-

Acylation -

→
Acylation is the process by which the acyl group is introduced into another molecule .

"° Difference between acyl group and

carbonyl group
:

The acyl group

is :
R -
c An carbon from
•

acyl group refers to

group derived a carboxylic aid whereas
\
a
carbonyl group is a more
general functional group with a c=O
?
.

What are acid derivatives

"°
Acid derivatives derived from have formula R C
are
carboxylic acids and
general : -
→

Iz
,

All acid derivatives have the

acyl of
'

their structure
group as
part .

✗
0
"°
Esters R
Acid chlorides R -
C
c)
-

leg ethanoyl \c ,
leg ethyl o p
, .

-
.

chloride )
ethanoate)

R -
C40
Acid anhydride
to
/
( e.g . ethanoic R -
C

anhydride to

Nucleophilic Attack of an Acid Derivative

g -1×0
si .
It is attacked
by nucleophiles at the C
& "

and nucleophile
" R -
C
replaces 2 and nucleophile acquires an
acyl group -

\
z

so
gt fo " - -

R -
C t :Nu > R -
C + :z

\z \Nu

Three factors that affect how readily theteaction Why are

acyl chlorides & acyl anhydrides good
?
acylating agents
Electron
releasing / attracting of
I -
2
power

How lost
g.
easily Z is The 2 of and anhydrides
•

chlorides acid
groups acyl
3 How the
good nucleophile is withdraw electrons from the
carbonyl carbon .

This carbon
makes the positive and makes these
'

more

Reactivity of nucleophiles
compounds reactive towards nucleophiles .

→
Nucleophiles are lone pair donors .

The best nucleophiles best

donating their
•

are ones that are at

lone pair .

H H "
"
/ !
É
I
:N -
R
} :N -
H > :O y
I
\
H
H \R \H
Primary Amine
Ammonia Alcohol water
 %
Products of Reactions of Acid Derivatives +
Nucleophiles
25°C)
( at room temperature
%

.÷÷÷
÷
.

<
Increase
Reactivity
"°
R -
c
°
Acid
derivative R -
Y0
R - C
1CI , @
Nucleophile
Acid chloride Anhydride
-

I R
'
-

NH2 R -
c"
\ '
amine NHR
N -

substituted amide

2
NH3 "°
ammonia R -
C
\
NH2

;É Amide

¥
"°
o
9
' R -
c
3 R OH
10
-

'
-
R
J alcohol
ester
15

°
"
R -
[
4 H20
hot
water

acid
carboxylic

Nucleophilic Addition -

Elimination Reactions %
1 " " / 11/11/71 - - - - -- - - - - ,
#
The of / addition
reaction called nucleophilic elimination
•

acyl chlorides acid anhydrides +

nucleophile are -

reactions . The
following is ranked from most reactive to least reactive .

One to been
these
acylation reactions
hydrogen of nucleophile has replaced by
•

way remember is that a atom the

an
acyl group .

What has been acylated ? •

The nucleophile ( e.g . amine / ammonia / alcohol / water)

which the acylating agent ?

Acyl chloride
-

is

" " " "" "" " " " " " " " "" " " " " " " " " " " " "" " " ""

[
=

)
"

( conditions : Room temperature )

CH3
6PT
°
s
'
CH3
p 1
d

tafawa
'
g. I "

H3C N H >
H3C
-
C -
N
-
H > H3C -

C ,
-
-

q
did
I
H
N -

CH3
it
-

" " ""

" "" " " " " " " " " "" " " " " " " " " " " " "" " " " " ""

)
"

( conditions : Room temperature )

/
←
i. NH3
-

"
40 µ "
°

"
" " -

"" " "" " "" " + " " "

> "" " -

"
\o/ 8- I
> \µ NH2
✓
a
+ NH3
"

NH4 C)
CH3 COCI +
2MHz > CH, CONHZ +
N1-4CI

÷" " "

" "" " " " " "" " " " " " " "" ""

...
( conditions : Room temperature )

1.*
.
-

i
:O "
4
% '
a-
to
0yzµ
c-
GH ; →
Hf c- > +
H +
- - -

\CzH5 ,

Ct+50HHH5
" " " "" "" " " " " " " " " "" " " " " " " "" " " " "" " " ""

[ /
"

( conditions : Room temperature )

-É£
" "
/
0+1
°

f-

a-a.tl
H3C Hsc c-
'

> >
Hse
-

:O
-

\, I ① ⑦
OH
-1 µ

anhydrides of acid scale ?

Why acid are used instead an chloride on an industrial

Ethanoic
anhydride ethanoyl chloride as
acylating agent
-

over an are :

1-
Cheaper
2 Less corrosive

3 Does not react with water as

readily ✓ ( toxic)
4 Safer ,
as
by-product of its reaction is ethanoic acid rather than hydrogen chloride