KO_ADDITION REACTIONS

Ira Lestari, S.Si., M.Si

Reaksi &
Mekanisme
Reaksi

ADDITION REACTIONS
Reaksi Adisi

Lecturer:
Ira Lestari, S.Si., M.Si
@chem.edu.untan.ac.id
2

Chemistry Education
FKIP UNTAN_1
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Introduction
Reaksi penambahan suatu gugus ke suatu ikatan
rangkap dan menghasilkan ikatan tunggal

Reaksi Adisi merupakan karakteristik bagi senyawa

yang memiliki ikatan rangkap

Ikatan rangkap karbon-oksigen

Aldehid/keton
Nu
R
C O + H Nu R C OH Adisi nukleofilik
H
H
Ikatan rangkap karbon-karbon
Alkena
adisi
C C + A B A C C B Adisi elektrofilik
4

Chemistry Education
FKIP UNTAN_2
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Reaksi Adisi Nukleofilik

Nucleophilic Addition Reactions

THE CARBONYL GROUP

nucleophilic
at oxygen
electrophiles H+ or E+
add here
.. d- .. -
O: :O :
d+
C C
+

Nu: nucleophiles attack

the electrophilic carbon
6

Chemistry Education
FKIP UNTAN_3
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

NUCLEOPHILIC ADDITION TO C=O

MECHANISMS
IN ACID AND IN BASE

Nucleophilic Addition to Carbonyl

Basic or Neutral Solution
.. _
.. :O:
O: an
+
-:Nu slow
C alkoxide
C ion
Nu
.. _ ..
:O: :O H
fast
C + H2O C

Nu or on adding acid Nu

Good nucleophiles
and strong bases BASIC SOLUTION
(usually charged)
8

Chemistry Education
FKIP UNTAN_4
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Nucleophilic Addition to Carbonyl

Acid Catalyzed
+ more reactive to
.. :O H
O: fast addition than the un-
+
+ H C protonated precursor
C

..
.. + :O H
O H slow
+ C
C :Nu

Nu

Acid catalysis speeds the rate of

addition of ACIDIC SOLUTION
weak nucleophiles and stronger acid
weak bases (usually uncharged). pH 5-6 protonates the
9
nucleophile

CYANOHYDRINS

10

Chemistry Education
FKIP UNTAN_5
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Addition of Cyanide :C N:
Buffered to pH 6-8 .. _
:O : :O :
_
R C R + CN R C R

CN
.. _ ..
:O : :O H

R C R + H2O R C R

CN CN
a cyanohydrin

In acid solution there would be little CN-,

and HCN (g) would be a problem (poison). 11

CYANIDE ION BONDS TO HEMOGLOBIN

..
CYANIDE IS
N Cyanide bonds
IS A POISON C (irreversibly) to the
.. site (Fe II) where
CH3 oxygen usually bonds.

H3C
N N You die of
Fe suffocation -
N N lack of oxygen.
H3C CH3

CH2CH2COOH
CH2CH2COOH

HCN is a gas that you can easily breathe into your lungs. 12

Chemistry Education
FKIP UNTAN_6
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

HYDRATES

13

Addition of Water
O O H
+
H
C + H2O R C R'
R R'
O H
aldehyde or ketone
favored a hydrate

hydrates are unstable

most hydrates revert to an aldehyde and cannot be isolated
or ketone as soon as they form in most cases
O H
O
R C R' + H2O
C
R R'
O H
14

Chemistry Education
FKIP UNTAN_7
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

ACID CATALYSIS
RECALL
H
+
O H
H ..
.. + ..
:O :O H :O H

Acid catalysis enhances the reactivity

of the carbonyl group - nucleophilic :Nu
addition proceeds more easily. weak nucleophiles
can react

Water is a weak nucleophile.

15

WATER ADDS TO THE CARBONYL GROUP OF

ALDEHYDES AND KETONES TO FORM HYDRATES
H catalyzed by a
+ trace of acid
O H
.. H .. .. ..
+ H H H
:O :O :O :O
C C
O+ :O a hydrate
.. H .. H .. H
O H
.. .. H
H O H
H
.. +
O H
H ..

for most compounds the equilibrium MICROREVERSIBILITY:

favors the starting materials In a reaction where all steps are
and you cannot isolate the hydrate reversible, the steps in the reverse
reaction are the same as those in
the forward reaction, reversed!16

Chemistry Education
FKIP UNTAN_8
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

ACETALS AND
HEMIACETALS

17

ACID CATALYSIS
RECALL
H
+
O H
H ..
.. + ..
:O :O H :O H

Acid catalysis enhances the reactivity

of the carbonyl group - nucleophilic :Nu
addition proceeds more easily. weak nucleophiles
can react

Alcohols are weak nucleophiles.

18

Chemistry Education
FKIP UNTAN_9
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Addition of Alcohols
TWO MOLES OF ALCOHOL WILL ADD

addition of one mole

O O H
H+
hemiketal
R C R' + ROH R C R'
O R
addition of second mole

O H O R
H+
R C R' + ROH R C R' + H O
O R O R H
an ketal

19

ACETALS AND HEMIACETALS

R R OH ROH R OR
ROH
C O C C
OR OR
H aldehyde H H

hemiacetal acetal

R R OH ROH R OR
ROH
C O C C
OR OR
R ketone R R
(hemiketal)* (ketal)*
*older term *older term
20

Chemistry Education
FKIP UNTAN_10
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

..
R OH + H 2S O4 R O H Like a
+ hydronium
H ion
R
H O
+
.. .. H + ..
:O :O H :O H

R C R R C R R C R
.. O+
O H .. R
H .. R ..
ACID CATALYZED :
FORMATION OF A
first R O
addition H
HEMIACETAL
.. H
Normally the starting :O H
material is favored -
but a second molecule R C R + R O+
of alcohol can react .. H
if in excess : ..
O
hemiacetal R 21

FORMATION OF THE ACETAL ( from the hemiacetal )

remove
R
H O
+ H ..
.. H O H
H
.. second
.. H H .. : ..
O
addition
:O H
+O R
R C R R C R R C R
R C R +
:O
.. : O..
SN1 :O + :O
R R R R
hemiacetal
Resonance
stabilized
.. .. .. carbocation
: H
:O R R O O R
+ H H +
R O
: R C R R C R
H :O :O
.. R .. R
acetal 22

Chemistry Education
FKIP UNTAN_11
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

STABILITY OF ACETALS AND HEMIACETALS

Most hemiacetals are not stable, except for those of sugars

(see later).

Acetals are not stable in aqueous acid, but they are stable to
aqueous base.

OR H2SO4 ROH
AQUEOUS
ACID
C C O +
H2O
OR
ROH

AQUEOUS OR NaOH
BASE C no reaction
OR H2O

23

ADDITION OF WATER AND ALCOHOLS

WATER O H2O HO OH
C hydrate

ALCOHOLS
O R-O-H R-O-H
HO OR RO OR
C
H2O
hemiacetal acetal

O acetals are
RO OR H+
+2 ROH stable to base
H2O
but not to
H2O aqueous acid
no reaction
NaOH 24

Chemistry Education
FKIP UNTAN_12
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Reaksi Adisi Elektrofilik

Electrophilic Addition Reactions

25

Adisi Alkena
H H
H C C H Hidrogenasi
Pt katalis

H X
H C C X Hidrogen Halida

C C H OSO3H H C C OSO H Sulfonasi

3

H OH Hidrasi
H C C OH
HA katalis

Halogenasi
X X X C C X

Hidroborasi
Sikloadisi 1,4 diena / Diels-Alder

Reaksi adisi elektrofilik

26

Chemistry Education
FKIP UNTAN_13
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Reaksi Adisi pada Alkena

Karakterisasi ikatan rangkap :
1. Pemutusan satu ikatan π dari alkena dan satu ikatan σ dari pereaksi,
menjadi dua ikatan σ  umumnya reaksi bersifat eksoterm.

adisi
C C + A B C C
A B

ikatan  ikatan  2 ikatan 

ikatan terputus ikatan terbentuk

2. Ikatan p sangat disukai pereaksi pencari elektron, yang disebut elektrofil.

Pereaksi tersebut adalah:

 pereaksi bermuatan positif, ex : H+

 pereaksi netral, ex : Br2
 asam lewis, ex : BH3, BF3 dan AlCl3.
 Ion logam, ex : Ag+, Hg2+, Pt2+
27

Adisi hidrogen halida pada alkena

H X

C C + H X C C

H
Tahap lambat X H + C C C C + X

elektrofil nukleofil karbokation

H H X
Tahap cepat + X
C C C C
elektrofil nukleofil

Reaktivitas relatif HX : HI > HBr > HCl > HF

28

Chemistry Education
FKIP UNTAN_14
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Aturan Markovnikov
CH3

H3CHC CHCH3 H3CHC CH2

simetris
Tak simetris
H
H
HCl CH3 C CH 2-kloropropana
H
Cl H
CH3 C C

H H H
H
CH3 C CH 1-kloropropana

H Cl

1869, Vladimir Markovnikov : Dalam adisi HX kepada alkena tak simetris,

H+ dari HX menuju ke karbon berikatan-
rangkap yang telah lebih banyak memiliki
hidrogen.

29

Anti Markovnikov
Pada halida, adisi anti markovnikov terjadi hanya apabila HBr
digunakan sebagai pereaksi elektrofil dan terdapat peroksida. Adisi
ini menggunakan mekanisme radikal.

H+ kesini
H H
H HCl
CH3 C C CH3 C C H
H
H Cl H
H+ kesini
CH3 CH3 H
HBr
H3C C CH2 CH3 C C H

Br H

Pada saat suatu reaksi berpotensi untuk

menghasilkan dua atau lebih isomer
konstitusional, namun ternyata menghasilkan
Regioselektif hanya satu senyawa, maka reaksi tersebut
dikatakan regioselektif 30

Chemistry Education
FKIP UNTAN_15
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Stereokimia adisi hidrogen halida pada

alkena X H

H
+ X

karbokation

H X H H
X
+
X

a X

C2H5 C
a H
H
+ X CH3
C2H5 C CH2 C2H5 C
H C H (S)-2-halobutana
H2
b H
H X CH3
b C2H5 C
trigonal planar X
karbokation 31
(R)-2-halobutana

Adisi Halogen
suhu kamar
C C + Br Br C C
CCl4
Br Br

• Alkena bereaksi cepat dengan Br2 dan Cl2 dalam pelarut inert (ex : CCl4)
• Reaksi Adisi yang terjadi merupakan reaksi adisi anti
• Reaksi stereospesifik :
reaksi dikatakan stereospesifik bila suatu reaktan dengan bentuk stereoisomerik
tertentu bereaksi sedemikian rupa sehingga memberikan produk yang memiliki
bentuk stereoisomerik yang spesifik
Mekanisme reaksi :

tahap 1 Br
tahap 2
C C C C + Br C C

d+ Br Br Br

d- Br ion karbonium 32

Chemistry Education
FKIP UNTAN_16
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Stereokimia pada adisi halogen terhadap alkena

Br
Br
H
H

Br2 Br Br enantiomer
trans-1,2-dibromo-
CCl4 siklopentana
H

Br
Br
H
Stereospesifik pada reaksi adisi halogen
Br H
CH3
C C
H H
H H3 C
H H Br
C C CH3
H3C CH3 H3C (2R,3R)-2,3-dibromobutana
C C + Br
d+ Br
Br H Br
H3C
d- Br C C
ion karbonium H
cis-butena Br CH3
(2S,3S)-2,3-dibromobutana

Bagaimana dengan trans-butena ?

33

Adisi H2SO4 pada Alkena

• Syarat : alkena direaksikan dengan asam sulfat dingin
• Mengikuti aturan Markovnikov
• Merupakan reaksi adisi yang regioselektif

Adisi H2O pada Alkena (Hidrasi)

• Syarat : alkena direaksikan dengan H2O dalam kondisi
asam
• Laju reaksi bergantung pada derajat keasaman dari
medium
• Asam yang sering digunakan : H2SO4 dan H3PO4
• Mengikuti aturan Markovnikov
• Reaksi Hidrasi biasanya regioselektif
34

Chemistry Education
FKIP UNTAN_17
 KO_ADDITION REACTIONS
Ira Lestari, S.Si., M.Si

Adisi Boron hidrida pada Alkena

(Hidroborasi)
• Ditemukan oleh Herbert C. Brown (Purdue Univ)
• Syarat : Alkena direaksikan dengan kompleks BH3:THF
dalam pelarut eter (dietil eter atau dietilena glikol dimetil
eter)
• Peringatan : diborane and alkilboran mudah terbakar di
udara terbuka
– Larutan BH3:THF harus digunakan dalam atmosfer yang inert (ex:
argon atau nitrogen)
• Anti-Markovnikov
• regioselektif

35

Reaksi 1,4 sikloadisi pada diena

(Reaksi Diels-Alder)
O O

100oC
+ O O
benzena

O O
Suatu adduct

• 1928, kimiawan Jerman, Otto Diels dan Kurt Alder

mengembangkan reaksi 1,4-sikloadisi pada diena
• produk diels-alder disebut adduct
• mekanisme reaksinya ????

36

Chemistry Education
FKIP UNTAN_18