Carbonyl compounds

The carbonyl compounds are the organic compounds that contain a carbonyl (>C=O) group.
O O If R = CH3 then the resultin aldehyde is called acetaldehyde.
H C H R C H If R = Phenyl (C6H5) group then the resultin aldehyde is called
Formaldehyde Aldehydes benzaldehyde.
O O
CH3 C H C6H5 C H
Acetaldehyde Benzaldehyde
O Where, R= alkyl or aryl group
R C R R= alkyl or aryl group
Structure of the carbonyl group (>C=O) O
The carbonyl carbon atom of the carbonyl group is sp2-hybridized. 120 C 120
R R
Orbital picture of carbonyl group 120
pz pz
sp2 2 sp2
sp C = sp2
C O C O O = sp2
2
sp2 sp sp2

The carbonyl group is planar around the trigonal planar sp2-hybridized carbonyl carbon atom.
Nomenclature of aldehydes and ketones

Nomenclature of aldehydes
Aldehydes are named according to the common (trivial) and IUPAC systems.
Common (trivial) names
The common names of aldehydes are derived from the common names of the corresponding
carboxylic acids.
The portion “ic acid” or “oic acid” ending in the common name of the corresponding
carboxylic acid is dropped and replaced by the new portion “aldehyde”.
Formic acid = Form + ic acid(HCOOH) Acetic acid = Acet + ic acid (CH3COOH)
Acet + ic acid = Acetic acid (CH3COOH)
Form + ic acid = Formic acid (HCOOH)
Acet + Aldehyde = Acetaldehyde (CH3CHO)
Form + Aldehyde = Formaldehyde (HCHO)
CH3  
     
C C C C C C O CH3 CH CH CHO CH3 CH CH2 CHO
 
CH2CH3 CH3
H  
-Methylbutyraldehyde
“Greek letters” α, β, γ, δ, etc ,-Dimethylpentaldehyde
,-Dimethylvalaraldehyde
IUPAC (systematic) systems
In the IUPAC (systematic) systems, the name of an aldehyde is derived from the name of
the parent alkane (having same number of carbon atoms) by changing the terminal “e” to
“al”. Alkane Alkan+ e Alkan+al=Alkanal
Methane = Methan + e Ethan + e = Ethane (CH3CH3)
Methan + e = Methane (CH4) Ethan + al = Ethanal (CH3CHO)
Methan + al = Methanal (HCHO)
CH3 CH2CH3 CH3
CH3 CH2 CH CH CHO CH3 CH2 CH2 CH CHO “Arabic number” (1, 2, 3, etc.)
5 4 3 2 1 5 4 3 2 1
2-Ethyl-3-methylpentanal 2-Methylpentanal

Nomenclature of ketones
Ketones are named according to the common (trivial), derive names and IUPAC
(systematic)
names.
The systematic (IUPAC) name of ketones are derived from the name of the parent alkane
having the same number of carbon atoms by changing the terminal suffix “e” of the alkane
by a new suffix “one”. Alkane Alkan+ e Alkan+one =Alkanone O
Propan + e = Propane (CH3CH2CH3) CH3 C CH3
Propan + one = Propanone (CH3COCH3) IUPAC name: Propanone
Common name: Acetone
Frequently derived names are used for “ketones”. Derived name: Dimethyl ketone
 O
CH3CH2 C CH2CH2CH3
IUPAC name: 3-Hexanone
Derived name: Ethyl propyl ketone
Only few ketones have common names. The smaller ketone, propanone is usually referred to
by its common name, acetone.
Preparations of aldehydes and ketones
Preparation of aldehydes
(i) Reductive ozonolysis of alkenes
H H H H DMS
(i) O3 can also be
R C C R R C O + R C O + ZnO + H2O used as an
(ii) Zn, H2O
Aldehyde Aldehyde reducing
agent
(ii) Addition of water to alkynes
H SO4, H2O O H
H C C H 2HgSO CH2 C CH3CHO
4 H Acetaldehyde
Or, Ethanal
(iii) Rosenmund reduction of acid chloride
O O
H2/Pd
R C Cl R C H +HCl
BaSO4,140C
(iv) Dehydration of alcohols
Cu
CH3 CH2 OH CH3 CHO + H2
300C
Ethanal
Or Acetaldehyde
(v) Oxidation of primary alcohols.

CrO3 2N
CH3 (CH2)5 CH2 OH CH3 (CH2)5 CHO
Anhydrous CH2Cl2
1-Heptanol Heptanal (84%)
(iv) Thermal decomposition (pyrolysis) of a mixture of the calcium salt of formic acid,
(HCOO)2Ca, and any other carboxylic acids, e.g. (RCOO)2Ca .

O O
(R C O)2Ca +(HCOO)2Ca Heat
R C H + 2CaCO3
Calcium salt of Calcium Aldehyde
carboxylic acid format
Preparation of ketones
(i) Reductive ozonolysis of alkenes
R R R R
(i) O3
R C C R R C O + R C O + ZnO + H2O
(ii) Zn, H2O Ketone Ketone

(ii) Addition of water to alkynes

O
H2SO4, H2O
CH3 C C H HgSO CH3 C CH2 CH3 C CH3
4
O H Propanone
Or, Acetone
(iii) Dehydration of alcohols
O
Cu
CH3 CH CH3 300C CH3 C CH3 + H2
OH Propanone
Or Acetone
(iv) Thermal decomposition (pyrolysis) of a suitable calcium salt of carboxylic acids, e.g.
(RCOO)2Ca.
O O O O
(CH3 C O)2Ca Heat
(R C O)2Ca Heat
R C R + CaCO3 CH3 C CH3 + CaCO3
Calcium salt of Ketone Calcium acetate Propanone
carboxylic acid Or Acetone
(v) Coupling reaction of acyl halides with organometallic compounds.
R O O
R CuLi + R C Cl R C R + RCu + LiCl
Lithium dialkylcuprate Ketone
(Gilman reagent)
(vi) Friedel-Crafts acylation reaction.
O O
AlCl3
+ CH3 C Cl C CH3 + AlCl3 + HCl
Anhydrous
Acetophenone
Physical properties of aldehydes and ketones  
C O
Aldehydes and ketones are boiled at higher temperatures than the ethers, alkanes,
alkenes and at lower temperature than alcohols that have the same number of carbon
atoms.

Low molecular weight aldehydes and ketones are soluble in water.

R    
C O H O
R  H
O H
H
Chemical properties
The structure of an aldehyde and a ketone is shown below:
O O
 
CH3 C H CH3 C CH3 C O
Acetaldehyde Acetone
The partially positive charge bearing carbonyl carbon atom of the carbonyl group acts an
electrophilc center. Therefore, a good nucleophile will easily attack to the partially positive
charge bearing carbonyl carbon atom of the carbonyl group.
Nu Nu
R2 
C O + Nu R2 C O R2 C O
R1 R1 R1
sp2-Hybridized, Becomming sp3-hybridized and Intermediate product. Complete
trigonal plannar tetrahedral. Partial negative charge negative charge on the oxygen
before the reaction. on the oxygen atom and on the atom. Complete sp3 hybridized
necleophile. Transition state. carbon atom.
Nu
H2 O
(Final product) R2 C OH
HO
R1
No atom or group is replaced after the addition of nucleophile to the carbon atom of the
carbonyl group. Because all the atoms or groups attached to the carbonyl carbon atom of the
carbonyl group of aldehydes or ketones are too stronger base (say hydride ion, H - or R-).
Thus aldehydes and ketones undergo “nucleophilic addition reaction”.
A poor nucleophile requires an acid catalyst to make the nucleophilic addition reaction faster.
R2 H R2 Nu
C O +H O H C OH + Nu R2 C OH
R1 R1 R1
If the attacking atom of the nucleophile has a pair of non-bonding electrons, then water will be
eliminated from the addition product. This is called a “nucleophilic addition-elimination
reaction”.
Z Z Z
H R 2 C + H2 O
R2 C OH R2 C OH2
H
R1 R1 R1
Reactivity of aldehydes and ketones
Aldehydes are more reactive than ketones towards the nucleophilic addition reaction.
The nucleophilic addition reaction of aldehydes and ketones proceed through the formation
of tetrahedral transition state and then tetrahedral intermediate state.
Nu Nu
R2 
C O + Nu R2 C O R2 C O
R1 R1 R1
2
sp -Hybridized, Becomming sp3-hybridized and Intermediate product. Complete
trigonal plannar tetrahedral. Partial negative charge negative charge on the oxygen
before the reaction. on the oxygen atom and on the atom. Complete sp3 hybridized
necleophile. Transition state. carbon atom.
Nu
H2O
(Final product) R2 C OH
HO
R1
More stable the resulting tetrahedral transition state and the tetrahedral intermnediate state
more easily it is formed and more readily undergoes the nucleophilic addition reaction.
(a) Electronic factors, and
(b) Steric factor.
(a) Electronic factors
Nu
R2 


C O + Nu  
R2 C O


R1
R1

Intensity of the Intensity of the

Nu negative charge Nu negative charge
 




  is high.   is low.
R2 C O R2 C O


R1 H
Relatively less stable Relatively more stable

  R2   R2  
C O C O C O
H R1
(b) Steric factor
The actual cause of the greater reactivity of an aldehyde than a ketone is the size of the
substituent group attached to the sp2-hybridized carbonyl carbon atom.

Nu Nu
R2 
C O + Nu R2 C O R2 C O
R1 R1 R1
sp2-Hybridized, Becomming sp3-hybridized sp3 hybridized carbon atom.
trigonal plannar (120) and tetrahedral. 109 109
before the reaction.
Less steric crowding.
The ketones with small size alkyl groups bonded to the sp2-hybridiz carbonyl group
are more reactive than those of the ketones with large alkyl groups.
Relative reactivity

CH3 CH3 (CH3)3CH

C O  C O  C O
CH3 (CH3)2CH (CH3)3CH
Aliphatic carbonyl compounds are more reactive than aromatic carbonyl compounds
O O R
C R C R C O
R
Electrophilic Diminish the Relatively strong
center electrophilicity electrophilic center

The reactions of aldehydes and ketones can be divided into the following three categories:
1. The reactions of the carbonyl group
2. Oxidation reactions of aldehydes and ketones
3. Reactions involving the α-carbon atom of the carbonyl compound (aldehydes or ketones)

1. The reactions of the carbonyl group

(a) Reactions with acids
The carbonyl oxygen atom of the carbonyl group is weakly basic in nature and thus reacts with
Lewis acids and Bronsted acids. With (E+) as a general electrophile, this reaction can be
represented as follows:
R R
R R C O +H C O H
C O +E C O E R R
R R
(b) Nucleophilic addition reactions
R O E
C O +E Y R C R
R Y
Reaction of aldehydes and ketones with hydrogen cyanide (HCN)
H
R
C O + HCN R C CN
H OH
Aldehyde Cyanohydrine
Mechanism
H2O
HCN H + CN
O H
R H
C O + CN R C CN R C CN
H H OH
Aldehyde
Intermediate alkoxide ion Cyanohydrine
Strongly basic
Using an aqueous solution of HCN and KCN or NaCN
H H2O
R KCN KCN K + CN
C O + HCN R C CN O
H2O R
H OH C O + CN R C CN
Aldehyde Cyanohydrine H Aldehyde H
Intermediate alkoxide ion,
O OH strongly basic
H OH
R C CN R C CN + OH
H H O OH
Cyanohydrine
H CN
Intermediate R C CN R C CN + CN
alkoxide ion,
strongly basic H H
Intermediate Cyanohydrine
HO + H CN H2O + CN alkoxide ion,
strongly basic
Addition of water with aldehydes and ketones
R O H A gem diol or
C O + H 2O R C H a hydrate or
H O H a 1,1-diol
The word “gem” comes from the Latin word “geminus” which means “twin”.
The hydrates of aldehydes and ketones are generally too unstable to be isolated .
Water is a weak base and is a very poor nucleophile.
 OH
CH3 H2O, Fast CH3 H2O, slow
C O +H O H C O H CH3 C O H O H
H3O H2O H
H H H H H
Weak electrophilic Strong electrophilic
before the protonation +H3O H3O
after the protonation
of the oxygen atom. of the oxygen atom. OH
(i) Electronic effect, and CH3 C OH
(ii) Steric effect. H 58%
Hydrate or Gem diol or 1,1-diol
As for eample, only 0.2% of
O sp2-Hybridized OH
H2 O sp3-Hybridized acetone is hydrated by the
C C reaction with water but 99.9%
H 2 O HO R
R 120o R o
R 109.5 of formaldehyde is hydrated
Trigonal planar Tetrahedral hydrate
(Less crowded)
by the reaction with water.
(More crowded)
(A) (B)
Electron donating and bulky substituents decrease the percentage of hydrate present in the
solution. Electron with drawing groups and small substituents increase the percentage of
hydrate present in the solution.

Cl3C OH H
Cl O
C Intramolecular hydrogen bonds that stabilized
H OH the hydrate from the lose of its water molecule. Cl C C H
Chloral hydrate (stable) Cl O
H
Addition of alcohols with aldehydes and ketones
When one equivalent of an anhydrous alcohol is treated with an anhydrous aldehyde then
forms “hemiacetal”. But when two equivalents of an anhydrous alcohol are treated with an
anhydrous aldehyde then forms “acetal”. The word “hemi” comes from the Greek word
which means “half”.
H OH OCH3
HCl CH3OH
C O + CH3OH CH3 C OCH3 CH3 C OCH3
CH3 Anhydrous HCl
H Anhydrous H
Hemiacetal Acetal

H OH
Very fast attack
C O H + CH3OH CH3 C OCH3
CH3 H
Hemiacetal
Strong electrophilic carbon atom.
(Protonated carbonyl group)
When an anhydrous alcohol is treated with an anhydrous ketone then the products form is
called a “hemiketal” and a “ketal” respectively.

CH3 OH OCH3
HCl CH3OH
C O + CH3OH CH3 C OCH3 CH3 C OCH3
CH3 Anhydrous HCl
CH3 Anhydrous CH3
Hemiketal Ketal
Acetals in the presence of mineral acid and excess water transformed rapidly back into the
corresponding carbonyl compounds and alcohols; this process is called “acetal
hydrolysis”.
OCH3 H
H3O
CH3 C OCH3 CH3 C O + 2CH3OH
H Aldehyde Alcohol
Acetal
Acetal formation is not favored when ketones are treated with simple alcohols and gaseous HCl.

Addition of ammonia, primary amines and other ammonia derivatives with aldehydes
and ketones.
Aldehydes and ketones react with primary amines (R-NH 2) and other ammonia derivatives
(Z-NH2) to form an “imines”. An imine is a compound with a “carbon-nitrogen double
bond” (C=N). The reaction is acid catalyzed. The formation of “imine” is very slow at very
low and at very high pH and generally the reaction occurs very fast at the pH 4.5.
R Trace H3O+, pH4.5 R Z
C O + NH2 Z C N + H2O
R R
Aldehyde Primary amines or other An imine
or, Ketone ammonia derivatives. (E) and (Z) isomers
 Some derivatives of ammonia
Compounds such as hydroxyl amine (NH2-OH), hydrazine (NH2-NH2), semicarbazide
(NH2-NHCONH2), thiosemicarbazide (NH2-NHCSNH2), phenylhydrazine (NH2-NHC6H5)
and primary amines (NH2-R) are all the derivatives of ammonia because each of them has
a substituent in place of one of the hydrogen atom of ammonia (NH 2-H) molecule.
The “imine” obtained from the reaction of a carbonyl compound and a primary amine is
called a “Schiff base”.
Mechanism of the reaction
O H
R H R H H R
R H2O H3 O
C O +NH2 R R C NH R R C NH R R C NH R
R H3 O +H3O
Aldehyde O OH OH
Dipolar H O H Nitrogen protonated Neutral
or, Ketone carbinolamine,
intermediate carbinolamine.
H tetrahedral tetrahedral
(Alkoxide ion)
intermediate I intermediate II
OH2
R R H R H3O +H3O
H3 O H 2O
R C N R R C N R R C NH R
Imine OH2
Protonated imine
(An iminium ion)
No protonation of the nucleophilic amine derivative NH 2-OH (or Z-NH2) occurs at
the pH 4.5
 y
Maximum rate pH 4.5 OH2
at pH  A R C NHR (Maximum)
R
OH2 H C O +NH2 R
R C NHR R (Maximum)
OH
H R C NHR (Not protonated)
Rate
R NH3 H
Region B Region C; pH>4.5
pH<4.5

x
0 1 2 3 4 5 6 7 8
pH
Addition of secondary amines with aldehydes and ketones
The reaction of an aldehyde or a ketone with a secondary amine produces an “enamine”.
An “enamine” is an α,β-unsaturated tertiary amine.
The name “enamine” comes from “ene” + “amine”= enamine, with the “e” of
“ene” is omitted in order to avoid the two successive vowels “e” of “ene” and “a”
of amine.
R R
 
R CH2 C O + R NH R CH CH N + H2O
H A secondary An enamine R
An aldehyde amine An -unsaturated
tertiary amine
Reduction of aldehydes and ketones or addition of hydride ion
Addition of hydride (H-) ion to an aldehyde or a ketone forms an alkoxide ion.
Subsequent protonation of the resulting alkoxide ion by water or a weak acid produces an
alcohol. LiAlH4 Li + AlH4
H OH
R R O
(i) LiAlH4 AlH 3 O H R C H
C O RCH 2 OH C O + H AlH 3 R C H
(ii) H2O H HO
H H H
Oxidation reactions of aldehydes and ketones
Aldehydes can be easily oxidized to form carboxylic acids.
O O O OH
O
R C H R C OH CH3 C CH3 CH3 C CH2
General test for carbonyl groups
When aldehydes and ketones are treated with 2,4-dinitrophenyl hydrazine then forms 2,4-
dinitrophenyl hydrazone which is a colored product.
O2N O2 N
R R
C O +NH2 NH NO2 C N NH NO2
H H
2,4-Dinitrophenyl hydrazine 2,4-Dinitrophenyl hydrazone
(A colored product)
Distinguish between aldehydes and ketones
We can distinguish between aldehydes and ketones by the oxidation reactions. Aldehydes are
oxidized more easily than ketones.
Oxidation of aldehydes and ketones
(i) Reaction with Tollen's reagent
All aliphatic and aromatic aldehydes give positive tests with Tollen's reagent. (Ag+ or Ag2O)
O O
R C H + 2[Ag(NH3)2]OH R C O NH4 + 2Ag +3NH3 +H2O
Oxidized Silver mirror
(Reduced)
(ii) Reaction with Fehling solution
Fehling solution is a strongly basic mild oxidizing agent. The main oxidizing agent is the
cupric ion (Cu2+).
O Sodium O Sodium
R C H + CuSO4 +NaOH+ potassium R C O Na + Cu2O+ potassium
Blue color tartarate Oxidized Red ppt tartarate
(iii) Reaction with Benedict’s solution
O O
Sodium H2O Sodium
R C H + CuSO4 +Na2CO3 + citrate R C O Na + Cu2O+ citrate
Blue color Oxidized Red ppt
(iv) Schiff's reagent

When aldehydes are treated with Schiff’s reagent then colorless Schiff’s reagent is
converted into “violet-purple” color which indicates the presence of aldehydic group in
the molecule.
H SO3H O O
H2SO3
Cl H2N C NH S + R C H
H O
Schiffs reagent
O O
NH S + R C H
H O OH
H O
Cl HN C NH S C H
O R
Pink color

O OH
NH S C H
O R
Addition of sodium bisulfite with aldehydes and ketones
Sodium bisulfite (NaHSO3) reacts with most aldehydes and unhindered ketones (usually
acetone and cyclic ketones) and forms sodium bisulfite addition product.
O OH
H2O
R C H+ NaHSO3 R C H
SO3 Na
O O O O H O O H OH O
R C + S O Na R C S O Na R C S O Na R C S O Na
H O H H O H O H O

OH O
H3O or OH
R C H R C H + SO2 in acidic solution and SO32- in basic solution.
Heat
SO3 Na
Wolff-Kishner reduction
R HOCH2CH2OH R KOH R
C O + NH2 NH2 C N NH2 + H2O CH2 + N2
110-130C 200C
R R R
The Wolff-Kishner reduction takes place in strongly basic media and can be used only
for those compounds that are sensitive to strong acid.
Mechanism of the step 2

R H R R R
OH HO
C N N H C N N H C N N H CH N N H
200C
R Hydrazone R R H OH
R OH
H2 O
Base catalyzed tautomerization of hydrzone
R R R
CH2 + OH H OH CH +N2 CH N N
R R R
Clemmensen reduction Elimination of nitrogen (N2)

O
Zn(Hg), HCl
C CH2CH3 Heat CH2 CH2CH3

Limitations
O
Zn(Hg), HCl
C CH Cl
3 Heat
CH2CH3

CH2CH3
NH2 NH2
HO
KOH, Heat
OH
 O
C CH CH2 CH3
3 Zn(Hg), HCl
Heat
CH3 CH3
CH2 CH2 N CH3 Cl CH2 CH2 N CH3 Cl
CH3 CH3
Wolff-Kishner reduction
O
C CH CH2 CH3 CH2 CH3
3 NH2 NH2 Heat
KOH, Heat + N(CH3)3 +H2O
CH3 KCl CH3
CH2 CH2 N CH3 Cl CH CH2 N CH3 OH CH CH2
CH3 H CH3
Thioacetal formation
Aldehydes and ketones react with thiols to form thioacetals.
R HS CH2 BF3 R S CH2
C O+ C + H2 O
R HS CH 2 R S CH2
Cyclic thioacetal
R R S CH2CH3
HCl C
C O + 2CH3CH2SH + H2O
R R S CH2CH3
Thioacetal
 R S CH2 Raney nickel (Ni) R
C CH2 + CH2 CH2 +NiS
R S CH2 H2 , Heat R H H

3. Reactions involving the α-carbon atom of the carbonyl compounds (aldehydes or

ketones).
O O O O
H 
R CH C R R CH C R R CH C R R CH C R
H Resonance stabilized carbanion
Delocalization of electrons of the carbanion
Reaction of aldehydes and ketone with halogens
Aldehydes and ketones that have an α-hydrogen atom can readily undergo substitution
reaction at the α-carbon atom with halogens. The rate of this halogenations reaction is
increased when acids or bases are added to the reaction mixture.
O O
H3 O
R CH C R + X2 or, HO R CH C R + HX (Here, X= Cl, Br, I)
H X
Acid catalyzed halogenation reaction at the α-carbon atom
H
H O H O O H O H
H2 O H3 O
R CH C R R CH C R R CH C R
Fast Slow Enol form
H H
Keto form H2 O
Protonated keto form

O H O H H2O O
Br
R CH C R + Br Br Fast R CH C R R CH C R + H3O
Br Br
-Substitution reaction

Base promoted substitution reaction at the α-carbon atom

O H2O O O
R CH C R R CH C R R CH C R
Slow (A) Enolate ion (B)
H OH
Keto form
O O
Br
R CH C R + Br Br R CH C R
Fast
Br
-Substitution reaction
In the case of the base promoted halogenations reaction when as excess amount of halogen
(X2=Cl2, Br2 and I2) is added to a basic (which is also an excess) solution of an aldehyde or
a ketone then the halogen reaction is repeated until all the α-hydrogen atoms from the
α-carbon atom are replaced by the halogen atoms.
O O Br O
(Excess) Br
R CH C R +Br2(Excess) HO R CH C R 2
/ HO
R C C R
Br Br
H Br Br
Keto form

O More basic oxygen O Less basic oxygen


R CH C R R CH  C R


H Br
Haloform reaction
When a methyl ketone is treated with an excess amount of base and an excess amount of
halogens then forms haloform and a salt of carboxylic acid.
O O
R C CH3 + I2(Excess) + OH(Excess) R C O + CHI3

Haloform reaction does not occur in the acidic medium because after the first addition of
halogen at the α-carbon atom makes the carbonyl oxygen atom less basic due to the
electron withdrawing inductive effect of the first halogen atom.
Mechanism of the haloform reaction involves the following steps
O O O O H
H2O I
R C CH2 + OH R C CH2 R C CH2 +I I R C C H
H I
HO
H2O
O I O I O I O
I I R C C HO I I
R C C I R C C H R C C H
I H2O I
I I I I
Triiodo ketone
O I O I O I
R C C I + HO R C C I R C OH+ C I
I OH I I
Tetrahedral intermediate Triiodomethyl ion
O I O I I


R C O H+ C I R C O +H C I CI


I I I
Iodoform Unusually more stable
triiodomethyl anion
Aldol condensation reaction
An aldol addition is a reaction between two molecules of an aldehyde or two molecules
of a ketone having alpha (α)-hydrogen atom. Aldo condensation reaction is a very good
method for the formation of “new carbon-carbon bond”.
O OH O
NaOH/H2O
2 R CH2 C H R CH2 C CH C H
R R
-Hydroxy aldehyde
Mechanism of the reaction
O O O
Fast
R CH2 C H+ OH R CH C H R HC C H
H2 O Enolate ion (A nucleophile)
O O O O
Slow
R CH2 C H + R CH C H R CH2 C CH C H
R R
Tetrahedral intermediate
H
O H O O OH O
R CH2 C CH C H R CH2 C CH C H+HO
R R R R
Tetrahedral intermediate -Hydroxy aldehyde
In the case of ketone
O OH O
NaOH/H2O
2CH3 C CH3 CH3 C CH2 C CH3
CH3
-Hydroxy ketone
The aldol addition reaction occurs more slowly with ketones than aldehydes.

Dehydration of the aldol addition product

The aldol addition products, beta (β)-hydroxyaldehydes or beta (β)-hydroxyketones can
undergo dehydration reaction under the acidic and basic conditions.
Mechanism of the dehydration of the aldol product in the acidic medium
H
O H
H OH O OH2 R O R O
H2 O
R CH2 C CH C R R CH2 C C C R R CH2 C C C R
R R R H R
Aldol addition product Condensation product
(,-Unsaturated
carbonyl compound)
Mechanism of the dehydration of the aldol product in the basic medium

OH O HO H OH O O
HO HO
CH3 C CH C CH3 2 CH3 C CH C CH3 CH3 C CH C CH3
CH3H OH CH3 CH3

Acid catalyzed aldol condensation reaction

O OH O O
HCl/H2O HCl/H2O
2CH3 C CH3 CH3 C CH2 C CH3 CH3 C CH C CH3
CH3 CH3
-Hydroxy ketone ,-Unsaturated
carbonyl compound

Mechanism of the acid catalyzed aldol condensation reaction

O O H
Cl (Protonated keto from of the
CH3 C CH3 + H Cl CH3 C CH3 carbonyl compound)
O H O H
CH3 C CH2 + Cl CH3 C CH2 + HCl
H Enol form

O H O H H2O H O CH3 O CH3

H3O
CH3 C CH2 + CH3 C CH3 CH3 C CH2 C CH3 CH3 C CH2 C CH3
OH OH
Tertiary hydroxyl group
 O CH3 O H CH3 O H CH3
H2 O H2 O
CH3 C CH2 C CH3+ H3O CH3 C CH C CH3 CH3 C C C CH3
OH OH2

Mixed or crossed aldol condensation reactions

When an aldol condensation reaction is carried out using two different carbonyl compounds
Examples 1
When both of them have alpha (α)-hydrogen atom
O O OH O OH O
NaOH/H2O
CH3 C H + CH3 CH2 C H CH3 C CH2 C H + CH3 C CH C H
-Hydrogen -Hydrogen H (A-A) H CH3 (A-B)
(A) (B)
OH O OH O
CH3 CH2 C CH C H + CH3 CH2 C CH2 C H
(B-B) H CH3 H (B-A)
Examples 2
When only one of them have alpha (α)-hydrogen atom

O O O
NaOH/H2O
C6H5 C H + CH3 CH2 C H C6H5 CH C C H
10C
-hydrogen -Hydrogen CH3
Claisen-Schmidt condensation reaction
Claisen-Schmidt condensation reaction is a type of mixed aldol condensation reaction.
Reaction between acetone and benzaldehyde
O
O O O
NaOH/H2O C6H5 C H
C6H5 C H + CH3 C CH3 C6H5 CH CH C CH3
NaOH/H2O
O
C6H5 CH CH C CH CH C6H5
Dibenzal acetone
Mechanism of the reaction involves the following steps
O O O
Fast
CH3 C CH2+ OH CH2 C CH3 CH2 C CH3
H 2O
H
O O HO H
O O
Slow
C6H5 C H + CH2 C CH3 C6H5 C CH2 C CH3
H HO
O OH O
H2O
C6H5 CH CH C CH3 C6H5 C CH C CH3
H H
Cannizzaro reaction
When any aldehydes having no α-hydrogen atom is heated with concentrated aqueous
sodium hydroxide (NaOH) or concentrated aqueous potassium hydroxide (KOH) solution
then two molecules of that aldehydes undergo mutual “oxidation-reduction reaction” that
is; one molecule of the aldehyde is oxidized to form a salt of the corresponding carboxylic
acid and another one molecule is reduced to form a corresponding primary alcohol. It is
called “cannizzaro reaction” .
O
50%NaOH
2HCHO CH3OH +H C O Na
Reflux Reduced Oxidized
O O O O O O
Heat
H C H+ OH H C H H C H+H C H H C H+C H
OH OH H OH
O O OH O
H C H +H O C H H C H+ O C H
H Acid H Salt of formic
Strong Methanol acid O O
base
H C O H+NaOH H C O Na +H2O
O Acid
50%NaOH/D2O
2HCHO CH2DOH + H C O Na O OH
Reflux
Not form Oxidized H C H + H OH H C H + OH
H H
Strong base Methanol
“Mixed or crossed cannizzaro reaction”.
O
50%NaOH
C6H5CHO + HCHO C6H5CH2OH + H C O Na
Reflux Oxidized
Reduced
O O O O H
Heat
H C H+ OH H C H C R C R C O
OH H
Hydrate anion Electrophilic
(Conjugate base) center

Knoevenagel reaction
When an aldehyde (may have α-hydrogen or not) is treated with a compound having
hydrogen atoms alpha (α) to two activating groups (such as C=O group of an ester or ketone
or aldehyde or cyano group, C≡N, etc) in the presence of a weakly basic catalyst such as
ammonia (NH3) or an amine or piperidine or pyridine as a catalyst then forms α,β-
unsaturated product (or ester, acid, etc.). This reaction is known as “Knoevenagel reaction”.
O
C5H11N
C6 H 5 C H + CH2(COOC2H5)2 C H CH C(COOC2H5)2 +H2O
C6H6, Heat 6 5
Mechanism of the Knoevenagel reaction

+ CH(COOC2H5)2 + CH(COOC2H5)2
N H N Nucleophile
H
O O
C H + CH(COOC2H5)2 C C(COOC2H5)2
H H
O OH
C C(COOC2H5)2 + C C(COOC2H5)2 +
H H N H H N
H
OH
C C(COOC2H5)2 C C(COOC2H5)2 + H2O
H H H

KOH/H2O
C C(COOC2H5)2 C C(COO K)2 + 2C2H5OH
Heat
H H

C C(COO K)2 +2HCl C C(COOH )2 +KCl

H H
O
C O H
C C 150-200C
CH CHCOOH + CO2
H C OH
O
Perkin reaction or Perkin condensation reaction
When benzaldehyde or any other aromatic aldehyde is heated with anhydride of an
aliphatic carboxylic acid having two alpha (α) hydrogen atoms in the presence of the
sodium salt of the same corresponding carboxylic acid of the acid anhydride as a catalyst,
then forms an α,β-unsaturated carboxylic acid. This reaction is known as “Perkin reaction
or Perkin condensation reaction”.
O
CH3COO Na
C H + (CH3CO)2O CH CHCOOH + CH3COOH
180C
Mechanism of the Perkin reaction
O O O O O O
CH3 C O C CH2 + O C CH3 CH3 C O C CH2 + HO C CH3
H Nucleophile (a carbanion)
O O O O O O
C + CH2 C O C CH3 C CH2 C O C CH3
H H
O O O O OH O O
C CH2 C O C CH3 + H O C CH3 C CH2 C O C CH3
H H O
+ O C CH3
O O O O O
CH3 C O C CH3 + O C CH3 CH3 C O C CH3
CH3 C O
O
 OH O O O O
C CH C O C CH3 C C C O C CH3 +H2O
H H H H H2O

CH CHCOOH + CH3COOH

Alternative mechanism (Peter Sykes; page: 227).

Reimer-Tiemann reaction
When phenol is treated with chloroform in the presence of aqueous base (NaOH or KOH)
under the influence of heat (60-70ºC) then forms an aldehyde, called salicylaldehyde (or, o-
hydroxybenzaldehyde or 2-hydroxybenzaldehyde). This reaction is known as the “Reimer-
Tiemann” reaction.
OH OH OH
CHO
(i) 60-70C
+ CHCl3 + KOH +
(ii) H3O
(Major product)
CHO
(Minor product)
H2O
KOH K + OH
Cl Cl
H2O Cl


Cl  C H + OH Cl C Cl C


Cl Cl Cl
Acidic hydrogen Dichlorocarbene
 OH O Na

+KOH +H2O

Highly electron rich

O O O H O H
H C Cl
C Cl
Cl
+ C Cl C Cl Cl
Cl Cl
HO
OH O O O O H OH O H
CHO C H C H C Cl
H3O Cl
H2 O H2O O H

Benzoin condensation
When aromatic aldehyde is treated with potassium cyanide (KCN) in the presence of
methanol (CH3OH) then forms benzoin.
O O H
CH3OH
2Ar C H + KCN Ar C C Ar + KCN
Benzoin OH
Mechanism
 Step:1
O O Acidic hydrogen O H O H
Ar C H + CN Ar C H Ar C Ar C
Donor CN C N C N
(A) Resonance stabilize carbanion
Step:2 Acidic
O H O hydrogen O H O O OH
Ar C + C Ar Ar C C Ar Ar C C Ar
C N H C N H C NH
Acceptor (B)
O OH
C N + Ar C C Ar
H
If Ar = Ph then the product is called benzoin.
Stobbe condensation
When diethyl succinate and its derivatives are treated with aldehydes and ketones in the
presence of a base such as C2H5ONa, NaH or (CH3)3COK then forms αβ-unsaturated ester.
This reaction is known as “Stobbe condensation” reaction.

CH2 COOC2H5 R R COOC2H5

C2H5ONa
+ C O C C
CH2 COOC2H5 R R CH2COO
Diethylsuccinate Ketone
Mechanism of the reaction is shown below:
Step:1
H CH COOC2H5 C2H5OH CH COOC2H5
C2H5O +
CH2 COOC2H5 CH2 COOC2H5

C2H5OOC H
Step:2 H
CH COOC2H5 C 2 H5 OOC OC2H5
R
R OC2H5
C O+
R CH2 COOC2H5 R O
C R O O
R O
C2H5OOC COOC2H5
H C2H5O
R COOC2H5 C2H5O
C C R R
R CH2COO C2H5OH
O O
R O R O
Wittig reaction
Aldehydes and ketones react with a phosphonium ylide (also called phosphorus ylide)
to form an alkene. This reaction is known as Wittig reaction. In 1954 the German
Chemist Georg Wittig. In 1979 he was awarded Nobel prize .
R1 R R1 R
C O + (C6H5)3P C C C + (C6H5)3P O
R2 R R2
Phosphonium ylide Alkene R Triphenyl phosphine
Aldehydes
or Phosphorus ylide (E/Z isomers) oxide
or Ketones
or Phosphorane
 About ylide
An ylide is a neutral covalent compound having a negative carbon atom adjacent to a
positive hetero atom (here the hetero atom is phosphorus).
R1 R1
(C6H5)3P C (C6H5)3P C
R2 R
Neutral double 2
Phosphonium ylide bonded form
Ionic form
Preparation of ylide
(i) R2CHBr, C6H6 R1 R
(C6H5)3P (C6H5)3P C (C6H5)3P C
(ii) C6H5Li R2 Neutral double R
Phosphonium ylide bonded form
Ionic form
The preparation of phosphonium ylide involves the following two separate steps:
R2 R1 Acidic hydrogen
SN2
(C6H5)3P + CH X (C6H5)3P C H X
R1 R2
2 Alkyl halide An alkyl triphenyl
phosphonium halide
R1 R1
(C6H5)3P C H X + R Li (C6H5)3P C + LiX + R H
R2 R2
An alkyl triphenyl Phosphonium ylide
phosphonium halide Ionic form
 Reaction of phosphonium ylide with aldehydes or ketones
R2 R R2 R R2 R
R1 C + C R R1 C C R R1 C C R
O P(C6H5)3 O P(C6H5)3 O P(C6H5)3
A betaine Oxaphosphetane
(May be not form) (Cyclic form)
R2 R
C C + (C6H5)3P O
R1 R Triphenylphosphine
An alkene oxide
Advantages of Wittig reaction
Preparation of alkene using Wittig reaction is more convenient than that of the E2
elimination reaction. Because Wittig reaction is “completely regioselective”.
H
CH3CH2CH2 C O + (C6H5)3P CHCH3 CH3(CH2)2CH CHCH3 + (C6H5)3P O
Double bond is only one position.
Only one constitutional isomer is
formed.
CH3 CH2 CH2 CH CH2 CH3 CH3CH2CH2CH CHCH3 + CH3CH2CH CHCH2CH3
Br 2-Hexene 3-Hexene
Double bond is two different positions.
Two constitutional isomers are formed.
Wittig reaction is also “stereoselective”.
H Ph H Ph Ph
Ph C O + (C6H5)3P CHC6H5 +
H Ph H H
(E)-1,2-Diphenylethene (Z)-1,2-Diphenyl ethene

Bi-functional compounds
C O
C O  C
C C C


C
 O C
 C O
C
 C O  C  O
C C  C C C C

The “carbon-carbon” double bond of the α,β-unsaturated aldehydes and ketones less
reactive than that of the simple alkenes towards the electrophilic addition reaction
and the beta-crbon atom becomes electrophilic in nature. The “isolated carbon-
carbon” double bond (C=C) of normal alkene is “non-polar”. But when the “carbon-
carbon” double bond (C=C) of normal alkenes is conjugated with a carbonyl group
then it becomes “polar”.
Addition reactions
H CH3CH CH3 Cl
CH3CH CH2 CH3CH CH3
Propene Cl
2-Chloropropane

Electrophilic addition reactions of α,β-unsaturated carbonyl compounds with hydrogen

chloride (HCl).
O Cl O
CH2 CH C H +HCl CH2CH2C H
Acrylaldehyde 3-Chloropropanol
(Propenal)

O H O H O H H O H
 H
CH2 CH C H CH2 CH C H CH2 CH C H CH2 C C H
Resonance stabilized

H O H Cl H O H Cl O
CH2 C C H + Cl CH2 C C H CH2CH2C H
An enol of an aldehyde An aldehyde
 O H O H O H
Cl
CH2 CH C H +Cl CH2 CH C H CH2 CH C H
Cl H O
Less stable product
CH2 CH C H
More stable
starting material

Therefore, when a “carbon-carbon” double bond (C=C) is in conjugation with a

carbonyl group then it easily undergoes “nucleophilic addition reaction” instead of
“electrophilic addition reaction”.
There are two electrophilic sites in the α, β-unsaturated carbonyl compound .
(i) The carbonyl carbon atom; and
(ii) The beta (β) carbon atom.
O O O
CH2 CH C H CH2 CH C H CH2 HC C H
Acrylaldehyde Electrophilic site
Electrophilic site
Thus when a “carbon-carbon” double bond (C=C) is in conjugation with a carbonyl
group then the “nucleophilic addition reaction” can occur either at the carbonyl
carbon atom or at the beta (β) carbon atom.
Direct addition reaction or normal addition reaction or 1, 2-addition reaction.
1O 1O
H 1OH
2 2 H O H 2
CH2 CH C R +Nu CH2 CH C R CH2 CH C R +H2O
Nu Nu
1,2-Addition
Conjugate addition reaction or 1, 4-addition reaction
H
1O O H O H O O H
2
Nu + CH2 CH C R CH2 CH C R CH2 CH C R CH2 CH C R
4 3
1,4-Addition Nu Nu Nu Enol form
Resonance structures of the enolate ion O
CH2 CH C R
Nu H
Keto form
(More stable)
(i) Nature of the nucleophile;
(ii) The structure of the carbonyl group or the reactivity of the carbonyl compounds;
(iii) The conditions under which the reaction is carried out.

(i) Nature of the nucleophile

If the nucleophile is a strong base (such as Grignard reagent, RMgX or hydride ion,
NaBH4, etc.) then the direct addition reaction (kinetically control reaction) .
OH
R CH2 CH C R
Strong C-Nu bond
O Nu
R CH2 CH C R +NuH Direct addition reaction
O
Strongly basic
nucleophile R CH2 CH2 C R
Nu
Conjugate addition reaction
(Kinetically control product)
If the nucleophile is a weak base (such as halide ion, cyanide ion, thiol, or amine)
then the direct addition (kinetically control reaction) reaction is reversible.
OH
R CH2 CH C R
O Weak C-Nu bond
Nu
R CH2 CH C R +NuH Direct addition reaction
O
Weakly basic R CH2 CH2 C R
nucleophile
Nu
Conjugate addition reaction
(Thermodynamically control product)
 Conjugate addition
O O
CH2 CH C CH3 +HBr CH2 CH2 C CH3
Acrylaldehyde Br
(ii) The structure of the carbonyl group or the reactivity of the carbonyl
compounds
The compounds with more reactive carbonyl groups forms primarily the direct
addition (1,2-addition or kinetically control addition) product and the compounds
with less reactive carbonyl groups forms conjugate addition (1,4-addition or
thermodynamically control addition) products and the carbonyl addition (direct
addition) products .
O
CH2OH
H (i)NaBH 4
More reactive (ii) C2H5OH
carbonyl group
O Less reactive O OH
carbonyl group
(i)NaBH4
+
(ii) C2H5OH
Cyclohexenone Conjugate Direct
addition addition
(49%) (51%)
(iii) The conditions under which the reaction is carried out
(a) If the direct addition product (1, 2 addition or kinetically control addition) is the
desired product from the reduction of cyclohexenone with the reducing agent sodium
borohydride (NaBH4) then the reduction should be carried out in the presence of the
Lewis acid cerium chloride (CeCl3).
Cl
O Less reactive OH O Ce Cl
carbonyl group
Cl
(i)NaBH4, CeCl3 More electrophilic
(ii) C2H5OH carbonyl carbon atom
Cyclohexenone Direct addition Cyclohexenone
(99%)
(b) Grignard reagents react with the more reactive α, β-unsaturated aldehydes and
unhindered (reactive) α, β-unsaturated ketones to form the direct addition products.
O OH
(i) CH3MgBr
CH2 CH C H (ii) C H OH CH2 CH C H
2 5
Acrylaldehyde CH3
Direct addition product
(c) The rate of the direct addition reaction is slowed down by the steric hindrance
and forms conjugate addition product .
O O
(i) C6H5MgBr
CH2 CH C CH2 CH2 C
(ii) C2H5OH
(d) When α, β-unsaturated aldehydes and ketones are treated with Gilman reagent
(lithium dialkylcuprate) then forms exclusively conjugate addition (1, 4- addition or
thermodynamically control) product.
O O

(i)(CH3)2CuLi
(ii) C2H5OH
CH3
Michael addition reaction
When a “carbon-carbon double bond” (C=C) is in conjugation with a carbonyl group
then it easily undergoes “nucleophilic addition reaction” instead of “electrophilic
addition reaction”. If an aldehyde or a ketone has a “carbon-carbon double bond”
(C=C) in the α, β-position then a nucleophile can add either to the carbonyl carbon
atom (direct addition) or to the beta (β) carbon atom (conjugate addition).

If the nucleophile Nü is an weak “enolate anion” (when an active methylene group has
a negative charge) then the above conjugate addition reaction is called the “Michael
addition reaction”. The “enolate anions” that work best in the Michael addition
reactions are those that are “flanked” by two electron withdrawing (aldehydes, ketone,
esters, nitriles, etc.) groups that is; the “enolate ions” of β-diketones, β-diesters, β-
keto-esters and β-keto-nitriles, etc.
 O O O O O O
H2O
R C CH C R + OH R C CH C R R C CH C R
H An enolate ion (weak base)
-Diketone
Michael addition reaction
O O O O
HO
CH2 CH C H + CH3 C CH2 C CH3 H O CH2 CH2 C H
2
Acrylaldehyde -Diketone CH3 C CH C CH3
O O
Mechanism for the Michael addition reaction
O O O O O O
H 2O
R C CH C R + OH R C CH C R R C CH C R
H An enolate ion (weak base)

O O O O
  HO
R CH CH C R + R C CH C R R CH CH C R
H O
R C CH C R H
O O O
R CH CH2 C R
R C CH C R
O O
Alternative way
O O O O O
 
R CH CH C R + R C CH C R R CH CH C R R CH CH C R
R C CH C R R C CH C R
O O O O
O
H CH(COR)2
CH(COR)2 + R CH CH2 C R
Enolate ion
R C CH C R
regenerate
O O
C 2H5 O
CH2 CH C N + 2 CH (COOC H )
2 5 2 C H OH H2C CH2 C N
Diethylmalonate 2 5
Acrylonitrile CH(COOC2H5)2
Same group
O O O
CH3 C OCH3 + OCH3 CH3 C OCH3 CH3 C OCH3 + OCH3
Same of the
OCH3
starting ester
 Active methylene compounds
CH2(COOC2H5)2 CH3COCH2COOC2H5 C2H5OOCCH2CN CH2(COCH3)2
Diethyl malonate Ethyl acetoacetate Ethyl cyanoacetate Acetyl acetone
(Malonic ester) (Acetoacetic ester) 2,4-Pentanedione)

CH2(CN)2 CH2(NO2)2
Malononitrle Dinitromethane
(Dicyanomethane)
Synthetic applications of the active methylene compounds
Synthesis of substituted ketones

O O Na O O Na O
C H O Na
CH3 C CH2 COOC2H5 2 5 CH3 C CH C OC2H5 CH3 C C C OC2H5
C2H5OH
Ethyl acetoacetate Na H
(Acetoacetic ester) O O
Enolate ion (Nucleophile)
CH3 C C C OC2H5
H

O Na O O O
Br-CH2CH2CH2CH3
CH3 C CH C OC2H5 CH3 C CH C OC2H5 +NaBr
SN2 Reaction
CH2CH2CH2CH3
 O O O O
Dilute NaOH, Heat
CH3 C CH C OC2H5 CH3 C CH C O Na
C2H5OH
CH2CH2CH2CH3 CH2CH2CH2CH3
H3 O
O o
O O
100 C
CO2 + CH3 C CH2 CH3 C CH C OH
CH2CH2CH2CH3 CH2CH2CH2CH3
If we want to prepare a disubstituted acetone.
O O
(i) C2H5O Na / C2H5OH
CH3 C CH2 COOC2H5 CH3 C CH COOC2H5
(ii) CH3CH2CH2CH2Br
Ethyl acetoacetate CH2(CH2)2CH3
(Acetoacetic ester)
(i) (CH3)3CO K
(ii) CH3(CH2)2CH2Br
O CH2(CH2)2CH3 O CH2(CH2)2CH3 (i)Dilute O CH2(CH2)2CH3
Heat NaOH
CH3 C C H CO2 CH 3 C C COOH CH3 C C COOC2H5
(ii) H3O
CH2(CH2)2CH3 CH2(CH2)2CH3 CH2(CH2)2CH3
3-Butyl-2-heptanone
Phenylation of active methylene compounds.
O O O
Liquid NH3
CH3 C CH2 COOC2H5 + C6H5Br + 2NaNH2 CH3 C CH C OC2H5
Ethyl acetoacetate C 6 H5
(Acetoacetic ester)
Mechanism of the reaction

O O Br
NaNH2 Na
CH3 C CH2 COOC2H5 CH3 C CH COOC2H5 
NH3
Ethyl acetoacetate Enolate ion
(Acetoacetic ester)
Br Br
NH3
+ Br
H
NH2
O O O O O
Na
+ CH3 C CH COOC2H5 CH3 C CH C OC2H5 CH3 C CH C OC2H5

Na +NaNH2
H NH2
Diels-Alder reaction
When a conjugated diene is treated with a compound containing a “carbon-carbon
double bond” (C=C) or “carbon-carbon triple bond” (C≡C) under the influence of
heat then the two compounds combine to form a cyclic compound.
4 Nucleophilic center New sigma () bond
CH2
3 CH2
+ Heat
2
CH2 Pressure
CH2 New sigma () bond
1 Ethylene Electrophilic Cyclic transition
Diene center New pi () bond
(Two pi() state
(Four pi() electrons)
electrons) (Six pi () electrons)

Effect of substituents on dienes and dienophiles

The electron withdrawing group in the dienophile
O O O

CH2 CH C CH3 CH2 CH C CH3 CH2 CH C CH3
Resonace structutres of the dienophile Resonance hybride

O New sigma () bond O

4
H 3 CH2 C C CH
CH3 30 o
C 3
+
H 2 CH2 CH2 New sigma () bond
1 New pi () bond
Electron releasing group in the diene
OCH3 O OCH3 O O
4CH
C C H C H
3 H Heat +
+
2
CH2 CH2 Major product
1 OCH3
Both are unsymmetrical Minor product

Constitutional isomers

OCH3 O OCH3 O O O
CH C C H CH2 C C H
H Heat or H Heat
+ +
CH2 CH2 Major product CH CH2
OCH3 OCH3
Minor product

CH2 CH CH CH O CH3 CH2 CH CH CH O CH3

 
CH2 CH CH CH O CH3
 Hydroxy ketones
O O
R C CH CH3 R C CH2 CH CH3
OH OH
-Hydroxy ketone -Hydroxy ketone
Only the alpha (α) hydroxy ketones that can tautomerize to form alpha (α) hydroxy
aldehyde in the presence of base will give a positive Tollen's test.
O O
CH3 C CH OH CH3 C CHO
H
-Hydroxy acetone