Carbonyl Compounds

Aldehydes and ketones contains the same functional group, the carbonyl group (> C = O).

Aldehydes behave as reducing agents due to presence of reducing hydrogen atom where as
ketones have no such property so aldehydes easily reacts with oxidising agent. Even HCOOH
shows some properties of carbonyl compounds due to presence of – CHO group. HCOOH
behaves as reducing agent while in other acids no reducing hydrogen atom, so no reaction with
oxidising agent.
Preparation

(i) Oxidation of alcohols

(a) From PCC or pyredeniumchlorochromate. Which is pyridine, CrO3 and HCl, in equal ratio

By Jones reagent (CrO3 and aq. CH3COCH3) reaction goes till acids as it is a strong oxidising
agent where as by PCC and Collins reagent reaction stops at aldehyde.

(ii) Rosenmund’s reduction

Reduction of acid halide into aldehydes by Pd and BaSO4 is known as rosenmund reduction,
only aldehydes can be prepared by this reaction.

HCOCl break down into CO + HCl so the first aldehyde from rosenmund reduction is CH3CHO.
Here Pd act as catalyst and BaSO4 as catalytic poison to prevent conversion of aldehyde into
alcohol by further reduction.

(iii) Stephan’s Reduction

When Cyanides are partially reduced by means of stannous chloride and hydrochloric acid
followed by hydrolysis yield aldehyde. Ketones can not be prepared by this process.

Here [H2SnCl4] is formed which works as powerful reducing agent.

(iv) Oxidation of alkyl halide by dimethyl sulphoxide

(v) From Grignard Reagent

(vi) Dry distillation of calcium salts of acids

(vii) Oxidation of vicinal glycols by periodic acid

This reaction can also be done by lead tetrs acetate. We have already studied the mechanism of
this reaction in last chapter.

(viii) Action of MnO on acids at 300oC temprature

(ix) By Hydrolysis of Acetoacetic ester

(x) Catalytic Dehydrogenetion by Cu at 300oC

(xi) Oppenauer oxidation

This is specific method for oxidation of secondary alcohol to ketone. Secondary alcohol is heated
with aluminium iso-propoxide in a ketone (usually acetone)- secondary alcohol is oxidised to
ketone whereas ketone is reduced to secondary alcohol.

Actually this is a reversible reaction and equilibrium can be shifted in either direction by
appropriate manipulation.
For example, by taking an excess of secondary alcohol, ketone can be reduced; this reduction is
called Meerwein Ponndorf - Verley reduction which has been discussed later.

The uniqueness of Oppenauer oxidation lies in the fact that it selectively oxidises hydroxy group
which means that if the compound besides hydroxy group has some other oxidisable
functionality, the latter will remain unaffected under these conditions.

For example :

(xii) Hydrolysis of gemdihalide

 
Properties

(i) Nucleophilic addition reaction

Six electron system of carbocation is formed if primary attack of electrophile takes place,
otherwise it is a eight electron system which is more stable when primary attack of nucleophile
takes place.

So Primary attack here is of the nucleophile due to more stable intermediate oxygen anion of
eight electron system. The reactivity of different carbonyl compounds towards formation of
nucleophilic addition decreases in the following order :

This order arises due to the following two factors :

(i) Electronic factor : We have seen above that carbon of the carbonyl group is susceptible to the
attack of nucleophile due to the presence of positive charge on it (i.e. on carbon). As the intensity
of positive charge on carbon decreases, the nucleophilic attack would occur less readily. On the
other hand, if intensity of positive charge increases nucleophilic attack would occur more
readily. Alkyl group exerts + I effect, due to which it reduces the intensity of positive charge on
carbonyl carbon, which decreases in the following order :

Intensity of positive charge on carbonyl carbon decreases. Hence the reactivity of these
compounds towards nucleophilic addition also decreases in this order.

(ii) Steric factor : The change in C - C - O angle as a result of nucleophilic addition may be
noted.

It is obvious that nucleophilic addition causes decrease in C – C – O bond angle and hence
groups are pushed closer. The bigger groups oppose coming closer, hence the reactivity of
carbonyl group decreases. Size of methyl group is much larger than hydrogen, hence
acetaldehyde is less reactive than formaldehyde. Similarly, acetone will be less reactive than
acetaldehyde.
(a) Reaction with HCN

In the presence of alkali the dissociation of HCN increases because HO- of alkali trap H+ of HCN
so that ionisation of HCN increases.

But in presence of acid the dissociation is suppresed due to common ion effect. Thus the
reaction shifts to backward direction.

(b) Reaction with NaHSO3 (sodiumbisulphite)

This reaction is most versatile test for separating carbonyl compounds from noncarbonyl
compounds, it first form white crystalline solid which when passed with dry HCl gas re-form
carbonyl compound.

Here the carbonyl compounds are reobtained by reaction with dry HCl, so these reaction are used
for separation test.

But always remember that for separation of aldehydes & ketones is done by Tollen’s reagent
(ammonical AgNO3 ) i.e. [Ag(NH3)2+], where aldehydes reacts to form white metallic silver.
(c) Reaction with sodio - derivatives of 1 - alkynes

(d) Reaction with C2H5SH (Ethanethiol)

(ii) Aldol Condensation

Aldehydes or ketones with when treated with dilute alkali like NaOH,K2CO3 etc.
undergo nucleophilic addition by active intermediate carbanion to form
known as aldols.

Various basic reagents such as potassium hydroxide, aqueous alkali carbonate, alkali metal
alkoxides, etc., may be used. The reaction is not favourable for all type of ketones but applicable
in some special cases like CH3COCH3.

Aldol condensation are of different type and it can occur between

  (i) two identical or different aldehydes,

  (ii) two identical or different ketones and
  (iii) an aldehyde and a ketone.

When the condensation is between two different carbonyl compounds, it is called crossed aldol
condensation.

(a) Simple Aldol

Above reaction is also called as Claisen Schimdt Condensation where one is aromatic carbonyl
compound and other is aliphatic carbonyl compound.

In cross aldol condensation possibility of more than one product is always there so these
reactions are not very much useful for synthatic chemistry. For example :
Acetone can also undergo aldol type reaction in the presence of dilute alkali (base catalyst) or
dry HCl gas.

Intraaldol condensation: Dicabonyl compounds, having two carbonyl groups within the same
molecule, undergo intramolecular aldol condensation reactions. Even bases as weak as sodium
carbonate are adequate in these reactions.

Intramolecular aldol condensations proceed best when five- or six- membered rings result
because these are of minimum strain ring.
(iii) Cannizaro’s Reaction

Aldehydes which do not have any , when treated with concentrated solution of
NaOH or KOH, undergo simultaneous oxidation and reduction (disproportionation) forming a
salt of carboxylic acid and alcohol.

Here 'R' should be –H or phenyl but not alkyl group with presence of .

The reaction follows third-order law (second order in aldehyde and first order in base),/ i.e.,
rate . This suggests the reaction between the first-formed anion (from base and
aldehyde) and another molecule of aldehyde in the rate-determining step.

In the presence of a high concentration of base, the reaction follows fourth-order law (second
order in both two molecules of base), i.e., rate

The hydride ion is directly transferred from one molecule of the aldehyde to the other, and does
not become free in solution has been proved by the observation that the recovered alcohol does
not contain deuterium when the reaction is performed in the presence of D2O.

Cannizaro Reaction of HCHO

Transfer of hydride ion due to back donation of oxygen charged electron give out hydride ion
which is used for reduction of other carbonyl molecule so oxidation of one molecule gives acid
salt while other by reduction forms alcohol.

(a) Simple cannizaro's reaction

Mechanism of Cannizaro's of benzaldehyde

(b) Cross Cannizaro's Reaction

Reaction of carbonyl compounds (does not having ) with alkali forms each
molecules of acid and alcolol.

Whenever HCHO is present, there are only two main products otherwise there will be four
products in all other cases. Because HCHO contains maximum reducing hydrogen atom so easily
undergo oxidation process.

One of the most important applications is the crossed Cannizzaro reaction between
formaldehyde and other aldehydes containing
(iv) Bimolecular Reduction or Pinacol Reaction

Two molecules of acetone undergo reduction in the presence of Mg/Hg to form Pinacol. Upon
treatment with mineral acids, 2,3-dimethyl 2,3- butane diol (pinacol) is converted into methyl
ter-butyl ketone (pinacolone). The 1,2-diol undergo dehydration in such a way that
rearrangement of the carbon skeleton occurs. Other 1,2 diols undergo analogous reactions, which
are known as pinacol pinacolone type rearrangement.

Mechanism
Pinacol–Pinacolone type Rearrangement

As the migrating group migrates with its electron pair, the more nucleophilic group might be
expected to migrate. Thus, the order of migratory attitude amongst the aryl groups is p-anisyl >
p-tolyl > phenyl > p-chlorophenyl, etc.

Remember, electron-attracting groups will retard the migration. The migratory aptitude amongst
the alkyl groups is Me3C > Me2CH > Me. However, the stability of the initially formed
carbocation may offset the migratory attitude order. Thus, in the compound 1, 1-dimethyl-2, 2-
diphenyl glycol, the resonance-stabilized carbocation (I) is formed instead of (II) and so it is the
methyl group and not the phenyl group which migrates, contrary to the above sequence.

Steric hinderance may affect the rate of migration–p-anisyl group migrates 1000 times faster
than o-anisyl group.

Migrating group attacks from the trans side or back side of to the leaving group. This has
significant aspect in cyclic systems. Thus, the two isomers of 1, 2-dimethyl-cyclohexane-1, 2-
diol give different products due to different orientations of the methyl and hydroxyl groups. The
one (III) in which the Me and OH groups are trans to each other gives 2, 2-
dimethylcyclohexanone by methyl shift. The other (IV) in which the Me and OH groups are cis
to each other undergoes ring methylene group shift instead of Me-shift with consequent ring
contraction to give 1-acetyl-1-methylcyclopentane (V).
Applications

Ketones from cyclic diols Pinacol rearrangement has been also applied to prepare ketones
which are very difficult to prepare by other method.
(v) Reaction with NH3

When carbonyl compounds reacts with ammonia, nucleophilic addition reaction occurs but
products are formed according to praportions between ammonia and carbonyl compound. For
example

 
(vi) Reaction with Ammonia Derivatives NH2 – Z is an example of nucleophilic addition
elemination reaction where – Z groups are following in nature. First attack from nucleophilic site
of nitrogen atom to electrophilic carbon atom then elimination of water occurs simultaneously.

These reactions are usually carried out in weakly acidic medium because weak acid catalyses the
reaction by protonating carbonyl oxygen but in presence of excess of acid nucleophile is also
protonated which reduces its reactivity, so optimum pH is necessary. When zine compounds
reacts with carbonyl compound they form crystalline solid as zone derivatives.

The reaction with 2,4–DNPH is used for sepration of carbonyl compound with noncarbonyl
compound.

Always remember, presence of traces of creates better polarity in the carbonyl

compound and more electrophilic nature of carbon atom but on the other hand presence of excess
H+ in the ammonia derivative makes it a bad nucleophile. For example when NH2NH2
(hydrazine) in presence of excess of acid converted into NH2N+H3 cation (hydrazinium) which is
a bad nucleophile. Hence optimum pH is a very important condition for this reaction,only tracer
amount of H+ are required.

(vii) Distinction between aldehydes & Ketones

Aldehydes having reducing hydrogen atom whereas ketones don’t, thus only aldehydes reacts
with oxidising agent and forms respective product.

(a) Ammonical AgNO3 (Tollen’s reagent)

Aldehydes reacts with silveroxide to form white precipitate of metallic silver while ketones
cannot, due to absence of reducing hydrogen atom.

(b) Reaction with HgCl2 (Mercuric chloride)

Aldehydes reacts with mercuric chloride to form white precipitate of mercurous chloride which
changes into black precipitate of metallic mercury.

 
(c) Fehling's solution

There are two solutions which contains cupric oxide as oxidising agent, when reacts with
aldehydes it forms red precipitate of cuprous oxide.

C6H5CHO and their aromatic derivatives do not give test with Fehling's solution because
aromatic aldehydes are not good reducing agents. It gives reaction with tollen's reagent due to
more oxidising nature of Ag2O than CuO. (Ag contains higher reduction potential than copper in
electrochemical series)

(d) Benedict's Solution

Similar chemical reaction and cupric oxide are present in benedict's solution but presence of
citrate gives differant complex. It reacts with aldehydes to form red precipitate of Cu2O. It cannot
reacts with benzaldehyde and its aromatic derivatives.
(e) Schiff’s Reagent

When dilute solution of p-rosaniline hydrochloride, pink in colour, passed through

sulphurdioxide gas forms colourless solution known as schiff's reagent. This restore it colour by
reducing nature of aldehyde while ketones gives no response.

(viii) Reformatsky Reaction

When an usually an reacts with carbonyl compound in the presence of

zinc metal to produce a . This is known as Reformatsky reaction.

When, a mixture of the carbonyl compound, and zinc in dry solvent benzene is
carefully heated under reflux when zinc undergo dissolution. Zinc may be activated by adding
traces of iodine, or copper powder. The mixture is then treated with ice-cold dilute sulphuric acid
and benzene layer separated. Benzene is distilled off when is obtained.

Aldol condensation, Knovengel’s reaction, Perkin reaction and Reformatsky reaction are base
catalysed reaction so these reactions are carbanian active process. The advantage of using zinc
in place of magnesium is that the organo-zinc compounds are less reactive than the organo-
magnesium derivatives of so that they do not normally react with their own ester
groups.

(ix) Perkin synthesis

In Perkin reaction, synthesis has been effected between aromatic aldehydes and aliphatic acid
anhydrides in the presence of sodium or potassium salt of the acid corresponding to the
anhydride, to yield
In this reaction active species also comes in the presence of base as carbanion (C–
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 –CH3 group oxidation at –CHO
group, we use chromic acid and anhydride mixture. Following reactions are given below
(x) Wittig reaction

Wittig 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 Wittig 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 C6H5Li, BuLi, NaNH2, NaH, C2H5ONa,
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 Manasse’s 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 themselves 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. (CH2)6N4 ,
which splits up to formaldehyde and ammonia, further methylene bridges are formed and a three-
dimensional polymer results.

(xii) Baeyer–villiger 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 H2O2 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, H2SO4, SOCl2, P2O5, PCl5,
Al2O3C6H5SO2Cl, H3PO4 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 general 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.

(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 - Manasse’s 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 115oC,
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 called 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 0°C 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.