 Karena basa berperan dalam laju reaksi, maka makin kuat basa makin cepat

terjadi reaksi E2
 Makin baik leaving group, makin cepat reaksi E2
 Pelarut : polar aprotic
 Substrat : makin banyak alkil (R) yang terikat pada karbon yang mempunyai
leaving group, makin cepat terjadi E2
Struktur keadaan transisi E2

WHY ? •
•
Saat TS , ikatan rangkap terbentuk sebagian
Makin tersubsitusi alkena, makin stabil, energi TS makin rendah
• Sehingga Ea makin kecil, reaksi makin cepat.
• Tdak terpengaruh oleh halangan sterik

Contoh

5
 Contoh

Stereokimia E2

 Reaksi E2 merupakan reaksi stereoselektif yang berlangsung dalam bentuk

konformasi anti periplanar (trans-diaxial untuk senyawa siklik)

Syn periplanar
Anti periplanar

6
 Terjadi eliminasi E2
Tidak terjadi eliminasi E2 (Cl dan H dalam posisi trans-diaxial
(Cl dan H tidak dalam posisi trans-diaxial

Contoh

7
 Contoh

Produk utama
mengacu pada aturan
saytzeff

REAKSI ELIMINASI UNIMOLEKULER (E1)

 Hanya substrat berperan dalam penentu laju reaksi
 Reaksi berlangsung dua tahap

Mekanisme reaksi

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  Karena basa tidak berperan dalam laju reaksi, maka reaksi E1 terjadi dengan
basa lemah
 Makin baik leaving group : makin cepat reaksi
 Pelarut : polar protic
 Substrat : makin banyak alkil (R) yang terikat pada karbon yang mempunyai
leaving group, makin cepat terjadi E1

B:
H
C C C C
X

B:
H H
C REAKSI
C ELIMINASIC UNIMOLEKULER
C CKARBANION
C (E1cb)
+
X E1cb MECHANISM
THE

B: carbanion
H
C C C C C C
proton halogen
X first X second

E1cb jarang terjadi karena memerlukan substrat yang memilki karakteristik sbb :
1. Proton nya harus sangat mudah dieliminasi (sangat asam).
Umumnya memerlukan stabilisasi resonansi dari basa konyugasi

2. Leaving groupnya sangat susah dilepas (lepas sebagai basa yang kuat sekali)

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 Contoh E1cb

O O CH3 O O
H
H
NaOCH3
H H
CH3OH
OCH3 OCH3 OCH3
H asam
Mudah dilepas fast slow conjugate base
step step stabilized by
resonance

+ O CH3
UNIMOLECULAR
Slow step does Basa kuat=
not involve base Leaving group jelek

COMPARISON OF b-ELIMINATION MECHANISMS

special alkyl halides alcohols

E1cb E2 E1 E1 E1 acid
assisted

strong strong weak acidic

neutral
base base base

stepwise - concerted stepwise - carbocation

carbanion
“solvolysis”
special case -
not common stereospecific
anti-coplanar not stereospecific
requires:
acidic H and Zaitsev if Zaitsev Zaitsev Zaitsev
poor leaving stereochem
group allows

carbocation rearrangements

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 The Competition between Elimination and Substitution

SN2 and E2

favored over SN1 and E1 by a strong base/Nu

SN2 is slowed by steric hindrance, but E2 is not

strong base, strong Nu

strong base means E2, not SN1

SN2 and E2

Stronger bases favor E2 over SN2

stronger base

weaker base

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 SN2 and E2

higher temperatures favor elimination

G = H - TS

SN2 E2

weaker bases stronger bases

less steric hindrance more steric hindrance
lower temperature higher temperature

SN1 and E1

favored over SN2/E2 by absence of strong base/Nu

often neutral or acidic conditions

tertiary or secondary substrates in polar solvents

SN1 is usually major, but some E1 always occurs also

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 Methyl Substrates: CH3L
SN2 only

Primary Substrates: RCH2L

good for SN2 with almost any nucleophile

no SN1/E1
can cause E2 with a sterically hindered strong base
potassium tert-butoxide (KOt-Bu)

Secondary Substrates: R2CHL

SN2 favored with good Nu that is not too basic
(especially in aprotic solvents)
CH3CO2–, RCO2–, CN –, RS –

E2 favored with strong bases

HO –, RO – (NaOH, NaOEt)

SN1 favored by absence of good Nu in polar solvent

often neutral or acidic conditions
some E1 product is usually formed

a solvolysis reaction

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 Tertiary Substrates
no SN2 (too hindered)
E2 favored with strong bases
HO –, RO – (NaOH, NaOEt)
SN1 favored by absence of good Nu in polar solvent
often neutral or acidic conditions
some E1 occurs

The effect of directing in Elimination reactions

Hofmann’s and Zaitsev’s Rule

 unsimilar alkyls on alkyl halides like 2-chloro-2-methylbutane, can form one

alkene or more. Depending on the relativity rate of beta elimination
 The use of HO - or NH2 - will form more stable alkene which contain less number
of Hydrogen and more number of alkyl groups bonded to double bond carbon
alkene is Zaitsev’s product.
 The other product which contain more number of hydrogen is Hofmann’s product

Hofmann’s rule: The major alkene product has
fewer alkyl groups bonded to the carbons of the
double bond (the less highly substituted product).

Zaitsev’s Rule:The major alkene product is the one

with more alkyl groups on the carbons of the
double bond (the more highly substituted
product).

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  Change of Base in this reaction will change yields

The effect of directing in Elimination reactions

Hofmann’s and Zaitsev’s Rule
 Hofmann’s and Zaitsev’s products will vary and depends on:
1. How easily of proton elimination from two adjacent beta carbons near leaving
group
2. the stability of olefins produces
3. Effect of strain on replacing Leaving group
4. How base is big in elimination rxn

Base + (CH3)2CBrCH2CH3 ..........> (CH3)2C=CHCH3 + H2C=C(CH3)CH2CH

3

I II

base EtO- 70% and 30%; Me3CO- 28% and 72% , Et3CO- 12% and 88%

15
  When substrate is a an ammonium salts, sulfur or quaternary phosphonium, will
produce less substituted alkene (Hofmann)

CH3CH2CH(S+Me2)CH3 ..........> CH3CH=CHCH3 (26%) + CH3CH2CH=CH2

CH3CH(N+Me3)CH2CH2CH3 ......> CH2=CHCH2CH2CH3 (Major) + CH3CH=CHCH2CH3 minor)

 Steric hindrance on alkyl halihes will prevent proton elimination hence the
products is Zaitsev’s products which contain many substituted groups. The
product with less substituted is more preferred (Hofmann)

Elimination Reactions with acidic catalyst

 Elimination and substitution reaction with Alcohols and ethers occur only in a
strong acids.
 Alkenes preparation from alcohols by E1and E2 reactions will depend on alcohol,
acid, solvent and temperature.

16
 Elimination Reactions with acidic catalyst

 Reaction Tertiary butyl alcohol in E1:

1st step: reversible and fast addition of proton to hydroxyl to
make it a good leaving group
2nd step: C-O cleavage and H2O as a good leaving group to
form carbocation. Rate determining step.
3rd convert carbocation to alkene by eliminate proton using
water

17
13/08/1441

GOOD LUCK

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