1

CARBONYL
COMPOUNDS

2
Objective

Describe aldehydes and ketones.

Draw the structure and name the

compound according to IUPAC
nomenclature and common names.

3
I!"ODUC!IO

#unctional group$ carbonyl% C&O

'eneral (ormula$ C
n
)
*n
O

Aldehyde + ,etone are isomeric

Carbonyl compounds are polar

In general% an aldehyde - reactive than ketone

towards nucleophilic addition reaction

4
I!"ODUC!IO

A.D/)0D/

" & alkyl% aryl 1 )

,/!O/
" + "2 & alkyl% aryl
C
O
R H
C
O
R R
34
35
34
35

5
aming o( Aldehyde

Aldehyde is named by substituting the letter 6e o(

the corresponding alkane with 6al

7asic name depends on the longest chain with

6C)O group

!he chain must be numbered by starting with

6C)O group as C58

6
aming o( Aldehyde
9tructure IUPAC name 'eneral name

)5C5)
methanal (ormaldehyde
C)
:
5C5)
ethanal acetyldehyde
C)
:
C)
*
5C5)
propanal propionaldehyde
O
O
O

7
aming o( Aldehyde
9tructure IUPAC name 'eneral name

C)
:
C)
*
C)
*
5C5)
butanal n5butyraldehyde
C)
:
;C)
*
<
:
5C5)
pentanal n5valeraldehyde
Ph5C5)
ben=aldehyde
;phenylmethanal<
ben=enecarbaldehyde
O
O
O

8
aming o( Aldehyde
O
C)
*
C5)
Phenylethanal
(phenylacetyldehyde)
CH
2
=CHCH
2
C-H
O
3-butenal
CH
3
CHCHC-H
O
OH
H
3
C-H
2
C
2-ethyl-3-hydroxybutanal
4 3 2 1
4 3 2 1
2 1

9
aming o( ,etone

,etone is named by substituting the letter 6e o(

corresponding alkane with 6one

!he longest chain with carbonyl group is

numbered so that C in carbonyl group gets the
smallest number

10
aming o( ,etone
9tructure IUPAC name 'eneral name

C)
:
CC)
:
propanone acetone
;dimethyl ketone<
C)
:
CC)
*
C)
:

7utanone methyl ethyl ketone
C)
:
CC)
*
C)
*
C)
:
*5pentanone
methyl propyl ketone
O
O
O

11
aming o( ,etone
9tructure IUPAC name 'eneral am

Ph5C5C)
:
phenylethanone
acetophenone
;phenyl methyl ketone<
Ph5C5Ph
diphenylmethanone
ben=ophenone
;diphenyl ketone<
C)
:
C)
*
CC)
*
C)
:
:5pentanone
diethyl ketone
O
O
O

12
O
C)
*
C5C)
:
phenylpropanone
CH
2
=CHCH
2
CCH
3
O
4-penten-2-one
CH
3
CCH
2
CH
2
CCH
3
O
2,5-hexanadone
O
O
OH
CH
2
CH
3
2-ethyl-2-hydroxycyclopentanone
5C)
*
C5C)
*
5
O
!,3-dphenylpropanone
5 4 3 2 1
1 2 3 4 5
1 2 3

13
a.
c.
b.
d.
EXCERCISE
8. >rite the names o( the (ollowing compounds according to
IUPAC nomenclature
C)
:
O
CH
3
CHCH
2
CH
2
CH
2
CH
CH
3
CH
2
CH
2
CHCH
O
C)
*
C)
:
CH
3
CH
2
CH
2
C
O
C)C)
:
C)
:
CH
3
CH
2
C
C)
*
C)
*
C)
*
C)
:
O

14
*. >rite down all structural (ormulae o( compound
with molecular (ormula C
?
)
8@
O and name them
according to IUPAC nomenclature.


15
Objective

/Aplain the preparation o( carbonyl compounds

through these reactions$
a<OAidation o( alcohols
b<O=onolysis o( alkenes
c< #riedel6Cra(ts acylation to produce aromatic
ketones

16
Preparation o( Carbonyl
8. OAidation o( Alcohols

BOC o( 8
o
"5O) to (orm aldehyde

BOC o( *
o
"5O) to (orm ketone
CH
3
CH
2
CH
2
CH
2
-OH " PCC CH
3
CH
2
CH
2
CH=O
CH
2
Cl
2
!-butanol butanal
-OH =O
KMnO
4
H
+
cyclopentanol cyclopentanone

17
*. O=onolysis o( alkene
() H
3
CC=CHCH
3
H
3
CC=O " O=CCH
3
CH
3
CH
3
H
() O
3
() #n$H
2
O
() O=CH(CH
2
)
4
CH=O
() O
3
() #n$H
2
O
Preparation o( Carbonyl

18
D. #riedel5Cra(ts Acylation
5a good method (or preparing o( aromatic ketones
" R-C-Cl " %lCl
3
-C-R

O
O
" R-C-O-C-R " %lCl
3
-C-R

O O O
Preparation o( Carbonyl

19
Practice Questions
(a) CH
3
CH(&r)CH(CH
3
)OH " '
2
Cr
2
O
(
$H
2
)O
4
(b) CH
3
CH=CCH(CH
3
)
2

CH
3

() O
3
()H
2
O$#n
(c) " -C=O
%lCl
3

Cl

20
8. OAidation
*. "eduction
:. ucleophilic addition reaction
D. Condensation
?. )alo(orm reaction
C)/EICA. P"OP/"!I/9

21

!o eAplain the chemical properties with

re(erence to these reactions $
a< oAidation with ,EnO
D
% ,
*
Cr
*
O
F
%!ollens% #ehling%
7enedict and 9chi(( reagents to di((erentiate
between aldehydes and ketones.
b< reduction to alcohol using .iAl)
D
%a7)
D
and
catalytic hydrogenation.

Objective

22
8.@ OAidation

Aldehydes are easily oAidised to carboAylic acid by

strong oAidising reagents e.g. ,EnO
D
G)
4
% ,
*
Cr
*
O
F
G)
4

Eild oAidising agents such as !ollens2% 9chi((% #ehlings2

+ 7enedicts2 solutions can also oAidise aldehydes.

,etones are resistant towards oAidation because they do

not have hydrogen attached to the carbonyl carbon
atom.
KMnO
4
H
+
H
+
KMnO
4
RCHO
RCR
O
*o reacton
RCOOH

23
8.8 !O../92 !/9!

#or identi(ying aldehydes and ke!nes"

It is a miAture o( aHueous silver nitrate and

ammonia.

It contains Ag;)
:
<
*
4

In this reaction aldehyde #s !$#d#sed !

%a&'!$ylae #!n and a&(en)* is deposited on
the wall o( the the test tube as s#l+e& *#&&!&"

24
CH
Contoh
2[Ag(NH
3
)
2
]
+
+ OH
-
+
RCOO
-
+ NH
3
+
Ag 2 2
+
NH
4
+
2
cermin perak
CH
3
CH
2
CHO + OH
-
[Ag(NH
3
)
2
]
+
2
+
RCH
O
O
+
2[Ag(NH
3
)
2
]
+
OH
-
+
cermin perak
NH
4
+
2
+
2 2Ag
+ NH
3
+ CH
3
CH
2
COO
-
cermin perak
NH
4
+
2
+
2 2Ag
+ NH
3
+
O
C O
-
s#l+e& *#&&!&
s#l+e& *#&&!&
s#l+e& *#&&!&
E$a*,le-

25
8.* #/).I' and 7//DIC! !/9!;Cu
*4

tartarate compleA<

#ehling reagent will oAidise aldehydes but not

ketones

Used to identi(y aldehydes

"eaction with aldehydes will produce

%a&'!$ylae #!n and %!,,e&.I/ !$#de which is
red in colour.

In this reaction copper;II< is reduced to

copper;I<

26
/HuationI
B&#%k &ed
B&#%k &ed
'l)e
'l)e
RCHO
C 4
2+
OH
-
! + +

RCOO
-
C
2
O 2
+
+ H
2
O 3
CH
3
CH
O
3H
2
O +
+ 2C
2
O

+ + OH
-
! C 4
2+
CH
3
CO
-
O
exa+ple

27
8.: 9chi((2s reagent

Aldehyde reacts with 9chi((2s reagent to

give a pink colouration

,etone give negative result

28

"eduction

Aldehydes are reduced to 8

o
"5O) + ketones to *
o
"5
O)

"eagents ;a< .iAl)

D
1 a7)
D
in ether 4 )
4

;b< Jn% )
4
% heat
;c< )
*
;g<% i 1 Pt% heat
*.@ "eduction

29
CH
3
CH
2
CH CH
3
CH
2
CH

O
OH
H
,%lH
4
H
"
-C-CH
3
-CH-CH
3


O
OH
H
2
, *
-xa+ple.

30

!o eAplain the chemical properties

with re(erence to these reactions $

a< nucleophilic addition with )C%
'rignard reagent% alcohol% sodium
bisulphite and water.

Objective

31

In C&O% the e5 density is drawn more towards

the O atom making the C atom de(icient in e.
!hus% the C atom becomes the site (or u
5

attack.

>hen carbonyl C is attacked by u

5
% breaking
the carbonyl bond + tetrahedral intermediate
is (ormed

)ybridisation o( sp
*
C atom changes to sp
:
:.@ ucleophilic addition

32

!he )C is prepared Kin situ2 by the &ea%#!n !0 a

*#$)&e !0 1CN !& NaCN 2#h 3
2
SO
4

"eagents $ aC 1 ,C ;aH< (ollowed by dilute )

*
9O
D

-C=O
H
*aC*
H
2
)O
4
-C-OH
H
C*
CH
3
CHCCH
3
CH
3
O
'C*
H
2
)O
4
CH
3
-CH-C-CH
3
CH
3
OH
C*
:.8 Addition o( )C

33

yields gem5diols
H



H



C=O " H
2
O

H
"


C

H



H



OH


OH



H
3
CH
2
C


H
3
C


C=O " H
2
O

H
"




C

OH


OH



H
3
CH
2
C


H
3
C


:.* Addition o( >ater

34

Aldehyde yields hemiacetal + ketone yields hemiketal

R



H



C=O " ROH

H
"


C

R



H



OH


OR


he+acetal

R



R



C=O " ROH

H
"


C

R



R



OH


OR


he+/etal

:.: Addition o( alcohol

35

)emiacetal + hemiketal in acidic solution react

(urther to (orm acetal + ketal
H
"


C

R



H



OR


OR


acetal

H
"


C

R



R



OR

OR


/etal


C " ROH

R



H



OH


OR


C " ROH

R



R



OH


OR



36
/Aamples$5
H



C=O " CH
3
OH

H
"


C

H



OH


OCH
3



CH
3



C=O " CH
3
OH

H
"


C

OH


OCH
3



CH
3



CH
3



CH
3




37
HCHO


()R012

()H
3
O
"


RCH
2
OH

!
o
%lcohol

RCHO


()R012

()H
3
O
"


R-CH-R

2
o
%lcohol

OH
RCR


()R012

()H
3
O
"


R-C-R

3
o
%lcohol

OH
O
R
-xa+ple.

38
3
*aH)O
3
react 4th aldehyde 5 /etone to 6or+
carbonyl b7ulphte 4hch 7 7oluble n 4ater
38h7 reacton 7 u7ed 6or pur6caton o6 aldehyde
9 /etone 6ro+ other non-7oluble or1anc
co+pound7
3Pure carbonyl co+pound 7 obtaned 4hen
treated 4th a:ueou7 ba7e

:.? Addition o( sodium bisulphite

39
*aH)O
3
" -C-CH
3
-C-CH
3


O
OH
O)O
2
-
*a
"
&7ulphte
7alt
)odu+
b7ulphte

40

!o eAplain the chemical properties with

re(erence to these reactions $

a< condensation with )
:
and ammonia
derivatives eg hydra=ine%
phenylhydra=ine% hydroAylamine and *%D 6
dinitrophenylhydra=ine as identi(ication
test (or carbonyl compounds.
b< iodo(orm test to identi(y compounds
with these structures
Objective

41
3
*H
3
5 t7 der;at;e7 react a7 nucleophle and
react 4th carbonyl co+pound7
3<n;ol;ed addton reacton 6ollo4ed by
dehydraton (el+naton o6 H
2
O +olecule to 6or+
C=*)
R




C=O " *H
3


D.@ Condensation
R




C

O-H

*-H


Carbnola+ne
=>n7table nter+edate
R




R




R




C=*H


R




H
" H
2
O
addton el+naton

42
R


C=O **H- -*O
2


R


H


H


*O
2



R


C=**H- -*O
2
" H
2
O

R


*O
2



2,4-dntrophenylhydra?ne

&rady7
rea1ent

yello4 9
oran1e
precptate

character7tc
reacton o6
carbonyl
co+pound7

-xa+ple.

43
)
:
derivatives ame Product ame
"5)
*
1
Ar5)
*
primary amine
C&5" 1
C&5Ar
imine
)
*
)
*
hydra=ine
C&)
*
)ydra=one
)
*
5O) hydroAyl amine
C&5O)
oAime

44
)
:
derivatives ame Product ame
)
*
)C
L
)
?
phenyl
hydra=ine
C&)C
L
)
?
phenyl
hydra=one
)
*
)C)
*
semi
carba=ide
C&)C)
*
semi
carba=one
O
O
3Carbonyl react 4th hydra?ne 9 phenylhydra?ne al7o 1;e
yello4 precptate

45

"eagent $ I
*
in aO);aH<% heat (orms aIO;9odium
iodate ;i<<

#ormation o( yellow precipitate% C)I

:
% indicate that
organic compound consist o( methyl carbonyl or
methyl alcohol$5
-C-CH
3
9 -C-CH
3


O
OH
H
?. Iodo(orm reaction

46
@-*-R%, R-%C8<O*.-
RCCH
3
RCC<
3
RCO
-
" CH<
3


O
O O
<
2
OH
-
OH
-
RCHCH
3
RCCH
3
RCC<
3
RCO
-
" CH<
3


OH
O
<
2
OH
-
OH
-
O
OH
-
O
<
2

47
-2%0P,-.-
CH
3
CH
2
CCH
3
CH
3
CH
2
C-O
-
" CH<
3


O
O
*a<O
-C-CH
3
-C-O
-
" CH<
3


O
O
<
2
$ *aOH

48
-2%0P,-.-
H-CCH
3
H-C-O
-
" CH<
3


O
O
<
2
$*aOH
-C-CH
3
-C-O
-
" CH<
3


OH
O
<
2
$ *aOH
H

49
Practice Questions
(a) CH
3
CCH
2
CH
3
" H
2
**H *O
2
*O
2

H
"
O
(b) CH
3
CCH
2
CH
3
" H
2
*OH

O
H
"
(c) CH
3
CCH
2
CH
3
" <
2
$ *aOH

O
(d) CH
3
C-CH
2
-Ph " ,%lH
4


O

50
Practice Questions
8he +olecular 6or+ula o6 an un/no4n co+pound % 7
C
(
H
!4
A O?onoly77 o6 % 1a;e t4o product7 & and C,
4hereby both & and C reacted 4th 2,4-
dntrophenylhydra?ne to 1;e 7old der;at;e7A &
1a;e po7t;e re7ult7 to 8ollen7 and <odo6or+ te7t7,
4hle C 1a;e ne1at;e re7ult to both o6 the te7t7A
)u11e7t the 7tructural 6or+ula o6 %, & and CA -xplan
your an74erA