Kelompok 1

Amrina Rosada
Ayu Lestari
Septi Andriani

Substitusi
Elektrofilik Alifatik

Tujuan Presentasi
1. Menjelaskan elektrofilisitas/keelektrofilan
2. Menuliskan mekanisme reaksi substitusi elektrofilik
unimolekuler, SE1
3. Menuliskan mekanisme reaksi substitusi elektrofilik
bimolekuler, SE2
4. Menjelaskan Diagram energi untuk reaksi substitusi
elektrofilik bimolecular
5. Menjelaskan mekanisme reaksi SE1
6. Membedakan perubahan stereokimia substrat pada
reaksi SE1 dan SE2
7. Menjelaskan Diagram Energi untuk reaksi Se1
senyawa alifatik

Define of Electhrofil
Elektrofilitas merupakan sesuatu
yang tertarik pada elektron, Dan
karena tertarik oleh daerah negatif,
elektrofil harus merupakan sesuatu
yang memebawa muatan positif
penuh atau memiliki sedikit muatan
positif disuatu daerah padanya.

Electrophilic substitution reaction

mechanism
Differences in the mechanism of electrophilic substitution
reactions with nucleophilic substitution reaction mechanism,
lies on the species and the attackers leaving group. In the
electrophilic substitution reaction, an attacker species and
goings group is an electrophile (acid according to the concept of
Lewis). Basically the changes that occur in electrophilic
substitution reaction is an electrophile (according to the concept
of Lewis acid) to form a new bond with carbon atoms of the
substrate and one of the substituents on the carbon off without a
pair electrons. Electrophile can be either positive ion, or the
positive end of a dipole
RX
+ Y+

RY
+ X+
Substrat elektrofil hasil substitusi gugus
pergi

Electrophilic substitution reaction mechanism

Aliphatic Compounds
The ability to release protons will determine the
reactivity of aliphatic compounds in electrophilic
substitution. Therefore leaving group most often found
in electrophilic substitution of aliphatic compounds
are protons.
The mechanism is divided into two, namely:
1. The mechanism of electrophilic substitution
unimolekuler (SE1)
2. Bimolecular electrophilic substitution mechanism
(SE2 and SEI)

1. The mechanism of electrophilic substitution unimolekuler (SE1)

Electrophilic substitution reaction mechanism unimolekuler (SE1)

consists of two stages, namely the ionization stage which takes
place slowly and is a decisive stage of the reaction rate, and the
jointing stage carbanions with electrophiles rapid.
lambat
Tahap 1. R-X
R - : + X+
cepat
Tahap 2. R-: + Y+R Y Elektrofil

The reaction rate which follows SE1 mechanism is not affected by

the concentration of electrophile as a determinant of the rate of the
reaction stage is the stage of ionization (carbanion formation).

The reaction products that follow SE1 mechanism can produce

products by maintaining its original configuration (retention), or
racemization or inversion configuration (inversion) in part,
depend on factors carbanion stability, concentration
electrophiles,
strength
electrophiles
and
carbanions
configuration.
The reaction will produce racemisation if:
1) .Karbanion stabilized by delocalization and low concentration
or strength electrophile electrophile low,
2) .Karbanion flat structure and a negative charge delocalized
carbanions so electrophile can attack from both sides,
3). Carbanion structure but form a tetrahedral anion equilibrium
enantiomeric mixture at a rate faster than the rate of formation
of the product.

Carbanions which tetrahedral structure is described as

follows:
c

C
a

C
a

SE1 reaction which takes place by maintaining the original

configuration (retention) can occur in two ways:
1). Flat and solvated carbanion structure is not symmetrical by
electrophiles on the same side of the position leaving group,
2). Carbanion structure tetrahedral and carbanions electrophile
bound before changing to enantiomernya structure.

Examples SE1 reaction which takes place

by maintaining the original configuration is:
H3 C

n-C6 H5
C

C6 H5SO2
enantiomer murni

OCH3

(CH3)2 SO
25 oC

n-C6H5
H3C

C
C6H5 SO2

HOCH3

H3C

n-C6 H5
C

C6H5 SO2
retensi 90 %

SE1 reactions that produce products with configuration

reversal (inversion) occurs on systems with flat and solvated
carbanion structure is not symmetrical as an intermediate
(intermediate). This anion solvated on the same side of the
position leaving group by a molecule that is formed from the
group to go and electrophile attack from the opposite side.
Example : The reaction between the anion of 3-phenyl-2,3dimethyl-2-pentanol with ethylene glycol.
C2 H5
H3C

C
C6 H5

OC
CH3

H3C

CH3

HOCH2 CH2 OH

210 oC

(elektrofil)

HOCH2 CH2 O-H

C 2H 5

O
C

CH3

C2 H5 CH3

karbanion tersolvasi
tak simetris sebagai zat antara
C 2H5
CH3
H - *C
C6H5

CH3
+ C=O
CH3

+ CH2OHCH2O-

2. Bimolecular electrophilic substitution mechanism (SE2 and SEI)

Bimolecular reaction mechanisms of electrophilic

substitution in aliphatic compounds occurs through breaking
the bond between the leaving group with a substrate and
forming a new bond between the electrophile with the
substrate takes place at the same time. Therefore, the reaction
rate is influenced by the concentration of electrophile and the
substrate. An example is the reaction of alkyl mercury iodide
changes into alkyl iodide to triiodide ion electrophile with the
following mechanism:
CH3CH2CH2

Hg

I + I

H2O
dioksan

CH3CH2CH2

I + HgI2 + I-

At SE2 mechanism, there are two possible

directions of electrophilic attack on substrates,
ie from the front, called SE2 (front) and from
the back, called SE2 (rear) can be described as
follows:
c

c
b

b
C

C
a

(S E 2 depan)

c
C

X+

Y+

c
Y+

C
a

X+

(SE 2, belakang)

If the reaction occurs in a chiral substrate is

formed by the reaction product retains its
original configuration (retention) in SE2
mechanism (front), and a reversal of
configuration (inversion) in SE2 mechanism
(rear). If electrophiles attack the substrate from
the front there is a possibility that a third
mechanism, which is one part of the escape
group electrophile help go and at the same
time to form a new bond with the substrate.
Z

Y
a
b
c

a
b

C
c

X-Z

Most reactions are bimolecular electrophilic substitution

(second order) to produce products with maintaining the
original configurations. This means that in general, the reaction
proceeds by a mechanism wherein the substrate electrophile
attack from the front, SE2 (front) or SEI.
C2H5

C2H5
CH3

C
H

Hg

Br

Br

Br

Br

+ HgBr2

CH3
H

This fact is contrary to the SN2 mechanism. In the SN2

mechanism, the nucleophile attacks the carbon atom with the
group away, while the attacking electrophile SE2 mechanism of
electron binding carbon atom and leaving group. Therefore, the
reaction proceeds more rapidly if electrophiles attack the
substrate from the same side of the position leaving group than
otherwise due to steric hindrance.

Energy diagram for bimolecular electrophilic

substitution reaction

Electrophilic substitution is accompanied

by displacement of the double bond
Rearrangement will occur in the reaction product, if the
electrophilic substitution reactions occur on allylic substrate.

The mechanism of formation of products that undergo

rearrangement can occur in two ways:
1. The reaction takes place as the mechanism SE1, where the
group went off first establish if a resonance stabilized
carbanion, followed by the electrophile attacks

2. electrophile Y + strike first substrate to form

carbocations and followed with the release of
X + as a leaving group.
C= C

-X+

C=C

C=C

Y+

C=C

produk

In general, the electrophilic allylic

rearrangement involving hydrogen as the
leaving group, although it can also occur in the
organometallic compound with a metal ion as
a leaving group
C= C

C
Y

Y+

C
+

C= C

Y
produk

X+

The relationship between the structure of the

substrate and its reactivity in electrophilic
substitution of aliphatic compounds
In the reaction mechanism SE1, has a decisive stage of the
reaction rate similar to the release of a proton from an acid.
Therefore, the electron booster groups will reduce the rate of
reaction and vice versa electron-withdrawing groups will
increase the rate of reaction. In the reaction mechanism SE2
(behind) the reactivity of the substrate as well as the SN2
mechanism, ie the greater the alkyl group, the greater the
obstruction steriknya so that the reaction rate will be smaller.
So the order of reactivity is: Me> Et> Pr> i-Pr> neopentyl.
In the reaction mechanism SE2 (front) reaction rate depends
on the type of reaction

Energy diagram for the reaction of aliphatic

compounds SE1
Such as analogue Sn2 reaction with SE2, so is the case
with the reaction between the SN1 reaction SE1. In the
mechanism both are experiencing the formation of an
intermediate. Where in SE1 formed carbanion, while in SN1
formed carbocation, but for the energy diagram, the two have
in common.
E

T1

T 2
T = T r a n s is i
R +

S
P

Terima kasih
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