IRA LESTARI, S.Si. M.

Si
CHEMISTRY EDUCATION STUDY PROGRAM
UNIVERSIT OF TANJUNGPURA
1
Rearrangement : The reactions in which the
carbon skeleton of the molecule is
rearranged to give a structural isomer of the
original molecule

 Rearrangement reactions involve the

migration of a group or an atom from one
center (migration origin) to another
(migration terminus) within the same
molecule.
ira.lestari 2
 Rearrangements can be classified on the basis
of the nature of the migrating group/atom
1) Nucleophilic or Anionotropic: migrating
group migrates with its electron pair.
2) Electrophilic or cationotropic: migrating
group migrates without its electron pair.
3) Free radical: migrating group migrates
with only one electron.
ira.lestari 3
Kunci utama terjadinya penataan
ulang berasal dari konversi
konfigurasi elektron sektet
menjadi oktet !!

ira.lestari 4
 Rearrangements can take place in two possible
modes,
 Intramolecular : migrating group do not
completely detach from the migration origin and
occurs within the same molecule
M ─ A─ B → A ─ B ─ M

 Intermolecular : migrating group is detached

from the migration origin. migration of a
group/atom can take place to different molecule.
M ─ A─ B + S ─ A─ C → A ─ B ─ S + A ─ C ─ M
ira.lestari 5
ira.lestari 6
  Migrasi ke suatu pusat karbokation
 Penataan ulang-1,2
 Direction of rearrangement is 3° > 2 ° > 1°

C C C C

M M

7
ira.lestari
 H+/ H2O
CH3 CH3
H2 H2 -H2O
H3C C C OH + H Cl H3C C C OH2

1) CH3 CH3

CH3 CH3
-H+
H3C C CH2 H3C C CH2 H3C C C CH3 (E1)
H
CH3 CH3 CH3
(a) (b)
(b) > (a) Cl
+Cl- H2
H3C C C CH3 (SN1)
Kestabilan produk dilihat dari : CH3
▪ C+ 3>2>1
▪Jumlah hiperkonjugasi
8
ira.lestari
 C
H3 C
H3
H
Cl
H
3C C C C
H2 H
3C CC
H C
H3
H A
dis
i
C
H3 C
H3
(
a )

CH3 CH3
-H+ (E1)
H3C C C CH3 H3C C C CH3
H
CH3 CH3

(b) Cl CH3
+Cl- (SN-1)
H3C C C CH3
H
CH3

ira.lestari 9
 Suatu diol diubah menjadi keton

❑ Produk : pinakolon (suatu keton),

❑ kestabilan C+ 3>2>1
❑ Dikatalisis oleh H+ (=asam kuat)
❑ Terjadi migrasi

(pinacol) (pinacolon)
ira.lestari 10
 OH OH CH3 O
H+
H3C C C CH3 H3C C C CH3

CH3 CH3 CH3

2,3-dimetil-2,3-butanadiol 3,3-dimetilbutanon
(pinakol) (pinakolon)

Mekanisme reaksi : ??

Selain diol, terjadi pula pada senyawa :

-hidroksi aldehid
-hidroksi keton
ira.lestari 11
 ?

O O
CH3O CH3 Cl NO2 Alkil 3 Alkil 2 Alkil 1O H

Kecepatan migrasi/pergeseran
12
ira.lestari
 OH OH OH OH2 OH
+
H -H2O
C C C C C C (a)

OMe OMe OMe OMe OMe OMe OMe

OMe

OH O
H+
C C C C

(b) OMe
OMe

Pada produk (b)

Lebih cepat mengalami migrasi daripada

OMe

ira.lestari 13
ira.lestari 14
 rearrangement with a base catalysed
reaction
 1,2-diketone (benzil) is reacted with strong
base followed by acidification to form -
hydroxy-carboxylic acid (benzilic acid)
 1,2-rearrangements

ira.lestari 15
Mekanisme reaksi

ira.lestari 16
ira.lestari 17
 OH-, Br2
amida amina
H2O
(dengan pengurangan 1 atom C)

O
OH X2
R' C NH R NH2
H2O
R
R=H

O
OH Br2
R' C N R R' N R
H2 O
R R

ira.lestari 18
 Mekanisme Reaksi :
O O

H3C H2C C NH + OH H3C H2C C NH2 + Br Br

O O

H3C H2C C NH + OH H3C H2C C N + H2O

Br Br

O
OH
H3C H2C C N Br H3C H2C N C O
H2O

O O
O
H3C H2C N C H3C H2C N C H3C H2C N C
OH OH O
H

OH
H3C H2C NH2 + CO2
H2O

ira.lestari 19
ira.lestari 20
 Keton Ester
O O
R C R' + ASAM PEROKSI R C OR'

keton direaksikan dengan asam peroksi menghasilkan ester dengan

adanya penyisipan oksigen.
Reaksi dikatalisis oleh adanya asam katalisator.
Mekanismenya :

ira.lestari 21
 O O
H3C C C6H5 + CF3CO3H H3C C O C6H5
as. Peroksi trifluoro asetat

Mekanisme Reaksi :
O OH OH

+ H3 C C C6H5 H3 C C C6H5
F3 C C O OH

F3 C C O OH
O
OH
OH
H3C C C6H5 OH
H3 C C C6 H5
H3C C OC6H5
F3 C C O OH F3C C O O
O O H

OH + O
-H
H3C C OC6H5 H3C C O C6H5
ira.lestari 22
▪ Hilangnya karboksilat dan migrasi R terjadi
bersamaan,
▪ reaksi akan menjadi lebih cepat jika terdapat
substituen penarik elektron pada gugus pergi
dan adanya substituen pendorong elektron pada
gugus migrasi
▪ Urutan kemampuan pada keton tak simetris :
H > 3° > cyclohexyl > 20 > benzyl > aryl > 10 >
methyl.
▪ Pada gugus Aril, kemampuan bermigrasi akan
meningkat dengan adanya gugus pendonor/
pendorong elektron pada cincin.
ira.lestari 23