Aldehyde Ketone
Aldehyde Ketone
Aldehyde Ketone
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In ketones, the carbonyl group is linked to two carbon containing groups which may be
same or different alkyl, aryl group. If two R and R groups are same, the ketone is called
simple or symmetrical ketone and if R and R are different, then ketone is known as mixed
or an unsymmetrical ketone.
STRUCTURE
Carbonyl carbon of both aldehyde and ketones is sp2 hybridised, One of the three sp2
hybridised orbital get involved in - bond formation with half filled p-orbital of oxygen
atom whereas rest of the two are consumed in -bond formation with hydrogen and carbon
depending on the structure of aldehyde or ketone.
Unhybridised p-orbital of carbonyl carbon form -bond with another half-filled p-orbital of
oxygen atom by sideways overlapping.
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ii)
C5H10O
(b) Position isomerism: aliphatic aldehydes do not show position isomerism, because CHO
group is always present at the end of carbon chain.
Aromatic aldehyde show position isomerism. Example
(c) Metamerism: Higher ketones show metamerism due to presence of different alkyl
groups attached to the same functional group
C5H10O
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(d) Functional isomerism : Aldehydes and ketones show functional isomerism in them. In
addition, they are also related to alcohols, ethers and other cyclic compounds. Example
C3H6O
(II)
C3H6O
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Since the oxidizing agent used in the above reactions is a strong oxidizing agent, it oxidizes
aldehydes and ketone further to carboxylic acids
To prevent further oxidation, a mild oxidizing agent such as pyridinium chlorochromate
(pcc), CrO3.C5H5NHCl or CrO3NH+CrO3Cl- are used Collins reagent [ (C5H5N)2 CrO3] can also
used.
(ii)
2. From alkenes
(i)
Reductive ozonolysis of alkenes.
(ii)
Wacker process.
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3. From alkynes
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By addition to nitriles
(ii)
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Reduction of acid chloride into ester can also be carried out by lithium tri-t-butoxy
aluminium hydride, LiAlH[OC(CH3)3]3
(iii)
Reduction of esters
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(ii)
(iv)
(v)
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1. Physical state
Lower members of aldehydes and ketones (upto C10) are colourless volatile liquids except
formaldehyde which is gas at ordinary temperature
Higher members of aldehyde and ketones are solids with fruity odour
Lower aldehydes have unplesent odour but ketones posses pleasant smell
2. Boiling point
Boiling point of aldehyde and ketones is slightly lower than corresponding alcohol due to
lack of hydrogen bonding. However their boiling point is slightly higher than that of
corresponding non-polar hydrocarbon or weakly polar ether. This may attributed to reason
that aldehydes and ketones are polar compounds and thus possess intermolecular dipoledipole interaction
Among isomeric aldehydes and ketones, boiling point of ketones is slightly higher than that
of aldehydes due to the presence of two electron donating alkyl groups making them more
polar.
3. Solubility
Lower members of aldehydes and ketones ( upto C4) are soluble in water due to H-bonding
between polar carbonyl group and water.
However, solubility decreases with increase in molecular weight
Aromatic aldehydes and ketones are much less soluble than corresponding aliphatic
aldehydes and ketones due to large benzene ring. However all carbonyl compounds are
fairly soluble in organic solvents.
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(ii)
Steric effect
In formaldehyde there is no alkyl group while in all other aldehyde there is one alkyl group
so here the nucleophile attack is relatively more easy but in ketones there are two alkyl
groups attached to carbonyl group and these causes hinderance, to the attacking group.
This factor is called steric hinderance (crowding). In other words the hindrance increases,
the reactivity decreases accordingly. Thus order of reactivity is
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Due to electron releasing resonance effect (+R effect) of benzene ring, the magnitude of
positive charge on carbonyl group decreases and consequently it becomes less susceptible
to nucleophilic attack.
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In this reaction carbon atom of carbonyl group changes from sp2 to sp3 hybridised
(i)
Addition of hydrogen cyanide (HCN)
Mechanism
Step I : The hydrogen cyanide interacts with the base to form nucleophile
StepIII: The proton from the solvent (usually water) combines with the anion to form
cyanohydrine.
Cyanohydrins are formed by all aldehydes but in ketones, only acetone, butanone, 3pethenone and pinacolone form cyanohydrins.
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All ketones do not undergo this reaction only methyl ketone form addition product with
sodium bisulphate
On reacting the crystalline solid bisulphate derivative with dilute HCl or alkali, these adducts
decompose to regenerate the original aldehyde or ketones. Hence, this reaction is used in
the separation and purification of aldehydes and ketones from non-carbonyl compounds.
(iii)
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(iv)
Addition of alcohols
Dry HCl protonates the oxygen atom of the carbonyl compounds and therefore, increases the
electrophilicity of the carbonyl carbon and hence facilitating the nucleophilic attack by the alcohol
molecule. Dry HCl gas also absorbs the water produced in these reactions and thereby shifting
equilibrium in forward direction.
Ketals can be prepared by treating the ketone with ethyl ortho formate
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(v)
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Step II : In ammonia derivatives, the nitrogen atom has a lone pair of electrons, which attack the
positively charged carbonyl carbon and results in positive charge on nitrogen atom
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Step III : The unstable intermediate loses a proton, H+ and water molecule to form stable product
(imines)
(vi)
Addition of alkynes
II.
Clemmensen reduction
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Wolf-Kishner reduction
IV.
V.
Reduction to pinacols
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3. Oxidation reactions
i.
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ii.
Fehlings solution is reduced by aliphatic aldehydes only. Aromatic aldehydes and ketones
so not give this reaction.
Oxidation with strong oxidizing agent
iii.
Haloform reaction
4. Condensation reactions
(1) Aldol condensation
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Mechanism
Aldehyde or ketones which do not contain -hydrogen atom like formaldehyde (HCHO),
benzaldehyde (C6H5CHO) and benzophenone (C6H5COC6H5) do not undergo aldol
condensation.
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# A- A Condensation
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# B-B Condensation
# A-B Condensation
# B-A Condensation
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5. Cannizzaro reaction
Mechanism
Step I : The OH- ion attacks the carbonyl carbon to form hydroxyl alkoxide
Step II : Anion (I) acts as hybride ion donor to the second molecule of aldehyde. In the
final step of the reaction, the acid and the alkoxide ion transfer H+ to acquire stability.
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