PCH 1101 ORGANIC CHEMISTRY

Aldehydes and Ketones

Nomenclature of Aliphatic Aldehydes

the group, C=O found in aldehydes, ketones, carboxylic acids and is known as the carbonyl group. C=O Aldehydes are carbonyl compounds because they contain the carbonyl group. The functional group of the aldehydes and the general formula of aliphatic aldehydes are shown below :

H -C=O

H CnH2n+1-C=O or CnH2nO

In the IUPAC system of nomenclature, the rules for naming aldehydes are similar to those for naming alkanes except the final e of the name of the corresponding alkane is dropped and replaced by suffix al

 In aldehydes, the functional group (-CHO) can only occur at the end of a chain. Hence, the carbon atom of the CHO group is always considered to be C1,even though the number is not shown in the name of the aldehyde Branched-chain aldehydes are named as derivatives of the aldehydes with the longest possible carbon chain.

Formula H H-C=O

IUPAC name Methanal

Common Name Formaldehyde

Boiling Point C -21.0

H CH3-C=O

Ethanal

Acetaldehyde

20.8

H
CH3CH2-C=O

Propanal

Propionaldehyde

48.8

Butanal CH3(CH2)2CHO

Butradehyde

75.7

Examples :
CH3 H 3CH- C2 C1=O H
H H C4H3C3H2C2 C1=O CH3

2-METHYLPROPANAL

2-METHYLBUTANAL

Try this :
Name the following aldehydes :
(a)CH3CH2CH(CH3)CHO (b)(CH3)2CHCH(CH3)CHO (c)(CH3)3CCHO

Solution
(a) 2-methylbutanal (b) 2,3-methylbutanal (c) 2,3-dimethylpropanal

PREPARATION OF ALDEHYDES
There are many methods of making aldehydes. For example, aldehydes may be prepared by the:

(a)Oxidation of primary alcohols (b)Dehydrogenation of primary alcohols (c)Ozonolysis of alkenes

(a) Oxidation of Primary Alcohols

Aldehydes are prepared in the laboratory by the oxidation of primary alcohols using acidified potassium (or sodium) dichromate (VI). To prevent further oxidation to a carboxylic acid, the oxidising agent is added slowly to the primary alcohol and the aldehyde produced is distilled off.

Continue
H H H C O H +[O] H-C=O + H2O H methanol methanal

CH3 C O H +[O] CH3-C=O + H2O

ethanal

H
ethanol

(b) Dehydrogenation of Primary Alcohols

When primary alcohol vapour is passed over finely divided copper ar 300C dehydrogenation occurs and an aldehyde is obtained.For example, H H
300C

H-C-O- H
H
methanol

--------> H-C=O + H 2 Cu
methanal

Example:
Write the chemical equation for dehydrogentaion of Ethanol under temperature 300C and copper metal act as catalyst.

(c) Ozonolysis of Alkenes

Ozonolysis is useful as a synthetic method as an analytical technique. For example, it is used to convert an alkene into an aldehyde or a ketone.The yields are generally good.

Ozonolysis breaks the carbon-carbon double bond of an alkene to form two carbonyl groups. For example,

Continue..
H H H
Ozonolysis

C=C
H
ethene

------- >
H

C=O + O=C
H
methanal methanal

CH3 H CH3 H C=C --------- > C=O + O=C CH3 H CH3 H

2-methylprop-1-ene propanone methanal

REACTIONS OF ALDEHYDES
OXIDATION REACTIONS REDUCTION REACTIONS ADDITION REACTIONS

(i) Oxidation of Aldehydes

REACTION OF ALDEHYDES WITH TOLLENS` REAGENT : SILVER MIRROR TEST

Tollens` Reagent is a mild oxidising agent. When an aldehyde is warmed with Tollens` reagent, the colourless complex ion [Ag(NH3)2]+ is reduced by the aldehyde to grey metallic silver.

 If the test tube is spotlessly clean, the precipitate forms a silver mirror on the walls of the test tube.
This reaction is called the silver mirror test CH3CHO + 2[Ag(NH3)2]+ + OH---- > CH3COO- + 2Ag(s) + 2NH4+ + 2NH3

 We can write a simplified equation for the redox reaction as follows: CH3CHO + 2Ag+ + H2O CH3COOH +2Ag(s)+2H+
The general equation for the reaction of an aldehyde with Tollen`s reagent is RCHO + 2Ag+ + H2O RCOOH +2Ag(s) + 2H+

Note the following:

1. Methanal (HCHO) reacts rapidly with Tollens` reagent at room temperature to form metallic silver. The metallic silver may appear as a black powder or as a silver mirror on the inside of a clean test tube. 2. Ethanal and other aldehydes react slowly with Tollens` reagent and warning is required for the reaction to occur.

 Tollens` reagent oxidises aldehydes to carboxylic acids and is itself reduced to metallic silver. In the presence of an alkali,the carboxylic acid is converted to the ammonium salt. The reaction is used to distinguish aldehydes from ketones. Ketones do not react with Tollens` reagent.

FEHLINGS SOLUTION
Fehlings solution A contains copper (II) sulphate solution while Fehlings solution B contains a mixture of sodium potassium tartrate and sodium hydroxide.

The common name for sodium potassium tartrate is Rochelle salt. Fehlings solution contains a copper (II) complex ion. It is prepared by mixing Fehlings solutions A and B to form a deep blue solution of a copper (II) complex ion.

REACTIONS OF ALDEHYDES WITH FEHLINGS SOLUTION

When Fehlings solution is warmed with aldehydes, the deep blue colour of the Fehlings solution disappears (reddish-brown) precipitate of copper (I) oxide, Cu2O, is obtained. H O R-C=O + 2Cu2+ + 5OH- R-C-O- + Cu2O + 3H2O
Fehlings solution Copper (I) oxide

 In this reaction, the copper (II) ion (Cu2+ ) acts as the mild oxidising agent. The aldehyde is oxidised to a carboxylic acid while the copper (II) ions are reduced to copper (I) oxide.
This reaction is used to distinguish between an aldehyde and a ketone. Ketones do not react with Fehlings solution.

REACTIONS OF ALDEHYDES WITH OTHER OXIDISING AGENTS

Many oxidising agents react with aldehydes to form carboxylic acids. Oxidising agents commonly used for oxidisig aldehydes are, acidified potassium manganate (VII) and potassium dichromate (VI)

When an aldehyde is heated with potassium dichromate (VI) solution acidified with dilute sulphuric acid, the solution changes colour from orange to green.
The orange dichromate in (Cr2O72-) is reduced to the green chromium (III) ion (Cr 3+ ) while the aldehyde is oxidised to the carboxylic acid.

(ii) Reduction of Aldehydes

Like the carbon-carbon double bond, the carbonoxygen double bond undergoes an addition reaction with hydrogen in the presence of a metal catalyst such as nickel or platinum.

The addition of hydrogen across the carbonyl group in the presence of a metal catalyst is called catalytic hydrogenation.
It can also be classified as a reduction reaction in which hydrogen acts as the reducing agent. Aldehydes are reduced to primary alcohols.

H H R C= O + H2 --------- > R C OH H Aldehydes are reduced to primary alcohol For example, ethanal is reduced to ethanol
H H CH3 C = O +H2 -------- > CH3 C OH H

Several reducing agents can be used for the reduction of aldehydes to primary alcohols (a)The reaction with sodium tetrahydridoborate (III), NaBH4 can be carried out in aqueos solution or in alcoholic solution.

(b)Lithium tetrahydridoaluminate (III) (LiAlH4) is also known as lithium aluminium hydride. It is a powerful reducing agent and reacts violently with water. It reduces water to hydrogen.

(c) The reaction with sodium in alcohol takes place at room temperature. (d) Hydrogen gas can be used in the presence of nickel or platinum as catalyst at high temperature.
(e) Zinc and hydrochloric acid react at room temperature.

Summary for Oxidation & Reduction of Aldehydes Aldehydes are intermediate products in the oxidation of primary alcohols. They can be oxidised to carboxylic acids or reduced to primary alcohols. H H OH Oxidation Oxidation R C OH RC=O RC=O reduction Aldehyde Carboxylic acid H
Primary Alcohol

KETONES

Aliphatic Ketones
In ketones, the carbonyl carbon is bonded to two hydrocarbon groups. The general formulae of aldehydes and ketones are shown below. R or R may be alkyl or aryl group. H R RC and C=O O R
ketones aldehyde

Nomenclature of Ketones
Aliphatic ketones are named by dropping the final e of the name of alkane with the same numeber of carbon atoms and replacing it with the suffix one the chain is then numbered in the way that gives the carbonyl carbon the lowest possible number. This number is shown in the systematic name of a ketone containing more than four carbon atoms to indicate the position of the carbonyl group. Exp : hexan-3-one means a ketones with six carbon atoms per molecule and C3 atom has the ketone group.

Molecular Formula

Structural Formula

Systematic name

C3H6O

CH3COCH3

PROPANONE

C4H8O

CH3CH2COCH3

BUTANONE

C5H10O

CH3CH2COCH2CH2

PENTAN-3-ONE

C5H10O

CH3CH2CH2COCH2

PENTAN-2-ONE

PREPARATION OF KETONES
In the laboratory, ketones are prepared by the oxidation of secondary alcohols or the dehydrogenation of secondary alcohols. Aromatic ketones such as phenylethanone can also prepared by Friedel-Crafts acylation.

(i) Oxidation of Secondary Alcohol

When a secondary alcohol is heated with a mixture of potassium dichromate (VI) and dilute sulphuric acid, the alcohol is oxidised to the ketone. H O CH3 C CH3 + [O] CH3 C CH3 + H2O O H Propanone
Propan-2-ol

(ii) Dehyrogenation of Secondary Alcohols when a secondary alcohol vapour is passed ober copper at 300C, a ketone is produced. This reaction is called dehydrogenation. H O
C2H5 C CH3 --------- > C2H5 C =CH3 +H2
Cu
butanone 300C

OH
Butan-2-ol

CHEMICAL PROPERTIES OF KETONES

We would expect aldehydes and ketones to show some similarities in properties that involve the carbonyl group. For example , both aldehydes and ketones underdo addition reactions. However, because the hydrogen atom in the aldehyde group is replaced by alkyl or aryl group in ketones, these two classes of compounds show some differences in their chemical properties.

(a) Oxidation of Ketones

Ketones are more difficult to oxidise. Oxidation only occurs if the ketone is boiled with a strong oxidising agent under reflux for a prolonged period of time.

When propanone is refluxed with acidified potassium dichromate (VI) or acidified potassium manganate (VII), the carbon-carbon bond joining the carbonyl group and alkyl group is broken. As a result, a propanone is oxidised to ethanoic acid, carbon dioxide and water.

Cont..
CH3 C CH3 + 4[O] --- > CH3COOH + CO2 + H20 O

On oxidation, an aldehyde will produce a carboxylic acid with the same number of carbon atoms per molecule as the aldehyde oxidised.
Ketones are not reducing agents, hence they do not react with Fehling`s solution or Tollen`s reagent.

(b) Reduction of Ketones

Ketones are reduced to secondary alcohols under suitable conditions. The common reducing agents are : Lithium tetrahydrodoaluminate (III) om ethoxyethane at 0C followed by dilute sulphuric acid. Sodium tetrahydridoborate (III) NaBH4, in aqueos solution or alcoholic solution, Sodium in ethanol at room temperature.

For example :

H CH3C CH3 + 2 [H] ---- > CH3 C CH3 O OH Propanone propan-2-ol

(c) Addition Reactions of Ketones with HCN Like aldehydes, ketones undergo addition reactions with hydrogen cyanide to form cyanohydrins. For example : O OH CH3 C + HCN ------- > CH3 C CN CH3 CH3
Propanone 2-hydroxy-2-methylpropanenitrile

TRIIODOMETHANE TEST
Ketones containing the CH3CO- group produce yellow crystals of triiodomethane (iodoform) when they react with a solution of iodine in aqueos sodium hydroxide. The overall reaction is : CH3COCH3 + 3I + NaOH CHI3 + CHCOO-Na+ + 3HI

PART II : Reaction & mechanism NEXT : carboxylic acid and ester (Wednesday) 10am -12noon (tutorial discussion) Carbonyl group compound & amines (Thursday)

Fri : Test 2 * 8-9am test 2.