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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
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:
Continue
H H H C O H +[O] H-C=O + H2O H methanol methanal
H
ethanol
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.
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
REACTIONS OF ALDEHYDES
OXIDATION REACTIONS REDUCTION REACTIONS ADDITION REACTIONS
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+
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.
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.
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.
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.
(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
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.
For example :
(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)