Chemistry

Aldehydes and ketones

 A- Aldehydes.

Introduction
 Aldehydes are oxygenated organic compounds.
 The general formula of a saturated, non-cyclic aldehyde is CnH2nO or RCHO or
 The functional group of an aldehyde is the carbonyl group – CO –.
 Carbon atom attached to functional group is called functional carbon.

I. Nomenclature of aldehydes (Systematic name according to IUPAC).

Alkane → alkanal
The position of functional group is not mentioned in the name since it is on carbon
number 1.
CH3−CH2−CHO : propanal
CH3―CH―CH―CHO 2,3-dimethyl butanal
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CH3 CH3

II. Isomerism.
Type of isomerism : 1) Skeletal isomerism : same position of – CHO but different
name.
2) Functional isomerism : they have same molecular formula but
different functional groups (different families). Aldehydes
possess functional isomerism with ketones (RCOR1).

B- Ketones.

I- Introduction
 Ketones are oxygenated organic compounds.
 The general formula of a saturated, non-cyclic ketone is CnH2nO (with n≥ 3) or
or RCOR1 .
 The functional group of a ketone is the carbonyl group – CO – .
 Carbon atom attached to functional group is called functional carbon.

II- Nomenclature of ketones (Systematic name according to IUPAC).

Alkane → alkanone
 The position of carbonyl group should be mentioned (from n > 4 ) x-alkanone with x
position of carbonyl group.
 Choose the longest chain containing the functional group – CO – .
 Number the carbon atoms in such a way the functional carbon has the lowest number.
  The branchings (ramifications) are named by alphabetical order.
CH3−CH2−CO−CH3 : butanone
CH3―CH―CO―CH −CH3 2,4-dimethyl-3- pentanone
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CH3 CH3

III- Isomerism.
Type of isomerism : 1) Positional isomerism: different position of -CO- but same
name.
2) Skeletal isomerism : same position of – CO- but different
name.
3) Functional isomerism : they have same molecular formula but
different functional groups (different families). Ketones
possess functional isomerism with aldehydes (RCHO).

C- Physical properties of aldehydes and ketones.

 Due to the absence of hydrogen bond in aldehydes and ketones, their boiling point is
less than that of alcohols.
 Aldehydes are more volatile than ketones than alcohols.
 b.p(alcohol) > b.p(ketone) > b.p(aldehyde).
 As molar mass of aldehydes and ketones increase (number of carbon atoms increases) ,
b.p increases but solubility decreases.
 Ethanal has an apple aroma which becomes pungent in strong dose.
 Carbonyl compounds are used in perfumes.

D- Chemical properties of aldehydes and ketones

 Due to the presence of lone pair of electrons on oxygen atom of carbonyl group , the
carbonyl compounds have a weak base character .
 Aldehydes are more reactive than ketones.
 Aldehydes are reductant while ketones aren’t.
 Types of reaction in aldehydes and ketones : 1- addition reactions .
2- oxidation-reduction reaction.
I. Addition reactions.
 Breaking down of double bond of carbonyl group.
 They are common reactions to aldehydes and ketones.
1 Addition of sodium bisulfite solution NaHSO3.
 This test is used to identify the carbonyl group.
 Aldehyde or Ketone + NaHSO3 → white crystals

Procedure Place in a test tube about 3 mL of NaHSO3 solution then add 1mL of
aldehyde or ketone and shake.
Observation White crystals are formed in the tube.
2 Addition of 2,4-dinitrophenyl hydrazine DNPH.
 This test is used to identify the presence of carbonyl group.
 Aldehyde or Ketone + DNPH → yellow-orange precipitate
 If aldehyde or ketone is used in excess then there will be dissolution of the
precipitate.

Procedure Place in a test tube about 3 mL of 2,4-DNPH then add 2-3 drops of
aldehyde or ketone.
Observation A yellow-orange precipitate is formed.
3
Catalytic hydrogenation.
This reaction is difficult to take place; for this reason, it is carried out at high
temperature and high pressure. The catalyst used (such as Ni , Pt or Pd ) is in the
powder form (to increase the surface of contact).
Ni
Aldehyde: RCHO + H2 → RCH2OH
Ni
Ketone: RCOR1 + H2 → RCHOHR1
II. Redox reactions .
 Aldehydes only undergo redox reaction due to the presence of hydrogen atom
attached to the carbonyl group.
 They are distinctive reactions.
 These reactions are used to distinguish between aldehydes and ketones and
therefore to identify the class of alcohol.
Catalytic Oxidation by Tollen’s Fehling Schiff’s
oxidation oxidant in reagent in reagent in reagent
acidic basic basic
medium medium medium
Aldehyde Carboxylic Carboxylic Silver Red-brick Pink
acid acid mirror precipitate color
Ketone
1 Catalytic oxidation. Ni
RCHO + ½ O2 → RCOOH
2 Mild oxidation by oxidant in acidic medium.
 The oxidant could be MnO4 - or Cr2O7 2- or any other oxidant.
 MnO4 – (purple ) , Mn 2+ (colorless) , Cr2O7 2- (yellow-orange) , Cr 3+ (green).
If K2Cr2O7 is used :
3 RCHO + Cr2O7 2- + 8 H+ → 3 RCOOH + 2 Cr 3+ + 4 H2O
If KMnO4 is used :
5 R CHO + 2 MnO4 - + 6 H + → 5 RCOOH + 2 Mn 2+ + 3 H2O
3 Oxidation by ammoniacal silver nitrate (Tollen’s reagent) in basic medium.
 Tollen’s reagent is a colorless solution.
Procedure Place in a test tube 3 mL of Tollen’s reagent then add 1 mL of
aldehyde solution. Shake and put the tube in a steam bath of about
50˚C.
Observation Silver mirror is formed on the wall of the test tube.
Sometimes we observe the formation of a black silver deposit instead of silver
mirror.
4 Oxidation by Fehling reagent in basic medium.
 Fehling reagent is a blue solution.
Procedure Place in a test tube 3 mL of Fehling reagent then add 1 mL of
aldehyde solution. Shake then heat gently.
Observation The blue color of solution gradually changes then a red-brick
precipitates appears in the tube.
Sometimes a copper mirror is formed.
5 Reaction with Schiff’s reagent.
 Schiff’s reagent is a colorless solution used usually to identify an aldehyde.
Procedure Place in a test tube 3 mL of Schiff’s reagent. Cool the content of test
tube in an ice-water bath for 2-3 minutes then add few drops of
aldehyde solution. Shake.
Observation The color of solution becomes pink.