Carboxylic acids and Amines(Synopsis)

CARBOXYLIC ACIDS
 Methods of preparation
By Oxidation of alcohols, aldehydes and ketones Using oxidising agents K2Cr2O7/H2SO4(dil.) or alkaline KMnO4
 Aldehydes can be oxidised to corresponding carboxylic acid even with mild oxidising agents such as ammoniacal
AgNO3 (Tollen’s reagent).
 Ketones and 2° alcohols can also form acids with less number of C-atoms. Oxidation of ketone occurs with
difficulty using strong oxidising agents like acidified K2Cr2O7.
 CrO3,/ H2SO4 in acetone solution selectively oxidise 1o alcohols to -COOH and 2° alcoholic group to ketone
respectively without affecting —CC— and >C=C<.
 MnO2 in acetone selectively oxidises 1° allylic alcohols to aldehydes.
 Alkaline KMnO4 oxidises 1o alcohol to carboxylic acid but its use is not preferred when alcohols has also double or
triple bond. 3o alcohols are not oxidized due to the lack of  hydrogen.
(ii) By hydrolysis of alkane nitriles with dil. Mineral acid or with alkali. Intermediate in this reaction is amide
(iii) By hydrolysis of terminal trihaloalkanes: With an aqueous alkali solution.
(iv) By hydrolysis of amides, anhydrides and acid halides: With a boiling dil. acid or alkali.
(v) By carbonation of Grignard reagents: When CO2 (solid ice) is passed through an ethereal solution of R—MgX. an
addition product is formed which on hydrolysis with a mineral acid yields a carboxylic acid.
 Physical properties The lower members are highly soluble in water but the solubility decreases with increase in
molecular mass. The solubility in water is due to the formation of H-bonds with water. Carboxylic acids are also soluble in
less polar solvents like ether , alcohol , benzene etc.
 Boiling points of carboxylic acids are higher than those of alcohols of same molecular mass. This is due to intermolecular
H-bonding between two acid molecules (Dimers). The lower members exist as dimers in vapour phase and in aqueous
solution, but in the liquid phase they exist as polymers.
 Acidity of carboxylic acids
(i) The acidity of carboxylic acid is due to powerful resonance stabilization of the anion.
(ii) Electron attracting group (-I effect) stabilises the anion and therefore increases ionization of the acid. The greater is the
-I effect, greater will be the acidic strength, i.e.,
Cl3CCOOH>Cl2CHCOOH>ClCH2COOH>CH3COOH and
FCH2COOH>ClCH2COOH>BrCH2COOH>ICH2COOH
(iii) Inductive effect is stronger at -position than -position and than -position.
(iv) Electron releasing group (+1 effect) destabilises the anion and so decreases the acidity, i.e.,
HCOOH > CH3COOH>CH3CH2COOH>(CH3)2CH—COOH>(CH3)3C—COOH
 Chemical properties
Salt formation: Monocarboxylic acids react with Na, K, NaOH, NaHCO3 or Na2CO3, etc forming corresponding salt.
 Reaction with organometallic reagents: RCOOH reacts with R’MgX (GR) rapidly to give an alkane (R’H) corresponding
to the alkyl group of Grignard reagent. (b) Reactions involving —OH group:
 Ester formation: RCOOH reacts with ROH in presence of conc. H2SO4 or dry HCI gas, to form esters.
 Formation of acid chlorides: By the action of PCl5, PCl3, SOCl2/pyridine carboxylic acids form acid halides
 Formation of acid anhydrides: Dehydration of monocarboxylic acids on heating with P2O5 gives acid anhydride or when
sodium salt of acid is heated with acid chloride, acid anhydrides are formed.
 Formation of amides and nitriles: Monocarboxylic acids on treatment with NH3 form ammonium salts which on heating
lose a molecule of water to form corresponding amides. The acid amide (RCONH2) on heating with P2O5 loses one more
water molecule forming a cyanide (RCN) or nitrile.
 Reduction:. By using LiAlH4(LAH) in ether solution or ruthenium (Ru) and carbon as catalyst or BH3/THF or H2 in
presence of copper chromite (CuO + Cr2O3), the —COOH group is reduced to —CH2OH (1° alcohol).
 Decarboxylation: On heating sodium salt of acid with sodalime, forms an alkane with the elimination of CO 2.
 Dry distillation of calcium salts of monocarboxylic acids: Calcium acetate gives acetone and calcium formate gives
formaldehyde. However, when a mixture of calcium acetate and calcium formate is heated, acetaldehyde is formed.
Calcium salt of diacarboxylic acids form cyclic ketones on heating. For eg. Calcium adipate forms cyclopentanone.
 Borodine Hunsdiecker reaction: When silver salt of monocarboxylic acid is refluxed with halogens in CCl4. An alkyl
halide is formed
 Schmidt reaction: Monocarboxylic acids react with hydrazoic acid (N3H) in presence of conc. H2SO4 to give a primary
amine containing one C-atom less than the parent acid.
 Halogenation: The -hydrogen atoms are highly reactive due to the presence of electronegative —COOH group. On
halogenation (Cl2 or Br2) in presence of catalyst a (red P or Fe, etc.,), the -H atoms are replaced by chlorine or bromine
atom.. This reaction is known as Hell-Volhard-Zelinsky (HVZ) reaction.
 Oxidation: Carboxylic acids having at least one -hydrogen convert into -hydroxy carboxylic acids on oxidation with
H2O2. Oxidation of -methylene group takes place by SeO2 to give -keto acid.\
 Decarboxylation: -keto acid and acids containing C = C at - position and gem dicarboxylic acids undergo
decarboxylation on heating.
 Hydroxy acids i.e. compounds containing both OH & COOH acid within the molecule on heating form cyclic esters called
lactones. -hydroxy acids forms five membered ring (-lactones). -hydroxy acids form 6 membered ring (-lactones).
Amines
 Amines are derivatives of ammonia in which one or more H atoms have been replaced by corresponding number of alkyl
groups. In addition to the above amines, tetra alkyl derivatives similar to ammonium salts also exist which are called
quaternary ammonium salts.
 Methods of preparation
(i) Ammonolysis of alkyl halides (Hofmann’s method) By heating an alkyl halide with an excess of aqueous or
alcoholic ammonia in a sealed tube at 100°C.
 A serious disadvantage of this method is the formation of mixture of amines.
 yields is maximum for 1o alkyl halides & is of no use with 3o alkyl halides because they undergo elimination to
form alkene.
(ii) Ammonolysis of alcohol: By passing a mixture of alcohol and excess of ammonia vapours over heated alumina or
thoria at 350°C.
(iii) Reduction of nitroalkanes: By the reduction of nitroalkanes with Sn/HCl or Zn/HCl or LiAlH4, the -NO2 group gets
reduced into -NH2 group.
(iv) Reduction of alkane nitriles: When an alkyl cyanide (nitrile) is reduced by Na/C2H5OH, the -CN group gets reduced
to -CH2 NH2 group.It is called Mendius reaction.Reduction can also be crried out with H2/Raney Ni or LiAlH4
(v) Reduction of amides: with LiAlH4 or Na/alcohol amides give p-amine containing same number of C atoms.
(vi) Reduction of Oximes: By Na/alcohol or LiAlH4 or H2/Ni gives 1° amine.
(vii) Hofmann’s Bromamide reaction : By this method an amide is converted into 1oamine containing one carbon atom
less. The amide is heated with Br2 and concentrated aqueous KOH solution.
(viii) Gabriel phthalimide reaction: Phthalimide is reacted with ethanolic solution of KOH to form potassium phthalimide
which on heating with RX gives N-alkyl phthalimide. Which form pure primary amine with dilute HCl .
(ix) Hydrolysis of isocyanides or isocyanates: with boiling aq. solution of KOH or NaOH gives primary amine.
(x) Reductive Amination of aldehydes & ketones Aldehydes or ketones when reduced with H2/Raney Ni in presence of
excess of NH3 at about 150°C under pressure forms 1° amine through the intermediate formation of an imine.
Separation of amines: The amine mixture may be separated by the following methods.
(i) Fractional distillation: The boiling points of 1o, 2° and 3° amines are quite different and thus these can be separated
by fractional distillation. This method is used satisfactorily in industry.
(ii) Hofmann’s method: The mixture of three amines is treated with diethyloxalate. The 1° amine forms a solid dialkyl
oxamide, 2° amine gives a liquid oxamic ester and 3° amine does not react.
(iii) Hinsberg’s method: It involves the treatment of the mixture with Hinsberg’s reagent (benzene sulphonyl chloride,
C6H5SO2Cl). The solution is then made alkaline with aqueous KOH solution where 1° amine forms N-alkylbenzene
sulphonamide (soluble in KOH). 2° amine forms N,N-dialkyl benzene sulphonamide (insoluble in KOH) & 3° amine does
not react.
Physical Properties: Amines are polar like NH3 & have comparatively higher boiling points than non-polar compounds of
similar molecular masses. This is due to the presence of intermolecular H-bonding. The boiling points rise gradually with
increase of molecular mass. Lower members are soluble in water because of the formation of H-bonding with water but
the solubility decreases with increase of molecular mass.
Chemical properties
(i) Basic nature: Amines form salts with mineral acids (HCl or H2SO4).
 The basic nature of aliphatic amines depends upon (i) inductive effect of alkyl group (ii) steric hindrance and (iii)
salvation effect
 In the gaseous phase the basic character of amines increases with increase in alkyl group
i.e. 3o amine > 2o amine > 1o amine > ammonia.
 In aqueous solution 3rd alkyl group decreases the basic character due to steric effect and the order is
NH3 < (CH3)3 N < CH3NH2 < (CH3)2NH.
(ii) Alkylation: With alkyl halide the H atoms of amino group are successively replaced alkyl groups and thus a mixture of
1o amine , 2o amine , 3o amine and ultimately quaternary ammonium salt is produced.
 The quaternary ammonium salt has the formula R4N+X-. When this salt is treated with silver oxide , R4N+OH- is
formed. This quaternary ammonium hydroxide on heating decomposes to yield H2O , 3o amine and an alkene.
Elimination proceeds in such a way that least substituted alkene is the major product. It is called Hoffmann
elimination. For e.g.

(iii) Acylation: Primary (1o) and secondary (2°) amines react with acid chlorides or acid anhydrides to give acyl
derivatives (N-substituted amides). Tertiary amines do not react since they do not have replacable H atom.
(iv) Reaction with Grignard reagents: 1oand2° amines form alkanes with Grignard reagents by providing H atom of
amines to alkyl (R) group of GR.
(v) Carbylamine reaction: Primary amines on heating with CHCl3 in presence of alcoholic KOH produce isocyanides
(carbylamine) which possess pungent (unpleasant) odour. It is a test of primary amines only and is used to distinguish 1 o
amines from 2° and 3° amines.
(vi) Reaction with nitrous acid (NaNO2 + dil. HC1): Primary amines form alcohols with nitrous acid, & N2 gas is
eliminated. 2o amines form yellow oily product, 3o amines form salts. (A distinction between 1o, 2°&3° amines)
(vii) Reaction with carbon disulphide: Primary amines on warming with CS2 to form alkyl derivative of dithiocarbamic
acid which is decomposed by HgCl2 to give alkyl isothiocyanate (RN=C=S) having pungent smell of mustard oil. This is
known as Hofmann’s mustard oil reaction.
(viii) Oxidation(a) 10 amines are oxidised with KMnO4 into aldimine or ketimine which on hydrolysis form aldehydes &
ketones respectively.
(b) Secondary amines on oxidation with KMnO4 form tetra-alkyl hydrazine (R2N—NR2) and with caro’s acid (H2SO5) give
dialkyl hydroxylamine (R2NOH).
(c) Tertiary amines are not oxidised by KMnO4 but are oxidised by caro’s acid or H2O2 or O3 or Fenton’s reagent to amine
oxides.
(ix) Condensation with aldehyde: 10amines condense with aldehydes to produce aldimine (Schiff’s base).
(x) Reaction with carbonyl chloride (Phosgene): Primary amines on heating with carbonyl chloride (COCl 2) form N, N’-
dialkyl urea. Secondary amine forms N,N,N’,N’-tetra alkyl urea.
Cyanides and isocyanides
Cyanides and isocyanide are functional isomers. cyanide and isocyanide groups are known as Ambient nucleophiles.
Preparation of cyanides: Alkyl cyanides can be prepared (I) By treating alkyl halides with potassium cyanide..
(II)By dehydration of primary acid amides (RCONH2) or aldoximes with phosphorous pentoxide.
Physical properties .Lower alkyl cyanides are colourless liquids but higher members are pleasant smelling
substances.Cyanides have dipole moment in the range of 4.0 D. Lower alkyl cyanides are water soluble but solubility
sharply decreases with increase in molecular mass..
Chemical properties.Alkyl cyanides,on (i)partial hydrolysis form 1o acid amides(ii) complete hydrolysis form carboxylic
acids(iii)Complete reduction of alkyl cyanides give primary amines (Mendius Reduction), while on partial reduction with
stannous chloride & hydrochloric acid, aldehydes are formed.(Stephen’s reaction)
Preparation of isocyanides :these are obtained (i)by reaction of alkyl halides with silver cyanide.
(ii) Primary amines on heating with chloroform and alcoholic potash yield isocyanide(Carbylamine reaction).
Physical properties Lower alkyl isocyanides, are colourless poisonous liquids, less polar than isomeric cyanides.
Isocyanides have lower boiling point than isomeric cyanides, but higher than corresponding halides.
Chemical properties Alkyl isocyanides on hydrolysis, with dil. Acids yield primary amines and formic acid On
reduction,isocyanide forms 2o amines.Isocyanides easily undergo addition reactions with O2,S etc. at isocyanide
carbon, first with an electrophile and then react with a nucleophile.