Aldehydes & Ketones

Aldehydes are compounds having general formula

H
R C O R= H, CH 3 , C 2 H 5 , C 6 H 5 , etc…

Ketones are compounds having general formula

R C R R=CH ,C H , C H etc...
3 2 5 6 5
O Slide 2
IUPAC names of Aldehydes

Formula Common Name IUPAC Name

HCHO Fomaldehyde Methanal

CH3CHO Acetaldehyde Ethanal

CH3CH2CHO Propionaldehyde Propanal

CH3CH2CH2CHO Butyraldehyde Butanal

(CH3)2CHCHO Isobutyraldehyde 2-Methylpropanal

Slide 3
IUPAC names of Aldehydes

Formula Common Name IUPAC Name

CH2=CH-CHO Acrolein Prop–2–enal

CH3CH=CH-CHO Crotonaldehyde But-2-enal

C6H5CH=CH-CHO Cinnamaldehyde 3-Phenylprop-2-enal

C6H5CHO Benzaldehyde Benzaldehyde

C6H4(OH)CHO Salicyaldehyde 2-Hydroxybenzaldehyde

Slide 4
IUPAC Names of Ketones

Formula Common Name IUPAC Name

CH3COCH3 Acetone Propanone
CH3COCH2CH3 Ethyl methyl ketone Butanone
CH3CH2COCH2CH3 Diethyl ketone Pentan-3-one
CH3COCH2CH2CH3 Methyl propyl ketone Pentan-2-one
Methyl phenyl ketone or
C6H5COCH3 Acetophenone
1-phenylethanone
Diphenyl ketone or
C6H5COC6H5 Benzophenone
Benzophenone
Slide 5
Structure of Carbonyl group
 
 
C O o
120 C O
o
120
2
Sp - hybridised
The carbon- oxygen double bond is polarized due to higher
electro negativity of oxygen than carbon. C+-O-

Hence Nucleophile
C O
Slide 6
Electrophile
From oxidation of primary and secondary alcohols

H OH H
PCC
R C OH R C OH R C O +H2O
[O]
H H

R-CH(OH)-R’ KMnO4/KOH R-CO-R’ + H2O

Slide 8
By dehydrogenation of alcohols

H H
Copper
R C OH R C O + H2
o
H 300 C

R-CH(OH)-R’ Cu/573K R-CO-R’ + H2O

Slide 9
From alkene by ozonolysis

H
Zn
R CH CH2 + O 3 R CH CH2 R C O + CH2O
O O H2O
O

Slide 10
From Acyl Chloride

By Rosenmund reduction

O O
H2
R C Cl R C H + HCl
Pd - BaSO4
o
140 C
Slide 11
From Nitrile by Stephen’s Reduction

H
SnCl2 H2 O
R C N R CH NH R C O + NH 3
+HCl H+

Slide 12
Preparation of Benzaldehyde from
Toluene

Etard's Reaction

CH3
CrO2Cl2 CHO
+H2O
CS2

Slide 13
By Gattermann – Koch reaction.

C6H6 + CO + HCl Anh AlCl3/CuCl C6H5CHO

Slide 14
 Dry distillation of calium salts give aldehyde and ketones.

Calcium formate – Formaldehyde

Calcium formate and calcium acetate - Acetaldehyde

Calcium formate and calcium benzoate - Benzaldehyde

Calcium acetate - Acetone

Calcium benzoate - Benzophenone

Slide 15
Calcium benzoate and calcium acetate - Acetophenone
From nitrile and Grignard reagent

Dry 2 H2 O X
-| +
R C N R Mg x R C N. Mgx R C O + NH 3 + Mg
+
Ether H OH
R' R'

R-MgX + HCN dry ether R-CH=NMgX H2O/H+ R-CHO

Slide 16
Ketones from Acyl chloride and dialkylcadmium

2 R' C Cl + R 2Cd 2 R' C R + CdCl 2

O O

Slide 17
Aromatic ketones from Benzene by Friedel – Craft
reaction

Anhydrous C R + HCl
R C Cl
AlCl3 O
O

Slide 18
Physical properties of Aldehydes and ketones

• Physical state: HCHO – Gas, Up to C13 are liquids and higher

ones are solids.

• Odour : Lower aldehydes have unpleasant odour where as

higher ones have pleasant odour.

• Boiling points: These compounds have higher boiling points

than ethers and hydrocarbons due to dipole interactions but
lower boiling points than that of alcohols due to the absence
of intermolecular hydrogen bonding.
Slide 19
Reactions of Aldehydes and Ketones

(i) Nucleophillic addition

Nu
Nu

  + Nu
slow + C
a   C fast H
C O a OH
a O
b
Planar b
b
Tetrahedral intermediate Addition Product

Slide 20
Reactions of Aldehydes and Ketones

With HCN
Both aldehydes and ketones react with HCN to form addition
product Cynohydrin (in presence of a base)
- -
HCN + OH CN + H 2O

 
  O H+ OH
C O C C
CN CN
CN
Tetrahedral
Intermediate Slide 21
Cyanohydrin
Reactions of Aldehydes and Ketones

With NaHSO3

  O Na
  Proton Transfer OH
+ -
C O + Na SO H C C
3
SO3H SO3Na
Bisulphite addition Compound

All aldehydes react with NaHSO3 to form a white crystalline

solid, bisulphite addition compound. Many ketones also react.
But acetophenone does not react with NaHSO3 due to stearic
hindrance. Slide 22
Reactions of Aldehydes and Ketones

With alcohols
Only aldehydes react with alcohols in presence of dry HCl to
form acetals.
H H
dry HCl OR '
R C O 2 R' OH R C +H 2 O
OR '
acetal
Slide 23
Reactions of Aldehydes and Ketones

With alcohols
Ketones react only with Ethylene Glycol to form cyclic product

R H 2C OH dry HCl R O CH 2
C O C +H 2 O
R H 2C OH R O CH 2

Ethylene Glycol Ketal

Slide 24
Reactions of Aldehydes and Ketones

With ammonia derivatives

NH2 Z Where Z=OH, NH2, C6H5NH, NHCONH2 alkyl, aryl

  OH
  C N Z +H2O
C O H2N Z C
NH Z

Slide 25
Reactions of Aldehydes and Ketones

• NH2-NH2 CH3CH=N-NH2 Hydrozone

• NH2-OH CH3CH=N-OH Oxime

• NH2-NHC6H5 CH3CH=N-NHC6H5 Phenyl hydrozone

• NH2NHCONH2 CH3CH=N-NHCONH2 Semicarbazone

Slide 26
Reactions of Aldehydes and Ketones

Mechanism
 -
 O H+ Transfer
  OH
C O : NH2 Z C Z C
N H N-Z
H H
Unstable
OH
C
N Z C N Z +H2O

H
Slide 27
Reactions of Aldehydes and Ketones

Oxidation:
Aldehydes readily get oxidized to give Carboxyacids

H
[O]
R C O R COOH
Na2Cr2O7 + H2SO4

Slide 28
Reactions of Aldehydes and Ketones

With Tollen’s reagent

H
+ -
O + 2[Ag(NH3)2] + 3 OH RCOO + 2 Ag + 2H2O + 4NH3
R C 
Silver Mirror

Slide 29
Reactions of Aldehydes and Ketones

With Fehling solution

H
2+
R C O + 2Cu +5OH RCOO + Cu2O +3H2O

Red ppt

Slide 30
Reactions of Aldehydes and Ketones

Oxidation of Ketones:
In presence of strong oxidising agents at high temperature
ketones get oxidized . Their oxidation involves C-C bond
cleavage. A mixture of Carboxylic acids having lesser number of
carbon atoms formed.
alkaline
Ex: H3C C CH3 CH3COOH + CO 2 + H 2O
KMnO4
O
4[O]
Slide 31
Reactions of Aldehydes and Ketones

Reduction: Aldehydes and Ketones are reduced to primary and

secondary alcohol by using LiAlH4 /NaBH4
H
LiAlH4
R C O R CH2 OH
THF Primary Alcohol

H
LiAlH4
R C R R C R
THF
O OH Slide 32
Secondary Alcohol
Reactions of Aldehydes and Ketones

Reduction to Hydrocarbons (Clemmensen reduction)

H
Zn - Hg
R C O R CH3 + H2O
Concentrated HCl

Zn - Hg
R C R R CH2 R + H2O
Concentrated HCl
O Slide 33
Reactions of Aldehydes and Ketones

Wolf-Kishner reduction

H
H2N NH2
R C O R CH3 + H2O
KOH/NaOH
H2N NH2
R C R
R CH2 R + H2O
O KOH
Slide 34
Reactions of Aldehydes and Ketones

Reactive α- Hydrogen
The α-Hydrogen in aldehydes and ketones is acidic in nature. It
is due to the strong electron withdrawing C O group.

Slide 35
Reactions of Aldehydes and Ketones

Aldol condensation
H H H H H
dil NaOH
H3C C O H3C C O H3C C CH2 C O H3C CH CH C O

acetaldehyde acetaldehyde OH  But - 2 - enal
aldol
3 - Hydroxy butanal
O O OH O O
Ba(OH)2
H3C C CH3 H3C C CH3 H3C C CH2 C CH3 H3C C CH C CH3

CH3
CH3 
4 - Methyl pent - 3en - 2 one
Ketal
(4 - Hydroxy, 4 - Methyl Pentan - 2 one)

Slide 36
Reactions of Aldehydes and Ketones

Cross aldol condensation

Benzaldehyde + Acetophenone OH-/ Δ 1,3-Diphenylprop-2-enone

O OH
OH C CH2 C
-H2O CH CH C
C H H3C C

O Dil NaOH H O  O

1.3 . diphenyl Propzentone

Slide 37
Reactions of Aldehydes and Ketones

Electrophilic Substiution:
Aromatic aldehydes and Ketones undergo electrophillic
substitution to give meta- substituted product
H
H
Concentrated HNO3 C O
C O
Concentrated H2SO4

NO2
Metanitro benzaldehyde
Slide 38
Reactions of Aldehydes and Ketones

Cannizzaro’s reaction
(Reactions + Aldehydes which have no α – Hydrogen
H
KOH HCOOK + CH 3OH
2
H C O 50% Potassium Methanol
formate

H
C O KOH COOK CH2 OH
2 50%

Potassium Benzylaclohol
Benzoate Slide 39
Reactions of Aldehydes and Ketones

Uses(i) :Formaldehyde
In the manufacture of latex rubber.
Preparation of Formalin(40% solution for preserving biological
specimen), Trioxane , Bakelite(Thermosetting polymer) &
Urotropine(urinary antiseptic)
Uses(ii) : Acetaldehyde
In the preparation of acetic acid , ethyl acetate & vinyl acetate.
Paraldehyde(hypnotic) and metaldehyde(solid fuel) Slide 40
Reactions of Aldehydes and Ketones

Uses(iii) : Benzaldehyde
Used in perfumery, dye industries
Used as flavoring agent
Used in the preparation of Cinnamic acid, Malachite green
Uses (iv) : Acetone
Used as industrial solvent
Used in the preparation chloretone(hypnotic), Mesityl oxide,
Phorone, Mesityline, chloroform and iodoform Slide 41
Reactions of Aldehydes and Ketones

Uses (v) :Acetophenone

Used in the preparation of Tear gas phenacyl chloride
Used in the preparation of a hypnotic ‘Dypnone’

Slide 42
1. Which is the most suitable oxidising agent used to convert
primary alcohol into an aldehyde?
(a) Acidified K2Cr2O7 (b) Acidified KMnO4
(c) Alkaline KMnO4 (d) PCC

2. When PCC is used as an oxidising agent, which is the solvent

used?
(a) T.H.F (b) Diethyl ether
Slide 44
(c) Dichloromethane (d) Carbon disulphide
3. Which is the product obtained 2–Pentene undergoes
ozonolysis followed by treating with Zn + H2O?
(a) Acetone (b) Acetaldehyde
(c) Propionaldehyde (d) Acetaldehyde and propionaldehyde

4. What is product formed, when vapours of acetic acid are

passed over heated MnO at 573K?
(a) Formaldehyde (b) Acetaldehyde
(c) Acetone (d) Acetic anhydride Slide 45
5. What is the product formed when propyne is treated with
dilute H2SO4 in presence of HgSO4 catalyst?
(a) Propene (b) Propanal
(c) Propanol (d)Propanone
(d) Propanone

6. Phenyl cyanide treated with SnCl2+ con. HCl and the product
formed treated with dilute acid gives
(a) Phenol (b) Benzoic acid
(c) Benzaldehyde (d) Benzyl alcohol Slide 46
 Dry Ether H2 O
7. CH MgI + A B CH3CHO
3 +
H
In this, reactant A is

(a) CO2 (b) H3C C CH3 (c) HCN (d) CH3OH

O

Slide 47
8. In the reaction
CHO
Anhydrous
+CO + HCl +HCl
AlCl3

which is the electrophile?

(a) (b) CHO (c) Cl (d)

CO CHO

Slide 48
9. A dihaloalkane on alkaline hydrolysis produces a ketone with
formula C3H6O. The compound is
(a) 1,2-Dichloropropane (b) 1,1-Dichloropropane
(c) 2,2-Dichloropropane (d) 1,3-Dichloropropane

10. Which one of the following is present in the blood of

diabetic patient?
(a) Methanol (b) Ethanoic acid
(c) Propanone (d) Propanal
Slide 49
11. 3-Pentanone and 2-Pentanone are
(a) Metamers (b) Chain Isomers
(c) Functional isomers (d) Optical isomers

12. In aldol condensation the intermediate formed is

(a) Carbonium ion (b) Nitrene
(c) Carbene (d) Enolate ion
Slide 50
13.The product formed when Benzaldehyde is treated with
acetaldehyde in presence of dilute NaOH is
(a) Benzyl alcohol (b) Ethanol
(c) Benzoic acid (d) 3–Phenyl prop-2-enal

Slide 51
14. NH2 - NH2
Dry
CH3 MgI + A B Propane
Ether KOH

Identify A in the above reaction.

(a) Acetone (b) Acetaldehyde
(c) Formaldehyde (d) Ethane nitrile
Slide 52
15. Haloform reaction is given by the compounds having
(a) CH2 – OH group (b) – COOH Group
O
(c) – COOCH3 group (d)
C CH3

16. Acetaldehyde and Benzaldehyde differ in reaction with

(a) Tollen’s Reagent (b) HCN
(c) NaHSO3 (d)Dilute NaOH
Slide 53
17. Dypnone, a hypnotic is obtained from
(a) Acetone (b) Acetaldehyde
(c) Acetophenone (d) Benzaldehyde

18. Phenacyl Chloride prepared from acetophenone is used as

(a) Polymer (b) Antioxidant
(c) Lachrymater (d) Antiseptic
Slide 54
19.Which one of the following statements is wrong?

(a) Aldehydes and ketones are good reducing agents.

(b) Aldehydes and ketones are polar compounds.
(c) Aldehydes are more reactive than ketones.
(d) Aldehydes and ketones are reduced to alcohols.

Slide 55
20. H2O 70 oC
R C C H A A is
H2SO4 +HgSO4
H
R C CH3
(a) R C O (b) (c) RCOOH (d) R CH2 OH
O

21. Both formaldehyde and acetaldehyde give similar reactions

with all the reagents except
(a) Schiff reagent (b) Tollen’s reagent
(c) Ammonia (d) Fehling solution Slide 56
22. In the Cannizzaro’s reaction, the slowest step is
(a) Attack of OH on Carboxyl group
(b) The transfer of Hydride ion to the Carboxyl group
(c) Removal of H+ from COOH
(d) Attack of H+ on Carboxyl group
H3C C CH3
23. C2H5CHO and can be distinguished using
O
(a) Phenyl hydrazine (b) Hydroxyl amine
(c) Sodium bisulphate (d) Fehling solution
Slide 57
24. Acetophenone is converted into Ethyl benzene by using
(a) NaBH4 (b) LiAlH4
(c) Sodium + Alcohol (d) Zn–Hg + Con. HCl

25. In Rosenmund reduction the role of BaSO4 is

(a) Catalyst
(b) Prometer
(c) To absorb the heat evolved
(d) To decrease the activity of catalyst palladium Slide 58
26. H LiAlH4
H3C C O + H2N OH A B


Here B is
(a) CH3CH2OH (b) CH3CN
(c) CH3CH=N – OH (d) CH3 – CH2 – NH2

Slide 59
27. Crossed aldol condensation is not given by

(a) Acetaldehyde and Acetone

(b) Acetaldehyde and Benzaldehyde

(c) Propionaldehyde and Acetaldehyde

(d) Benzaldehyde and Formaldehyde

Slide 60
28.
Ether H2 O Copper
H3C C CH3 + CH3 MgI A B C
H+ 300 oC
O

Here C is
CH3
(a) H3C CH CH2 (b) H3C C CH2

(c) H3C CH2 CH2 OH (d) CH3 COOH

Slide 61
29. A compound gave a positive Tollen’s test. It also answered
haloform test. The compound was
(a) Ethanal (b) Acetone
(c) Acetophenone (d) Propanal

30. On reduction with LiAIH4, which of the following gives an

optically active compound?
(a) Propanal (b) Propanone
(c) Butanol (d) Butanone Slide 62
31. Which of the following has highest boiling point ?
(a) Propanone (b) 2-Pentanone
(c) Butanone (d) 2-Hexanone

32. Benzaldehyde does not react with

(a) Tollen’s reagent (b) Fehling solution
(c) 2,4-DNP solution (d) NaHSO3

Slide 63
33. Which one of the following gives violet colour with neutral
Ferric Chloride solution?
(a) Acetaldehyde (b) Benzaldehyde
(c) Salicylaldehyde (d) Formaldehyde

34. Which one of the following is used to convert Benzaldehyde

into Toluene?
(a) LiAlH4 (b) NaBH4
(c) Sodium and alcohol (d) Zn-Hg + Con. HCl Slide 64
35. A carbonyl compound reacts with hydrogen cyanide to form
cyanohydrin which on hydrolysis forms a racemic mixture of α-
hydroxy acids. The carbonyl compound is
(a) Diethyl ketone (b) Dimethyl ketone
(c) Formaldehyde (d) Acetaldehyde

Slide 65
36. Iodoform test is not given by

(a) Pentan-2-one (b) Ethanol

(c) Pentan-3-one (d) Ethanal

37. CH3CHO and C6H5CH2CHO can be distinguished by

(a) Benedict’s test (b) Tollen’s reagent test
(c) Iodoform test (d) Fehling’s reagent test

Slide 66
38. An aromatic compound X with molecular formula C9H10O gives
2,4-DNP test, Tollen;s test, undergoes Cannizaro reaction and on
vigarous oxidation gives 1,2-benzene dicarboxylic acid. X is
(a) 2-Methylacetophenone (b) 3-Ethylbenzaldehyde
(c) 2-Ethylbenzaldehyde (d) 3-Methylacetophenone

Slide 67
39. Aldol condensation between which of the following two
compounds followed by dehydration gives methyl vinyl ketone?
(a) Formaldehyde and acetone
(b) Formaldehyde and acetaldehyde
(c) Two molecules of acetaldehyde
(d) Two molecules of acetone

Slide 68
40. Which of the following reactions will not result in the formation

of carbon-carbon bonds?

(a) Friedel-Craft acylation

(b) Reimer- Tiemann reaction

(c) Wurtz reaction

Slide 69
(d) Cannizzaro reaction
41. Trichloroacetataldehyde is subjected to Cannizzaro’s reaction

by using NaOH. The mixture of the products contains sodium

trichloroacetate and another compound. The other compound is

(a) Trichloromethanol

(b) 2,2,2-Trichloropropanol

(c) Chloroform
Slide 70
(d) 2,2,2-Trichloroethanol
42. Consider the reaction:
RCHO+NH2NH2 → RCH=N-NH2
What sort of reaction is this?
(a) Electrophilic addition-elimination reaction
(b) Free radical addition-elimination reaction
(c) Electrophilic substitution-elimination reaction
(d) Nucleophilic addition-elimination reaction

Slide 71
43. Which of the following ketones cannot be prepared by
pyrolysis of a suitable calcium salt of a fatty acid?
(a) Benzophenone (b) Pentan-3-one
(c) Butanone (d) Propanone

44. Cyanohydrin of which of the following gives lactic acid on

hydrolysis?
(a) CH3COCH3 (b) HCHO
(c) C6H5CH2CHO (d) CH3CHO Slide 72
45. Which of the following reagents can help in separating a
mixture of acetone and isopropyl alcohol?

(a) NaOH (b) NaCl

(c) NaHSO3 (d) NaHSO4

Slide 73
46. Arrange the following compounds in increasing order of their
reactivity in nucleophilic addition reactions; Ethanal(I),
Propanal(II), Propanone(III) and Butanone(IV).

(a) III<II<I<IV (b) II<I<III<IV

(c) IV<III<II<I (d) I<II<III<IV

Slide 74
47. Which of the following compounds does not react with sodium
bisulphate?
(a)Benzaldehyde (b)Acetophenone
(c)Acetone (d)Acetaldehyde

Slide 75
48. A compound A has molecular formula C2Cl3OH. It reduces
Fehling’s solution and on oxidation gives a monocarboxylic
acid B. A is obtained by the action of Cl2 on ethyl alcohol. A is
(a) Chloral (b) Chloroform
(c) Chloromethane (d) Chloroacetic acid

49. Acetone on distillation with conc. H2SO4 forms

(a) Phorone (b) Acrolein
(c)Mesitylene (d) Mesityl oxide Slide 76
50. Compound A C5H10O forms a phenylhydrozone and gives negative
Tollen’s & iodoform test. On reduction it gives n-pentane. A is
(a) Pentanal (b) Pentan-2-one
(c) Pentan-3-one (d) Amyl alcohol

51. With which of the following reagents, carbonyl compound shows

addition cum elemination reaction?
(a) Carbonium ion (b) Brady’s reagent
(c) HCN (d) NaHSO3 Slide 77
52. Which one of the following is crotonaldehyde?
(a) CH2=CH-CHO (b) C6H5-CH=CH-CHO
(c) CH3-CH=CH-CHO (d) C6H5(OH)CHO

53. Which of the following will give negative test with Brady’
reagent?
(a)CH3CHO (b) CH3-O-CH3
(c) CH3-CO-CH3 (d) C6H5CHO Slide 78
54. The reaction of chloroform with acetone gives
(a) Mesityline (b) Ethylidene chloride
(c) Chloretone (d) Chloral

55. Hexamethylene tetramine is used as

(a) Analgesic (b) Antipyrtic
(c) Hypnotic (d) Urinary antiseptic
Slide 79
56. Reaction involving formation of trioxane from methanal is
called
(a) Aldol condensation
(b) Condensation polymerization
(c) Addition polymerzation
(d) Cannizzaro’s reaction

Slide 80
57. What is Stephan’s reaction?
(a) An alkyl isocyanide is reduced with Na/alcohol.
(b) An alkyl cyanide is reduced with LiAlH4.
(c) An alkanoyl chloride is reduced with Pd/BaSO4.
A
(d) An alkyl cyanide is reduced with SnCl2 and HCl.

Slide 81
58. Schiff’s reagent is:
(a) Magenta solution decolourised with chlorine.
(b) Ammonical cobalt chloride solution.
(c) Rosaniline hydrochloride decolourised with H2SO3.
(d) Cannizzaro’s reaction

Slide 82
59. Which of the following reactions is a condensation reaction?
(a) HCHO → Paraformaldehyde
(b) CH3COCH3 → Mesityl oxide
(c) CH3CHO → Paraldehyde
(d) H2C=CH2 → Polyethylene

Slide 83
60. In the following sequence of reaction, end product is
CaC2 H2O A Hg2+/H2SO4 B [O] C Ca(OH)2/ heat D

(a) Acetaldehyde (b) Formaldehyde

(c) Acetic acid (d) Acetone

Slide 84
Thank You.

Slide 85