MEKANISME REAKSI

ORGANIK
Klasifikasi Reaksi Organik
 Reaksi adisi
 Reaksi eliminasi
 Reaksi substitusi
 Reaksi kondensasi
 Prinsip Le Chatelier
 Reaksi Tata-ulang
 Reaksi isomerisasi
 Reaksi Oksidasi-Reduksi
 Mekanisme reaksi
 PEMBENTUKAN DAN PEMUTUSAN
IKATAN
 Pemecahan homolitik
 Pemecahan ikatan σ antara atom A dan B
dimana 2 elektron ikatan terbagi rata
membentuk suatu spesies netral yang
disebut radikal
 Pemecahan heterolitik
 Umumnya terjadi pada ikatan σ yg polar
 Distribusi elektron tidak merata.
 Elektron akan lebih ditarik pada atom yang
lebih elektronegatif.
 Terbentuk karbokation dan karbanion
Heterolytically cleave each of the carbon-hetratom bonds
and label the organic intermediate as a carbocation or
carbanion

a)
OH + OH

carbocation

b) H3CH2C Li H3C CH2 + Li

carbanion

7
 Kestabilan jenis-jenis karbokation
Faktor Induksi:

R R H H
R C > R C > R C > H C
R H H H

3° 2° 1° Methyl
Faktor resonansi:
Faktor Hiperkonjugasi
- Overlapping  menyumbang densitas elektron pd atom C
yg kekurangan elektron, maka semakin banyak jumlah
interaksi hiperkonjugasi akan meningkatkan kestabilan
karbokation.

- Jika jumlah ikatan yg terikat pada karbokation bertambah

melalui bertambahnya jumlah gugus alkil yang terikat pada
karbokation  meningkatkan kestabilan karbokation.
Reaksi Radikal
Free Radical Chlorination
Experimental Evidence Helps to
Determine Mechanism
 Chlorination does not occur at room
temperature in the dark.
 The most effective wavelength of light is
blue that is strongly absorbed by Cl2 gas.
 The light-initiated reaction has a high
quantum yield (many molecules of product
are formed from each photon of light).
Free Radical Species are Constantly
Generated Throughout the Reaction
Propagation
Termination: Reaction of any 2 Radicals
Chlorination of Propane

40%

60%
H’s are not abstracted at the same rate.

Reactivity of Primary (1 o) H abstraction

40%
= 6.7
6H

Reactivity of Secondary (2 o) H abstraction

60%
= 30
2H
Rate of 2 o H abstraction : 1 o H abstraction
= 4.5:1
3o Radicals are Easiest to Form
Stability of Free Radicals
Bromination is Very Selective
Bromination is Very Selective
Reaksi Substitusi Nukleofilik
 Substitusi nukleofilik unimolekular (SN1)
 Substitusi nukleofilik bimolekular (SN2)
 Substitusi nukleofilik internal (Sni)
Reaksi Substitusi nukleofilik bimolekular (SN2)
Substitution Reaction with
Halides
(1)
(2)

bromomethane methanol

If concentration of (1) is
doubled, the rate of the
reaction is doubled. If concentration of (1) and
(2) is doubled, the rate of
the reaction quadruples.
If concentration of (2) is
doubled, the rate of the
reaction is doubled.
Substitution Reaction with
Halides
(1)
(2)

bromomethane methanol

Rate law:

rate = k [bromoethane][OH-]

this reaction is an example of a SN2 reaction.

S stands for substitution
N stands for nucleophilic
2 stands for bimolecular
Mechanism of SN2 Reactions
Alkyl halide Relative rate

The rate of reaction depends on the 1200

concentrations of both reactants.

When the hydrogens of bromomethane

40
are replaced with methyl groups the
reaction rate slow down.

The reaction of an alkyl halide in which 1

the halogen is bonded to an asymetric
center leads to the formation of only
one stereoisomer
≈0
Mechanism of SN2 Reactions
Hughes and Ingold proposed the following mechanism:

Transition state

Increasing the concentration of either of the

reactant makes their collision more probable.
Mechanism of SN2 Reactions
Steric effect

activation
energy: DG2
Energy

activation
energy: DG1

reaction coordinate reaction coordinate

Inversion of configuration

(R)-2-bromobutane (S)-2-butanol
Factor Affecting SN2 Reactions
The leaving group
relative rates of reaction pKa HX
HO
- + RCH I RCH2OH + I
- 30 000 -10
2
HO
- + RCH2Br RCH2OH + Br
- 10 000 -9
HO
- + RCH2Cl RCH2OH + Cl
- 200 -7
HO
- + RCH2F RCH2OH + F
- 1 3.2

The nucleophile

In general, for halogen substitution the

strongest the base the better the
nucleophile.

pKa Nuclephilicity
SN2 Reactions With Alkyl Halides
an alcohol

a thiol

an ether

a thioether

an amine

an alkyne

a nitrile
Reaksi Substitusi nukleofilik unimolekular (SN1)
Substitution Reactions With Halides

1-bromo-1,1-dimethylethane 1,1-dimethylethanol

Rate law:
If concentration of (1) is
doubled, the rate of the rate = k [1-bromo-1,1-dimethylethane]
reaction is doubled.
this reaction is an example of a SN1
reaction.
If concentration of (2) is S stands for substitution
doubled, the rate of the N stands for nucleophilic
reaction is not doubled. 1 stands for unimolecular
Mechanism of SN1 Reactions
Alkyl halide Relative rate

The rate of reaction depends on the ≈0*

concentrations of the alkyl halide only.

When the methyl groups of 1-bromo- ≈0*

1,1-dimethylethane are replaced with
hydrogens the reaction rate slow down.

The reaction of an alkyl halide in which 12

the halogen is bonded to an asymetric
center leads to the formation of two
stereoisomers
1 200 000

* a small rate is actually observed as a result of a SN2

Mechanism of SN1 Reactions
nucleophile attacks the
carbocation

slow

C-Br bond breaks

fast

Proton dissociation
Mechanism of SN1 Reactions

Rate determining step

Carbocation
intermediate

DG R++ X-
+
R-OH2

R-OH
Mechanism of SN1 Reactions

Inverted
configuration relative Same configuration
the alkyl halide as the alkyl halide
Factor Affecting SN1 reaction

Two factors affect the rate of a SN1 reaction:

• The ease with which the leaving group dissociate from the carbon
• The stability of the carbocation

As in the case of SN2, the

The more the substituted the
weaker base is the leaving
carbocation is, the more
group, the less tightly it is
stable it is and therefore the
bonded to the carbon and the
easier it is to form.
easier it is to break the bond

The reactivity of the

nucleophile has no effect on
the rate of a SN1 reaction
Comparison SN1 – SN2

SN1 SN2
A two-step mechanism A one-step mechanism
A unimolecular rate-determining step A bimolecular rate-determining step
Products have both retained and inverted Product has inverted configuration
configuration relative to the reactant relative to the reactant
Reactivity order: Reactivity order:
3o > 2o > 1o > methyl methyl > 1o > 2o > 3o
Reaksi Substitusi nukleofilik internal (Sni)
SNi or Substitution Nucleophilic internal stands for a
specific but not often encountered nucleophilic aliphatic
substitution reaction mechanism. The name was introduced
by Cowdrey et al. in 1937 to label nucleophilic reactions
which occur with retention of configuration, but later was
employed to describe various reactions that proceed with
similar mechanism.

- A typical representative organic reaction displaying

this mechanism is the chlorination of alcohols with
thionyl chloride
- the main feature is retention of stereochemical
configuration.
Reaksi Eliminasi
* Reaksi eliminasi unimolekular (E1)
* Reaksi eliminasi bimolekular (E2)
Reaksi eliminasi bimolekular (E2)
Elimination Reactions

1-bromo-1,1-dimethylethane 2-methylpropene

Rate law:

rate = k [1-bromo-1,1-dimethylethane][OH-]

this reaction is an example of a E2 reaction.

E stands for elimination
2 stands for bimolecular
The E2 Reaction
A proton is
removed

Br- is eliminated
The mechanism shows that an E2
reaction is a one-step reaction
Elimination Reactions

1-bromo-1,1-dimethylethane 2-methylpropene

Rate law:
If concentration of (1) is
doubled, the rate of the
rate = k [1-bromo-1,1-dimethylethane]
reaction is doubled.
this reaction is an example of a E1
If concentration of (2) is reaction.
doubled, the rate of the E stands for elimination
reaction is not doubled. 1 stands for unimolecular
The E1 Reaction
The base
removes a proton

The alkyl halide

dissociate, forming a
carbocation

The mechanism shows that an E1

reaction is a two-step reaction
 Products of Elimination Reaction

30% 50% 80%

2-butene

2-bromobutane 20%
1-butene
The most stable alkene is the
major product of the reaction
for both E1 and E2 reaction

The greater the number of

For both E1 and E2 reactions, tertiary alkyl halides alkyl substituent the more
are the most reactive and primary alkyl halides stable is the alkene
are the least reactive
Competition Between
SN2/E2 and SN1/E1
SN1 SN2 E1 E2

rate = k1[alkyl halide] + k2[alkyl halide][nucleo.] + k3[alkyl halide] + k2[alkyl halide][base]

• SN2 and E2 are favoured by a high concentration of a good

nucleophile/strong base
• SN1 and E1 are favoured by a poor nucleophile/weak base, because a
poor nucleophile/weak base disfavours SN2 and E2 reactions
Competition Between
Substitution and Elimination
 SN2/E2 conditions:
In a SN2 reaction: 1o > 2o > 3o
In a E2 reaction: 3o > 2o > 1o

90% 10%

25% 75%

100%
Competition Between
Substitution and Elimination
 SN1/E1 conditions:

All alkyl halides that react under SN1/E1 conditions will give
both substitution and elimination products (≈50%/50%)
SN1 and SN2: Factors Influencing Rate
1. Substrate Structure

SN2: methyl > 1° > 2 ° >> 3° (unreactive)

SN1: carbocation stability limiting factor (3°)

2. Nucleophile Concentration and Reactivity

SN2: anionic nucleophile better than conjugate acid

SN2: for like atoms, nucleophilicity || basicity

RO- > HO- > RCO2- > ROH > H2O

SN1 and SN2: Factors Influencing Rate

3. Solvent

SN2: Strongly Solvated Nucleophiles are Weaker!

(this explains relative halide nucleophilicity)

SN1: Ionizing Ability of Solvent is Critical

Polar, Protic Solvents Best (Solvate Cations and Anions)

4. Leaving Group Stability

Typically Don’t See Strong Bases as Leaving Groups

More Leaving Group Stability = Greater Reaction Rate
 SN1 and SN2: Differentiating Factors
Reactions Involving Alkyl Halide Substrates

Factor SN1 SN2

Substrate 3° (Stable C+) Methyl > 1° > 2°

Nucleophile Weak Lewis Base Strong Lewis Base

Neutral High [Nu]

Solvent Polar Protic Polar Aprotic

Leaving Group

I > Br > Cl > F (SN1 and SN2)

KEY Consideration: For a Given Reaction, Look at These Factors

Now We’re Ready to Tackle Some Specific Examples

Summary
 Alkyl halides undergo two kinds of nucleophilic subtitutions:
SN1 and SN2, and two kinds of elimination: E1 and E2.
 SN2 and E2 are bimolecular one-step reactions
 SN1 and E1 are unimolecular two step reactions
 SN1 lead to a mixture of stereoisomers
 SN2 inverts the configuration od an asymmetric carbon
 The major product of a elimination is the most stable alkene
 SN2 are E2 are favoured by strong nucleophile/strong base
 SN2 reactions are favoured by primary alkyl halides
 E2 reactions are favoured by tertiary alkyl halides