ARAH REAKSI, GUGUS AKTIVASI DAN DEAKTIVASI

ACTIVATED RING

Nitration of Anisole
O CH3
O CH3

O CH3
+

HNO3 H2SO4

NO2

NO2

anisole
Reacts faster than benzene

ortho

para

= ACTIVATED

The -OCH3 group when it preexists on the ring gives only ortho and para products, and no meta. Substituents that cause this result are called o,p directors and they usually activate the ring.

DEACTIVATED RING

Nitration of Methyl Benzoate

O C OMe

C OMe

HNO3 H2SO4 methyl benzoate

Reacts slower than benzene

NO2

meta

= DEACTIVATED

The -COOMe group when it preexists on the ring gives only meta, and no ortho or para products. Substituents that cause this result are called m directors and they usually deactivate the ring.

SUBSTITUENT CATEGORIES
Most ring substituents fall into one of these two categories:

G
o,p - directors activate the ring m- directors deactivate the ring

We will look at one of each kind in order to understand the difference..

NITRATION OF ANISOLE

Nitration of Anisole
BENZENIUM ION INTERMEDIATES

O CH3

O N+ O

O CH3 H NO2 + H

O CH3 H + H NO2 H

O CH3 +

ortho activated ring

O CH3 NO2

meta

para

H NO2

O CH3

actual products ortho + para

NO2

orth o

O CH3 H NO2 + H

O CH3 H NO2 H

:O

CH3 H + NO2 H

+ O CH 3 H NO2 H

EXTRA!

meta

O CH3 H + H NO2

O CH3 H + H NO2

O CH3 H + H

NO2

para
+ H

O CH3

:O
+

CH3

+O CH 3

O CH3

+ H H H NO2 H NO2 H H NO2

H NO2

EXTRA!

Energy Profiles
NITRATION OF ANISOLE RECALL: HAMMOND POSTULATE benzenium intermediate

meta ortho para

benzenium intermediates have more resonance

Ea

ortho-para director

BENZENIUM IONS GIVE ELIMINATION INSTEAD OF ADDITION ADDITION REACTION doesnt happen resonance would be lost

O CH3 H +

O CH3 H :B _

NO2

X
O CH3 H

B H NO2

addition

O CH3 H + NO2 :B _

ELIMINATION REACTION restores aromatic ring resonance ( 36 Kcal / mole )

NO2 elimination

NITRATION OF METHYL BENZOATE

Nitration of Methyl Benzoate

BENZENIUM ION INTERMEDIATES

C OMe

O O N+ O

C OMe H + NO2 H

C OMe H + H NO2 H

C OMe

deactivated ring

ortho

meta

para

H NO2

C OMe

actual product meta

NO2

orth o
O

C OMe H + NO2 H

C OMe H NO2 H

O +

C OMe H BAD! + NO
2

H
O C OMe H + H

meta

C OMe H + H NO2

C OMe H

+ H NO2 NO2

para

C OMe

O +
+

C OMe

C OMe

BAD!
+ H

+ H H NO2 H H NO2

H NO2

Energy Profiles
NITRATION OF METHYL BENZOATE
some benzenium resonance structures have a bad situation

ortho para meta

meta director

DIRECTIVITY OF SINGLE GROUPS

ortho, para - Directing Groups

X
Groups that donate electron density to the ring. E+
increased reactivity

PROFILE:

:X

+I Substituent These groups also activate the ring, or make it more reactive. CH3RThe +R groups activate the ring more strongly than +I groups.

+R Substituent

.. CH3-O.. ..
CH3-N-

.. -O-H ..

-NH2

..

meta - Directing Groups

X
Groups that withdraw electron density from the ring. E+
decreased reactivity

PROFILE:

-I Substituent These groups also deactivate the ring, or make it less reactive.
R + N R R CCl3

-R Substituent
O C R O C OR O C OH C N

+O
N O

-SO3H

THE EXCEPTION

Halides - o,p Directors / Deactivating

:X:
E+

..

Halides represent a special case: They are o,p directing groups that are deactivating They are o,p directors (+R effect ) They are deactivating ( -I effect ) Most other other substituents fall into one of these four categories: 1) 2) 3) 4) +R / o,p / activating +I / o,p / activating -R / m / deactivating -I / m / deactivating

+R / -I / o,p / deactivating -F -Cl -Br -I

PREDICT !
CH3 NO2

o,p

O CH3

O C O CH3

o,p

DIRECTIVITY OF MULTIPLE GROUPS

GROUPS ACTING IN CONCERT

steric crowding o,p director

O CH3 NO2
very little formed

O CH3

O2N
m-director HNO3 H2SO4

NO2

O CH3 NO2

When groups direct to the same positions it is easy to predict the product.

NO2

major product

GROUPS COMPETING
o,p-directing groups win over m-directing groups
O CH3 O2N NO2

O CH3

too crowded

HNO3 H2SO4

NO2

O CH3

NO2 NO2

RESONANCE VERSUS INDUCTIVE EFFECT

+R

O CH3
HNO3 H2SO4

O CH3 NO2

CH3
+I resonance effects are more important than inductive effects

CH3

major product

SOME GENERAL RULES

1) Activating (o,p) groups (+R, +I) win over deactivating (m) groups (-R,-I). 2) Resonance groups (+R) win over inductive (+I) groups. 3) 1,2,3-Trisubstituted products rarely form due to excessive steric crowding. 4) With bulky directing groups, there will usually be more p-substitution than o-substitution. 5) The incoming group replaces a hydrogen, it will not usually displace a substituent already in place.

PR : HOW CAN YOU MAKE ...

O C O CH3
O2N NO2

NO2

NO2

CH3

NO2 only, no para

CH2CH2CH2CH3