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 () 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 () bond

P ORBITAL

ORBITAL
PLANAR OVERLAP
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 () bond

P ORBITAL

ORBITAL
PLANAR OVERLAP
WITH NEW
BOND ORBITAL
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 () bond

P ORBITAL

ORBITAL
PLANAR OVERLAP
WITH NEW
BOND ORBITAL
ANGLES
OF 120°

as oxygen is more electronegative than carbon the bond is polar

 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 C=C NON-POLAR ELECTROPHILES ADDITION

CARBONYLS C=O POLAR NUCLEOPHILES ADDITION
 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Reagent hydrogen cyanide - HCN (in the presence of KCN)

Conditions reflux in alkaline solution

Nucleophile cyanide ion CN¯

Product(s) hydroxynitrile (cyanohydrin)

Equation 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 TO SHOW

HOW DIFFERENT ISOMERS ARE FORMED
 CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH 4

Conditions aqueous or alcoholic solution

Mechanism Nucleophilic addition (also reduction as it is addition of H¯)

Nucleophile H¯ (hydride ion)

 CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH 4

Conditions aqueous or alcoholic solution

Mechanism Nucleophilic addition (also reduction as it is addition of H¯)

Nucleophile H¯ (hydride ion)

Product(s) Alcohols Aldehydes are REDUCED to primary (1°) alcohols.

Ketones are REDUCED to secondary (2°) alcohols.

Equation(s) CH3CHO + 2[H] ——> CH3CH2OH

CH3COCH3 + 2[H] ——> CH3CHOHCH3

Notes The water provides a proton

 CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH 4

Conditions aqueous or alcoholic solution

Mechanism Nucleophilic addition (also reduction as it is addition of H¯)

Nucleophile H¯ (hydride ion)

Product(s) Alcohols Aldehydes are REDUCED to primary (1°) alcohols.

Ketones are REDUCED to secondary (2°) alcohols.

Equation(s) CH3CHO + 2[H] ——> CH3CH2OH

CH3COCH3 + 2[H] ——> CH3CHOHCH3

Notes The water provides a proton

Question NaBH4 doesn’t reduce C=C bonds. WHY?

CH2 = CHCHO + 2[H] ———> CH2 = CHCH2OH
 CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH 4

Conditions aqueous or alcoholic solution

Mechanism Nucleophilic addition (also reduction as it is addition of H¯)

Nucleophile H¯ (hydride ion)

 CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH 4

Conditions aqueous or alcoholic solution

Mechanism Nucleophilic addition (also reduction as it is addition of H¯)

Nucleophile H¯ (hydride ion)

Water is added
 CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH 4

Conditions aqueous or alcoholic solution

Mechanism Nucleophilic addition (also reduction as it is addition of H¯)

Nucleophile H¯ (hydride ion)

Aldehyde Primary alcohol

Water is added
 CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH 4

Conditions aqueous or alcoholic solution

Mechanism Nucleophilic addition (also reduction as it is addition of H¯)

Nucleophile H¯ (hydride ion)

ANIMATED MECHANISM
 THE TETRAHYDRIDOBORATE(III) ION BH4

B H H H H B
each atom needs one H
electron to complete
atom has three
its outer shell boron shares all 3 electrons to
electrons to share
form 3 single covalent bonds

H H

H B H H B H

The hydride ion forms a

H dative covalent bond
H
 CARBONYL COMPOUNDS - REDUCTION WITH HYDROGEN

Reagent hydrogen

Conditions catalyst - nickel or platinum

Reaction type Hydrogenation, reduction

Product(s) Alcohols Aldehydes are REDUCED to primary (1°) alcohols.

Ketones are REDUCED to secondary (2°) alcohols.

Equation(s) CH3CHO + H2 ——> CH3CH2OH

CH3COCH3 + H2 ——> CH3CHOHCH3

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 is reduced to CH-CH
C=O is reduced to CH-OH
CN is reduced to CH-NH2

Hydrogen H• H2
H+ (electrophile) H¯ (nucleophile)
 CARBONYL COMPOUNDS - REDUCTION

Introduction Functional groups containing multiple bonds can be reduced

C=C is reduced to CH-CH
C=O is reduced to CH-OH
CN is reduced to CH-NH2

Hydrogen H• H2
H+ (electrophile) 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 CHO CHO
Cl

Cl
Cl
 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 CHO CHO
Cl

Cl
Cl
Boiling point 213°C 214°C 214°C
 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 CHO CHO
Cl

Cl
Cl
Boiling point 213°C 214°C 214°C

Melting point of
2,4-dnph derivative 209°C 248°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.
 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 CHO CHO
Cl

Cl
Cl
Boiling point 213°C 214°C 214°C

Melting point of
2,4-dnph derivative 209°C 248°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.