H2COOCOCH3).
Besides simple aromatic aldehydes, their vinyl derivatives, heterocyclic aldehydes and even phathalic anhydride (as the carbonyl
component) give this reaction.
When carbonyl compounds reacts with acetic anhydride in the presence of base to form active carbanian species, which give
nucleophilic addition with carbonyl compounds. But remember, absence of base gives simple fission of anhydride (no carbanian)
which on reaction with carbonyl forms stable alkyledene acetates.
Toluene oxidation by chromic acid forms benzoic acid while in the presence of acetic anhydride reaction stops at benzaldehyde due
to formation of stable intermediate benzeledene di-acetate which on hydrolysis again form CHO group. So protection of CH
3
group oxidation at CHO group, we use chromic acid and anhydride mixture. Following reactions are given below
Witting reaction
(x) Witting reaction
Witting reaction gives an important and useful method for the preparation of alkenes by the reaction of aldehydes or ketones with
alkylidenetriphenylphosphorane (Ph3P = CR2) or simply called as phosphorane.
The
Witting reagent
, alkylidenetriphenylphosphorane, is prepared by reaction of trialkyl or triarylposphine usually the latter with an alkyl halide in
ether solution. Finally resulting phosphonium salt is reacted with a strong base (such as C
6
H
5
Li, BuLi, NaNH
2
, NaH, C
2
H
5
ONa, etc.) which removes a haloacid to give the reagent, methylenetriphenyl phosphorane (II).
In end, carbonyl compound is directly treated with the ethernal solution of the above reagent to form many compounds.
Mechanism
The reaction go through by the nucleophilic attack of the ylide on the carbonyl carbon. The dipolar complex (betain) so formed
undergo electronic exchange decomposes to olefin and triphenylphosphine oxide through a four -centred transition state.
The mechanism is strongly supported by an example that an optically active phosphonium salt reacts to produce a phosphine oxide
with retention of configuration in the final product.
(xi) Lederer Manasses Reaction
When phenol is treated with 40% aqueous solution of formaldehyde (formalin) in the presence of a dilute acid or alkali at low
temperature, a mixture of o-and p-hydroxy benzyl alcohol is formed.
This reaction is called
Lederer-Manasse reaction.
On heating for a short time, these compounds unergo condensation reaction with themsel ves and unchanged phenol and give linear
polymers by elimination of water.
These reactions are the basis of the preparation of phenol formaldehyde resins. These materials were developed by Backland and
are hence called
bakelite.
They are thermoplastic solids soluble in many organic solvents. When warmed with hexa methylene tetramine. (CH
2
)
6
N
4
, which splits up to formaldehyde and ammonia, further methylene bridges are formed and a three-dimensional polymer results.
(xii) Baeyervilliger rearrangement
Baeyer--Villiger rearrangement
is an example of the migration of a group from carbon to electron-deficient oxygen.The reaction first involves the oxidation of
ketones to esters by the treatment with peracids such as peracetic acid, performic acid, meta chloroperbenzoic acid (MCPBA),
perbenzoic acid, pertrifluoroacetic acid, permonosulphuric acid, etc. This reaction can also be done by H
2
O
2
and base.
Cyclic ketones are converted to lactones with expansion of ring.
(xiii) Beckmann rearrangement
The acid-catalyzed conversion of ketoximes to
N
-substituted amides is known as
Beckmann rearrangement
. The reaction is catalysed by acidic reagents such as, H
2
SO
4
, SOCl
2
, P
2
O
5
, PCl
5
, Al
2
O
3
C
6
H
5
SO
2
Cl, H
3
PO
4
and many others.
The reaction proceeds by the migration of a group from carbon to electron-deficient nitrogen.
Some aldoximes undergo the rearrangement process in the presence of polyphosphoric acid (PPA) but the reaction is not a gener al
one. The migration of the group not depends on the migrational activity but upon the orientation of the group in relation to the OH
group. It is found that the migrating group is always anti (i.e.,
trans
) to the hydroxyl group. So we can say that, the reaction is stereospecific.
Mechanism of reaction
(xiv) Benzilic acid rearrangement (modified intra molecular cannizaro's reaction)
When we mix a strong base to a carbonyl group first the formation of an anion takes place and the reversal of the anionic charge
may cause removal of the attached group, but in case of 1,2-diketone the attched group may migrate to the adjacent electron-
deficient carbonyl carbon forming
Thus, benzil on reaction with a strong base forms benzilic acid (salt), reaction is known as
benzilic acid rearrangement
. Basically this reaction is intracannizaro reaction where formation of benzillic acid takes place.
Barium hydroxide (barayta water) is more effective than sodium or potassium hydroxides due to strong basic nature. Alkoxide ions
(methoxide, ethoxide,
t
-butoxide, etc.) in place of hydroxide ion give the corresponding esters.
Phenoxide ions are too weak for nucleophile to attack. Besides aromatic 1, 2-diketones, aliphatic and heterocyclic diketones, for
example
o
-quinones can also undergo this type of reaction.
Polymerization Reactions
(xv) Polymerization Reactions
When two or more molecules combine to form bigger molecule accompanied by the loss of simple molecule like water, alcohol or
ammonia, etc. the process is called condensation polymerisation.
But if the number of molecules (of the same substance or of different substances) combine to form larger molecule, the process is
called polymerisation.
Condensation and polymerisation products of some carbonyl compounds are as follows -
Condensation and polymerisation product of formaldehyde
(a) Condensation with ammonia : Formaldehyde condenses with ammonia to form hexa methylene tetramine (urotropine)
The reaction occurs in the following manner :
(b) Condensation with phenol - Lederer - Manasses reaction :
Formaldehyde condenses with phenol in alkaline medium to form o-and p-hydroxy benzyl alcohol which further condenses with
phenol to give polymer,
Bakelite
. This is called
Lederer-Manasse reaction.
(c) Formation of penta erythritol :
Formaldehyde and acetaldehyde combine to form trihydroxy aldehyde
(Claisen-Schmidt reaction)
which reacts with alkali to give pentaerythritol (Cannizaro reaction) :
(d) Formation of formose :
On treating formaldehyde with dilute barium hydroxide (baryta water), a mixture of several sugars (monosaccharides) is formed
which is called
formose.
Above reaction resembles aldol condensation although formaldehyde does not have
Polymers of formaldehyde :
Formaldehyde forms three polymers :
(a) Trioxan or trioxymethylene :
On distilling formaldehyde with a small quantity of dilute sulphuric acid,
trioxan
is formed. On allowing formaldehyde to stand, it slowly changes to trioxan.
(b) Paraformaldehyde :
When a concentrated aqueous solution of formaldehyde is evaporated off to dryness, a long linear polymer is obtained which is
called
paraformaldehyde.
On heating paraformaldehyde, formaldehyde is regenerated. Hence formaldehyde is transported in the form of paraformaldehyde.
when paraformaldehyde is heated in a sealed tube at 115
o
C, trioxan is formed.
(c ) Polyoxymethylene :
When dilute sulphuric acid is added into cold aqueous solution of formaldehyde, a white insoluble solid is formed which is ca lled
polyoxymethylene
. This is also a linear polymer. In this case chain length is longer than in paraformaldehyde.
Condensation and polymerisation products of acetaldehyde
(a) Reaction with ammonia :
Ammonia reacts with acetaldehyde to form simple nucleophilic addition product - acetaldehyde ammonia which subsequently
losses water to give acetaldemine.
(b) Polymerisation:
Acetaldehyde when treated with hydrogen chloride gas at 0C forms a solid tetramer called
metaldehyde
. However, if temperature is not controlled, a trimer, called
paraldehyde
is formed which is liquid.
Metaldehyde burns with a smokeless non-luminous flame and is used as a killer for snails and slug and is marketed under the name
Snarol.
Paraldehyde is used as a hypnotic (sleep-inducing drug).
Both the polymers of acetaldehyde get depolymerised on heating with dilute sulphuric acid and thus they act as source of
acetaldehyde reactions in acid medium.
The polymeric aldehydes do not show characteristic aldehyde reactions. Higher aldehydes and ketones do not give definite isolable
polymers.