TH E CHE MI STR Y OF ALD EHY DE S AN D KET ON ES

A guide for A level students

KNOCKHARDY PUBLISHING

KNOCKHARDY PUBLISHING

ALDEHYDES & KETONES
INTRODUCTION
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ALDEHYDES & KETONES
CONTENTS
• Prior knowledge • Bonding in carbonyl compounds • Structural differences • Nomenclature • Preparation • Identification • Oxidation • Nucleophilic addition • Reduction • 2,4-dinitrophenylhydrazine

ALDEHYDES & KETONES
Before you start it would be helpful to… • know the functional groups found in organic chemistry • know the arrangement of bonds around carbon atoms • recall and explain the polarity of covalent bonds

CARBONYL COMPOUNDS - BONDING
Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar

PLANAR WITH BOND ANGLES OF 120°

CARBONYL COMPOUNDS - BONDING
Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar the unhybridised 2p orbital of carbon is at 90° to these

P ORBITAL

PLANAR WITH BOND ANGLES OF 120°

CARBONYL COMPOUNDS - BONDING
Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar the unhybridised 2p orbital of carbon is at 90° to these it overlaps with a 2p orbital of oxygen to form a pi (π) bond
P ORBITAL

PLANAR WITH BOND ANGLES OF 120°

CARBONYL COMPOUNDS - BONDING
Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar the unhybridised 2p orbital of carbon is at 90° to these it overlaps with a 2p orbital of oxygen to form a pi (π) bond
P ORBITAL

PLANAR WITH BOND ANGLES OF 120°

ORBITAL OVERLAP

CARBONYL COMPOUNDS - BONDING
Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar the unhybridised 2p orbital of carbon is at 90° to these it overlaps with a 2p orbital of oxygen to form a pi (π) bond
P ORBITAL

PLANAR WITH BOND ANGLES OF 120°

ORBITAL OVERLAP NEW ORBITAL

CARBONYL COMPOUNDS - BONDING
Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar the unhybridised 2p orbital of carbon is at 90° to these it overlaps with a 2p orbital of oxygen to form a pi (π) bond
P ORBITAL

PLANAR WITH BOND ANGLES OF 120°

ORBITAL OVERLAP NEW ORBITAL

as oxygen is more electronegative than carbon the bond is polar

CARBONYL COMPOUNDS - STRUCTURE
Structure carbonyl groups consists of a carbon-oxygen double bond the bond is polar due to the difference in electronegativity

Difference

ALDEHYDES - at least one H attached to the carbonyl group

H C=O H

CH3 C=O H

CARBONYL COMPOUNDS - STRUCTURE
Structure carbonyl groups consists of a carbon-oxygen double bond the bond is polar due to the difference in electronegativity

Difference

ALDEHYDES - at least one H attached to the carbonyl group

H C=O H CH3 C=O CH3

CH3 C=O H C2H5 C=O CH3

KETONES - two carbons attached to the carbonyl group

CARBONYL COMPOUNDS - FORMULAE
Molecular Structural

C3H6O C2H5CHO CH3COCH3

C2H5 C=O H
Displayed

CH3 C=O CH3 H C H O H C O H H C H O O C H C H H

H H C H

Skeletal

CARBONYL COMPOUNDS - NOMENCLATURE
Aldehydes

C2H5CHO

propanal

Ketones

CH3COCH3 CH3CH2COCH3 CH3COCH2CH2CH3 CH3CH2COCH2CH3 C6H5COCH3

propanone butanone pentan-2-one pentan-3-one phenylethanone

CARBONYL COMPOUNDS - FORMATION ALDEHYDES
Oxidation of primary (1°) alcohols beware of further oxidation RCH2OH + [O] ——> RCHO + H2O RCHO + [O] ——> RCOOH

Reduction of carboxylic acids

RCOOH + [H] ——> RCHO + H2O

KETONES
Oxidation of secondary (2°) alcohols RCHOHR + [O] ——> RCOR + H2O

CARBONYL COMPOUNDS - IDENTIFICATION
Method 1 strong peak around 1400-1600 cm-1 in the infra red spectrum

Method 2

formation of an orange precipitate with 2,4-dinitrophenylhydrazine

Although these methods identify a carbonyl group, they cannot tell the difference between an aldehyde or a ketone. To narrow it down you must do a second test.

CARBONYL COMPOUNDS - IDENTIFICATION
Differentiation Tollen’s Reagent to distinguish aldehydes from ketones, use a mild oxidising agent

ammoniacal silver nitrate mild oxidising agent which will oxidise aldehydes but not ketones contains the diammine silver(I) ion - [Ag(NH3)2 ]+ the silver(I) ion is reduced to silver Ag+(aq) + e¯ ——> Ag(s) the test is known as THE SILVER MIRROR TEST

CARBONYL COMPOUNDS - IDENTIFICATION
Differentiation Tollen’s Reagent to distinguish aldehydes from ketones, use a mild oxidising agent

ammoniacal silver nitrate mild oxidising agent which will oxidise aldehydes but not ketones contains the diammine silver(I) ion - [Ag(NH3)2 ]+ the silver(I) ion is reduced to silver Ag+(aq) + e¯ ——> Ag(s) the test is known as THE SILVER MIRROR TEST

Fehling’s Solution

contains a copper(II) complex ion giving a blue solution on warming, it will oxidise aliphatic (but not aromatic) aldehydes the copper(II) is reduced to copper(I) a red precipitate of copper(I) oxide, Cu2O, is formed

The silver mirror test is the better alternative as it works with all aldehydes

Ketones do not react with Tollen’s Reagent or Fehling’s Solution

CARBONYL COMPOUNDS - CHEMICAL PROPERTIES OXIDATION
• • • • provides a way of differentiating between aldehydes and ketones mild oxidising agents are best aldehydes are easier to oxidise powerful oxidising agents oxidise ketones to a mixture of carboxylic acids

ALDEHYDES

easily oxidised to acids RCHO(l) + [O] ——> RCOOH(l) CH3CHO(l) + [O] ——> CH3COOH(l)

KETONES

oxidised under vigorous conditions to acids with fewer carbons C2H5COCH2CH3(l) + 3 [O] ——> C2H5COOH(l) + CH3COOH(l)

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Mechanism occurs with both aldehydes and ketones involves addition to the C=O double bond unlike alkenes, they are attacked by nucleophiles attack is at the positive carbon centre due to the difference in electronegativities alkenes are non-polar and are attacked by electrophiles undergoing electrophilic addition

Group

Bond

Polarity

Attacking species

Result

ALKENES CARBONYLS

C=C C=O

NON-POLAR POLAR

ELECTROPHILES NUCLEOPHILES

ADDITION ADDITION

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Reagent Conditions Nucleophile Product(s) Equation hydrogen cyanide - HCN (in the presence of KCN) reflux in alkaline solution cyanide ion CN¯ hydroxynitrile (cyanohydrin) CH3CHO + HCN ——> CH3CH(OH)CN 2-hydroxypropanenitrile

Notes

HCN is a weak acid and has difficulty dissociating into ions HCN H+ + CN¯

the reaction is catalysed by alkali which helps produce more of the nucleophilic CN¯

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Mechanism Nucleophilic addition

STEP 1

Step 1

CN¯ acts as a nucleophile and attacks the slightly positive C One of the C=O bonds breaks; a pair of electrons goes onto the O

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Mechanism Nucleophilic addition

STEP 1

STEP 2

Step 1

CN¯ acts as a nucleophile and attacks the slightly positive C One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2

A pair of electrons is used to form a bond with H+ Overall, there has been addition of HCN

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Mechanism Nucleophilic addition

STEP 1

STEP 2

Step 1

CN¯ acts as a nucleophile and attacks the slightly positive C One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2

A pair of electrons is used to form a bond with H+ Overall, there has been addition of HCN

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Mechanism Nucleophilic addition

STEP 1

STEP 2

Step 1

CN¯ acts as a nucleophile and attacks the slightly positive C One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2

A pair of electrons is used to form a bond with H+ Overall, there has been addition of HCN

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

ANIMATED MECHANISM

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Watch out for the possibility of optical isomerism in hydroxynitriles CN¯ attacks from above

CN¯ attacks from below

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Watch out for the possibility of optical isomerism in hydroxynitriles

CN¯ attacks from above

CN¯ attacks from below

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

ANIMATED MECHANISM

CARBONYL COMPOUNDS - REDUCTION WITH NaBH4
Reagent Conditions Mechanism Nucleophile Product(s) sodium tetrahydridoborate(III) (sodium borohydride), NaBH4 aqueous or alcoholic solution Nucleophilic addition (also reduction as it is addition of H¯) H¯ (hydride ion) Alcohols Aldehydes are REDUCED to primary (1°) alcohols. Ketones are REDUCED to secondary (2°) alcohols. CH3CHO + 2[H] CH3COCH3 + 2[H] ——> ——> CH3CH2OH CH3CHOHCH3

Equation(s)

Notes Question

The water provides a proton NaBH4 doesn’t reduce C=C bonds. WHY? CH2 = CHCHO + 2[H] ———> CH2 = CHCH2OH

CARBONYL COMPOUNDS - REDUCTION WITH HYDROGEN
Reagent Conditions Reaction type Product(s) hydrogen catalyst - nickel or platinum Hydrogenation, reduction Alcohols Aldehydes are REDUCED to primary (1°) alcohols. Ketones are REDUCED to secondary (2°) alcohols. CH3CHO + H2 ——> ——> CH3CH2OH CH3CHOHCH3

Equation(s)

CH3COCH3 + H2

Note

Hydrogen also reduces C=C bonds CH2 = CHCHO + 2H2 ——> CH3CH2CH2OH

CARBONYL COMPOUNDS - REDUCTION
Introduction Functional groups containing multiple bonds can be reduced C=C C=O C≡N Hydrogen H• H+ (electrophile) is reduced to is reduced to is reduced to CH-CH CH-OH CH-NH2 H2 H¯ (nucleophile)

Reactions

Hydrogen reduces C=C and C=O bonds CH2 = CHCHO + 4[H] ——> CH3CH2CH2OH

Hydride ion H¯ reduces C=O bonds CH2 = CHCHO + 2[H] ——> CH2=CHCH2OH

Explanation

C=O is polar so is attacked by the nucleophilic H¯ C=C is non-polar so is not attacked by the nucleophilic H¯

CARBONYL COMPOUNDS - REDUCTION
Example What are the products when Compound X is reduced?

COMPOUND X

H2

NaBH4

CARBONYL COMPOUNDS - REDUCTION
Example What are the products when Compound X is reduced?

COMPOUND X

H2

NaBH4

C=O is polar so is attacked by the nucleophilic H¯ C=C is non-polar so is not attacked by the nucleophilic H¯

2,4-DINITROPHENYLHYDRAZINE
Structure

C6H3(NO2)2NHNH2

Use

reacts with carbonyl compounds (aldehydes and ketones) used as a simple test for aldehydes and ketones makes orange crystalline derivatives - 2,4-dinitrophenylhydrazones derivatives have sharp, well-defined melting points also used to characterise (identify) carbonyl compounds.

Identification / characterisation
A simple way of characterising a compound (finding out what it is) is to measure the melting point of a solid or the boiling point of a liquid.

2,4-DINITROPHENYLHYDRAZINE C6H3(NO2)2NHNH2
The following structural isomers have similar boiling points because of similar van der Waals forces and dipole-dipole interactions. They would be impossible to identify with any precision using boiling point determination.
CHO Cl CHO CHO

Cl Cl

Boiling point Melting point of 2,4-dnph derivative

213°C 209°C

214°C 248°C

214°C 265°C

By forming the 2,4-dinitrophenylhydrazone derivative and taking its melting point, it will be easier to identify the unknown original carbonyl compound.

REVISION CHECK

What should you be able to do?
Recall the structure of and bonding in the carbonyl group Explain the difference in structure between aldehydes and ketones Recall the different response to oxidation of aldehydes and ketones Recall and understand the mechanism of nucleophilic addition Recall the products from the reduction of carbonyl compounds

CAN YOU DO ALL OF THESE?

YES

NO

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WELL DONE!
Try some past paper questions

TH E CHE MI STR Y OF ALD EHY DE S AN D KET ON ES
THE END

© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING

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