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REAKSI ELIMINASI

PELEPASAN MOLEKUL YZ DARI ATOM-ATOM C BERDAMPINGAN DLM SUATU MOLEKUL PEREAKSI. DEHIDROHALOGENASI DAN DEHIDRASI

Y C Z C
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YZ

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 CH3OH
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2 C2H5O-Na+ + H2 CH3O-Na+ + H2
2

+ NaH

CONTOH

DEHIDROBROMINASI ALKIL BROMIDA


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

C2H5ONa (C2H5OH, 25oC)

H2C

H3C
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CH3 C + NaBr + C2H5OH CH3 91%


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DEHIDRASI ALKOHOL
PELEPASAN/ PENARIKAN H2O DARI ATOM-2 C BERDAMPINGAN DLM SEBUAH ALKOHOL DILAKUKAN DG ASAM KUAT MISALNYA: H2SO4 DAN H3PO4
H3C-CH2-CH2 OH OH H2SO4 PEKAT 170oC H3C-CH2 CH2 + H O 2

H3PO4 85% 165-170oC

+ H2O

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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:-

H2C

C
Br

C2H5O:- H CH3 H2C

H C .. Br CH3

H C H

H C + Br- + C2H5OH CH3

PROPENA

ISOPROPIL BROMIDA
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MEKANISME REAKSI E2
1. BASA MENYERANG AT. H DARI 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


1. H3C H3C H3C 2. C2H5O:H H3C
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Br

H3C H3C

C+ CH3 + Br-

CH2

C+ CH3

H2C

CH3 C + C2H5O:H CH3


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2-METILPROPENA

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


1. C2H5ONa + H3CCH2Br T=550C (1o) H3C 2. C2H5ONa + H3C H3C CH (2o) ETANOL T=250C Br ETANOL C2H5OCH2CH3 + SN2= 90% CH3 H2C CH2 + NaBr E2 = 10% CH-CH3 + NaBr

ETANOL T=550C

C2H5O-CH-CH3 + H2C SN2= 21% CH3 C2H5O-C-CH3 + H2C CH3 SN2= 9%

E2 = 79% CH3 C + NaBr CH3 E2 = 91% E2 = 100%

3. C2H5ONa + Br H3C C H3C o (3 )

T=550C

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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 99% + CH3(CH2)15CH2 CH2 1% CH3 CH3-C-O:CH3
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CH3O:- + CH (CH ) CH CH METANOL 3 2 15 2 2 Br DIREFLUX

CH3

CH3(CH2)15CH2CH2 Br

t-BUTIL ALKOHOL 40o

CH3(CH2)15CH2CH2 OC-CH3 15% CH3 + CH3(CH2)15CH2 CH2 85%


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KEBASAAN
1. 2. BASA LEMAH SPT Cl-, CH3COO-, Br-, IMENDORONG SN2 BASA KUAT: C2H5O-, OH-, NH2- MENDORONG E2
CH3 CH3COO:- + CH3-CH CH3 + CH3-CH Br Br CH3 O

CH3-CH O-CCH3 + Br: 100% CH3 CH2=CH 79% + Br:-

C2H5O:-

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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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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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ATURAN ZAITSEV
1. DEHIDROBROMINASI 2-BROMO-2-METILBUTANA DG NATRIUM ETOKSIDA
C2H5O:A H CH3-CH B CH2 B CH3CH2C (31%) CH3 2-METIL-1-BUTENA CH3 A CH3CH C (69%) CH3 2-METIL-2-BUTENA

CH2

C CH3 Br

2-BROMO-2-METILBUTANA

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 H H H
CH(CH3)2

H H

C2H5O:H
H3C

CH(CH3)2

C2H5O:-

MENTILKLORIDA C2H5O:B H H A
CH(CH3)2

2-MENTEN (100%)

CH(CH3)2

H3C

H H Cl

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

NEOMENTILKLORIDA
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B. 2-MENTEN (22%)
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ANTI ZAITSEV
1. DEHIDROBROMINASI 2-BROMO-2METILBUTANA DG KALIUM t-BUTOKSIDA ELIMINASI DG BASA MERUAH MEMBERIKAN ALKENA YG KURANG TERSUBSTITUSI.
H3C CH3-C-O:H3C A H H B B CH3CH2C CH2 (72,5%) CH3 2-METIL-1-BUTENA CH3 A CH3CH2 C (27,5%) CH3 2-METIL-2-BUTENA
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2.

CH 2
Br

CH3-CH C CH3

2-BROMO-2-METILBUTANA
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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-tertBUTYLCYCLOHEXENE. UNDER THE SAME

CONDITIONS, TRANS-1-BROMO-4-tertBUTYLCYCLOHEXANE REACTS VERY SLOWLY. WRITE CONFORMATIONAL STRUCTURE AND EXPLAIN

THE DIFFERENCE IN REACTIVITY OF THIS CIS-TRANS


ISOMERS.

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REAKSINYA
H HH H H CIS C2H5O:H H H Br H

TRANS H

H HH H H H H

H Br SULIT

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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 HH H H CIS C2H5O:H H H Br H

TRANS H

H HH H H H H

H Br SULIT

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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 METIL (1o) (2o) REAKSI BIMOLEKULER
MEMBERIKAN REAKSI SN2
MEMBERI SN2, KECUALI DG BASA MERUAH MEMBERI REAKSI E2 MEMBERIKAN REAKSI SN2 DG BASA LEMAH

(R)3CX (3o)
SN1/E1/E2
DLM SOLVOLISIS BEREAKSI SN1/E1, PD T RENDAH SN1 DOMINAN
BASA KUAT REAKSI E2 DOMINAN

MEMBERIKAN REAKSI E2 DG BASA KUAT

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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 -OOC-CH-CH2-CH2-S NH3+ METHIONINE HO HO CH-CH2NH ADRENALINE CH3 CH3 CH3 N+ CH3

CH2-CH2-OH CHOLINE

N N
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CH3

NICOTINE
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METHYL TRANSFER MECHANISM


OH NUCLEOPHILE CH3 O P O CH2 O H H OH O OH P O O OH P OH LEAVING GROUP O ADENINE H OH H

-OOCCH-CH2CH2S: + NH2

CH3 -OOCCH-CH2CH2S NH2 H CH2 O H OH ADENINE H OH H + -:O

OH P O O

OH P O O

OH P O OH

TRIPHOSPHAT ION

S-ADENOSYMETHIONINE
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ACTIVE METHYL TRANSFERER

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

S-ADENOSYMETHIONINE ACTIVE METHYL TRANSFERER

.. -OOCCH-CH2CH2S NH3+ H

CH2 O H OH

ADENINE H OH H +

CH3

CH3 N+ CH3

CH2-CH2-OH CHOLINE
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DEHIDRASI ALKOHOL
1. PELEPASAN H2O DR ALKOHOL-2 MELALUI PEMANASAN DG ASAM KUAT
ASAM LEWIS: ALUMINA (Al2O3) DLM INDUSTRI

2. ASAM BRONSTED: H2SO4 DAN H3PO4

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 170oC CH3-CH PROPENA CH2 + H2O PROPIL ALKOHOL OH CH3-CH2-CH2-OH

85% H3PO4 170oC

H2O

SIKLOHEKSANOL CH3 H3C C OH 85oC

SIKLOHEKSENA (80%) CH3 H3C C CH2 2-METILPROPENA (84%) + H2O

20% H2SO4

CH3 t-BUTIL ALKOHOL

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CAMPURAN ALKENA
1. BBP ALKOHOL TERDEHIDRASI MEMBERIKAN HASIL CAMPURAN ALKENA
H C H2SO4 PKT 3 170oC H
TRANS

H3C-CH2-CH2-CH2 OH

H H C 3 C C + CH3 H CIS

CH3 H C + H H C C

CH2CH3 H

CH3 OH 85% H PO 3 4 170oC 2-METIL-SIKLOHEKSANOL

UTAMA CH3

CH3

3-METILSIKLOHEKSENA 2. MENGIKUTI 1-METILSIKLOHEKSENA ATURAN ZAITZEV

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PENATAAN ULANG
BBP ALKOHOL 1o DAN 2o MENGALAMI PENATAAN ULANG SELAMA DEHIDRASI
1) CH3 H3C C CH CH3 H3C OH ..
3,3-DIMETIL-2-BUTANOL

H3C C H3C C

CH3 + CH3 H2C

CH3 CH3 C CHCH3

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
STEP 1: C H H STEP 2: C H STEP 3: C H
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.. + OH + H O : 3 ..

(FAST) C H C

H O+-H + H2O : ..

(SLOW) C H

O+-H .. (FAST)

C+

+ H2O :

.. + C + H2O :

+ H3O :+

MEKANISME PENATAAN ULANG


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

H3C

H3C

3,3-DIMETIL-2-BUTANOL

2) H3C

CH3 C CH CH3 H3C + O .. H2


+

CH3 C C+ CH3 H (2o) + H2O

H3C 3) H3C
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H3C CH3 H3C C C H

CH3 C C+ CH3 H H3C

CH3 CH3
+

H3C

CH3

H3C

H3C

H (3o)
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FINAL PRODUCT
H3C A) H CH2 C+ B) H C CH3 B) H3C CH3 A) H2C C CH3 CHCH3

MINOR PRODUCT H3C C C CH3 MAJOR PRODUCT CH3

H3C

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BEBERAPA PERGESERAN DLM PENATAAN ULANG ION KARBONIUM


CH3 H3C-C CH+ (2o) H PERGESERAN METIDA CH3 H3C-C+ CH3 C CH3

CH3

CH3 H (3o) PERGESERAN HIDRIDA H3C-CH2C+H (2o) + CH3 H CH2

H3C-CH2CH C+H2 (1o) CH3 CH+ CH3

(2o)
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CH3 H (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 WITH A SOLUTION OF H3C SODIUM IODIDE IN ACETON OR MIXTURE OF ZINC DUST IN ETHANOL. DEBROMINATION BY SODIUM IODIDE TAKE PLACE BY AN E2 MECHANISM.
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Br CH CH2 H3C CH2 CH Br GEM

Br Br VIC

2.

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THE MECHANISM OF DEBROMINATION


I:Br CH H3C I:CH2 Br + IBr H3C I2 + Br:CH CH2 + IBr + :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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