ALLEN CAREER INSTITUTE

ASHOKNAGAR_CHENNAI

Section: Synopsis
Name of the student: Aldehydes and Ketones CPR Sir
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I. Preparation
(a) From alkanes/arenes
 RCH3 + O2 
Mo 2O3
 RCHO
 PhCH3 
 PhCHO
 Etard’s reaction
 Mechanism uncertain – there are different proposals
 CrO2Cl2 oxidizes propyl benzene to mixture of products, benzyl methyl
ketone being the major product.
 Ethyl benzene gives mixture of phenyl acetaldehyde and
acetophenone almost in equal proportions.
 α-chloroketones are often side products.
 CrO3 – Ac2O – Ca(OH)2
 Cl2, UV – Ca(OH)2
(b) From Alkenes
 Wacker’s Process
 Oxo process
 MCPBA – HIO4
 NaIO4 – KMnO4
 OsO4 or cold KMnO4 – HIO4
 Reductive ozonolysis
(c) From alkynes
 Hydration – H2O/H2SO4/HgSO4 – MK
 HBO - Sia2BH – H2O2 – OH- - aMK
 Reductive ozonolysis – O3/DMS
 Cold dil. Alkaline KMnO4
 X2/H2O – MK
(d) From Alcohols
 Controlled oxidation by K2Cr2O7/Con.H2SO4 or Jones reagent
  PCC or PDC
 Ag or Cu, 573 K
 MnO2 – allylic/benzylic
 Oppenauer Oxidation
(e) From Alkyl halides
 DMSO
 Alkaline hydrolysis of gem dihalides
(f) From Acids and derivatives
 From RCOCl
 Rosenmund’s reduction
 Gilman’s reagent
 R2Cd
 Li(t-BuO)3AlH
 From Nitro alkanes (primary – KOH followed by Con.H 2SO4 and secondary –
Con.H2SO4
 From RCN
 Stephen’s reduction (SnCl2/Con.HCl)
 DIBAL-H – H2O
 RMgX followed by Hydrolysis – not to HCN
 From Esters
 DIBAL-H – H2O
 RMgX (1 equiv.) followed by Hydrolysis
 From carboxylic acids or their salts
 Dry distillation of (RCOO)2Ca
 RCOOH with MnO
 Dicarboxylic acids (6 or 7 carbons in straight chain) on heating with BaO
 Decarboxylation of β-keto acids
 From Ethyl acetoacetate (EAA)
 Aromatic aldehydes and ketones
 Gatterman – Koch Reaction: CO –HCl – AlCl3
 Gattermann reaction: HCN-HCl-ZnCl2/H2O
 Vilsemier – Haack reaction - Me2NCHO-POCl3
 Friedel – Crafts Acylation
 Reimer-Tiemann Reaction
II. Reactions
(a) Nucleophilic additions
(i) Hydration
 Catalysed by acid as well as base
 hydrogen bonding and stability of hydrates
 ring strain relief
 effect of –I groups
 isotope exchange with H2O*
(ii) Addition of alcohols
 Hemi acetal formation is nucleophilic addition.
 Conversion of hemi acetal to acetal is SN1 reaction.
 Hemiacetals are cleaved by aqueous acid as well as base while acetals are stable
in alkaline conditions and are cleaved by acids.
(iii) Addition of HCN
 Traces of CN- or NaOH is added as HCN does not dissociate to sufficient extent to
generate the nucleophile.
 RCHO, simple aliphatic ketones and cyclic ketones give good yields.
 ArCOR gives poor yields.
 ArCOR does not react.
 ArCHO: cycohydrin formation and benzoin condensation both take place.
 C=C – C=O : 1,4-addition competes.
 Me3SiCN
(iv) Addition of NaHSO3
 nucleophile is not HSO3- but SO32-
 nucleophilic atom is not O but S
 Used to purify impure aldehydes and ketones
 All aldehydes, methyl ketones and some sterically unhindered cyclic ketones give this
reaction.
(v) Addition of RMgX
 Nucleophile is polarized RMgX and not R-.
 Proceeds through a six membered or four membered TS.
 C=C – C=O : 1,4-addition competes and often major product especially in presence of
Cu2+
 (vi) Addition of ammonia derivatives (Addition – elimination reactions)
 NH3 – urotropine with formaldehyde
 RNH2
 R2NH
 NH2OH – Beckman rearrangement
 NH2NH2
 PhNHNH2
 Addition to α-hydroxyaldehydes or ketones
 NH2CONHNH2
(b) Substitution of α-hydrogen
(i) α-deuteration – acid as well as base catalyzed
(ii) α-halogenation – acid as well as base catalyzed
 Under acidic reaction conditions, selective monohalogenation at the -postion is
observed.

 Chlorination, bromination and iodination all occur at the same rate.

 The reaction can be catalyzed by addition of acid, but it is actually autocatalytic as

the by-product is the hydrogen halide.

 The reaction proceeds via the enol tautomer.

 Under basic conditions, -halogenation occurs.

 Typically the reaction cannot be limited to monohalogenation and

polyhalogenation occurs.

 This is because each electronegative halogen further enhances the stability of

the enolate.

 Chlorination, bromination and iodination all occur at the same rate.

 The reaction proceeds via the very reactive enolate

 RCOCH3 ketones give haloforms

(iii) Favorski rearrangement
(iv) α-alkylation – LDA – RX
(v) α-racemization - enolization
(c) Redox reactions
(i) Tollen’s test
(ii) Fehling’s test
(iii) Benedict’s test
(iv) Schiff’s test
(v) Cannizzaro reaction – Inter and intra molecular
  At relatively low concentration of base rate = k[Aldehyde]2 [OH-]
 At high concentration of base rate = k[Aldehyde]2[OH-]2
 In crossed Cannizzaro reaction, the more reactive aldehyde towards nucleophilic
addition undergoes oxidation.
 Me2CHCHO undergoes disproportion under special conditions.
 OH, NH2, NHR, NR2 groups at ortho and para positions do not give this reaction.
(vi) Tischenko reaction
(vii) Baeyer Villeger oxidation – migratory aptitude : H>3°>2°≥Ph>1°>Me
(viii) Oxidation by SeO2
 Oxidzes methylene group of aldehydes or ketones to C=O group.
 If there are two methylene groups, the one that forms more stable enol gets
oxidized.
 Oxidizes allyl positions to –OH.
 Oxidizes benzyl positions to C=O
(d) Addition enolates/enols to carbonyl compound
(i) Aldol condensation – nucleophilic addition followed by dehydration
 Acid and base catalyzed
 Intra and intermolecular

Dicarbonyl compounds can be used to give intramolecular Aldol reactions.

This means the enolate component and the carbonyl component are parts of a
single larger molecule.

The selectivity is typically controlled by the stability of the cyclic Aldol product.

This favors the formation of the more stable 5- or 6-membered rings

To work out the best product, check the permutations that are possible and look
for the favorable ring sizes.

Ring sizes being same, prefer to use aldehyde as the electrophile to decide major
product.

 Crossed
Acid catalysed: More stable enol acts as the nucleophile to give major
product.
Base Catalysed: Less substituted carbon loses H+ to give enolate which in turn
adds to the other reactant to give major product.
 Directed
(ii) Tollen’s reaction
 (iii) Claisen – Schmidt condensation
(iv) Perkin Condensation – cyclic mechanism
(v) Knovenegal condensation : CH2(COOEt)2 in presence of EtOK
(vi) Stobbe condensation : EtOOCCH2CH2COOEt in presence of EtOK
(e) Misc. Reactions
 Benzoin condensation
 Benzilic acid rearrangement
 Schmidt Reaction