ORGANIC CHEMISTRY –II

3. CARBONYL COMPOUNDS
CARBONYL COMPOUNDS :
• The compounds with C = O are called as carbonyl compounds.
• Aldehydes and ketones are carbonyl compounds.
• –CHO group is a terminal group.
−C−
||
O

H R
C=O C=O
R R1
Aldehyde Ketone
Nomenclature :
Formula of Aldehyde IUPAC Common
HCHO Methanal Formaldehyde
CH3 – CHO Ethanal Acetaldehyde
CH3 – CH2 – CHO Propanal Propionaldehyde
CH3 – CH2 – CH2 – CHO Butanal Butonaldehyde
CH 3 − CH − CHO
|
CH
2 –methyl propanal α - methyl propionaldehyde
3
CH3 − CH − CH− CHO 2 – Chloro, 3 –Hydroxy α − Chloro, β - hydroxy
| |
OH Cl butanal butanaldehye

Formula of ketones IUPAC Common

CH3 − C− CH3
|| Propanone Acetone
O

CH3 − C− C 2H5
|| Butanone Ethyl methyl ketone
O

C 2H 5 − C − C 2 H 5
|| 3-Pentanone Diethyl ketone
O

CH3 − CH − C − CH− CH3 2-hydroxy– 4– chloro– α - chloro ethyl –α1–oxy ethyl

| || |
Cl O OH 3- pentanone ketone
CH3 − CH − C − C − CH3
| || | 2,4-diemthyl –3-hexanone Isopropyl secondary butyl ketone
CH O C H
3 2 5

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 Organic Chemistry – II
CH3 − CH − CH − CH2 − CH3
| |
CHO CO 2-methyl-3-ethyl-
| 4-ketopentanal
CH3

• Isomerism in Aldhydes :

Aldehydes will exhibit chain, functional and tautromerism.

CH3 − CH2 − CH2 − CHO
CH3 − CH − CHO [chain isomers]
|
CH3

• CH3 − C = O CH2 = CH – OH [Tautromers]

|
H
• CH3 − CH2 − C = O CH3 − CH = CH − OH [Tautomers ]
|
H
• Aldehydes, ketones, unsaturated alcohols and cyclic ethers are functional isomers of each other.
Ex: C2H4O : CH3 − CHO
H2C − CH2 (epoxide)
O
CH3 − CHO
( Tautomers )
CH2 = CH − OH
Ex. C3H6O :
CH3 − CH2 − CHO → CH3 − CH = CH − OH
CH3 − C− CH3
||
O
CH2 = CH − CH2 − OH
CH3 − HC − CH2
O
Ex. C4H8O : CH3 − CH2 − CH2 − CHO → CH3 − CH2 − CH = CH − OH
O
||
CH3 − C− CH 2 − CH3

C 2 H 5 − C− C 2 H 5 metamers (position)
||
O
CH3 − C− CH 2 − CH 2 − CH3
||
O
• Ketones are of two types based on the nature of alkyl groups attached to the functional groups.
Simple ketones mixed ketones
R=R 1
R ≠ R1
CH3 − C− CH3 CH3 − C− CH 2 − CH 2 − CH3
|| ||
O O

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 Organic Chemistry – II
C 2H 5 − C− C 2 H5 CH3 − C− CH − CH3
|| || |
O O CH3

[chain isomers ]
• Acetaldehyde and acetone are not isomers.

METHOD OF PREPARATION OF ACETALDEHYDE AND ACETONE

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 Organic Chemistry – II

Acetaldehyde : CH3 − C = O Acetone : CH3 − C = O

| |
H CH
3
1) By the oxidation of isopropyl alcohol
1) By the oxidation of ethyl alcohol O
1 PDC ( or ) PCC ||
CH3 − CH2 − OH + O2 ⎯⎯⎯⎯⎯⎯ ⎯→ CH3 –CHO + 1
⎯→ CH3 − C + H 2 O
K Cr O7
2 CH2 Cl2 CH3 − CH − OH + O 2 ⎯⎯2 ⎯2⎯
| 2 dil H2SO 4 |
H 2O CH3 CH3
2) BY the dehydrogenation of isopropyl alcohol
2) By the dehydrogenation of ethyl alcohol Cu 300 0 C
Cu 300 0 C
CH3 − CH − OH ⎯⎯ ⎯ ⎯ ⎯→ CH3 − C = O + H2
CH3 − CH2 − OH ⎯⎯ ⎯ ⎯⎯→ CH3 − CHO + H2 | |
CH3 CH3
3) By the hydration of propyne
3) By the hydration of Acetylene CH3 − C ≡ CH + H − OH ⎯⎯⎯⎯2 ⎯⎯
4 40%, H SO
→ CH3 − C = CH2
CH ≡ CH + H − OH ⎯⎯ ⎯ ⎯2⎯ ⎯
⎯440%, H SO
→ CH2 = CH − OH
1% HgSO 4 , 600 C |
1% HgSO 4 , 60 C 0 OH

⎯⎯ ⎯ ⎯ ⎯⎯→
rearrangem ent
CH3-CHO ⎯⎯ ⎯ ⎯ ⎯⎯→ CH3 − C− CH3
rearrangem ent
||
O
4) By the hydrolysis of gem dichloride that is
4)By the hydrolysis of gem dichloride that is CH3– isopropy- ldene chloride
CHCl2 CH3 − CCl2 + 2KOH ⎯⎯ ⎯→ CH3 − C(OH)2 ⎯⎯
−H2O
⎯→
| (aq ) 2KCl
|
⎯→ CH3 − CH(OH)2 ⎯⎯ ⎯
−H O
CH3 − CHCl2 + 2KOH ⎯⎯ ⎯ 2
⎯→ CH3 CH3
(aq) − 2KCl

CH3 − CHO CH3 − C = O

|
CH3
5) Wacker’s process : ethylene reacts with aqueous 5) Propene reacts with aqueous palladium chloride
palladium chloride in presence of catalyst to give to give acetone.
Acetaldehyde. CH3 − CH = CH2 + PdCl2 + H2O → CH3 − C− CH3 + 2HCl + Pd
||
CuCl
CH2 = CH2 + PdCl2 + H2O ⎯⎯ ⎯
⎯2
→ CH3 − CHO + 2HCl + Pd O
H+

6) The distillation of calcium acetate and calcium 6) By the dry distillation of calcium acetate alone
formate COOCH 3 CH3 COO
Δ
OOCCH 3
Ca + Ca ⎯⎯→ 2CH3 − CO − CH3 + 2CaCO 3
HCOO
Δ COOCH 3 CH3 COO
Ca + Ca ⎯⎯→ 2CH3 − CHO + 2CaCO 3
OOCCH 3 HCOO

Calcium ethanoate calcium methanoate

7) Rosenmund’s reduction : Acetyl chloride (acid
chloride ) on reduction with H2 in presence
Lindlar’s catalyst gives acetaldehyde
CH3 − C − Cl + H 2 ⎯⎯ ⎯ ⎯ ⎯
4 Pd.BaSO / Quinoline
⎯ ⎯ ⎯⎯→ CH3 − C − H + HCl
7). Ketones can not be prepared by this method
|| ||
O O
only aldehydes can be prepared by this method
Physical properties : Physical properties :
1) Colourless liquid with pungent smell 1) Colourless liquid with pleasent smell
2) Soluble in water, alcohol, ether etc, . 2) Soluble in water, alcohol, ether etc.
3) It is more volatile with very low boiling point [210C] 3) It is less volatile with higher boiling point 56°C].
4) Its aqueous solution has pleasant smell as it 4) Highly inflammable .
exist as ethyledene glycol.
CH3- CHO + H – OH → CH3- CH(OH)2
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 Organic Chemistry – II
PREPARATION OF BENZALDEHYDE
1.OXIDATION OF METHYLBENZENE:
a) With chromyl chloride followed by hydrolysis
CH3 CH(OCrOHCl2)2 CHO

CS2 H3O +
+ CrO2Cl2

Toluene Chromium complex Benzaldehyde

This reaction is known as Etard reaction.
b) With chromtic oxide CrO3 in acetic anhydride
CH3 CH(OCOCH3) 2

+ CrO3 + (CH3CO)2O 273 - 283K

H3O+

CHO

2. By side chain chlorination followed by hydrolysis

3. Gatterman - Koch benzal chloride reaction:

Here benzene is treated with carbon monoxide and HCl in the presence of anhydrous AlCl3 and
CH2Cl2

Chemical reactions :
1) They under go nucleophilic additions due to the presence of C = O
2) In case of nucleophilic attack a stable intermediate is formed that is anion.
3) In case electrophilic attack occurs first an unstable intermediate is formed. Therefore
nucleophilic attack occurs first and it is called nucleophilic addition.
δ+ δ− N u δ+ δ− δ+ δ−
C − O − → C − OH
R R
C = O ⎯⎯⎯→ C=O C=O
| | H R1
E+ Nu Nu
C+ − OE (Aldehydes) (Ketones)

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 Organic Chemistry – II
CHEMICAL REACTIONS : Carbonyl group is highly polar. Carbon of carbonyl group gets partial
+ve charge and oxygen gets partial – ve charge. Carbon is added with nucleophile and forms a stable
intermediate i.e. anion. Then electrophile is added to oxygen to complete the addition reaction.
• Thus aldehydes and ketones undergo nucleophilic additions.
• Aldehydes are more reactive than ketones due to greater magnitude of +ve charge on carbon of
carbonyl group.
I. Nucleophilic additions:
1) Addition of HCN : Acetaldehyde and acetone give corresponding cyanohydrins.
2) Addition of NaHSO3 : Acetaldehyde and acetone give corresponding sodium bisulphites. These
are white crystalline and give back original acetaldehyde and acetone on treating with mineral
acids. Thus NaHSO3 is useful in the purification of carbonyl compounds.
3) Addition of NH3 : Acetaldehyde gives acetaldehyde ammonia and acetone gives diacetone
amine.
4) Addition of Grignard reagent : Aldehydes (except formaldehyde) give secondary alcohols and
ketones give tertiary alcohols on addition with R – MgX.

CH3 – CH = CN
CH3 – CH – OH
OH
CH3
HCN
H – OH
δ+ δ−
CH3 – MgBr NH3
CH3 – CH –OMgBr CH3 − C = O CH3 – CH – OH
|
CH3 H NH2

NaHSO3

CH3–CH –SO3 Na+

OH

CN
CH3 – C – OH
CH3

HCN

SO3− Na + CH3 CH3

δ+ δ− CH3MgBr
NaHSO3 H–OH
CH3 – C – OH CH 3 − C = O CH3 – C –OMgBr CH3 – C –OH
|
CH3 CH3 CH3 CH3

(CH3)2 CO+NH3
CH3 NH2
C
CH3 CH2 C CH3
O

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 Organic Chemistry – II
Addition of alcohols:
Aldehydes react with one molecule of alcohol in the presence of dry HCl to give alkoxyalcohol
intermediates known as hemiacetals. Hemiacetals further react with one more molecule of
alcohol to give a gem-dialkoxy compound called acetals.

R ⎡ R OR ′′ ⎤ R ′′OH ⎡ R OR ′′ ⎤
R ′′OH, dry HCl ⎢ ⎥ ⎢ ⎥+ H O
ZZZZZZZZZZX
C = O YZZZZZZZZZZ Z
Z ⎢ C ZZZZZZ
YZZZZZ X
Z⎢ C
R′ R′ ⎥
OH ⎥ H O + R ′ OR ′′ ⎥⎥
2

H ⎢
⎣ H ⎦ 3 ⎢
⎣ H ⎦
Hemiacetal Acetal

R CH 2 OH HCl R O − CH 2
C=O + | ZZZZZZ
YZZZZZX
Z C |
R′ + R′
Ketone
CH 2 OH H O O − CH 2
Glycol Ethylene glycolketal

y CANNIZZARO’S REACTION :
Aldehydes that have no hydrogen atom undergo this reaction involving disproportionation (self
oxidation and reduction) on treating with strong conc. alkali.
Eg. 1) HCHO + HCHO ⎯⎯⎯⎯ conc.NaOH
⎯→ CH 3 OH + HCOONa

Eg. 2) C 6 H 5 CHO + C 6 H 5 CHO ⎯⎯⎯⎯

conc.KOH
→ C 6 H 5 CH 2 OH + C 6 H 5 COOK

y During electrophilic substitution reactions, -CHO group deactivates benzene ring and it is a meta
directing group.

Conc.HNO 3 + Conc.H2 SO 4
Eg. ⎯⎯⎯⎯⎯⎯⎯⎯
at 1000 − 1100 C
→

II. Condensation reactions:

Acetaldehyde and acetone condense with ammonia derivatives such as
i) H2N – OH ii) H2N – NH2 iii) phenyl hydrazine iv) 2, 4-DNP v) semicarbazide
• In all these reactions, H2O is eliminated.
C = O + H2 N – X → C = N – X + H2O

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 Organic Chemistry – II

CH3 – CH = NOH
NH–NH2
NO2
H2N – OH
NH–N=CH–CH3
NO2
NO2 H2N – NH2
CH3 – CHO CH3 – CH = N – NH2

NO2
H2N– NH–CO–NH2 H2N–NH–C6H5

CH3 – CH = N – NH–CO-NH2
CH3 – CH = N – NH–C6H5

CH3 – CH = NOH
NH–NH2
CH3
NO2
H2N – OH
NH–N=C–CH3
CH3
H2N – NH2
NO2 NO2 CH3 − C = O CH3 – C = N – NH2
|
CH3 CH3

NO2 H2N– NH–CO–NH2

H2N – NH – C6H5

CH3 – C = N – NH–CO-NH2
CH3 – C = N – NH–C6H5
CH3
CH3

III. Other Reactions:

1) With PCl5 : Both acetaldehyde and acetone gives gem dichlorides
CH3 – CHO + PCl5 → CH3 – CHCl2 + POCl3
CH3 − C = O + PCl5 → CH3 − CCl2 + POCl3
| |
CH CH3
3
2) α-chlorination: The three α-hydrogens are substituted by chlorine or bromine on reaction with
Cl2 or Br2
CH3 – CHO + 3Cl2 → CCl3 – CHO + 3HCl
CH3 − C = O + 3Cl2 → CCl3 − C = O + 3HCl
| |
CH 3 CH3
3) Iodoform reaction : (Haloform reaction)
Aldehydes and ketones containing α – methyl groups reacts with X2 and a base to give CHX3.
CH3 – CHO + 3I2 + 4NaOH → HCOONa + CHI3↓ + 3H2O + 3NaI
CH3 – CO – CH3 + 3I2 + 4NaOH → CH3COONa + CHI3 ↓+ 3H2O + 3NaI
4) Distillation with bleaching powder :
Acetaldehyde and acetone on distillation with bleaching powder gives CHCl3.

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 Organic Chemistry – II
5) Aldol condensation :
− Aldehydes and ketones having atleast one α - hydrogen will give aldol condensation in
presence of dilute base.
− It involves shifting of one α - hydrogen from one molecule to oxygen of another molecule.
− Two acetaldehyde molecules will condense to give aldol or β - hydroxy butyraldehyde.
O H or H +
2CH3–CHO ⎯⎯ ⎯ ⎯ ⎯⎯→ CH3 − CH− CH2 − CHO
|
OH (aldol)
− Aldol on heating forms unsaturated aldehyde, with the elimination of H2O.
Δ CH − CH = CH − CHO
CH3 − CH− CH2 − CHO ⎯⎯→
| 3
OH
(Crotonaldehyde)
− Two acetone molecules undergo aldol condensation in presence of Ba(OH)2 to give
diacetone alcohol.
OH
Ba(OH)2 |
2CH 3 − C − CH 3 ⎯⎯ ⎯ ⎯⎯→ CH 3 − C − CH 2 − C − CH 3 ( Diacetone alcohol)
|| | ||
O CH3 O
6) Condensation of acetone in presence of HCl:
In presence of con.HCl, two acetone molecules will condense to give mesityl oxide.
HCl
2CH3COCH3 ⎯⎯⎯→ CH3 − C = CH − CO− CH3 + H2O
| (Mesityl oxide)
CH3

In presence of HCl, three acetone molecules will condense to give phorone.

HCl
3CH 3 − CO − CH 3 ⎯⎯⎯→ CH 3 − C = CH − C − CH = C − CH 3 + 2 H 2 O
| || |
CH3 O CH3

7) Condensation of acetone in presence of conc. H2SO4 :

Three acetone molecules condenses to give mesitylene or 1, 3, 5 – trimethyl benzene in
presence of CH3
con.H2SO4.
⎯→ C 6 H 3 (CH3 )3 (or)
conc.H SO4
3CH3 COCH3 ⎯⎯ ⎯ ⎯2⎯ ⎯ + 3H2O
Mesitylene CH3 CH3

y Crossed aldol condensation : If the aldol condensation is between two different aldehydes or
ketones, it is called crossed aldol condensation. When both of them have hydrogen, a mixture of
four products are formed.
i ) NaOH , ii ) Δ
Eg : CH 3 − CHO + CH 3 − CH 2CHO ⎯⎯⎯⎯⎯⎯ →

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 Organic Chemistry – II

y Acetone may also be involved in cross condensation

OH − ,293 K
Eg: C6 H 5CHO + CH 3 − CO − C6 H 5 ⎯⎯⎯⎯ → C6 H 5 − CH = CHCO.C6 H 5
. 1,3 − diphenyl prop − 2 − en − 1 − one
(benzal acetophenone)

8) Polymerisation of acetaldehyde :
Acetaldehyde polymerizes to paraldehyde at high temperature in presence of conc. H2SO4.
CH3 O CH3
CH CH
conc.H SO4
3CH 3 − CHO ⎯⎯ ⎯ ⎯2⎯ ⎯⎯→ (Trimer)
O O
Paraldehyde (Pleasant smelling liquid)
CH

CH3

Acetaldehyde polymerizes to tetramer (metaldehyde) in presence of conc. H2SO4 at 0°C.

CH3 CH O CH CH3
conc.H SO 4
4CH 3 − CHO ⎯⎯ ⎯ ⎯2⎯ ⎯⎯ → O O

CH3 CH O CH CH3 (tetramer) Metaldehyde (white

solid)

9) Reduction : Aldehydes and ketones on reduction will give alcohols or alkanes depending on the
nature of reducing agent.
i) H | Ni ii) LiAlH4
i) C = O ⎯⎯ ⎯2⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯→ CH– OH Aldehydes give 1°-alcohol and ketones give
iii) NaBH4 iv ) Na | alcohol
secondary alcohol.
i) Zn−Hg + HCl
ii) C = O ⎯⎯ ⎯ ⎯ ⎯⎯→ CH2
ii ) N2H4 +KOH + alcohol

i) Clemensen' s reduction
( Zn −Hg+HCl) i) H / Ni ii) LiAlH4
CH3 − CH3 ←⎯ ⎯ ⎯ ⎯⎯ ⎯ ⎯ ⎯ ⎯⎯ ⎯⎯⎯ CH3 − CHO ⎯⎯ ⎯2⎯ ⎯ ⎯⎯ ⎯ ⎯ ⎯→ CH − CH2 − OH
ii) Wolff −kishner reduction iii) NaBH4 iv ) Na / alcohol 3
(N2H4 +KOH+ alcohol)
i) Clemensen' s reduction
( Zn −Hg+HCl) i) H / Ni ii) LiAlH4
CH3 − CH2 − CH3 ←⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯⎯⎯ CH3 − C − CH3 ⎯⎯ ⎯2⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯→ CH − CH− CH3
ii) Wolff −kishner reduction || iii) NaBH4 iv ) Na / alcohol 3 |
O OH
(N2H4 +KOH+ alcohol)
10) Oxidation :
• Aldehydes are easily oxidised than ketones because ketones involve C – C bond cleavage
aldehydes do not involve C – C bond cleavage
• Aldehydes on oxidation give carboxylic acids having same number of carbons and ketones give
carboxylic acids having less number of carbons.
• Aldehydes can be oxidised by mild oxidising agents like Ag+, Cu2+

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 Organic Chemistry – II
(O )
i) CH3 – CHO ⎯⎯ ⎯→ CH3COOH
ii) CH3 − CO − CH3 + 4(O ) ⎯⎯
K 2 Cr2 O 7
⎯⎯ ⎯→ CH 3 − COOH + CO 2 + H 2 O
H 2 SO 4

11) Distinguishing tests for aldehydes :

• Aldehydes are easily oxidised than ketones. Aldehydes easily respond to mild oxidising agents like
Ag+, Cu2+ etc but ketones do not respond to the mild oxidising agent.
• Based on the difference in their reducing nature, aldehydes can be distinguished from ketones.
a) Tollen’s test or silver mirror test :
− Tollen’s reagent is ammonical silver nitrate i.e. NH4OH + AgNO3 (or) [Ag(NH3)2] OH (or)
[Ag(NH3)2]+
− Acetaldehyde reduces Ag+ to Ag
CH3 – CHO + 2[Ag(NH3)2] OH → 2Ag↓ + 4NH3 + CH3COOH + H2O
b) Fehling’s test :
− Fehling’s reagent is alkaline copper sulphate complexed with Rochelle’s salt ( Na –K
tartarate)
− Acetaldehyde reduces Cu2+ of Fehling’s solution to Cu+ giving yellow or brick red color.
− CH3 – CHO + 2Cu2+ + 5OH–→ CH3COO– + Cu2O↓+ 3H2O
(Red)
c) Benedict’s test:
− Benedict’s solution is alkaline copper sulphate complexed with citrate ions.
− Acetaldehyde reduces Benedict’s solution (Cu2+) also as that of Fehling’s solution.
d) Schiff’s Base test :
− Schiff’s reagent is decolorized pink colored p – rosaniline hydrochloride with SO2.
− Acetadehyde restores the pink color of Schiff’s reagent.

Tests for Acetone :

sodium nitro long
1) Legal test : Acetone ⎯⎯ ⎯ ⎯ ⎯ ⎯⎯→ wine red solution ⎯⎯ ⎯→ yellow
prusside +NaOH s tan ding
orthonitro benzaldehy de
• 2) Indigo test : Acetone ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯⎯→ blue color (indigotin)
+ KOH
USES OF ACETALDEHYDE :
• In the preparation of acetic acid, chloral , rubber, dyes and drugs
• In the preparation of paraldehyde, used as hypnotic drug
• In the preparation of metaldehdye, used as solid fuel.
• In the silver coating of mirrors
• As antiseptic inhalent in nose troubles.
Uses of Acetone :
• As solvent for cellulose acetate, cellulose nitrate, resins.
• As nail polish remover
• For storing of acetylene
• In the preparation of plexiglass (unbreakableg lass)
• In the preparation of synthetic rubber
• In the preparation of CORDITE (smokeless bomb)
• As reaction medium and as extractant.

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