CHM301

ORGANIC CHEMISTRY IIII

CHAPTER 2
CARBONYL COMPOUND
(ALDEHYDE AND KETONE)
By the end of this chapter, the students should be able
to:
• write general formulas of aldehyde and ketone
(IUPAC & common name)
• reactivity of aldehyde and ketone
• Preparations of aldehyde and ketone.
• Reactions of aldehyde and ketone.
• Chemical test for aldehyde and ketone.
 SUBTOPICS
• Structure and bonding
• Reactivity of aldehydes and ketones
• Reactions of aldehydes and ketones:
Nucleophilic addition reaction
(mechanisms)
 STRUCTURE AND BONDING

δ+ δ-

• sp2 hybridized
• Planar
• 120° angle between groups bonded to carbonyl carbon.
• Oxygen atom has a strong tendency to withdraw
electrons in a carbon-oxygen bond towards itself
because oxygen is more electronegative than carbon.
- make the carbon-oxygen double bond highly polar.
 ALDEHYDES AND KETONES
● Aldehyde: one hydrogen atom is bonded to the
carbon in the carbonyl group.
● Ketone: the carbon atom in the carbonyl group is
bonded to two hydrocarbon groups.
 REACTIVITY OF ALDEHYDES AND
KETONES

• Aldehydes are more reactive than ketones.

- reactivity depends on the size and electronic effect of the
substituent.
- large substituent cause the steric hindrance and make it
more difficult for the nucleophile to attack the C=O.
- alkyl groups (electron donor) cause the carbonyl carbon
becomes less reactive towards nucleophiles.
 REACTIONS OF ALDEHYDES AND
KETONES: NUCLEOPHILIC ADDITION
REACTION (MECHANISMS)

• Three fundamentals events in nucleophilic addition

reaction:

i) formation of the new σ bond between the electrophilic C

of the C=O group and the nucleophile.
ii) breaking of the π bond to the oxygen atom resulting in
the formation of an intermediate alkoxide ion, -C-O-
iii) protonation of the intermediate alkoxide to yield an
alcohol derivative.
• Two possible general mechanisms:
i) Strong nucleophiles (negative ions)
- the nucleophiles approach directly to the C=O to form
intermediate alkoxide.
- the alkoxide is then protonated with dilute acid.
- examples of strong nucleophiles: RMgX, Rli, LiAlH4,
NaBH4

NUCLEOPHILIC ADDITION UNDER BASIC CONDITION WITH STRONGER

NUCLEOPHILES
Example:

Nucleophilic addition of propanone with Grignard reagent

δ- δ+
ii) Weak nucleophiles (neutral molecules)
- the nucleophiles is added to activated C=O under acidic
conditions.
- carbonyl group is a weak base, and can become protonated in
an acidic solution.
- carbonyl group that is protonated (or bonded to some other
electrophile) is strong electrophilic, inviting attack by a weak
nucleophile.
- examples of weak nucleophiles: H2O, ROH, R-NH2

NUCLEOPHILIC ADDITION UNDER ACIDIC CONDITION WITH WEAKER

NUCLEOPHILES
Example:
Acid-catalyzed nucleophilic addition of water across the
carbonyl group of acetone
 ALDEHYDES AND KETONES
• Functional group: carbonyl group

● Aldehyde: one hydrogen atom is bonded to the carbon in

the carbonyl group.
● Ketone: the carbon atom in the carbonyl group is bonded to
two hydrocarbon groups.
 NAMING ALDEHYDE AND KETONE
(IUPAC SYSTEM)
1) ALIPHATIC ALDEHYDES 1) ALIPHATIC
KETONES

propanone 3-pentanone
butanal

2-butanone
4-methylpentanal
2) ALDEHYDES WITH 2 2) KETONES WITH 2 DIFFERENT
DIFFERENT FUNCTIONAL GROUP FUNCTIONAL GROUP

3- 5-hydroxy-3-hexanone
hydroxybutanal

2-pentenal @ pent-2-enal
5-octen-4-one
@ oct-5-ene-4-one
3) ALDEHYDES AS SUBSTITUENTS 3) KETONES AS SUBSTITUENTS

3-oxobutanoic acid

2-formylbenzoic acid

3-
oxopentanal
4) CYCLIC ALDEHYDES 4) CYCLIC KETONES

Cyclohexanecarbaldehyde
cyclohexanone

3-methylcyclohexanecarbaldehyde
5-ethyl-2-methylcyclohexanone
 5) AROMATIC ALDEHYDES 5) AROMATIC KETONES

benzaldehyde phenylethanone
2-phenylethanal

diphenylmethanone

p-nitrobenzaldehyde 3-phenyl-2-propenal
6) DIALDEHYDES 6) DIKETONES

2,4-hexanedione
pentanedial
 NAMING ALDEHYDE AND KETONE
(COMMON OR TRIVIAL NAME)
7) ALDEHYDES 7) KETONES
From R-COOH common name

Ethyl propyl Β-bromoethyl isopropyl ketone

ketone
Butyric acid

Butyraldehyde acetone
acetophenone
PREPARATIONS OF ALDEHYDES

i) Oxidation of primary alcohols

ii) Reduction of acid chlorides
i) OXIDATION OF PRIMARY ALCOHOLS
 ii) REDUCTION OF ACID CHLORIDES
* Lithium aluminium tri(t-butoxy)hydride is a milder reducing agent
that reacts faster with acid chlorides than with aldehydes.
PREPARATIONS OF KETONES

i) Oxidation of secondary alcohols

ii) Fridel-craft acylation
i) Oxidation of secondary alcohols

H+ = dilute H2SO4
ii) Friedel-Crafts acylation
 Effects of substituent groups on the
benzene ring
Activating groups Deactivating groups
(electron donating) (electron-withdrawing)
-NH2 -R -F
-OH -Cl
-OR -Br
-NHCOCH3 -I

ortho-para directors ortho-para meta directors

directors
 REACTIONS OF
ALDEHYDES AND KETONES
 OXIDATION
i) OXIDATION OF ALDEHYDES WITH KMnO4 AND K2Cr2O7
aldehydes [O] carboxylic acids

p/s: ketones cannot be oxidize, so no reaction for ketones

• When an aldehyde is heated with potassium dichromate (VI)
solution acidified with dilute H2SO4, the solution changes
colour from orange to green.
ii) REACTIONS OF ALDEHYDES WITH TOLLENS’ REAGENT:
SILVER MIRROR TEST

- Tollens’ reagent is called ‘ammoniacal silver nitrate’ solution.

- contains the silver amine complex ion, [Ag(NH3)2]+
- Tollens’ reagent is a mild oxidising agent.
- when aldehyde is warmed with Tollens’ reagent, the colourless
complex ion, [Ag(NH3)2]+ is reduced by aldehyde to grey metallic
silver.
- the precipitate forms a silver mirror on the walls of test tube.
• Equation:
CH3CHO + 2 [Ag(NH3)2]+ + OH- → CH3COO- + 2Ag(s) + 2NH4+ + 2NH3
aldehyde Tollen’s reagent grey metallic silver

• A simplified equation:
CH3CHO + 2 Ag+ + H2O → CH3COOH + 2Ag(s) + 2H+

• General equation:
RCHO + 2Ag+ + H2O → RCOOH + 2Ag(s) + 2H+

* Tollens’ test is used to distinguish aldehydes from

ketones. Ketones DO NOT react with Tollens’s reagent.
iii) REACTIONS OF ALDEHYDES WITH FEHLING’S SOLUTION
- Fehling’s solution contains a copper (II) complex ion.
- Fehling’s solution: mixing copper (II) sulphate solution with a
solution of sodium potassium tartrate in NaOH (aq).
- When Fehling’s solution is warmed with aldehydes, the deep
blue colour of the Fehling’s solution dissapears and a brick-red
(reddish-brown) precipitate of copper (I) oxide (Cu2O) is
obtained.
• Fehling’s solution can be used to distinguish
between:
a) Aldehydes and ketones (ketones do not react
with Fehling’s solution).
b) Aliphatic aldehydes and benzaldehyde
(benzaldehyde does not react with Fehling’s
solution).
SUMMARY
 REDUCTION
i) Reduction to primary and secondary alcohols:
• Aldehydes and ketones can be reduced to alcohols using:
a) lithium aluminium hydride (LiAlH4)
b) sodium borohydride (NaBH4)
c) catalytic hydrogenation
 ALDEHYDE
S

EXAMPLE:
 KETONE
S

EXAMPLE:
ii) Reduction to hydrocarbons:
⚫Clemensen reaction:
- refluxing aldehydes & ketones with amalgamated zinc (zinc with
a layer of Hg on the surface) in concentrated HCl reduces the
compound to hydrocarbons.

Examples:
⚫Wolff-Kishner reaction:
- refluxing aldehyde & ketones with hydrazine and concentrated
KOH.

Examples:
SUMMARY
 NUCLEOPHILIC ADDITION
• The carbonyl groups in aldehydes and ketones are polarised
because of the difference in the electronegativity of carbon and
oxygen.
• The carbon atom carries a partial positive charge while oxygen
atom carries a partial negative charge.
• Aldehydes and ketones are susceptible to attack both by
nucleophiles at the carbonyl carbon atom and by electrophiles at
the oxygen atom.

nucleophilic attack electrophilic attack

i) Nucleophilic addition with HCN

* Cyanohydrin may be formed using liquid HCN with a catalytic amount

of sodium cyanide or potassium cyanide.
- Reaction of ketones with HCN is similar as aldehydes.
- Ketone react with hydrogen cyanide (HCN) in cold alkaline solution to
produce 2-hydroxynitriles (cyanohydrins)
⚫Cyanohydrin can be hydrolysed to give α-hydroxyacids.
⚫The nitrile (-CN) group is converted to the –COOH group by reflux
the cyanohydrin with dilute sulphuric acid (H2O/H+) or
concentrated HCl.
ALDEHYDES
KETONES
ii) Nucleophilic addition with water

• Ketones and aldehyde react with water to form carbonyl

hydrates.
iii) Nucleophilic addition with Grignard reagent
• A Grignard reagent (a strong nucleophile resembling a
carbanion, R:- attacks the electrophilic carbonyl carbon
atom to give an alkoxide intermediate.
• Subsequent protonation gives an alcohol.
⚫ Grignard reagents + ketones → tertiary alcohols
⚫ Grignard reagents + aldehydes → secondary alcohols
⚫ Example:
ALDEHYDES
KETONES
SUMMARY
 CONDENSATION
• Aldehydes and ketones condense with ammonia derivatives such as
hydroxylamine and substituted hydrazines to give imine derivatives.
i) hydroxylamine
ii) hydrazine
iii) phenylhydrazine
iv) 2,4-dinitrophenylhydrazine
i) Condensation with hydroxylamine
Hydroxylamine reacts with ketones and aldehydes to form oximes.

ALDEHYDES
KETONES
ii) Condensation with hydrazine
Hydrazines derivatives reacts with aldehydes or ketones to form
hydrazones.
ALDEHYDES
KETONES
iii) Condensation with phenylhydrazine

ALDEHYDES
KETONES
 iv) Condensation with 2,4-dinitrophenylhydrazine

● A solution of 2,4-DNP in methanol and H2SO4: Brady’s reagent.

● Aldehydes reacts with 2,4-DNP at room temperature to give a
yellow-orange precipitate of 2,4-dinitrophenylhydrazone.

REAGENT POSITIVE TEST

 ALDEHYDES

• 2,4-Dinitrohydrazones have characteristic sharp melting points.

• The formation of a yellow or orange precipitate when 2,4-DNP reacts with an
organic compound at room temperature is used
a) As chemical test for aldehydes or ketones,
b) To identify an aldehyde or a ketone by measuring the melting point of the 2,4-
dinitrophenylhydrazone formed.
KETONES
SUMMARY
 IODOFORM REACTION
ALDEHYDES

- a solution of I2 in an alkaline medium such as NaOH or KOH is a

oxidising agent.
- when ethanal warmed with this solution, triiodoethanal will be
formed as the intermediate product.
- triiodoethanal then reacts with the base to form a yellow
precipitate of triiodomethane (iodoform).

CH3CHO + 3I2 → CI3CHO + 3HI

triidoethanal

Cl3CHO + -OH → CHI3 + HCOO-

iodoform
• Iodoform test is useful for the methyl ketone group (CH3C=O)
in ethanal and methyl ketones.
• If an alkaline solution of iodine is warmed with an organic
compound and a yellow precipitate of triiodomethane is
produced, the organic compound is likely to be one of the
following:
• Iodoform test can be used to distinguish:

i) ethanal from other aldehydes, because ethanal is the only

aldehydes that gives a positive iodoform test.
ii) ethanol and secondary alcohols that contains the CH 3CH(OH)-
group give a positive iodoform test.
iii) methyl ketones (ketones that contain CH 3CO- group) give positive
iodoform test.
For example, propanone and phenylethanone give a yellow
precipitate, but 3-pentanone and diphenylmethanone give negative
iodoform tests.
 KETONES

• Reagent: solution of I2 in an alkaline medium such as NaOH or KOH.

• Iodoform test is useful for the methyl ketone group (CH3CO-) in ketones.

• When ketones containing methyl ketone group is warmed

with iodoform reagent, a yellow precipitate of triiodomethane (iodoform) is
formed.
• The overall reaction is:
CHEMICAL TEST FOR
ALDEHYDES AND
KETONES
i) Tollen’s test
ii) Fehling’s test
iii) Schiff’s test
iv) Brady’s test
 TESTS TO DISTINGUISH ALDEHYDES AND KETONES AND
ALIPHATIC ALDEHYDES AND AROMATIC ALDEHYDES
TESTS ALDEHYDES KETONES

Tollens’ Test / silver mirror Observation: Observation:

test Formation of silver mirror Silver mirror did not formed
Reagent and condition: * Ketones do not react with
- ammoniacal silver nitrate Tollens’ reagent
solution ([Ag(NH3)2]+)
Fehling’s test / Benedict’s test Observation; Observation:
Reagent and condition: Blue colour of the Blue colour remains.
- Solution of Cu2+ (aq) ions in Fehling’s solution * Ketones do not react with
an alkaline solution of sodium dissappears and brick-red Fehling’s/Benedict’s reagent
potassium tartate. precipitate is obtained
* Except benzaldehyde
*Can be used to distinguish
between:
i) Aldehydes and ketones
ii) Aliphatic aldehydes and
benzaldehyde
Schiff’s test Observation: Ketones (except propanone)
Reagent and condition: Formation of magenta- do not react with Schiff’s
- Schiff’s reagent pink colour (simple reagent.
aldehydes)
* Except benzaldehyde
and a few aromatic
 TESTS TO DISTINGUISH CARBONYL COMPOUNDS FROM
NON-CARBONYL COMPOUNDS

TESTS CARBONYL COMPOUNDS NON-CARBONYL

(ALDEHYDES AND COMPOUNDS
KETONES)
Brady’s test Observation: Observation:
Reagent: Formation of orange Orange precipitate did
- A solution of 2,4-DNP precipitate not formed
in methanol and
sulfuric acid

Condition:
Room temperature