Unit-II-CarboxylicAcid
Carboxylicacids are organic acids characterized by the presence of
a Carboxyl group. It has the formula. usually written –
COOH or - CO2H. Carboxylic acids are Bronsted-Lowry acids-
they are proton donors. Salts and anions of carboxylicacids are
called carboxylates. Organic compounds with alcohols are known
as esters.
Methods of Preparation of Carboxylic Acids:
a. From primary alcohols and aldehydes:
Primary alcohols are readily oxidized to carboxylic acids with common
oxidising agents such as potassium permanganate (KMnO4 ) in neutral,
acidic or alkaline media.
The acid is first obtained as its potassium salt, which on treatment with
a mineral acid gives the carboxylic acid.
Oxidation with K2Cr2O7 or CrO3 in acidic medium often gives some
amount of esters. Hence the oxidation by KMnO4 is preferred.
Readily available aldehydes can also be used to obtain carboxylic
acids, which may be oxidized even by milder oxidising agents.
b. From nitriles:
Hydrolysis of nitriles with aqueous acid or alkali gives carboxylic
acids.
c. From Grignard's reagent:
Grignards reagents react with carbon dioxide to form salts of
carboxylic acids which give carboxylic acids on acidification with
mineral acids.
Physical properties:
a. Physical state:
1. The first three acids are colourless, pungent - smelling liquids. The acids
from butyric to non anoic are oily liquids. Butyric acid has odour of rancid
butter. The acids higher than decanoicacid are odour less solids
2. Boiling points:
Organic acids have high boiling points. It is due to
a. Inter molecular hydrogen bondings
b. Strong van der Waals forces due to their polar nature
Lower members exist as
a. Dimers in the aqueous solutions and vapour phase
b. Polymers in the liquid phase
Higher boiling points of acids relative to alcohols are due to the higher
degree and strength of hydrogen bonding in them (because of the presence
of two oxygen atoms)
3. Solubility:
The first few members are highly soluble in water. This solubility is due to
the hydrogen bonding between carboxylic acid and water
The solubility decreases with the increase in molecular masses aromatic
acids like benzoic acids are less soluble in water due to large number of
C-atoms in them. Carboxylic acids are soluble in organic solvents like
alcohol, ether and benzene.
Chemical properties:
Acidic nature:
The aqueous solutions of carboxylic acids dissociate as follows:
Since they liberate hydrogen ion s in solution, they are acidic.
However they are weaker than mineral acids like HCI, HNO3 etc. But
stronger acids than alcohols and phenols.
Carboxylic compounds are amongst the most acidic organic
compounds we have studied this far. This can be explained as follows:
Carboxylic acids as well as carboxylate ion both are stabilized by
resonance. However, carboxylate ion is more stabilized by resonance
because its contributing structures are exactly identical. The
contributing structures of carboxylic acid involve charge separation.
Since carboxylate ion is more stabilized by resonance than carboxylic
acid therefore equilibrium in above reaction lies very much in forward
direction i.e., in favor of ionized form. Hence carboxylic acid behave
as strong acids.
Carboxylic acids are stronger acids than phenols. It can be understood
by comparing the hybrid structures of carboxylate ion and phenoxide
ions. In carboxylate ion, the negative charge is equally distributed over
two electronegative atoms (oxygen atoms) while in phenoxide ion, it is
present only on one oxygen. Thus, carboxylate ion is more stabilized as
compared to phenoxide ion. Hence, carboxylic acids ionize to the
greater extent than phenols furnishing higher concentration of H+ ions.
Therefore carboxylic acids behave as stronger acids than phenols.
1. Esterfication (acid to ester):
Carboxylic acids react with alcohols in the presence of few drops of
conc. H2SO4 to form esters.
When dry hydrogen chloride is used in this reaction, we called it
Fischer Esterfication.
2. Action with SOCl2 [acid to acid chloride]:
Carboxylic acids react with SOCl2 to form acid chlorides.
3. Formation of anhydride (dehydration):
Acid on heating with a phosphorus pentoxide to form acid anhydrides.
4. Decaboxylation:
Simple mono carboxylic acids donot lose carbon dioxide
(decarboxylation) when heated alone. However, when sodium salt of
the carboxylic acids are heated with sodalime (NaOH+CaO), they
yield hydrocarbons.
The reaction is known as Kolbe's electrolysis.
5. Reduction:
Acids are not easily reduced by catalytic hydrogenation or with
sodium and ethanol. Strong reducing agent as
lithiumaluminiumhydride reduces an acid into primary alcohol
6. Halogenations:[ HVZ reaction.]
When carboxylic acids react with chlorine or bromine in the
presence of red phosphorous, the α-hydrogen atoms are replaced by
halogen atoms. It is called Hell–Volhard-Zelinsky (HVZ)
reaction.
Acetic acid reacts with chlorine in presence of red phosphorus to form
chloroacetic acid, dichloroacetic acid or trichloro aceticacid depending
on the quantity of chlorine reacting.
Organic compounds containing Nitrogen
Introduction:
Functional groups containing nitrogen are present in a variety of
naturally occurring and manmade organic compounds. These
functional groups impart physico-chemical characteristics to these
molecules. There are many functional groups, which contain one or
more nitrogen atoms. Some categories of compounds based on these
functional groups Include nitro compounds, amines, cyanides,
isocyanides and diazo compounds.
Classification:
Amines are regarded as the alkyl or aryl derivatives of ammonia.
They are obtained by the replacement of one or more hydrogen
atoms of ammonia by alkyl or aryl groups. They are classified into
primary, secondary or tertiary amines depending upon whether two
or three H atoms of ammonia have been replaced by alkyl or aryl
groups.
Preparation of amines:
1. Ammonolysis of Alkyl halides:
An alkyl halide or a benzyl halide reacts with ammonia to form a mixture
of primary secondary and tertiary amines. If ammonia is used in excess
primary amine is the major product.
Example:
2. Reduction of Nitro Compounds:
Nitro compounds are reduced to amines either by catalytic hydrogenation
or chemically by using a metal and acid.
Or
3. Reduction of Nitriles:
Alkyl nitriles, on reduction with LiAIH4 or Catalytic hydrogenation,
form primary amines which have one more carbon than the alkyl halide
used. This reaction is used for ascent of amines homologous series.
4. Gabriel Synthesis:
Gabriel synthesis is used for the preparation of primary amines.
Phthalimide on treatment with ethanolic potassium hydroxide forms
potassium salt of phthalimide which on heating with alkyl halide
followed by alkaline hydrolysis produces the corresponding primary
amine.
Secondary and tertiary amines cannot be prepared by Gabriel synthesis. Also
aniline cannot be prepared by this method as arylhalides donot undergo
nucleophilic substitution under ordinary condition.
5. Hofmannbromamide degradation reaction:
Acid amides on reaction with bromine in the presence of alkalis at about 343 K
give primary amines.
Physical Properties:
Physical state and odor:
Lower members of aliphatic amines are gases while higher members are
liquids. Among, arylamines, lower members are liquids and higher members
are solids.
Methylamine and ethylamine have ammonical smell but higher amines have
fishy smell.
Most of the aromatic amines are colorless in pure form . However, they
become colored on keeping due to oxidation in air. Aromatic amines are
generally toxic. They are easily absorbed through the skin.
Boiling point:
Amines are polar compounds and have higher boiling points than non-polar
compounds such as hydrocarbons of same molecular mass.
All amines can form hydrogen bonds as proton acceptors by coordination with the
lone pair of electrons on the-N atom. But only primary and secondary amines can
donate proton in hydrogen bonding. The 1° and 2° amines because of
intermolecular hydrogen bonding have higher boiling points than tertiaryamines.
However amines have lower boiling points than those of corresponding
alcohols or carboxylic acids. This is due to there as on that 0-H bond is
more polar than N-H bond and hence hydrogen bonds in alcohols and
carboxylic acids are stronger than hydrogen bonds in amines.
Solubility:
Smaller amines are soluble in water but as the hydrophobic part (i.e. hydrocarbon
part) of the amine becomes larger than six carbons, their solubility in water
decreases and still larger amines are essentially insoluble in water.
As the hydrogen bonds in amines are weaker than those in alcohols, the
solubility of amines in water is less than that of alcohols of similar molecular
weights.
The solubility of lower aliphatic amines in water is due to their capability to form
hydrogen bonds with water molecules.
Amines are soluble in organic solvents like ether, benzene, alcohol etc.
Chemical Properties of Ami nes:
The main reactions of amines are due to the presence of a lone pair
of electrons on nitrogen atom. Am ines are nucleophilic reagents as the
lone pair of electrons can be donated to electron seeking reagents,
(i.e., electrophiles).
Except the amines containing tertiary buty l group, all lower aliphatic amines
are stronqer bases than ammonia because of +I (inductive) effect. The
alky lgroups , wh ich are electron releasing groups , increase the electron
dens ity around the nitrogen there by increasing the availability of the lonepair
of electrons to proton or Lewis acids and making the amine more bas ic. Thus,
it is expected that the bas ic nature of amines should be in the order
tertiary > secondary > primary > NH3,
but the observed order in the case of methylamine is found to be as
secondary > primary > tertiary > NH3;
This anoma lous behavior of tertiaryamines is due to steric factors,
i.e., crowd ing of nitrogen atom from all s ides by the alky l groups
makes the approach and bonding by a proton or an electrophile relatively
difficult. The maximum steric strain results in tertiary am ines. The electrons are
there but the path is bloc ked, resulting the reduced in its basicity.
1) Alkylation:
An alkyl halide can react with a primary or secondary amine which
acts as a nucleophile.
On undergoing nucleophilic substitution, a 1°-amine is Converted to
a 2°- amine and a 2°-amine is Converted to a 3°-amine. The
tertiary amine reacts with alkyl halides to form a quarternary
ammon ium salt.
Aromatic amines also react in a s imilar manner.
2) Acylation:
Aliphatic and aromatic primary and secondary amines undergo
acylation through nucleophilic substitution with acid derivatives such
as acidhalides or anhydrides to form amides.
3) Reaction with nitrous acid:
Three classes of amines react differently with nitrous acid It is
prepared from amine ral acid and sodium nitrite in the reaction
mixture.
a. Primary aliphatic amines react with nitrous acid to form aliphatic
diazonium salts which being unstable, liberate nitrogen gas
quantitatively and form alcohols.
b. Aniline (or any aromatic 1°-amine) react with nitrous acid at low
temperatures (273-278K) to form diazonium salts . These are a very
Important class of compounds used for synthesis of a variety of
aromatic compounds.
4) Carbylamine reaction (lsocyanide test):
Aliphatic and aromatic primary amines on heating with chloroform
and ethanolic potassiumhydroxide for m isocyan ides or carbylamines
which are foul smelling substances. Secondary and tertiary amines do
not show this reaction. This reaction is known as carbylamines
reaction or isocyanide test and is used as a test for primary amines
only.
5) Reaction with Hinsberg's Reagent:
Primary and secondary amines combine with Hinsberg's Reagent
(benzene sulphonyl chloride) to form sulphonamides.
Aniline
Methods of preparation:
1. Reduction of nitro compounds:
This is a very convenient and most widely used method of
preparing aniline.
2. Ammonolysis of aryl chlorides:
Aniline is prepared by treating chloro benzene with ammonia
in the presence of copper salts at high temperature and
pressure.
Chemical properties:
1. Reaction with strong acids to form salts:
10
Aniline is a weak base (Kb=4.2x10- ) and forms salts with mineral
acids.
2. Reaction with alkyl halides (alkylation reaction):
Aniline reacts with alkyl halides to form 2° - amine. The 2°-
amines can further react with an alkyl halide to form 3°-
amines and finally quaternary ammonium salts. The salt can
be treated with aqueous NaOH to regenerate free 2°amine.
3. Reaction with acid chlorides (acylation reaction):
Aniline reacts with acid chloride (or acid anhydrides) to form the
corresponding amides called anilides.
4. Reaction with benzene sulphonyl chloride (or Hinsberg reagent):
Aniline reacts with benzene su lphonyl chloride to form
Nphenylbenzene sulphonamide.
5. Reaction with benzaldehyde:
An iline condenses with benzaldehyde to give benzylidene aniline (a
Schiffsbase).
6. Carbylamine reaction:
An iline reacts with chloroform and alcoholic KOH to give phenyl
isocyanide (phenylcarbylamine) wh ich has an offensive smell. It can
be identified by its smell.
7. Reaction with nitrous acid:
An iline reacts with nitrous acid (from NaNO2 + HCl) in the presence of
HCl at 0-5 °C to give benzene d iazon iumchloride.
8. Electrophiic Substitution Reactions:
All the types of amino groups -NH2, -NHR, -NR2 are most
powerful ring activating groups in aromatic electrophilic
substitution reactions and are ortho and para directing.
Aniline gets instantaneously brominated at all of the three
positions (all o-, p-, positions) to give a white precipitate in
aqueous solutions with Bromine water. This is a test for
identifying aniline.
Nitration of aniline gives unexpectedly high percentage yield of m-
nitroaniline.