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
