Anda di halaman 1dari 48

CHAPTER 4: ORGANIC CHEMISTRY

Carbonyl compounds have functional group called


carbonyl (C=O)

Carbon and oxygen are joined together by double
bond which consist of sigma () and a pi () bond

The carbon and oxygen in the carbonyl group are
sp
2
-hybridized, trigonal planar with bond angles of
120
O
C
1
2
0
o
The carbonyl group.
Class
General
formula
Class
General
formula
Aldehydes




Ketones
Carboxylic
acids




Esters
Amides




Acid
chlorides
Some common classes of carbonyl compounds
C
O
R H
C
O
R OH
C
O
R NH
2
C
O
R R
1
C
O
R O
R
1
C
O
R Cl
ALDEHYDES & KETONES
Aldehyde
Ketone
C
O
R H
C
O
R
R
1
R: H, alkyl, aryl (eg: benzene)
R and R
1
: alkyl or aryl
R and R
1
cannot be
hydrogen
ALDEHYDES & KETONES
Contain the carbonyl group
Aldehydes = at least 1 side H
Ketones = both sides R groups
Many aldehydes and ketones have pleasant tastes
and aromas
Formaldehyde : H
2
C=O
pungent gas
formalin = a preservative
wood smoke, carcinogenic
Acetone : CH
3
C(=O)CH
3

nail-polish remover
Aldehyde Odors and Flavors
butanal = butter
vanillin = vanilla
benzaldehyde = almonds
cinnamaldehyde = cinnamon
7
Physical properties
At room temperature, Formaldehyde (simplest
aldehyde) is a gas but heavier aldehydes are and
ketones are liquid

The carbonyl compounds are POLAR due to the
presence of carbonyl functional group; with
oxygen being more electronegative



C O
R
R

Electrophilic carbon
(electron acceptor)
C=O bond are shorter and stronger than C=C
bond

Since there is no hydrogen on the carbonyl oxygen,
aldehydes and ketones do not form hydrogen
bonds with themselves but they can hydrogen-
bond to water through the carbonyl oxygen.

Low-molecular weight aldehydes and ketones are
water-soluble; water solubility decreases as the size
of the molecule increases.
Nomenclature of Aldehydes
Choose the longest carbon chain that contains
the CHO

The CHO is always numbered as carbon 1
because it always at end chain

Aldehyde ending is al

If the CHO group is bonded to a ring, name the
ring and add the suffix carbaldehyde. The carbon
to which the aldehyde group is attached is C1




Examples: Simple aldehyde
C
O
H H
C
O
H CH
3
C
O
H CH
2
-CH
3
methanal ethanal
propanal
Examples: Substituted aldehyde
O
H H
O
Cl
H
O OH
4,4-dimethylpentanal 4-chloro-4-methylpentanal
3-hydroxybutanal
Examples: Dial
H
H
O
O
H
O
H
O
butanedial
pentanedial
CH
O
CH
O
Cl
cyclohexanecarbaldehyde
2-chlorocyclobutanecarbaldehyde
Examples: Cyclic aldehyde
Common Names of the Aldehydes
O
C
H H
O
C
CH
3
H
O
C
CH
2
H CH
3
O
C
CH
2
H CH
2
CH
3
O
C
CH
2
H CH
2
CH
2
CH
3
O
C
CH
2
H CH
2
CH
2
CH
2
CH
3
Formaldehyde Acetaldehyde Propionaldehyde
Butyraldehyde Valeraldehyde
Caproaldehyde
1 2 3
4 5
6
C
O
H
Benzaldehyde
Nomenclature of Ketones
Choose the longest continuous carbon chain that
contains the carbonyl carbon

Number the chain starting with the end closest to
the ketone group

Ketone ending is one

Molecules with more than one ketone group are
named by preceding the suffix with a counting
prefix (dione, trione, etc.); position numbers must
be used for each ketone group

Examples: Simple ketones
C
O
H
3
C CH
3
C
O
H
3
CH
2
C CH
3
propanone
(acetone)
butanone
C
O
H
3
C-H
2
C CH
2
CH
3
3-pentanone
Pentan-3-one
Examples: Substituted ketones
C
O
H
3
CHC CH
3
CH
3
O
C
CH
2
CH
CH
3
CH
2
CH
2
CH
3
CH
3
3-methyl-2-butanone
4-ethyl-3-hexanone
Examples: multiple ketones
O O
O
O
Cl
O
2,4-pentadione
4-chloro-2,5,7-octanetrione
Examples: cyclic ketones
O
C
O
CH
2
-CH
3
cyclopentanone
3-chloro-2-methylcyclopentanone
O
CH
3
Cl
1-cyclobutyl-1-propanone
Common Names of the Ketones
alkyl alkyl ketone
CH
3
C
CH
2
CH
2
CH
3
O
Methyl propyl ketone
O
C
CH
2
CH
2
CH
3
CH
3
Diethyl ketone
V
Sleepy???
CHALLENGE
TIME!!
In 5 minutes answer these questions:-
1. Name the following aldehydes and ketone:


CH
O
Cl
H
O O
H
H
O Br
H
O
(a) (b)
(c) (d)
2-chloro-3-methylbenzaldehyde
propanedial
2-butenal
3-bromobutanal
2. Draw structures corresponding to the following
IUPAC names:
a) 3-methylbutanal

b) 2,2-dimethylcyclohexanecarbaldehyde

c) 5-hexen-3-one

d) 1-cyclobutyl-1-propanone

e) 1,3-cyclohexanedione

H
O a)
O
H
b)
O
c)
O
d)
e)
O
O
Reaction of Aldehydes & Ketones
1. Nucleophilic addition
2. Reduction to Alcohol
3. Oxidation
4. Iodoform test
Nucleophilic addition
The carbonyl group in aldehydes and ketones has
a constant polarity.


C=O
+

The O atom attracts electrophiles; the C atom attracts
nucleophiles
Nucleophilic addition

Carbonyl compounds have oxygen atom which
is more electronegative than carbon atom
The carbonyl carbon is electron deficient and
susceptible to be attacked by nucleophile
Examples of nucleophile are
i. Hydrogen cyanide, HCN

ii. Water, H
2
O
iii. Alcohol
iv. Grignard Reagent

Nucleophilic addition
i. Nucleophilic addition of HCN




mechanism
C
O
1. CN
-
(nucleophilic attack)
2. H
+
(protonantion)
C
CN
OH
cyanohydrin
ii. Nucleophilic addition of H
2
O
Hydration reaction which produce carbonyl
hydrate
Hydrate is a molecule with two OH group
bonded to same carbon atom gem-diols





R
C
R
O
+ H
2
O
R C OH
R
OH
cat. H
+
or OH
-
Based catalyzed addition of H
2
O
1. Nucleophile (OH-) attacks the carbonyl group,
cleaving the bond and moving electron pair onto
oxygen
2. Protonation of negatively charged oxygen atom by
H
2
O
Acid catalyzed addition of H
2
O
iii. Nucleophilic addition of Alcohol





C
O
+ ROH, H
+
C
OR
OR
C
OH
OR
catalyst
(dry HCl)
acetal/ketal
hemiacetal/hemiketal
Mechanism
iv. Nucleophilic addition of Grignard reagents





C
O
+ RMgX
C
O
R
MgBr
C
O
R
MgBr
+ H
2
O
C
OH
R
+ Mg(OH)Br
larger alcohol
(a)
(b)
Reduction to alcohols
Reducing agents commonly used are:-
i. Lithium aluminium hydride, LiAlH
4
in
ether, H
3
O
+
ii. Sodium boronhydride, NaBH
4
iii. Nickel with hydrogen gas at 180C
(catalytic hydrogenation)

LiAlH
4
and NaBH
4
provides nucleophile, H
-

(hydride ion) which attack the electron
deficients carbonyl carbon.

Oxidation
Aldehydes are oxidized to carboxylic acids.
Oxidation reactions:
i. KMnO
4
, K
2
Cr
2
O
7

ii. Tollens reagents (silver mirror test)
iii. Fehlings solutions
Color changes









Ketones cannot undergo
oxidation!!!
i. Oxidation of aldehydes with KMnO
4
and K
2
Cr
2
O
7





ii. Tollens reagents (silver mirror test)
Contains the complex diamine silver ion
complex, Ag(NH
3
)
2
+

Aldehyde is oxidised to form carboxylate,
RCOO-
Colourless Ag(NH
3
)
2
+
ion is reduced to
silver which appear as silver mirror on the
wall of the test tube




C
O
R H
+
-
C
O
R O
-
+
2Ag
+
2H
2
O

C
O
CH
3
CH
2
H
2Ag(NH
3
)
2
+
+
3OH
+
4NH
3
+
-

2Ag(NH
3
)
2
+
+
3OH C
O
CH
3
CH
2
O
-
2Ag
+
2H
2
O
+
4NH
3 +
iii. Fehlings Solutions
Contains basic complex of Cu
2+
ion made
by mixing copper (II) sulphate with
alkaline sodium potassium tartarate
Only, ALIPHATIC ALDEHYDES react
with Fehlings reagent
aldehydes is oxidised to form carboxylate,
RCOO
-
and copper (II) ions is reduced to
Cu
2
O which appear as brick-red precipitate



C
O
R H
+
2Cu
2+
+
5OH
-
C
O
R O
-
+
Cu
2
O
+
3H
2
O

C
O
C H
3
H
+
2Cu
2+
+
5OH
-
C
O
C H
3
O
+
Cu
2
O
+
3H
2
O

-
brick red
precipitate
C
O
C H
3
CH
3
+
2Cu
2+
+
5OH
-

no reaction (no change of colour)


Can be use to distinguish between;
Aldehydes (+ve) & ketones (-ve)
Aliphatic aldehydes (+ve) & benzaldehyde (-ve)
Iodoform test
Similar to alcohol, carbonyl compounds can also
react with iodine in alkaline solution, NaOH,
warm to form yellow precipitate or
triiodomethane, CH
3
I
Useful test for methyl ketone group (CH
3
C=O)
Carbonyl compounds which give positive result
have the following structure

C H
3
O
C R
R can be H/ / any C chain
R
O
C CH
3
+
3I
2
+
4NaOH
CHI
3
(s)
+
C R O
O
Na
+
+
3NaI
+
3H
2
O
Triiodomethane
(yellow precipitate)

V
The time that we are waiting for!!!!
Questions:-
1. Draw the structure of the products formed when
the following compounds undergo reduction under
suitable condition:-

a) HCHO
C H CH
2
CH
2
-C
O O
CH
3
c)
b)
C
O
CH
3
d)
HOCH
2
CH
2
C-H
O
OH
a)
C
H
H
H
CH
3
b)
C
OH
H
H CH
2
CH
2
OH
C
H
a) HCHO
C H CH
2
CH
2
-C
O O
CH
3
c)
b)
C
O
CH
3
d)
HOCH
2
CH
2
C-H
O
CH
3
c)
C
OH
H
H

d)
C
OH
H
H CH
2
OH
C
H
2. Suggest how you would differentiate between the
following pairs of compounds.
a) Propanal and propanone

b) 3-pentanone and 2-pentanone

c) Butanal and benzaldehyde


Oxidation with KMnO
4
; propanal will be oxidized
(purple colour decolorised) while propanone will not.
Iodoform test; 2-pentanone will give positive result (yellow
precipitate) while 3-pentanone will give negative result.
Fehling test; butanal will give positive result (brick red
precipitate) while benzaldehyde will give negative result.
summary
Define and determine the carbonyl
compound
Differentiate between aldehyde and ketone
compound
Naming and draw aldehydes and ketones
compound
Determine the reactions of aldehyde and
ketones