Chemical properties of aliphatic aldehydes and ketones

ADDITION REACTIONS

Aldehydes and ketones are reduced to the corresponding alcohols by

a) Addition of hydrogen in the presence of catalysts like finely divided platinum, palladium, nickel and ruthenium.

Addition of hydrogen with aldehyde

This method is called catalytic hydrogenation.

b) Treatment with chemical reagents such as sodium borohydride (NaBH4) or Lithium aluminium hydride (LiAlH4).

Aldehydes yield primary alcohols

Aldehydes yield primary alcohols while ketones give secondary alcohols.

 ketones give secondary alcohols

OXIDATION REACTIONS
Aldehydes differ from ketones in their oxidation reactions. Aldehydes are easily oxdised to carboxylic acids on treatment with common oxidising agents like nitric acid, potassium permanganate, potassium dichromate etc.

Aldehydes are easily oxidised to carboxylic acids containing the same number of carbon atoms, as in parent aldehyde.

oxidation of aldehydes

The reason for this easy oxidation is the presence of a hydrogen atom on the carbonyl carbon, which can be converted into -OH group without involving the cleavage of any other bond. Thus even weak oxidising agents like bromine water, Ag+, Cu2+ etc are effective. As a result aldehydes act as strong reducing agent.

Ketones are not easily oxidised. Under vigorous condition, their oxidation involves carbon-carbon bond cleavage giving a mixture of carboxylic acids having lesser number of carbon atoms than the parent ketone.

oxidation of ketones

These oxidation reactions can be used to distinguish aldehydes from ketones.

i) Aldehydes gives the Tollen's test on warming an aldehyde with freshly prepared ammoniacal silver nitrate solutions (Tollen's reagent) in a clean test tube in a water bath, a bright silver mirror is produced due to deposition of silver metal on the sides of the test tube. The reaction occurs in alkaline medium.

Ketones do not respond to this test.

formation of ammoniacal silver nitrate

formation of silver mirror

(ii) Aldehydes respond to the Fehlings' test.

Fehlings' solution is an alkaline solution of copper sulphate containing sodium potassium tartrate (Rochelle Salt) as a complexing agent. Aldehydes on warming with solution, give a red precipitate of cuprous oxide as a result of the redox reaction. Aromatic aldehydes give very poor results in this test.

Aldehydes respond to the Fehlings test

Ketones do not reduce Fehling solution.

Oxidation of ketones

Ketones are oxidised only under vigorous conditions using powerful oxidising agents such as conc. HNO3, KMnO4/H2SO4, K2Cr2O7/H2SO4 etc. Oxidation of ketones involves cleavage of bond between carbonyl carbon and a-carbon on either side of keto group giving a mixture of carboxylic acids.

oxidation of ketones

Haloform reaction

Ketones having at least one methyl group linked to the carbonyl carbon atom (i.e., methyl ketones) are oxidised by sodium hypohalite to sodium salts of carboxylic acids with one carbon atom less than that of the ketones. The methyl group is converted to haloform, which appears as a yellow precipitate. This oxidation does not affect a carbon-carbon double bond, if present in the molecule.

Haloform reaction

formation of iodoform

This test is shown by acetaldehyde as well.


REDUCTION REACTIONS
Aldehydes and ketones can be reduced to a variety of compounds under different conditions with different reducing agents.

Reduction to alcohols

Aldehydes and ketones on mild reduction give primary and secondary alcohols respectively. This type of reduction is carried out either catalytically with H2 in the presence of Ni, Pt or Pd or chemically by LiAlH4(Lithium Aluminium Hydride) or NaBH4 (Sodium borohydride).

formation of methanol from formaldehyde

formation of ethyl alcohol from acetaldehyde

formation of alcohol from ketone

Ketones can also be reduced to secondary alcohols with aluminium isopropoxide in propan-2-ol solution.

Meerwein-Ponudorf reduction

This reaction is called Meerwein - Ponudorf reduction.

Reduction to hydrocarbon

symbol for carbonyl methylene group

resulting in the formation of alkanes by any of the following reagents.

a) Zinc amalgam and concentrated hydrochloric acid reduce and the reaction is called Clemmenson's reduction.

Clemmenson s reduction

b) Wolff - Kishner reduction use by hydrazine followed by heating with potassium hydroxide in high boiling solvent ethylene glycol.

formation of toluene from benzaldehyde

c) Hydro iodic acid and phosphorus reduce carbonyl compounds at 425 K.

formation of methane from actaldehyde

Aldol condensation

Two molecules of an aldehyde or a ketone having at least one a-hydrogen atom condense in the presence of a dilute acid to give a b-hydroxyaldehyde or b-hydroxy - ketone.

This reaction is called aldol condensation. The name is derived from the names of two functional groups, aldehyde and alcohol present in the product. Though ketones give ketols (a compound containing a keto and alcohol groups) the general name aldol condensation applies.

formation of acetaldol

formation of diacetone alcohol

The aldol condensation involves the formation of bond between carbonyl carbon of one molecule and the a-carbon atom of the other molecule.

Mechanism of Reaction

a-hydrogen">

Acidity of a-hydrogen

The a-hydrogen in aldehydes and ketones is weakly acidic and may be removed by a base such as NaOH. The acidity of a-hydrogen is due to resonance staiblization of the conjugate base called the enolate anion.

acidity of a-hydrogen

[Enolate stands for the suffixes for the carbon-carbon double bond (ene) and the alcoholate group present.]

In the next step nucleophilic addition of the enolate anion occurs. The a-carbon of the enolate anion has considerably negative character and is thus nucleophilic. It adds to the carbonyl group of the unreacted aldehyde or ketone to give the aldol product.

Cross aldol condensation

Aldol condensation of a mixture of two different aldehydes or / and ketones each containing an a-hydrogen gives a mixture of four products. In this reaction, each carbonyl compound produces the corresponding enolate anion. This enolate anion may add on to the compound with the same carbonyl group to give a simple aldol condensation products. The other two products arise when a different carbonyl compound may add on. This is cross aldol condensation and gives rise to the formation of cross aldol condensation products.

Example: A reaction between ethanol and propanal.

reaction between ethanol and propanal

cross aldol condensation

This cross aldol condensation has no synthetic value except when one of the carbonyl compounds has no a-hydrogen.

For e.g., in the reaction between benzaldehyde and acetoldehyde, the cross aldol product easily losses water molecule to give cinnamaldehyde.

reaction between benzaldehyde and acetaldehyde

In conclusion, all aldehydes and ketones which contain a-hydrogen atom undergo aldol condensation. Those which do not contain a-hydrogen like HCHO, C6H5CHO etc do not undergo this reaction.

However cross aldol condensation can occur between carbonyl compound having no a-H atom with aldehydes or ketones possessing a-H atom.

Nucleophilic Addition Reactions

Being unsaturated, aldehydes and ketones undergo addition reactions. They have a polar carbonyl group. The carbon of the carbonyl group being electrophilic, is readily attacked by the nucleophiles. Hence the most typical reactions of aldehydes and ketones are nucleophilic addition reactions to carbon-oxygen double bond.

Mechanism of nucleophilic addition

The nucleophile (Nu-) attacks the carbonyl carbon from above or below the plane of the carbonyl group leading to a C-Nu bond formation.

This is accompanied by heterophilic cleavage of the weaker carbon-oxygen pi-bond. The electron pair of the pi-bond is completely transferred to the oxygen atom. The electronegative oxygen atom thus gets a negative charge. During this process, the hybridization of the carbonyl carbon changes from trigonal to tetrahedral and the oxygen atom is pushed out of the plane of the carbonyl group.

The negatively charged tetrahedral intermediate is basic and captures, a proton from the medium to give the electrically neutral product. The net result is addition of Nu- and H+ across the carbon-oxygen double bond.

Mechanism of nucleophilic addition

Relative Reactivity of Aldehydes and Ketones

In general ketones are less reactive than aldehydes on account of the following facts.

(i) Electron releasing effect

In the mechanism of nucleophilic addition, the first step involving the formation of the tetrahedral intermediate, is accelerated by electron withdrawing groups and retarded by electron donating groups.

In ketones, the carbonyl carbon is attached to two alkyl groups, which are electron releasing in nature. These alkyl groups push electrons towards carbonyl carbon and thus decrease the magnitude of positive charge on it and make it less susceptible to nucleophilic attack. In an aldehyde there is only one electron donating group as against two in ketones.

(ii) Steric effect

The tetrahedral intermediate is more crowded when bulkier groups are attached to carbonyl carbon. In ketones the presence of two bulky alkyl groups hinders the approach of the nucleophile to the carbonyl carbon. This factor is called the steric factor.

Some important examples of nucleophilic addition reactions.

a) Addition of hydrogen cyanide (HCN). HCN adds to aldehydes and ketones to form cyanohydrins.

HCN adds to aldehydes and ketones

Cyanohydrins are useful synthetic intermediates.

b) Addition of sodium bisulphite (NaHSO3)

NaHSO3 adds to aldehydes and ketones to form crystalline addition products.

bisulphite addition compounds are for separation and purification of aldehydes

The bisulphite addition compound can be converted back to the original carbonyl compound by treating it with dilute mineral and or alkali. Therefore the bisulphite addition compounds are useful for separation and purification of aldehydes.

c) Addition of Grignard reagents

Aldehydes and ketones add on to Grignard's reagents to form alcohols on hydrolysis.

action of aldehydes with grignard reagent

action of ketones with grignard reagent

Grignard's reagents gives a primary alcohol with HCHO, a secondary alcohol is produced with any other aldehyde and a tertiary alcohol with a ketone.

d) Addition of alcohols

Aldehydes react with alcohols in the presence of dry HCl gas to form acetals a gem-dialkoxy compound. In this reaction, the addition of one molecule of alcohol to one molecule of aldehyde results in the formation of an alkoxy alcohol intermediate known as a hemiacetal. A hemiacetal contains both an ether as well as alcohol functional groups. It is an unstable compound and cannot be isolated. It further reacts with alcohol to form stable acetal.

formation of acetal

Ketones react with ethylene glycol under similar conditions to form cyclic products known as ethylene glycol ketals.

formation of ethylene glycol ketals

Dry hydrogen chloride absorbs the water produced in these reactions and drives the equilibrium in the forward direction. Acetals and Ketals are hydrolyzed with aqueous mineral acids.

e) Addition of ammonia and its derivatives

Nitrogen nucleophiles such as ammonia and its derivatives H2N - Z add to carbonyl group of aldehydes and ketones. The reaction is reversible and catalyszed by acid. The equilibrium favors the product formation due to rapid dehydration of the tetrahedral addition product.

The net result is replacement of the >C = O group with >C = N - Z group.

Aldehydes and ketones react with primary amines to form Schiff's base. These compounds are also called imines.

formation of aldinine

formation of ketimine

Aldehydes and ketones react with hydrazine to form hydrazones.

acetaldehyde with hydrizine

acetone with hydrizine

Aldehydes and ketones react with hydroxylamine to form oximes.

The oximes can be hydrolyzed back to aldehydes and ketones by reaction with acids.

formation of oxime

Aldehydes and ketones react with 2,4-dinitrophenyl hydrazine to form

2,4-dinitrophenylhydrazones commonly known as DNP or Brady's reagent.

2,4-DNP derivatives are yellow, orange or red solids useful for characterization of aldehydes and ketones.

action of aldehydes with 2 4-dinitrophenyl hydrazine

Like ammonia derivatives ammonia also reacts with aldehydes (except formaldehyde) and ketones to form the products called imines.

formation of acetaldimine from acetaldehyde

However formaldehyde reacts with ammonia to form hexamethylene tetramine (CH2)6N4 also known asurotropine.

formation of urotrophine

Urotropine is used as a medicine to treat urinary infections. Nitration of urotropine under controlled condition gives an explosive RDX (Research and development explosive).

Acetone reacts with ammonia to form diacetonamine.

formation of diacetonamine

Unlike aliphatic aldehydes and ketones benzaldehyde on reaction with ammonia produces a complex product hydrobenzamide.

formation of hydrobenzamide
Formalin and its uses
Methanol is extremely soluble in water and its 40% aqueous solution is called formalin. Formalin is a disinfectant and a preservative for biological samples. Methanol is used in the manufacture of bakelite, resins and other polymers.