CARBONYL COMPOUNDS

ALDEHYDES AND KETONES

Aldehyde Ketone
RCHO, --CHO group RCOR, > C=O group
AROMATIC CARBONYL COMPOUNDS
Alkanal Alkanone

Functional group Functional group in

attached to ring side chain
Benzaldehyde 1-Phenyl-2-propanone
Acetophenone 2-Phenylethanal
 ALDEHYDES

COMMON NAME
1 C: FORM+ALDEHYDE
2 C S: ACET+ALDEHYDE
3 C S: PROPION+ALDEHYDE
4 C S: BUTYR+ALDEHYDE.

Note:
The location of the substituent in the carbon chain is
indicated by greek letters , , , , etc.
-carbon being the one directly linked to the aldehyde
group, carbon the ne t, and so on
IUPAC NAME
ALDEHYDES ALKANAL
• Replace –e of primary suffix with -al.
• The aldehyde carbon is number 1.
• If -CHO is attached to a ring, use the suffix -carbaldehyde.
eg:
HCHO: METH+AN+AL
CH3CHO: ETHANAL
 EXAMPLES

CH3 O
1. CH3 CH2 CH CH2 C H 3-Methylpentanal

2. CHO Cyclopent-2-enecarbaldehyde

3.
Propane-1,2,3-tricarbaldehyde
 Ketone Alkanone
• Replace -e of primary suffix with -one. Indicate the position of
the carbonyl with a number.
• Number the chain so that carbonyl carbon has the lowest number.
• For cyclic ketones the carbonyl carbon is assigned the number 1.
O
1. CH3 C CH CH3 3-Methylbutan-2-one
CH3

O
2.
3-Bromocyclohexanone
Br

O
3.
CH3 C CH CH2OH 4-Hydroxy-3-methylbutan-2-one
CH3
 O
CH3 C CH3 Acetone

O
C Acetophenone
CH3

O
C
Benzophenone
 QUESTION:
Write the structures of the following compounds.

(i) -Methoxypropionaldehyde

(ii) 3-Hydroxybutanal

(iii) 2-Hydroxycyclopentane carbaldehyde

(iv) 4-Oxopentanal

(v) Di-sec. butyl ketone

(vi) 4-Fluoroacetophenone
 STRUCTURE OF >C=O GROUP

• Carbon is sp2 hybridised.

• 3 sp2 hybrid obitals form 3 bonds (with O, H/R).
• Unhybridised p orbital forms bond with O.
• O has 2 lone pairs.
• Thus carbonyl C and the three atoms attached to it lie in
and the electron cloud lie above and below the plane.
angles are 1200
 STRUCTURE OF >C=O GROUP

• C=O is polarized due to high electronegativity of O relative to C.

• Hence CO group is an electrophilic and its O, a nucleophilic
centre.
• High polarity of CO group is explained on basis of resonance
Similarity between C=C and C=O bonds
1.Both contain 1 and 1 bond.
2.Both are planar.
3.C is sp2 hybridised in both.
4.Both undergo addition reactions

Differences between C=C and C=O bonds

1.C=O is polar while C=C is non polar.
2.C=O undergoes nucleophilic addition while C=C undergo
electrophilic addition.
3.Geometrical isomerism is possible in C=C but not in C=O bond.
4.Bond length and bond strength are different.
I) Preparation of Aldehydes and Ketones (both)

a) From Alcohols
i) By oxidation:
RCH2OH → RCHO →RCOOH

Oxidising agents :
Acidified KMnO4 or K2Cr2O7, CrO3 / H2SO4

NOTE:
To stop reaction at aldehyde level, pyridinium chloro chromate (PCC) or
Jones reagent (CrO3/Acetone ) are used → donot affect double bond
RCH2OH → RCHO
R2CHOH → RCOR
ii) By Catalytic Dehydrogenation of Alcohols

Cu/573 K
• RCH2OH ----------- RCHO

Cu/573 K
• R2CHOH ----------- RCOR
b) From Hydrocarbons

i) By Ozonolysis of Alkenes
Note: We get aldehyde, ketones or a mixture of both depending
on the alkene
ii) By Hydration of Alkynes
 II) Preparation of Aldehydes(only)
a) From RCOCl (R e d reduction)

Pd/BaSO4
C6H5 /RCOCl + H2 ------------------------ C6H5 / RCHO

Catalyst is poisoned by S or Quinoline to stop reaction at aldehyde level

otherwise it get reduced to alcohol

b) By reduction of RCN

i) Stephen Reduction followed by hydrolysis to give aldehydes

SnCl2/HCl H3O +
RC≡N + 2H --------------------------- RCH=NH------- RCHO + NH3
ii)Reduced by Diisobutylaluminium hydride, (DIBAL-H) to imines
followed by hydrolysis to aldehydes:

c)From Esters
 III) Preparation of Aromatic Aldehyde

a)From Hydrocarbon

i) Gatterman Koch reaction (from Benzene)

b) From Methylbenzene:

i) Etard Reaction
 ii) By Chromic oxide (CrO3)

iii) By side chain chlorination followed by hydrolysis

 IV Preparation of Ketones (only)

a) From Acyl chloride(RCOCl)

2R MgX + CdCl2 ---------- R 2Cd + 2MgXCl

2RCOCl + R 2Cd ---------- 2RCOR + CdCl2

b) By reaction of Grignard reagent with RCN

VPreparation of aromatic aldehydes and ketones:

Friedel-Crafts acylation reaction

 PHYSICAL PROPERTIES

a)Physical State:
Methanal is a gas at room temperature. Ethanal is a volatile
liquid. Other aldehydes and ketones are liquid or solid at room
temperature.

b) Boiling points:
For compounds of comparable molecular weight:
Alkanes, ethers < aldehydes, ketones < alcohols < carboxylic acids

Dispersion Dipole-dipole Inter molecular Hydrogen

Forces Bonding
 c) Solubility:
Ketones and Aldehydes, upto 4C , carbonyl compounds are
soluble in water due to H-Bonding with it. With increase in size
of R , solubility decrease due to increase in non polar part

QUESTION

Arrange the following compounds in the increasing order of their

boiling points:
i) CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2 -O-C2H5 ,
CH3CH2CH2CH3
ii) CH3CHO, CH3CH2OH, CH3OCH3 , CH3CH2CH3
 Mechanism of nucleophilic addition reactions
Step 1 A nucleophilic attack on carbon atom of the polar carbonyl group ,
hybridisation of carbon changes from sp 2 to sp 3

tetrahedral alkoxide
Step 2 Intermediate captures a proton
 REACTIVITY

Factors:
(i) +I effect : HCHO is most reactive. On replacing H by alkyl
group(R) , due to +I effect, +ive charge on C of C=O
decrease, so reactivity decrease.
In ketones , there are 2 R groups , so more + I so
reactivity further decrease.

(ii)Steric factors: With increase in no. of Alkyl group(R) , due to more

steric hinderance to attack of Nu, reactivity decrease.
HCHO > RCHO > RCOR

If R = C6H5: resonance stabilization reactivity further decrease

RCHO > C6H5CHO > C6H5COCH3 > C6H5COC6H5

 A. Addition of hydrogen cyanide

basic

Think of what the mechanism should

pH issue.
Slightly basic
media so that
HCN has
partially
ionized to
Followed by protonation of the alkoxide ion (perhaps by cyanide ion,
unionized HCN). the actual
nucleophile.
 Follow-up reactions on the cyanohydrins
H2O
R

N
RHC

acid catalysis
dehydration
We saw this hydrogenation before.
OH
O dil acid
N aC N OH
H2
NH2
R N
R CH2R
C H 2R catalyst R
CH2R
Hydrolysis. Acid, heat
or
base, heat O H

CO2H
R
CH2R
 B. Addition of sodium hydrogen sulphite

The position of the equilibrium lies largely to the right

hand side for most aldehydes and to the left for most
ketones due to steric reasons.
Product is water soluble and can be converted back to
the original carbonyl compound by treating it with dilute
mineral acid or alkali.
Therefore, these are useful for separation and purification of
aldehydes.
 C. Addition of grignard reagents

Step-1
Nucleophilic addition of Grignard reagent to the carbonyl group

Step-2
Hydrolysis of the adduct to form alcohol
 The reaction with formaldehyde gives a primary alcohol.

With all other aldehydes, secondary alcohols are formed.

Tertiary alcohols are formed with ketones.
 D. Addition of alcohols
(Hemiacetal and acetal formation in acid)

Dry hydrogen chloride protonates the oxygen of the carbonyl

compounds and therefore, increases the electrophilicity of the
carbonyl carbon facilitating the nucleophilic attack
 Hemiacetal formation (in presence of acid)

Protonation of
carbonyl (making the
oxygen more
electronegative)

Attack of the (poor)

nucleophile on (good)
electrophile.

Deprotonation

Overall, we have added

the alcohol to the
carbonyl.
E. Addition of ammonia and its derivatives
Control of pH : It is to be maintained at 3.5 due to:
(i) If medium is too acidic, ammonia derivatives being basic in
nature , react to form salt instead of desired reaction
(ii)If medium is too alkaline, protonation of C=O group do not take
place .
 DISTINCTION TEST

S.no Compound Reagent Observation

1 Ethanal 2,4- yellow/orange ppt

Dinitrophenylhydrazine observed

2 Ethanol 2,4- No
Dinitrophenylhydrazine yellow/orange
ppt observed
 2. REDUCTION

a)To Alcohols :

>C=O + 2H >CHOH

Reducing Agents: Ni,Pt,Pd /H2, NaBH4, LiAlH4

HCHO CH3OH
CH3CHO C2H5OH
CH3COCH3 (CH3)2CHOH
 b) To Alkane

I) Clemmensen reduction:
 II) Wolff-kisher reduction

• Form hydrazone, then heat with strong base like KOH or

potassium t-butoxide.
• Use a high-boiling solvent: ethylene glycol, diethylene
 3. OXIDATION

(i) Aldehydes easily oxidised by:

Stronger O.A :conc. HNO3, acidified KMnO4 or K2Cr2O7

Weaker O.A : Bromine water, reagent,

solution and solution

RCHO RCOOH
(ii) Ketones Difficult to oxidise

Oxidised only by strong O.A

RCOR RCOOH + HCOOH

In unsymmetrical Ketones , rule is followed

CO group stays with lower R group

Example:
 The mild oxidizing agents can be used to distinguish
aldehydes and ketones.

(i) Test:

Tollens reagent consists of silver ammonia complex in ammonia

solution.
Aldehydes reacts with Tollens reagent gives a silver mirror.
Aldehydes are oxidised to the corresponding acid and silver in
Tollens reagent is reduced from +1 oxidation state to its elemental
form.

Note :
Test given by both aliphatic and aromatic
aldehydes
Ketones do not respond to this test
 Test:

It is a mixture of two solutions. Fehling solution A and Fehling

solution B

Fehling solution A: Aqueous solution of CuSO4,

Fehling solution B: Alkaline solution of sodium potassium
tartarate (Roschelle salt)

Aldehydes when heated with this mixture gives reddish brown

ppt.

Note :Test given ONLY by Aliphatic aldehydes

(iii) HALOFORM REACTION (IODOFORM REACTION)

Aldehydes and ketones having at least one methyl group

linked to the carbonyl carbon atom (methyl ketones) are
oxidised by sodium hypohalite to sodium salts of
corresponding carboxylic acids having one carbon atom less
than that of carbonyl compound

CH3CHO + I 2 + NaOH -------- CHI3 + HCOONa + H 2 O

Yellow

CH3COCH 3 + I 2 + NaOH -------- CHI3 + CH3COONa + H 2 O

 DISTINCTION TEST

Compound Reagent Observed change

CH3CHO I2 + NaOH Yellow ppt

HCHO I2 + NaOH No Yellow ppt

Distinguish Between:
1. CH3 CH2 OH CH3OH
2.Pentan-2-one Pentan-3-one
3.Propan-2-ol Propan-1-ol
4. Acetophenone Benzophenone
5. Butan-2-ol Butan-1-ol
 WORD
PROBLEM
An organic compound (A) with molecular formula C8H8O
forms an orange-red precipitate with 2,4-DNP reagent and
gives yellow precipitate on heating with iodine in the
presence of sodium hydroxide. It neither reduces or
reagent, nor does it decolourise bromine water or
reagent. On drastic oxidation with chromic acid, it
gives a carboxylic acid (B) having molecular formula
C7H6O2 . Identify the compounds (A) and (B) and explain
the reactions involved.
a)Aldol condensation: Aldehyde must have α—H.

hydrogens

Note: HCHO and C6H5CHO donot give

B) CROSS ALDOL CONDENSATION:
 5. OTHER REACTIONS
i) Cannizaro Reaction
conc. K O H
Overall:
2 RCHO R C O 2 - + R C H 2O H
h eat

Restriction: no hydrogens in the aldehydes.

CHO CHO
O H

H3C

hydrogens No hydrogens

Why the restriction? The hydrogens are acidic leading to ionization.

ii) Electrophilic substitution: CHO and CO groups are
meta directing deactivating groups
Nitration:
CARBOXYLIC ACID
 CARBOXYLIC ACID – NOMENCLATURE
COMPOUND COMMON NAME IUPAC NAME
•
HCOOH FORMIC ACID Methanoic acid

CH3COOH ACETIC ACID Ethanoic acid

HOOC-COOH OXALIC ACID Ethandioic acid

HOOC-CH2-COOH MALONIC ACID Propanedioicacid

HOOC-(CH2)2-COOH SUCCINIC ACID Butanedioic acid

 CARBOXYLIC ACID – NOMENCLATURE

COMPOUND COMMON NAME IUPAC NAME

•

HOOC-(CH2)3-COOH Glutaric acid Pentandioic acid

HOOC-(CH2)4-COOH Adipic acid Hexan-dioic acid

C6H5COOH Benzoic acid Benzenecarboxylic acid

C6H5CH2COOH Phenyl acetic acid 2-Phenlyethanoic acid

Pthalic acid Benzene-1,2,dicarboxylic

acid
 PREPARATION - CARBOXYLIC ACIDS
•
 FROM ALDEHYDES AND KETONES
•

POP OFF RULE : SMALLER ALKYL

GROUP GETS THE CO , IN
UNSYMMETRICAL KETONES
 FROM ALKYL BENZENE

•
 FROM NITRILES AND AMIDES
•
 FROM GRIGNARD S REAGENT
•
 FROM ACYL HALIDES AND ANHYDRIDES
•
 FROM ESTERS
•
 PHYSICAL PROPERTIES OF ACID
•
 Solubility in water
• Carboxylic acids are soluble in water. Carboxylic acids do not dimerise in water, but forms
hydrogen bonds with water.

• Carboxylic acids are polar and due to the presence of the hydroxyl in the carboxyl group,
they are able to form hydrogen bonds with water molecules. Smaller carboxylic acids (C1 to
C5) are soluble in water, whereas larger carboxylic acids (C6 and above) are less soluble due
to the increasing hydrophobic nature of the hydrocarbon chains.
 Boiling point
• The boiling points of carboxylic acids increases as the molecules get bigger.
Carboxylic acids have even higher boiling points then alkanes and alcohols.
• Carboxylic acids, similar to alcohols, can form hydrogen bonds with each other as
well as van der Waals dispersion forces and dipole-dipole interactions. However,
unique to carboxylic acids, hydrogen bonding can occur between two molecules to
produce a dimer.
•
 Acidic strength
• When a carboxylic acid donates its proton, it becomes a
negatively charged ion, RCOO−, called a carboxylate ion.
• Carboxylic acids are weak acids. They partially dissociates
into H+ cations and RCOO- anions in neutral aqueous solvents
such as water.
• The carboxylic acids are acidic in nature because hydrogen
belongs in the -COOH group. Carboxylic acids dissociate in
water to form carboxylate ion and hydronium ion. ...
Therefore, the carboxylate ion exhibits higher stability in
comparison to phenoxide ion. Hence, the carboxylic acids are
more acidic than phenols
 REACTION INVOLVING
CLEAVAGE OF O-H BOND
•
 FORMATION OF ANHYDRIDE
•
 ESTERIFICATION
•
 REACTION WITH PCl5 PCl3 and SOCl2
•
 Reaction with NH3
•
 Reaction with NH3
•
 REDUCTION
•
 DECARBOXYLATION
•
 HALOGENATION – HVZ
HELL- VOLHARD- ZELINSKY REACTION
•
 FRIEDEL CRAFT S REACTION
•