From this chapter, you will be able to write the common and IUPAC names of aldehydes, ketones and carboxylic acids. You will also be able to write the structures of the compounds containing functional groups namely carbonyl and carboxyl groups. Description of the important methods of preparation and reactions of these classes of compounds. Correlation of physical properties and chemical reactions of aldehydes, ketones and carboxylic acids with their structures. Explanation of mechanism of a few selected reactions of aldehydes and ketones are also given. You will also be able to understand various factors affecting the acidity of carboxylic acids and their reactions. Description of the uses of aldehydes, ketones and carboxylic acids are also given.
(i)
(ii)
(iii)
(iv)
(v)
(vi)
The molecular masses of the given compounds are in the range 44 to 46. CH3CH2OH undergoes extensive intermolecular H-bonding, resulting in the association of molecules. Therefore, it has the highest boiling point. CH3CHO is more polar than CH3OCH3and so CH3CHO has stronger intermolecular dipole - dipole attraction than CH3OCH3┹”¦CH3CH2CH3has only weak van der Waals force. Thus, the arrangement of the given compounds in the increasing order of their boiling points is given by:
CH3CH2CH3< CH3OCH3< CH3CHO < CH3CH2OH
(i)
The +I effect of the alkyl group increases in the order:
Ethanal < Propanal < Propanone < Butanone
The electron density at the carbonyl carbon increases with the increase in the +I effect. As a result, the chances of attack by a nucleophile decrease. Hence, the increasing order of the reactivities of the given carbonyl compounds in nucleophilic addition reactions is:
Butanone < Propanone < Propanal < Ethanal
(ii)
The +I effect is more in ketone than in aldehyde. Hence, acetophenone is the least reactive in nucleophilic addition reactions. Among aldehydes, the +I effect is the highest in p-tolualdehyde because of the presence of the electron-donating -CH3 group and the lowest in p-nitrobezaldehyde because of the presence of the electron-withdrawing -NO2 group. Hence, the increasing order of the reactivities of the given compounds is:
Acetophenone < p-tolualdehyde < Benzaldehyde < p- Nitrobenzaldehyde
< p-Nitrobenzaldehyde
(i) 3-Phenylpropanoic acid
(ii) 3-Methylbut-2-enoic acid
(iii) 2-Methylcyclopentanecarboxylic acid
(iv) 2,4,6-Trinitrobenzoic acid
(i)
(ii)
(iii)
(iv)
The +I effect of -CH3group increases the electron density on the O-H bond. Therefore, release of proton becomes difficult. On the other hand, the -I effect of F decreases the electron density on the O-H bond. Therefore, proton can be released easily. Hence, CH2FCO2H is a stronger acid than CH3CO2H.
(ii)
F has stronger -I effect than Cl. Therefore, CH2FCO2H can release proton more easily than CH2ClCO2H. Hence, CH2FCO2H is stronger acid than CH2ClCO2H.
(iii)
Inductive effect decreases with increase in distance. Hence, the +I effect of F in CH3CHFCH2CO2H is more than it is in CH2FCH2CH2CO2H. Hence, CH3CHFCH2CO2H is stronger acid than CH2FCH2CH2CO2H.
(iv)
Due to the -I effect of F, it is easier to release proton inthe case of compound (A). However, in the case of compound (B), release of proton is difficult due to the +I effect of -CH3group. Hence, (A) is a stronger acid than (B).
(i) Cyanohydrin:
Cyanohydrins are organic compounds having the formula RR“²C(OH)CN, where R and R“² can be alkyl or aryl groups.
Aldehydes and ketones react with hydrogen cyanide (HCN) in the presence of excess sodium cyanide (NaCN) as a catalyst to field cyanohydrin. These reactions are known as cyanohydrin reactions.
Cyanohydrins are useful synthetic intermediates.
(ii) Acetal:
Acetals are gem - dialkoxy alkanes in which two alkoxy groups are present on the terminal carbon atom. One bond is connected to an alkyl group while the other is connected to a hydrogen atom.
When aldehydes are treated with two equivalents of a monohydric alcohol in the presence of dry HCl gas, hemiacetals are produced that further react with one more molecule of alcohol to yield acetal.
(iii) Semicarbarbazone:
Semicarbazones are derivatives of aldehydes and ketones produced by the condensation reaction between a ketone or aldehyde and semicarbazide.
Aldehydes and ketones react with hydrogen cyanide (HCN) in the presence of excess sodium cyanide (NaCN) a a catalyst to field cyanohydrin. these reactions are called cyanohydrin reactions. These are useful synthetic intermediates. Semicarbazones are useful for identification and characterization of aldehydes and ketones.
(iv) Aldol:
A Ã�²–hydroxy aldehyde or ketone is known as an aldol. It is produced by the condensation reaction of two molecules of the same or one molecule each of two different aldehydes or ketones in the presence of a base.
(v) Hemiacetal:
Hemiacetals are α - alkoxyalcohols
General structure of a hemiacetal
Aldehyde reacts with one molecule of a monohydric alcohol in the presence of dry HCl gas.
(vi) Oxime:
Oximes are a class of organic compounds having the general formula RR“²CNOH, where R is an organic side chain and R“² is either hydrogen or an organic side chain. If R“² is H, then it is known as aldoxime and if R“² is an organic side chain, it is known as ketoxime.
On treatment with hydroxylamine in a weakly acidic medium, aldehydes or ketones form oximes.
(vii) Ketal:
Ketals are gem - dialkoxyalkanes in which two alkoxy groups are present on the same carbon atom within the chain. The other two bonds of the carbon atom are connected to two alkyl groups.
Ketones react with ethylene glycol in the presence of dry HCl gas to give a cyclic product known as ethylene glycol ketals.
(viii) Imine:
Imines are chemical compounds containing a carbon nitrogen double bond.
Imines are produced when aldehydes and ketones react with ammonia and its derivatives.
(ix) 2, 4 - DNP - derivative:
2, 4 - dinitrophenylhydragones are 2, 4 - DNP - derivatives, which are produced when aldehydes or ketones react with 2, 4 - dinitrophenylhydrazine in a weakly acidic medium.
To identify and characterize aldehydes and ketones, 2, 4 - DNP derivatives are used.
(x) Schiff's base:
Schiff's base (or azomethine) is a chemical compound containing a carbon-nitrogen double bond with the nitrogen atom connected to an aryl or alkyl group-but not hydrogen. They have the general formula R1R2C = NR3. Hence, it is an imine.
It is named after a scientist, Hugo Schiff.
Aldehydes and ketones on treatment with primary aliphatic or aromatic amines in the presence of trace of an acid yields a Schiff's base.
(i) 4-methylpentanal
(ii) 6-Chloro-4-ethylhexan-3-one
(iii) But-2-en-1-al
(iv) Pentane-2,4-dione
(v) 3,3,5-Trimethylhexan-2-one
(vi) 3,3-Dimethylbutanoic acid
(vii) Benzene-1,4-dicarbaldehyde
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
(i) CH3CO(CH2)4CH3
IUPAC name: Heptan-2-one
Common name: Methyl n-propyl ketone
(ii) CH3CH2CHBrCH2CH(CH3)CHO
IUPAC name: 4-Bromo-2-methylhaxanal
Common name: (Ã�³-Bromo-α-methyl-caproaldehyde)
(iii) CH3(CH2)5CHO
IUPAC name: Heptanal
(iv) Ph-CH=CH-CHO
IUPAC name: 3-phenylprop-2-enal
Common name: �²-Pheynolacrolein
(v)
IUPAC name: Cyclopentanecarbaldehyde
(vi)PhCOPh
IUPAC name: Diphenylmethanone
Common name: Benzophenone
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(i)
(ii)
(iii)
(iv)
(v)
Aldehydes and ketones having at least one α-hydrogen undergo aldol condensation. The compounds (ii) 2-methylpentanal, (v) cyclohexanone, (vi) 1-phenylpropanone, and (vii) phenylacetaldehyde contain one or more α-hydrogen atoms. Therefore, these undergo aldol condensation.
Aldehydes having no α-hydrogen atoms undergo Cannizzaro reactions. The compounds (i) Methanal, (iii) Benzaldehyde, and (ix) 2, 2-dimethylbutanal do not have any α-hydrogen. Therefore, these undergo cannizzaro reactions.
Compound (iv) Benzophenone is a ketone having no α-hydrogen atom and compound (viii) Butan-1-ol is an alcohol. Hence, these compounds do not undergo either aldol condensation or cannizzaro reactions.
Aldol condensation
(ii)
(v)
(vi)
(vii)
Cannizzaro reaction
(i)
(iii)
(ix)
(i) On treatment with dilute alkali, ethanal produces 3-hydroxybutanal gives butane-1, 3-diol on reduction.
(ii) On treatment with dilute alkali, ethanal gives 3-hydroxybutanal which on heating produces but-2-enal.
(iii) When treated with Tollen's reagent, But-2-enal produced in the above reaction produces but-2-enoic acid .
(i) Taking two molecules of propanal, one which acts as a nucleophile and the other as an electrophile.
(ii) Taking two molecules of butanal, one which acts as a nucleophile and the other as an electrophile.
(iii) Taking one molecule each of propanal and butanal in which propanal acts as a nucleophile and butanal acts as an electrophile.
(iv) Taking one molecule each of propanal and butanal in which propanal acts as an electrophile and butanal acts as a nucleophile.
It is given that the compound (with molecular formula C9H10O) forms 2, 4-DNP derivative and reduces Tollen's reagent. Therefore, the given compound must be an aldehyde.
Again, the compound undergoes cannizzaro reaction and on oxidation gives 1, 2-benzenedicarboxylic acid. Therefore, the -CHO group is directly attached to a benzene ring and this benzaldehyde is ortho-substituted. Hence, the compound is 2-ethylbenzaldehyde.
The given reactions can be explained by the following equations.
An organic compound A with molecular formula C8H16O2 gives a carboxylic acid (B) and an alcohol (C) on hydrolysis with dilute sulphuric acid. Thus, compound A must be an ester. Further, alcohol C gives acid B on oxidation with chromic acid. Thus, B and C must contain equal number of carbon atoms.
Since compound A contains a total of 8 carbon atoms, each of B and C contain 4 carbon atoms.
Again, on dehydration, alcohol C gives but-1-ene. Therefore, C is of straight chain and hence, it is butan-1-ol.
On oxidation, Butan-1-ol gives butanoic acid. Hence, acid B is butanoic acid.
Hence, the ester with molecular formula C8H16O2 is butylbutanoate.
All the given reactions can be explained by the following equations.
(i) When HCN reacts with a compound, the attacking species is a nucleophile, CN - . Therefore, as the negative charge on the compound increases, its reactivity with HCN decreases. In the given compounds, the +I effect increases as shown below. It can be observed that steric hindrance also increases in the same.
Hence, the given compounds can be arranged according to their increasing reactivities toward HCN as:
Di-tert-butyl ketone < Methyl tert-butyl ketone < Acetone < Acetaldehyde
(ii) After losing a proton, carboxylic acids gain a negative charge as shown:
Now, any group that will help stabilise the negative charge will increase the stability of the carboxyl ion and as a result, will increase the strength of the acid. Thus, groups having +I effect will decrease the strength of the acids and groups having - I effect will increase the strength of the acids. In the given compounds, - CH3group has +I effect and Br - group has - I effect. Thus, acids containing Br - are stronger.
Now, the +I effect of isopropyl group is more than that of n-propyl group. Hence, (CH3)2CHCOOH is a weaker acid than CH3CH2CH2COOH.
Also, the - I effect grows weaker as distance increases. Hence, CH3CH(Br)CH2COOH is a weaker acid than CH3CH2CH(Br)COOH.
Hence, the strengths of the given acids increase as:
(CH3)2CHCOOH < CH3CH2CH2COOH < CH3CH(Br)CH2COOH < CH3CH2CH(Br)COOH
(iii) As we have seen in the previous case, electron-donating groups decrease the strengths of acids, while electron-withdrawing groups increase the strengths of acids. As methoxy group is an electron-donating group, 4-methoxybenzoic acid is a weaker acid than benzoic acid. Nitro group is an electron-withdrawing group and will increase the strengths of acids. As 3,4-dinitrobenzoic acid contains two nitro groups, it is a slightly stronger acid than 4-nitrobenzoic acid. Hence, the strengths of the given acids increase as:
4-Methoxybenzoic acid < Benzoic acid < 4-Nitrobenzoic acid
< 3,4-Dinitrobenzoic acid
(i) Propanal and propanone can be distinguished by the following tests.
(a) Tollen's test
Propanal is an aldehyde. Thus, it reduces Tollen's reagent. But, propanone being a ketone does not reduce Tollen's reagent.
(b) Fehling's test
Aldehydes respond to Fehling's test, but ketones do not.
Propanal being an aldehyde reduces Fehling's solution to a red-brown precipitate of Cu2O, but propanone being a ketone does not.
(c) Iodoform test:
Aldehydes and ketones having at least one methyl group linked to the carbonyl carbon atom respond to iodoform test. They are oxidized by sodium hypoiodite (NaOI) to give iodoforms. Propanone being a methyl ketone responds to this test, but propanal does not.
(ii) Acetophenone and Benzophenone can be distinguished using the iodoform test.
Iodoform test:
Methyl ketones are oxidized by sodium hypoiodite to give yellow ppt. of iodoform. Acetophenone being a methyl ketone responds to this test, but benzophenone does not.
(iii) Phenol and benzoic acid can be distinguished by ferric chloride test.
Ferric chloride test:
Phenol reacts with neutral FeCl3 to form an iron-phenol complex giving violet colouration.
But benzoic acid reacts with neutral FeCl3 to give a buff coloured ppt. of ferric benzoate.
(iv) Benzoic acid and Ethyl benzoate can be distinguished by sodium bicarbonate test.
Sodium bicarbonate test:
Acids react with NaHCO3 to produce brisk effervescence due to the evolution of CO2 gas.
Benzoic acid being an acid responds to this test, but ethylbenzoate does not.
(v) Pentan-2-one and pentan-3-one can be distinguished by iodoform test.
Iodoform test:
Pentan-2-one is a methyl ketone. Thus, it responds to this test. But pentan-3-one not being a methyl ketone does not respond to this test.
(vi) Benzaldehyde and acetophenone can be distinguished by the following tests.
(a) Tollen's Test
Aldehydes respond to Tollen's test. Benzaldehyde being an aldehyde reduces Tollen's reagent to give a red-brown precipitate of Cu2O, but acetophenone being a ketone does not.
(b) Iodoform test
Acetophenone being a methyl ketone undergoes oxidation by sodium hypoiodite (NaOI) to give a yellow ppt. of iodoform. But benzaldehyde does not respond to this test.
(vii) Ethanal and propanal can be distinguished by iodoform test.
Iodoform test
Aldehydes and ketones having at least one methyl group linked to the carbonyl carbon atom responds to the iodoform test. Ethanal having one methyl group linked to the carbonyl carbon atom responds to this test. But propanal does not have a methyl group linked to the carbonyl carbon atom and thus, it does not respond to this state.
(i) Acetylation
The introduction of an acetyl functional group into an organic compound is known as acetylation. It is usually carried out in the presence of a base such as pyridine, dimethylaniline, etc. This process involves the substitution of an acetyl group for an active hydrogen atom. Acetyl chloride and acetic anhydride are commonly used as acetylating agents.
For example, acetylation of ethanol produces ethyl acetate.
(ii) Cannizzaro reaction:
The self- oxidation reduction (disproportionation) reaction of aldehydes having no α-hydrogens on treatment with concentrated alkalis is known as the Cannizzaro reaction. In this reaction, two molecules of aldehydes participate where one is reduced to alcohol and the other is oxidized to carboxylic acid.
For example, when ethanol is treated with concentrated potassium hydroxide, ethanol and potassium ethanoate are produced.
(iii) Cross-aldol condensation:
When aldol condensation is carried out between two different aldehydes, or two different ketones, or an aldehyde and a ketone, then the reaction is called a cross-aldol condensation. If both the reactants contain α-hydrogens, four compounds are obtained as products.
For example, ethanal and propanal react to give four products.
(iv) Decarboxylation:
Decarboxylation refers to the reaction in which carboxylic acids lose carbon dioxide to form hydrocarbons when their sodium salts are heated with soda-lime.
Decarboxylation also takes place when aqueous solutions of alkali metal salts of carboxylic acids are electrolyzed. This electrolytic process is known as Kolbe's electrolysis.
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
(ix)
(x)
(xi)
(i) Cyclohexanones form cyanohydrins according to the following equation.
In this case, the nucleophile CN - can easily attack without any steric hindrance. However, in the case of 2, 2, 6 trimethylcydohexanone, methyl groups at α-positions offer steric hindrances and as a result, CN - cannot attack effectively.
For this reason, it does not form a cyanohydrin.
(ii) Semicarbazide undergoes resonance involving only one of the two - NH2 groups, which is attached directly to the carbonyl-carbon atom.
Therefore, the electron density on - NH2 group involved in the resonance also decreases. As a result, it cannot act as a nucleophile. Since the other - NH2 group is not involved in resonance; it can act as a nucleophile and can attack carbonyl-carbon atoms of aldehydes and ketones to produce semicarbazones.
(iii) Ester along with water is formed reversibly from a carboxylic acid and an alcohol in presence of an acid.
If either water or ester is not removed as soon as it is formed, then it reacts to give back the reactants as the reaction is reversible. Therefore, to shift the equilibrium in the forward direction i.e., to produce more ester, either of the two should be removed.
% of carbon = 69.77 %
% of hydrogen = 11.63 %
% of oxygen = {100 - (69.77 + 11.63)}%
= 18.6 %
Thus, the ratio of the number of carbon, hydrogen, and oxygen atoms in the organic compound can be given as:
= 5.81:11.63:1.16
= 5:10:1
Therefore, the empirical formula of the compound is C5H10O. Now, the empirical formula mass of the compound can be given as:
5 × 12 + 10 ×1 + 1 × 16
= 86
Molecular mass of the compound = 86
Therefore, the molecular formula of the compound is given by C5H10O.
Since the given compound does not reduce Tollen's reagent, it is not an aldehyde. Again, the compound forms sodium hydrogen sulphate addition products and gives a positive iodoform test. Since the compound is not an aldehyde, it must be a methyl ketone.
The given compound also gives a mixture of ethanoic acid and propanoic acid.
Hence, the given compound is Pentan-2-one.
The given reactions can be explained by the following equations:
Resonance structures of phenoxide ion are:
It can be observed from the resonance structures of phenoxide ion that in II, III and IV, less electronegative carbon atoms carry a negative charge. Therefore, these three structures contribute negligibly towards the resonance stability of the phenoxide ion. Hence, these structures can be eliminated. Only structures I and V carry a negative charge on the more electronegative oxygen atom.
Resonance structures of carboxylate ion are:
In the case of carboxylate ion, resonating structures I”² and II”² contain a charge carried by a more electronegative oxygen atom.
Further, in resonating structures I”² and II”², the negative charge is delocalized over two oxygen atoms. But in resonating structures I and V of the phexoxide ion, the negative charge is localized on the same oxygen atom. Therefore, the resonating structures of carboxylate ion contribute more towards its stability than those of phenoxide ion. As a result, carboxylate ion is more resonance-stabilized than phenoxide ion. Hence, carboxylic acid is a stronger acid than phenol.
(iv) 
