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REAKSI ELIMINASI

 PELEPASAN MOLEKUL YZ DARI ATOM-


ATOM BERDAMPINGAN DLM SUATU
MOLEKUL PEREAKSI.
 DEHIDROHALOGENASI DAN DEHIDRASI

Y Z

C C C C + YZ

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• DEHIDROHALOGENASI ALKIL HALIDA

• PELEPASAN/ PENARIKAN HX DARI ATOM-2


C BERDAMPINGAN DLM SEBUAH ALKIL
HALIDA
• DILAKUKAN DG BASA KUAT
• MISALNYA: CH3ONa, C2H5ONa DAN
(CH3)3COK
2 C2H5OH + 2 Na 2 C2H5O-Na+ + H2

CH3OH + NaH CH3O-Na+ + H2

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• DEHIDRASI ALKOHOL
• PELEPASAN/ PENARIKAN H2O DARI ATOM-2 C
BERDAMPINGAN DLM SEBUAH ALKOHOL
• DILAKUKAN DG ASAM KUAT
• MISALNYA: H2SO4 DANH3PO4

H2SO4 PEKAT
H3C-CH2-CH2 H3C-CH2 CH2 + H O
2
170oC
OH

OH H3PO4 85%
+ H2O
165-170oC

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CONTOH

DEHIDROBROMINASI ALKIL BROMIDA


H3C
C2H5ONa H
H C Br H2C C + NaBr + C2H5OH
(C2H5OH, 55oC) CH3
H3C 79%

H3C CH3
C2H5ONa
H3C C Br H2C C + NaBr + C2H5OH
(C2H5OH, 25oC) CH3
H3C
91%
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MEKANIME REAKSI ELIMINASI
1. REAKSI ELIMINASI BIMOLEKULER (E2)
r = k [R-X].[:B-]
r = k [CH3CHBrCH3].[C2H5O-]

2. REAKSI ELIMINASI UNIMOLEKULER (E1)


r = k [R-X]
r = k [(CH3)3C-Cl]

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REAKSI E2
 DEHIDROBROMINASI ISOPROPIL BROMIDA
DG LARUTAN NATRIUM ETOKSIDA DLM
ETANOL
C2H5O:-

H H C2H5O:- H H
 
H H
H2C C CH3 H2C C CH3 C C + Br- + C2H5OH
Br .. - H CH3
Br
PROPENA
ISOPROPIL BROMIDA

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MEKANISME REAKSI E2

1. BASA MENYERANG AT H  DR ARAH


BERLAWANAN DG X (Br)
2. AT X (Br)  PERGI DR ARAH BERLAWANAN
DG BASA SBG ION X- (Br-)
3. AT-2 C  DAN  MEMBENTUK IKATAN
RANGKAP MENGHASILKAN ALKENA

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REAKSI E1
 DEHIDROBROMINASI t-BUTIL BROMIDA DG
LARUTAN NATRIUM ETOKSIDA DLM ETANOL
H3C
1.
H3C
C Br C+ CH3 + Br-
H3C

H3C H3C

2. C2H5O:- CH3
CH2 H2C C
C+ CH3 + C2H5O:H
H CH3
H3C
2-METILPROPENA
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MEKANISME REAKSI E1

1. ALKIL HALIDA MENGALAMI


IONISASI MENGHASILKAN ION
KARBONIUM
2. BASA MENYERANG AT H 
3. AT C  MEMBENTUK IKATAN
RANGKAP DENGAN AT C 
MENGHASILKAN ALKENA

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KOMPETISI SN2 DAN E2
ETANOL
1. C2H5ONa + H3CCH2Br C2H5OCH2CH3 + H2C CH2 + NaBr
T=550C
(1o) SN2= 90% E2 = 10%
H3C CH3
2. C2H5ONa + ETANOL
CH Br C2H5O-CH-CH3 + H2C CH-CH3 + NaBr
T=550C
H3C SN2= 21% E2 = 79%
(2o)
H3C CH3 CH3
3. C2H5ONa + ETANOL
C2H5O-C-CH3 + H2C C
H3C C Br + NaBr
T=250C
H3C o CH3 CH3
(3 )
SN2= 9% E2 = 91%
T=550C E2 = 100%

PD HALIDA 3o KENAIKAN T TERJADI REAKSI E2


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KERUAHAN BASA PEREAKSI
1. KERUAHAN BASA PEREAKSI MENDORONG
REAKSI ELIMINASI
CH3(CH2)15CH2CH2 OCH3
CH3O:- + CH (CH ) CH CH METANOL
3 2 15 2 2 99%
DIREFLUX +
Br
CH3(CH2)15CH2 CH2
1% CH3
CH3 t-BUTIL CH3(CH2)15CH2CH2 OC-CH3
ALKOHOL
CH3-C-O:- CH3(CH2)15CH2CH2 15% CH3
40o +
CH3 Br CH3(CH2)15CH2 CH2

85%
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KEBASAAN
1. BASA LEMAH SPT Cl-, CH3COO-, Br-, I-
MENDORONG SN2
2. BASA KUAT: C2H5O-, OH-, NH2- MENDORONG E2

CH3 CH3 O
CH3COO:- + CH3-CH Br CH3-CH O-CCH3 + Br:
-

100%
CH3
CH3
C2H5O:- + CH3-CH Br + Br:-
CH2=CH

79%
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KOMPETISI SN2 DAN E2
1. REAKSI SN2 MELIBATKAN BASA
LEMAH, BASA SEDERHANA DLM
PELARUT POLAR, DAN SUHU
RENDAH
2. REAKSI E2 MELIBATKAN BASA KUAT,
BASA MERUAH, DLM PELARUT
POLAR, DAN SUHU TINGGI.

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ATURAN ZAITSEV
1. DEHIDROBROMINASI 2-BROMO-2-METILBUTANA
DG NATRIUM ETOKSIDA

CH2
C2H5O:- B
H B CH3CH2C (31%)
A
H CH3
 CH2
2-METIL-1-BUTENA
CH3-CH C Br
  CH3
CH3
A CH3CH C (69%)
2-BROMO-2-METILBUTANA CH3
2-METIL-2-BUTENA
2. REAKSI ELIMINASI TERJADI DG MEMBERIKAN
ALKENA YG LEBIH TERSUBSTITUSI.
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BUKTI LAIN ATURAN ZAITSEV
1. DEHIDROKLORINASI NEOMENTIL KLORIDA
DAN MENTIL KLORIDA DG NATRIUM ETOKSIDA
H3C
Cl CH(CH3)2
C2H5O:H
H H
H H3C
H
H CH(CH3)2
2-MENTEN (100%)
C2H5O:- MENTILKLORIDA

C2H5O:-

CH(CH3)2
H A
B H

H3C CH(CH3)2
A. 3-MENTEN (78%)
H
H CH(CH3)2
H Cl

NEOMENTILKLORIDA B. 2-MENTEN (22%)


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ANTI ZAITSEV
1. DEHIDROBROMINASI 2-BROMO-2-
METILBUTANA DG KALIUM t-BUTOKSIDA
2. ELIMINASI DG BASA MERUAH MEMBERIKAN
ALKENA YG KURANG TERSUBSTITUSI.
H3C
CH2
CH3-C-O:- B
H B CH3CH2C (72,5%)
A
H3C H  CH CH3
2
2-METIL-1-BUTENA
CH3-CH C Br
 
CH3
CH3
A CH3CH2 C (27,5%)
2-BROMO-2-METILBUTANA CH3
2-METIL-2-BUTENA
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BAGAIMANA KOMPETISI SN1 DAN E1

1. REAKSI E1 MELIBATKAN
KARBOKATION STABIL, BASA
LEMAH, PELARUT POLAR DAN
SUHU TINGGI
2. REAKSI SN1 MELIBATKAN
KARBOKATION STABIL, BASA
LEMAH, PELARUT POLAR DAN
SUHU RENDAH

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PROBLEM 1
• WHEN CIS -1-BROMO-4-tert-BUTYLCYCLOHEXANE IS
TREATED WITH SODIUM ETHOXIDE IN ETHANOL, IT
REACT RAPIDLY. THE PRODUCT IS 4-tert-
BUTYLCYCLOHEXENE. UNDER THE SAME
CONDITIONS, TRANS-1-BROMO-4-tert-
BUTYLCYCLOHEXANE REACTS VERY SLOWLY.
WRITE CONFORMATIONAL STRUCTURE AND EXPLAIN
THE DIFFERENCE IN REACTIVITY OF THIS CIS-TRANS
ISOMERS.

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JAWAB PROBLEM 1

• PD ISOMER CIS TERDAPAT 2 AT H  DG


POSISI AKSIAL, BEGITU JUGA Br BERADA
PD POSISI AKSIAL SHG REAKSI E2
BERLANGSUNG LEBIH CEPAT.
• PD ISOMER TRANS BAIK AT H  MAUPUN
Br YG AKAN BEREAKSI DLM POSISI
EQUATORIAL, SEHG MENYEBABKAN
REAKSI E2 SANGAT LAMBAT (SULIT).

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REAKSINYA

H Br
HH
H
H
H H
H
H H
CIS

C2H5O:-

H H
TRANS HH
H SULIT
H Br
H H
H H
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PROBLEM 2
• A). When cis-1-bromo-2-methylcyclohexane
undergoes an E2 reaction, two product
(cycloalkenes) are formed. What are these two
cycloalkenes, and which would you expect to be
the major product? Write conformational
structures showing how each is formed.
• B) When trans-1-bromo-2-methylcyclohexane
reacts in an E2 reaction, only one cycloalkene is
formed. What is this product? Write
conformational structures showing why is the only
product.

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KESIMPULAN
CH3X RCH2X (R)2CHX (R)3CX
METIL (1o) (2o) (3o)
REAKSI BIMOLEKULER SN1/E1/E2
MEMBERIKAN MEMBERI MEMBERIKAN DLM
REAKSI SN2 SN2, KECUALI REAKSI SN2 DG SOLVOLISIS
DG BASA BASA LEMAH BEREAKSI
MERUAH SN1/E1, PD T
MEMBERI RENDAH SN1
REAKSI E2 DOMINAN
MEMBERIKAN BASA KUAT
REAKSI E2 DG REAKSI E2
BASA KUAT DOMINAN

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A BIOLOGICAL NUCLEOPHILIC SUBSTITUTION
REACTION: BIOLOGICAL METHYLATION

1. THE CELLS OF LIVING ORGANISMS SYNTHESIZE


MANY OF THE COMPOUNDS THEY NEED FROM
SMALLER MOLECULES.
2. A NUMBER OF REACTIONS TAKE PLACE IN THE
CELLS OF PLANTS AND ANIMALS THAT
INVOLVE THE TRANSFER OF A METHYL GROUP
FROM AN AMINO ACID CALLED METHIONINE
TO SOME OTHER COMPOUND.

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SOME OF THE COMPOUNDS THAT GET
THEIR METHYL GROUP FROM METHIONINE
CH3 CH3
-OOC-CH-CH2-CH2-S
CH3 N+ CH2-CH2-OH
NH3+ CH3
CHOLINE
METHIONINE HO

HO CH-CH2NH CH3

ADRENALINE

N
NICOTINE
N CH3
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METHYL TRANSFER MECHANISM
OH OH OH
NUCLEOPHILE P O P O
CH3 O P OH
LEAVING GROUP
O O O
-OOCCH-CH2CH2S: + CH2
O ADENINE
NH2 H
H
H H

OH OH

CH3
OH OH OH
-OOCCH-CH2CH2S CH2
O ADENINE -:O P O P O P OH
NH2 H + O O
H O
H H
TRIPHOSPHAT ION
OH OH
S-ADENOSYMETHIONINE

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BIOSYNTHESIS OF CHOLINE
CH3
-OOCCH-CH2CH2S CH2 CH3
O ADENINE
NH3+ H + :N CH2-CH2-OH
H
H H
CH3
OH OH
S-ADENOSYMETHIONINE N,N-DIMETHYLAMINOETHANOL

ACTIVE METHYL TRANSFERER

.. CH3
-OOCCH-CH2CH2S CH2 ADENINE
O CH3 N+ CH2-CH2-OH
NH3+ H
H
H H + CH3
CHOLINE
OH OH
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DEHIDRASI ALKOHOL
1. PELEPASAN H2O DR ALKOHOL-2
MELALUI PEMANASAN DG ASAM KUAT
2. ASAM BRONSTED: H2SO4 DAN H3PO4
ASAM LEWIS: ALUMINA (Al2O3) DLM
INDUSTRI
3. REAKSI DEHIDRASI ALKOHOL
MENUNJUKKAN BBP KARAKTERISTIK
PENTING.

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KONDISI REAKSI
1. ALKOHOL PRIMER MEMERLUKAN ASAM
PEKAT DAN SUHU TINGGI
H2SO4 PKT
CH3-CH2-CH2-OH CH3-CH CH2 + H2O
170oC
PROPIL ALKOHOL PROPENA

OH 85% H3PO4
+ H2O
170oC
SIKLOHEKSANOL SIKLOHEKSENA (80%)

CH3
20% H2SO4 CH3
H3C C OH H3C C + H2O
85oC
CH3 CH2
t-BUTIL ALKOHOL
2-METILPROPENA (84%)
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CAMPURAN ALKENA
1. BBP ALKOHOL TERDEHIDRASI
MEMBERIKAN HASIL CAMPURAN ALKENA
H H C CH3 H
H C 3 CH2CH3
H2SO4 PKT 3
H3C-CH2-CH2-CH2 C C
C C + + C C
170oC
OH H CH3 H H H H
TRANS
CIS
UTAMA
CH3
CH3 CH3
OH 85% H PO
3 4
170oC

2-METIL-SIKLOHEKSANOL
2. MENGIKUTI 1-METILSIKLOHEKSENA
ATURAN ZAITZEV 3-METILSIKLOHEKSENA

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PENATAAN ULANG
• BBP ALKOHOL 1o DAN 2o MENGALAMI
PENATAAN ULANG SELAMA DEHIDRASI

CH3
1) H3C CH3 CH3 CH3
H3C C CH CH3
C C + H2C C CHCH3
H3C OH
.. H3C CH3

3,3-DIMETIL-2-BUTANOL 2,3-DIMETIL-2-BUTENE 2,3-DIMETIL-1-BUTENE

(80%) (20%)

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MEKANISME UMUM DEHIDRASI
ALKOHOL TERKATALISIS ASAM
• MENGIKUTI MEKANISME E1
H
(FAST)
.. +
STEP 1: C C OH
.. + H3O : C C O+-H + H2O :
..
H H
H (SLOW)
STEP 2: C C O+-H C C+ + H2O :
..
H H

.. (FAST)
STEP 3: C +
C + H2O : C C + H3O :+

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MEKANISME PENATAAN ULANG
• PENATAAN ULANG SELAMA DEHIDRASI DARI 3,3-
DIMETIL-2-BUTANOL
CH3 CH3
1)
H3C C CH CH3 + H O+ H3C C CH CH3 + H2O
3
H3C OH H3C O +
.. .. H2
3,3-DIMETIL-2-BUTANOL

CH3 CH3
2)
H3C C CH CH3 H3C C C+ CH3 + H2O

H3C O + H3C H (2o)


.. H2
CH3 CH3
CH3
3) + +
H3C C C+ CH3 H3C C C CH3 H3C C C CH3

H3C H H3C H H3C H (3o)


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FINAL PRODUCT

H3C CH3
A)
B) H A) H2C C CHCH3
H CH2 C+ C CH3 MINOR PRODUCT
H3C CH3 H3C CH3
B) C C
H3C CH3
MAJOR PRODUCT

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BEBERAPA PERGESERAN DLM
PENATAAN ULANG ION KARBONIUM
CH3 PERGESERAN METIDA CH3
H3C-C CH+ CH3 H3C-C+ C CH3

CH3 CH3 H
(2o)
(3o)
H PERGESERAN HIDRIDA H
H3C-CH2CH C+H2 H3C-CH2C+H CH2
(1o)
(2o)
CH3
CH3
+
CH+ CH3

CH3
H
(2o) (3o)
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DEBROMINATION OF VICINAL DIBROMIDES

1. VIC-DIBROMIDES
UNDERGO THE LOSS OF
A MOLECULE OF
BROMINE (Br2)WHEN
THEY ARE TREATED Br
WITH A SOLUTION OF
SODIUM IODIDE IN H3C CH CH2 H3C CH2 CH
ACETON OR MIXTURE
OF ZINC DUST IN
Br Br Br
ETHANOL. VIC GEM
2. DEBROMINATION BY
SODIUM IODIDE TAKE
PLACE BY AN E2
MECHANISM.

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THE MECHANISM OF DEBROMINATION

I:-
Br

CH CH2 CH CH2 + IBr + :Br-


H3C H3C
Br

I:- + IBr I2 + Br:-

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PROBLEM 1

• Although ethyl bromide and isobutyl bromide


are both primary halides, ethyl bromide
undergoes SN2 reactions more than ten times
faster than isobutyl bromide. When each
compound is treated with a strong base
(CH3CH2O-), isobutyl bromide gives a greater
yield of elimination products than
substitution products, whereas with ethyl
bromide this behavior is reversed. What factor
accounts for these results?

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PROBLEM 2

• Consider the reaction of I- with CH3CH2Cl. (a).


Would you expect the reaction to be SN1 or SN2?
The rate constant for the reaction at 60o is 5x10-5
liter mole-1 sec-1. (b). What is the reaction rate if
[I-] = 0.1 mole liter-1 and [CH3CH2Cl] = 0.1 mole
liter-1? (c). If [I-] = 0.1 mole liter-1 and
[CH3CH2Cl] = 0.2 mole liter-1? (d). If [I-] = 0.2
mole liter-1 and [CH3CH2Cl] = 0.1 mole liter-1?
(e). If [I-] = 0.2 mole liter-1 and [CH3CH2Cl] = 0.2
mole liter-1?

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PROBLEM 3
• When tert-butyl bromide undergoes SN1 hydrolisis,
adding a “common ion” (i.e NaBr) to the aqueous
solution has no effect on the rate. On the other
hand when (C6H5)2CHBr undergoes SN1
hydrolisis, adding NaBr retards the reaction. Given
that the (C6H5)2CH+cation is known to be much
more stable than the (CH3)3C+ cation, provide an
explanation for the different behavior of the two
compounds.

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