Aldehydes, Ketones and Carboxylic Acids

Aldehydes (RCHO), Ketones and Carboxylic acids (RCOOH) are most important and widely used compounds in organic chemistry. They play an important role in biochemical processes of life. These compounds and their derivatives are used in many food products, pharmaceuticals, for artificial flavouring, as Solvents and for preparing a number of materials. In this unit we shall study about the organic compounds containing carbon-oxygen double bond most important groups in organic chemistry. is called carbonyl group, one of the

Nomenclature
(i) Aldehydes: In aldehydes C of carbonyl group is attached to one alkyl group and one H.
In IUPAC system of nomenclature C of aldehyde is given in number if it is included in the longest continuous chain. The suffix e of the parent hydrocarbon is replaced by al.

If CHO group is attached to a cyclic chain, carbaldehyde is written as a suffix to the parent hydrocarbon.

If CHO group is attached to benzene ring it is written as benzaldehyde.

(ii) Ketones:
In Ketones C of carbonyl group is given lowest number in the longest C-chain. The suffix e of the parent hydrocarbon is replaced by one.

If more than one carbonyl groups are present, the nomenclature of the compound is done in following way:

Structure of the Carbonyl Group

The carbonyl C is hybridised and forms three Fourth electron of carbon atom remains in unhybridised p-orbital and form bond with oxygen by overlapping with p-orbital of oxygen. Carbon and three atoms attached to it lie in the same plane and form a trigonal coplanar structure.
Carbonyl group is polar due to high electronegativity of oxygen atom.

Carbonyl compounds have higher polarity than ethers due to the presence of above structures.

Preparation of Aldehydes and Ketones

(i) By oxidation of alcohols

(ii) By Dehydrogenation of alcohols

(iii) By ozonolysis of alkenes

(iv) By hydration of alkynes

(v) Rosenmund reaction

(vi) Treatment of acyl chloride with dialkylcadmium gives ketones (vii) From nitriles and esters This reaction is called Stephens Reaction Nitriles are selectively reduced by di-isobutyl-aluminium hydride (DIBALH) to imines followed by hydrolysis to give aldehydes.

Esters are also reduced to aldehydes with DIBALH.

Nitriles react with Grignard reagent which on hydrolysis gives Ketones.

(viii) Aromatic aldehydes are prepared from aromatic hydrocarbons by the following methods: (a) Etards reaction: Toluene reacts with chromyl chloride benzaldehyde to form

(b) (c) Gatterman-Koch reaction: When mixture of CO and HCl gas is passed through benzene in presence of anhydrous , benzaldehyde is formed.

(d) Friedel-Crafts acylation:

Physical Properties of Aldehydes and Ketones

Methanal is a gas at room temperature. With increasing number of C-atoms aldehydes and ketones are liquids or solids. Boiling points of aldehydes and ketones are higher than the corresponding hydrocarbons and ethers but lower than alcohols.

Reason: Hydrocarbons have no H-bonding or dipole-dipole interactions. Ethers have dipole-dipole interactions but weaker than aldehydes and ketones. Alcohols have intermolecular H-bonding

Lower members of aldehydes and ketones (upto 3-C atoms) are miscible with water due to the formation of Hbonding

The solubility of aldehydes and ketones decreases with increasing number of C-atoms. Aldehydes and ketones are soluble in organic solvents. Lower members of adehydes and ketones have pungent odours but higher members have fragrant smell and hence they are used as flavouring agents.

Chemical Reactions of Aldehydes and Ketones

Nucleophilic addition reactions Mechanism

Aldehydes are generally more reactive than ketones due to the following reasons: Presence of two alkyl groups cause more steric hindrances in the approach of nucleophile to carbonyl carbon. In aldehyde only one alkyl group is present. In Ketones +I effect of two alkyl groups reduce the +ve charge of carbonyl carbon and reduces its electrophilicity. Reactions

(i) Presence of base catalyses the reaction.

(ii)

Most aldehydes give this reaction however in case of ketones yield is poor. (iii)

(iv)

(v) Reaction with Grignard reagent for preparation of alcohols (a) Reduction

(b) Clemmensen reduction

(c) Wolf-Kishner reduction

(vi) Oxidation: Aldehydes are easily oxidised to carboxylic acids with common oxidising agents like , nitric acid and even with mild oxidising agents like Tollens reagent and Fehling solution also. Ketones are generally oxidised under vigorous conditions with strong oxidising agents. Oxidation of ketones involve CC bond cleavage and as a result a mixture of carboxylic acids are formed.

Tollens Test: The test is used to distinguish between aldehydes and ketones. Aldehyds form silver mirror with ammonical silver nitrate (Tollens reagent). Ketones do not react with it.

Fehlings Test: Fehling reagent = Fehling Solution A tartarate) + Fehling Solution B (alk. Sodium-potassium

Ketones and aromatic aldehydes do not give this test. (vii) Haloform reaction: Aldehydes and ketones having at least one carbonyl carbon give this reaction. group linked to the

In this reaction if R group contains a double bond it does not get affected. Iodoform test (using the reagent ) is used to identify the presence of

group or in a compound. (viii) Aldol condensation: This reaction is given by those aldehydes and ketones which have of carbonyl compounds is acidic due to strong electron withdrawing nature of carbonyl group in presence of a base

(Aldols have both OH group and carbonyl group) Cross Aldol condensation: When aldol condensation takes place between two different aldehydes or ketones or one aldehyde and one ketone it is known as cross aldol condensation. For this at least one aldehyde or ketone should have a

(ix) Cannizaros Reaction: This reaction is given by those aldehydes which do not have

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This is a disproportionation reaction in which aldehyde undergoes self reduction and oxidation. Electrophilic Substitution reactions: when carbonyl group is attached to benzene ring, it deactivates the ring and it is meta directing.

Uses of Aldehydes and Ketones Used as solvents and as flavouring agents. Formaldehyde is used as formalin (40% solution) to preserve biological specimens. Used as starting material for the preparation of a number of organic compounds, dyes, polymers, etc.

Carboxylic Acids
Carboxylic acids are C-compounds containing a carboxyl group which consists of a carbonyl group attached to a hydroxyl group. But carbon in carboxylic group is less electrophilic than carbonyl carbon in aldehydes and ketones due to the possible resonance structures.

The bonds to the carboxyl carbon lie in one plane with an angle of 120.

Carboxylic acids are aliphatic (RCOOH) and aromatic The higher members of aliphatic acids are known as fatty acids. Nomenclature of RCOOH C of carboxylic acid is included in the chain and is given number 1. In the name of the alkane corresponding to longest chain, the suffix e is replaced by oic acid.

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(i) Preparation (a) From primary alcohols and aldehydes

(b) From alkylbenzene

The alkyl chain in alkyl substituted benzene is completely oxidised to COOH irrespective of the length of the chain. Primary and secondary alkyl groups also get oxidized, only tertiary group remains unaffected.

(c) From nitriles and amides

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(d) From Grignard reagent

(e) From acyl halides and anhydrides

(f) From Esters

(ii) Physical Properties Lower members of carboxylic acids (upto 9-C) are liquids at room temperature, and have foul odour. Higher members are solid and odourless. Carboxylic acids have higher boiling point than alcohols of corresponding molecular mass due to extensive H-bonding. Carboxylic acids remain in associated (dimer) form in vapour state and in aprotic solvents (like organic solvents).

In protic solvents like carboxylic acids remain in dissociated form.

The solubility of carboxylic acids decreases with increasing number of C-atoms as the nonpolar hydrophobic alkyl part gets bigger. Carboxylic acids are soluble in organic solvents like benzene, ether, chloroform, etc.

Chemical reactions of carboxylic acids

Acidic character of carboxylic acids Carboxylic acids are weaker than mineral acids but stronger than alcohols and simple phenols.

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Carboxylic acids are stronger acids than phenol because carboxylate ion is more resonance stabilised than phenoxide ion. As in carboxylate ion resonance structure ve charge is on electronegative O-atoms while it is on less electronegative C-atoms in phenoxide ion resonance structure.

Alcohols are even less acidic as alkoxide ion shows no resonance. Carboxylic acids dissociate in water to give carboxylate ion and hydronium ion.

Higher the

value less is the acidic strength.

Effect of Substituents on the Acidic Strength of Carboxylic Acids Electron withdrawing group (EWG) increases the acidic strength as it increases the polarity (I effect) of OH bond facilitating the release of Electron withdrawing group stabilises the carboxylate ion by dispersing ve charge. Presence of electron donating group (EDG) decreases the acidic strength as it decreases the polarity of OH bond due to its +I effect. Also EDG destabilises the carboxylate ion by further increasing e-density towards the carboxylate ion.

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The effect of some

is as follows:

Closer the presence of EWG to the carboxylic group more is the acidic strength.

When carboxylic group is attached to vinyl or phenyl group its acidic strength increases due to resonance.

The presence of EWG increases the acidic strength in benzene ring while presence of EDG decreases the acidic strength.

Reactions (i) Formation of anhydrides

(ii) Esterification

(iii) Formation acyl chlorides

Thionyl chloride method is preferred because both the by-products are gaseous as a result pure product is obtained. (iv) Reaction with Ammonia

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(v) Reduction

Number of carbon atom remains the same. (vi) Sodalime decarboxylation

One carbon atom-is reduced in this method. (vii) Kolbes Electrolysis

In this method alkyl part of the carboxylic acid gets double in the product. (viii) Hell Volhard Zelinsky reaction: By this method substituted carboxylic acids can be prepared.

This reaction is given by only those carboxylic acids which have . X in -position of carboxylic acid can be replaced by any group in its reaction with aq KOH, alc. KCN, etc.

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(ix) Aromatic carboxylic acids undergo electrophilic substitution reaction. The COOH group attached to benzene ring is a deactivating group and is m-directing.

Aromatic carboxylic acids do not undergo Friedel-Crafts reaction.

Summary

Aldehydes, ketones and carboxylic acids have carboxyl group and are highly polar compounds.

Carboxylic acids although contain ketones.

group but do not give the reactions given by aldehydes and

Aldehydes and ketones have higher boiling points than the corresponding hydrocarbons and ethers due to higher polarity (stronger dipole-dipole interactions) Carboxylic acids have also higher boiling points due to extensive H-bonding. Carboxylic acids are stronger acids than phenols and alcohols but weaker than mineral acids. Aromatic acids are in general more acidic than aliphatic acids due to the presence of electron withdrawing benzene ring.

Higher the pKa value of an acid weaker is the acid, i.e., it is poor proton donor. Ketones are more polar and have higher boiling point than aldehydes of comparable molecular mass. Aldehydes are more reactive towards nucleophilic substitution reactions than ketones. Aldehydes oxidise to give carboxylic acids. Aldehydes on reduction give 1 alcohols. Ketones on reduction give 2 alcohols. Ketones are oxidised only under drastic conditions and breaking of CC bond takes place at the carboxyl group. Aldol condensation is given by only those aldehydes and ketones which have

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Cannizaros reaction is given by only those aldehydes which do not have Aldehydes and ketones can be converted to corresponding hydrocarbons (having same number of C-atoms) by Clemensons reduction and Wolf-Kishner reduction. Carboxylic acids on reduction give 1 alcohols. Sodalime decarboxylation method can be used to reduce a C-atom in carboxylic acids. Hell Volhard Zelinsky reaction is used to introduce a substitute like CN, X, OH, etc., at carboxylic acid. in a

Carbonyl group and carboxylic group both are ring deactivating and m-directing groups when attached to benzene ring. Aldehydes can be oxidised with mild oxidising agents like Tollens reagent and Fehlings solution but not ketones. Aromatic aldehydes are oxidised by Tollens reagent but not with Fehlings solution. Formic acid is the only acid which gives the tests given by aldehyde groups. This is because formic acid have

group and can be easily oxidised to

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