e.g., a neopentyl halide: CH3

Unreactive for SN2

High Steric Hindrance
steric effect:
an effect for space-filling properties

steric hindrance:
the spatial arrangement of the groups near the
reacting site hinders(retards) a reaction

Large groups can often hinder the formation

 Effect of Substrate structure On SN2
The back side of the electrophilic carbon
becomes increasingly hindered as the number or
size of its substituents increases
Order of Reactivity in SN2
The more alkyl groups connected to the
reacting carbon, the slower the reaction
 Characteristics 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.
 Key factor determining SN1 reaction

The relative stability of the formed carbocation

Most cases, tertiary halides (beside allylic and benzylic halides) react by
an SN1 mechanism, sometimes, secondary halides do, too.

R C+
R
 Effect of structure on SN1

Tertiary halida is the most reactive because its

form stable carbocation
 Allylic and benzylic Carbocation
Delokalisasi muatan kation menambah stabilitas.
allyl primer lebih stabil daripada alkyl primer

benzyl primer lebih stabil dari pada allyl

 Halida Alilik dan Benzilik
Produk antara Allylic dan benzylic distabilkan
oleh delokalisasi muatan

allylic and benzylic primer lebih reaktif pada

mekanisme reaksi SN2 dan SN1
Pengaruh Konsentrasi dan Kekuatan Nukleofil

Laju reaksi tidak bergantung identitas

Reaksi SN1
dan konsentrasi nucleophile

Reaksi SN2 Rate is directly proportional to the

concentration of nucleophile

42
 RELATIVE STRENGTHS OF NUCLEOPHILES:

depends on:
charge, basicity, solvent, polarizability and substituents

A negatively charged nucleophile is always a more

reactive nucleophile than it s conjuagte acid:
HO- is better than H2O,
RO- is better than ROH
CH3O- is berter than CH3OH
CH3CH2O- is better not (CH3)3CO-
 Reactivity of Nucleophile
Anions is more nucleofilic than neutral
Stronger nucleophilic with increasing atomic
size.
Depend on solvent
Neutral or negatively charged Lewis base
experiments:
-
1. CH3Cl + OH : CH3OH + Cl Fast
2. CH3Cl + H2O : CH3OH2 + Cl Very slow
nucleophilicities:
basicity: OH- > H2O

3. CH3Cl+H2N - : CH3NH2 + Cl Very fast

4. CH3Cl+H3N : +
CH NH + Cl
3 3 Slow
nucleophilicities:
H2N - > H3N
basicity:
 Nucleophilicity decrease to the right in an
row of the periodic table:

1. CH3CH2Br + H3N: CH3 CH2NH3 + + Br Fast

2. CH3CH2Br + H2O: CH3CH2OH2 + + Br Slow

nucleophilicities: H3N > H2O

3. CH3CH2Br + H2N CH3 CH2NH3 + Br Fast
4. CH3CH2Br + HO CH3CH2OH + Br Slow

nucleophilicities: H N > HO
2

NH2 > HO > NH3 > F > H2O
 Sterically hindered nucleophiles
are poor ones

-
CH3 I + CH3 O - CH3O CH3 + I

very easy
CH3 CH3
- -
CH3 I + CH3 C O CH3 C CH3 + I
CH3 CH3

very difficult
 RELATIVE STRENGTHS OF NUCLEOPHILES:

depends on:
charge, basicity, solvent, polarizability and substituents
1. A negatively charged nucleophile is always a more
reactive nucleophile than it s conjuagte acid: e.g., HO- is
better than H2O, RO- is better than ROH

2. In a group of nucleophiles having the same nucleophilic

atom, nucleophilicities parallel basicities(the order of
basicity)
experiments:
-
1. CH3Cl + OH : CH3OH + Cl Fast
2. CH3Cl + H2O : CH3OH2 + Cl Very slow
nucleophilicities:
basicity: OH- > H2O

3. CH3Cl+H2N - : CH3NH2 + Cl Very fast

4. CH3Cl+H3N : +
CH NH + Cl
3 3 Slow
nucleophilicities:
H2N - > H3N
basicity:
 Nucleophilicity decrease to the right in an
row of the periodic table:

1. CH3CH2Br + H3N: CH3 CH2NH3 + + Br Fast

2. CH3CH2Br + H2O: CH3CH2OH2 + + Br Slow

nucleophilicities: H3N > H2O

3. CH3CH2Br + H2N CH3 CH2NH3 + Br Fast
4. CH3CH2Br + HO CH3CH2OH + Br Slow

nucleophilicities: H N > HO
2

NH2 > HO > NH3 > F > H2O
 Sterically hindered nucleophiles
are poor ones

-
CH3 I + CH3 O - CH3O CH3 + I

very easy
CH3 CH3
- -
CH3 I + CH3 C O CH3 C CH3 + I
CH3 CH3

very difficult
 Effect of Leaving Group on SN2
A good leaving group reduces the barrier to a reaction
Stable anions that are weak bases are usually excellent
leaving groups and can delocalize charge
Very weak base of Leaving Group

54
 Poor Leaving Groups
If a group is very basic or very small, it is
prevents reaction

Problem 11.6
Rank in order of SN2 reactivity
CH3Br, CH3OTs, (CH3)3Cl, (CH3)2CHCl
p-Toluensulfonate (TosO-)
 Poor leaving group

Good leaving group

 how the solvent affects the
outcome of nucleophilic
substitution reactions
 The Effect Solvent on SN2
POLAR PROTIC solvents that can donate hydrogen bonds (-
OH or NH) slow SN2 reactions by associating with reactants
(Energy is required to break interactions between reactant and solvent)

POLAR APROTIC solvents (no NH, OH, SH) form weaker

interactions with substrate and permit faster reaction
 Pelarut Protic and Aprotic pada reaksi SN2

Polar Protic Solvents

Polar solvents memiliki atom hidrogen yang
terikat kuat pada atom elektronegatif
Mensolvasi nukleofil dan mejadikannya
kurang reaktif

Nukleofil besar kurang tersolvasi, relatif

lebih reaktif dalam pelarut polar protik

Nucleophilicity (in methanol solution)

CH3CO2 (-) < Cl(-) < Br(-) < N3(-) < CH3O(-) < CN(-) < I(-) < SCN(-) < I(-) < CH3S(-) 59
 POLAR, APROTIC SOLVENTS :

DMSO (dimethyl sulfoxide), CH3-SO-CH3

DMF (dimethylformamide),(CH3)2NCOH
and acetonitrile

do not solvate anions nearly as well as methanol, but provide

good solvation of the accompanying cations

Nucleophilicity in DMSO solution:

I(-) < SCN(-) < Br(-) < Cl(-) ~ N3(-) < CH3CO2 (-) < CN(-) ~ CH3S(-) < CH3O(-)

Nucleophilicity (in methanol solution)

CH3CO2 (-) < Cl(-) < Br(-) < N3(-) < CH3O(-) < CN(-) < I(-) < SCN(-) < I(-) < CH3S(-)
 -MeOH
1. CH3 CH2 CH2 OSO2CH3 + Cl CH3 CH2 CH2 Cl
slow
- MeOH
2. CH3 CH2 CH2 OSO2CH3 + Br CH3 CH2 CH2 Br
faster
MeOH
-
3. CH3 CH2 CH2 OSO2CH3 + I CH3 CH2 CH2 I
fastest
 Pelarut Polar Aprotic Terhadap SN2
Polar aprotic solvents tidak memiliki hydrogen terikat dengan atom
electronegative

Polar aprotic solvents membiarkan anions tak tersolvasi (naked)

karena pusat positif dalam pelarut terhalangi secara sterik
(sterically hindered).
Nucleophiles menjadi lebih reaktif, membantu reaksi SN2

Trends untuk nukleofilitas berlawanan dengan yang diamati dalam pelarut polar
protic dan sama dengan trends kebasaan

Nucleophilicity in DMSO solution:

I(-) < SCN(-) < Br(-) < Cl(-) ~ N3(-) < CH3CO2 (-) < CN(-) ~ CH3S(-) < CH3O(-)
 Pelarut Protic and Aprotic pada reaksi SN2

Polar Protic Solvents

Polar solvents memiliki atom hidrogen yang
terikat kuat pada atom elektronegatif
Mensolvasi nukleofil dan mejadikannya
kurang reaktif

Nukleofil besar kurang tersolvasi, relatif

lebih reaktif dalam pelarut polar protik

Nucleophilicity (in methanol solution)

CH3CO2 (-) < Cl(-) < Br(-) < N3(-) < CH3O(-) < CN(-) < I(-) < SCN(-) < I(-) < CH3S(-) 63
 POLAR, APROTIC SOLVENTS :

DMSO (dimethyl sulfoxide), CH3-SO-CH3

DMF (dimethylformamide),(CH3)2NCOH
and acetonitrile

do not solvate anions nearly as well as methanol, but provide

good solvation of the accompanying cations

Nucleophilicity in DMSO solution:

I(-) < SCN(-) < Br(-) < Cl(-) ~ N3(-) < CH3CO2 (-) < CN(-) ~ CH3S(-) < CH3O(-)

Nucleophilicity (in methanol solution)

CH3CO2 (-) < Cl(-) < Br(-) < N3(-) < CH3O(-) < CN(-) < I(-) < SCN(-) < I(-) < CH3S(-)
Effect of Leaving Group on SN1
Critically dependent on leaving group
Reactivity: the larger halides ions are better leaving
groups

In acid, OH of an alcohol is protonated and leaving group

is H2O, which is still less reactive than halide

p-Toluensulfonate (TosO-) is excellent leaving group

 Solvent Is Critical in SN1
Stabilizing carbocation also stabilizes
associated transition state and controls
rate

Solvation of a carbocation by
water stabilizes carbocation
 Polar Solvents Promote Ionization
Polar, protic and unreactive Lewis base solvents facilitate formation of R+

Solvent polarity is measured as dielectric polarization (P)

Nonpolar solvents have low P
Polar SOLVENT have high P values
 Effects of Solvent on Energies
Polar solvent stabilizes transition state and
intermediate more than reactant and product
 -MeOH
1. CH3 CH2 CH2 OSO2CH3 + Cl CH3 CH2 CH2 Cl
slow
- MeOH
2. CH3 CH2 CH2 OSO2CH3 + Br CH3 CH2 CH2 Br
faster
MeOH
-
3. CH3 CH2 CH2 OSO2CH3 + I CH3 CH2 CH2 I
fastest
 Pelarut Polar Aprotic Terhadap SN2
Polar aprotic solvents tidak memiliki hydrogen terikat dengan atom
electronegative

Polar aprotic solvents membiarkan anions tak tersolvasi (naked)

karena pusat positif dalam pelarut terhalangi secara sterik
(sterically hindered).
Nucleophiles menjadi lebih reaktif, membantu reaksi SN2

Trends untuk nukleofilitas berlawanan dengan yang diamati dalam pelarut polar
protic dan sama dengan trends kebasaan

Nucleophilicity in DMSO solution:

I(-) < SCN(-) < Br(-) < Cl(-) ~ N3(-) < CH3CO2 (-) < CN(-) ~ CH3S(-) < CH3O(-)
 Pengaruh Aprotic pada reaksi SN1

Kation disolvasi oleh pelarut protic dan aprotic

Menstabilkan karbokation

73
 Question A :

- ?
Br + CH3I CH3Br+I-

-
?
I + CH3 Br CH3I+ Br -
 Answer to Question A :
actone or DMF
Cl-+ CH3I CH3Cl+I-
in aprotic solvents: - -
nucleophilicity: Br>I
- -
leaving group: I > Br
methanol or water
I- + CH3 Cl CH3I+ Cl -

in protic solvents: - -
nucleophilicity: I > Cl
- -
leaving group: Cl > I
 Pengaruh POLAR PROTIC pada reaksi SN1

Tdk memperkuat nukleofil, tapi menstabilkan

carbocation-like transition state menuju pembentukan,
jadi merendahkan DG, jadi membantu reaksi SN1,
Water-ethanol merupakan pelarut umum.

continue.
 Halida Alilik dan Benzilik
Produk antara Allylic dan benzylic
distabilkan oleh delokalisasi muatan

allylic and benzylic primer lebih reaktif

pada mekanisme reaksi SN2 dan SN1

77
 Summary SN1 versus SN2
Untuk kedua jenis reaksi, alkyl iodides bereaksi lebih cepat
karena gugus pergi lebih superior.

Factor SN1 SN2

continue.
78
 Overall Summary

Factor SN1 SN2

F: SN1and SN2 reactions:
aspects SN1 favors: ---forming stable carbocations
by use of weak nucleophiles
by use of highly ionizing solvents
aspects SN2 favors:
by use of relatively unhindered alkyl halide
by use of a strong (or a concentrated) nucleophile
by use of a polar aprotic solvent
the order of reactivity SN2 :
methyl > R-CH2-X > (R)2CH-X
tertiary halides do not react by an SN2 mechanism
Organic Synthesis: Functional Group Transformations
Using SN2 Reactions

continue.

81
Organic Synthesis: Functional Group Transformations

Stereochemistry can be controlled in SN2 reactions

continue.
 Elimination Reaction of RX
two substituents are lost from adjacent (usually)
carbons, forming a new p bond

H H
CH3CH3
-
H H CH3CH3
CH O
H H
C C
C CCH3CH3 3
C C
C C
H H CH CH3
H H
Br Br 3

Example : Dehydrohalogenation:
an elimination reaction in which H+ and X- are lost,
forming an alkene
 Reaksi Eliminasi Alkil halida

Eliminasi berkompetisi dengan substitusi

Basa kuat seperti alkoksida membantu eliminasi

Dehidrogenasi continue.

84
 Reaksi Eliminasi Alkil halida(cont)
Alkoksida dibuat dari alkoholnya

continue.

85
 Aturan Zaitsevs untuk Eliminasi (1875)

Eliminasi HX dari alkyl halide, menghasilkan alkena

yang paling tersubstitusi sebagai produk dominan
 Reaksi E2

Reaksi E2 melibatkan secara serempak (concerted)

mengambilan proton, pembentukan ikatan rangkap,
dan lepasnya gugus pergi

Baik konsentrasi alkyl halide maupun basa

mempengaruhi laju reaksi dan oleh karena itu
reaksinya orde 2.
 Mechanisms of Elimination Reactions

Ingold nomenclature: E elimination

E1: X- leaves first to generate a
carbocation
a base abstracts a proton from the
carbocation
E2: Concerted (one step) transfer of a
proton to a base and departure of leaving
group
The E2 Reaction Mechanism
A proton is transferred to base as leaving
group begins to depart
Transition state combines leaving of X and
transfer of H
Product alkene forms stereospecifically
Reaksi E2 (cont)
 E2 Stereochemistry
Overlap of the developing orbital in the
transition state requires periplanar geometry,
anti arrangement

Allows orbital overlap

 Geometry of Elimination E2
Antiperiplanar allows orbital overlap and
minimizes steric interactions
 Predicting Product
E2 is stereospecific
Meso-1,2-dibromo-1,2-diphenylethane with base gives
cis 1,2-diphenyl
RR or SS 1,2-dibromo-1,2-diphenylethane gives trans
1,2-diphenyl
 Elimination From Cyclohexanes
Abstracted proton and leaving group should
align trans-diaxial to be anti periplanar (app) in
approaching transition state (see Figures 11-19
and 11-20)
Equatorial groups are not in proper alignment
 E2 Reaction Kinetics
One step rate law has base and alkyl
halide
Transition state bears no resemblance to
reactant or product
Rate = k[R-X][B]
Reaction goes faster with stronger base,
better leaving group
 Kinetic Isotope Effect
Substitute deuterium for hydrogen at position
Effect on rate is kinetic isotope effect (kH/kD = deuterium isotope effect)
Rate is reduced in E2 reaction
Heavier isotope bond is slower to break
Shows C-H bond is broken in or before rate-limiting step
MEKANISME REaksi E1
Reaksi E1 (cont)
(SN2 versus E2)
Substatenya Primer

Jika basanya kecil,

SN2 >E2

karena pendekatan kepada

karbon tak terhalangi
Substitusi versus Eliminasi (cont)
(SN2 versus E2)

Substrate sekunder

SN2 < E2

Pendekatan kearah
karbon sedikit
terhalangi secara sterik
 Substitution versus Elimination (cont)
(SN2 versus E2)

Ukuran Basa/Nukleofil
Besar

SN2 < E2
terhalang secara sterik tidak dapat
berada cukup dekat karbon untuk
bereaksi substitusi

Potassium tert-butoxide
(bulky base),
dipergunakan untuk
melaksanakan reaksi E2
 Reaksi E1 vs SN1
Keduanya melalui produk antara carbocation
Substrate Tersier
Suhu rendah
SN2 < SN1 or E1
SN1 > E1
 Substitution versus Elimination (cont)
(SN1 versus E1)
Substrate Tersier Keduanya melalui produk antara carbocation
Suhu tinggi dinaikan
SN2 < SN1 or E1
SN1 < E1

Suhu lebih membantu eliminasi daripada

substitusi

<

 SN1, SN2, E1, E2 : Dapatkah dibuat batas yang jelas?

Untuk suatu kasus, bagaimana memprediksi apa yg akan terjadi? Apakah

terjadi Eliminasi atau Substitusi? Reaksinya bimolekuler atau unimolekuler?
Sayangnya tidak ada jawab yang rigid tegas, akan tetapi memungkinkan
memahami beberapa kecenderungan dan membuat generalisasi.

Ringkasan reaksi substitusi dan eliminasi

Halida SN1 SN2 E1 E2

RCH2X Sangat terbantu Terjadi jika
Tak ada Tak ada digunakan basa
kuat

R2CHX Dpt terjadi dgn Terjadi bersaingan Dpt terjadi dgn Terbantu jika
halida alilik dan dengan E2 halida alilik dan digunakan basa
benzilik benzilik kuat

R3CX Terbantu dalam Terjadi bersaingan Terbantu jika

pelarut hidroksilik Tak ada dengan SN1 digunakan basa

SN1 dan E1 biasanya terjadi pada kondisi solvolysis

SN1 and E1 usually occur only under solvolysis conditions.
 CONTOH KASUS Alkil Halida Primer

CH3CH2CH2CH2Br Na+ -CN CH3CH2CH2CH2CN

THF-HMPA
1- Bromobutana Pentananitril (90%)
SN2
APROTIC RS-, I-,CN-, NH3, Br-
Anion NAKED nukleofil kuat

CH3CH2CH2CH2Br CH3CH2CH2=CH2
(CH3)3CO-K+
1- Bromobutana 1-Bromobutena (85%)
E2
tert-butoksida
basa kuat, sterically hindered
 CONTOH KASUS SN2, E2 ? SN1, E1
SN1, E1 Aprotik,basa lemah SN2
SN2, E2
protik Aprotik,basa kuath E2
Nu/Basa lemah SN2, E2 >> SN1, E1
aprotik
Alilik, benzilik
SN2> E2
Alkil halida sekunder

SN2< E2
basa kuat
CH3CH2O-, OH-, NH2-
 SN2 E2

SN1 E1

Solvolysis
 Suhu tinggi E1>SN1
Nu LemahSN1, E1 Basa Kuat E2
CONTOH KASUS

SN2 sulit SN2 E2

Halida tertier

SN1 E1

Solvolysis
 Tugas Presentasi
Topik : Produk Industri Kimia yang dibuat melewati reaksi
substitusi/eliminasi

Pendahuluan : Penting produk tersebut, jumlah kebutuhan, dunia,

nasional, apakah ada di indonesia dll. Maksud khusus yang hendak
disampaikan .

Proses umum pembuatan : reaksi kimia yang berkaitan, mekanisme

reaksi, katalis, suhu operasi, solvent dll. Tinjauan khusus yang akan
disampaikan (dikaitkan dengan isi kuliah : reaksi substitusi dan faktor
yang mempengaruhi)

Penutup