Aldehyde Ketone Notes

Brilliant STUDY CENTRE LT.
22 (RES) (ONLINE CLASS NOTESA)
LT.22 (RES)
CHAPTER - 00
ALDEHYDES AND KETONES
In aldehydes the functional group is –CHO while in ketones the functional group is C O. Therefore
both aldehydes are ketones are collectively called carbonyl compounds due to the presence of
common C O group in their functional groups. They can be represented by the general formula
CnH2nO. They are functional isomers. They are widely spread in plants and animals kingdom. They
are responsible for a fragrance and flavour of the naturally occuring compounds. Eg : Vanillin from
vanilla beans. Cinnamaldehyde from (Cinnamon)
CHO CHO
OH
CH CH CHO
OCH3
Salicylaldehyde
OH (from meadow sweet)
Structure and Nomenclature

The carbonyl carbon is sp2 hybridised having trigonal planar structure and approximately 120° bond
angles.

C O C O

The carbon-oxygen double bond is polarised due to higher electronegativity of oxygen and as a result
of this, carbonyl carbon is an electrophile (Lewis acid) and oxygen is nucleophile (Lewis base). Hence
they have high dipole moments.
1
Brilliant STUDY CENTRE LT.22 (RES) (ONLINE CLASS NOTESA)
H–CHO Methanal or Formaldehyde
CH3 – CHO Ethanal or Acetaldehyde
CH3 – CH2 – CHO propanal
CH3 CH CHO Isobutyl or 2-methyl propene
CH3
CHO
3-Methyl cyclohexane carbaldehyde

CH3
CHO
Benzaldehyde
CHO
CHO
Phthalaldehyde or Benzene 1, 2-dicarbaldehyde
CHO
Glyoxal or Ethane 1, 2-Dial
CHO
CH2 CH CH2 Propane-1, 2, 3-Tricarbaldehyde
CHO CHO CHO
CH3 C CH3 Acetone or propanone
CH3 C CH2 CH3 But-2-one
2
O O
CH3 C CH2 C CH3 Pent-2, 4-Dione
O
Cyclopropanone
Cyclohex-1, 3-dione
O
C
CH3 1-Phenyl ethanone or acetophenone
C CH2 CH3 1-Phenyl propanone
C Benzophenone
CH3 C CH2 CHO 3-oxo butanal
CHO
2-Bromo-6-oxo-cyclohexenecarbaldehyde
Br
3
CH2 = CH – CHO Acrolein or Acraldehyde prop-2-enal

CH3–CH = CH – CHO Crotonaldehyde or but-2-enal
O
CH3
C CH C CH3
4-Methylpent-3-en-2-one
CH3 (MEO)
O
CH3 CH3
C CH C CH C
2, 6-Dimethyl-hept-2, 5-dien-4-one
CH3 Phorone CH3
PREPARATION OF ALDEHYDES AND KETONES

1. Oxidation of alchols : A number of mild oxidising agents like, PCC (pyridinium chloro chromate) a
mixture of pyridine, HCl and CrO3 in CH2Cl2.
, PDC pyridiniumdichromate Collius reagent.

HCrO3Cl
and CrO3 in CH2Cl2, etc are used to oxidise 1° alcohols to aldehydes and 2° alcohols to
N
ketones.
R R
PCC
CHOH C O
ie R  CH 2 OH 
 O   R  CHO
R R
These reagents do not attack the double bonds during their oxidation.
OH O
(O)
PCC
  CH 2  CH  CH 2OH  CH 2  CH  CHO
Alkylalcohol
4
Similarly active MnO2 (prepared by reducing KMnO4 with MnSO4/OH–) oxidises allylic and Benzylic
alcohols to ,  -unsaturated aldehydes.
CH CH CH2OH
CH CH CHO


Acidified KMnO4, K2Cr2O7 etc are not used as the aldehydes first formed oxidised carboxylic acid.
This is because water present in it reacts with initially formed aldehyde to form aldehyde hydrate
which further reacts H2CrO4 to form chromate ester and which is oxidised to form carboxylic acid.
Saturated and unsaturated 2° alcohols are oxidised to unsaturated ketones by aluminium tert-butoxide,
and is called oppenauer oxidation.
R CH3 R CH3
 CH 3 3 CO  3 Al
 
CH OH + C O   C O+ CHOH
R CH3 R CH3
This oxidation occurs through hydride transfer from 2° alcohol to acetone.

2. By catalytic dehydrogenation of alcohols: 1° alcohol vapours when passed over heated Cu at 573
K form an aldehyde, while 2° alcohol from a ketone. But 3° form at an alkene due to elimination.
Cu /573K
CH 3  CH 2  OH   CH 3  CHO  H 2
CH3
Cu/573 K
CH OH CH3 CHO + H2
CH3
O
CH3 Cu/573 K
CH OH CH3 C CH3 + H2
CH3
CH3
Cu/573 K
C OH CH3 C CH2 + H2O
CH3
CH3 CH3
5
3. By dry distillation of calcium salts and fatty acids: Calcium formate on dry distillation form methanal
while any other acid salts gives symmetrical ketones.
H COO
Ca H CHO + CaCO3
H CO O
O
O
CH3 C O
CH3 C CH3 + CaCO3
Ca
CH3 C O
But a mixture of calcium salt of formic acid and acetic acid on distillation form H–CHO, CH3 C CH3
and CH3 – CHO. No propanal is formed.
O
H COO C
CH3 H-CHO + CH3CHO + CH3 C CH3 + CaCO3
Ca + Ca
H COO CH3 C O
This method is not suitable for the preparation of aldehydes except formaldehyde due to low yield
formation.
But if calcium salt of dicarboxylic acids are used, 5 or 6 membered cyclic ketones are formed having
one carbon atom less than the acid.
CH2 CH2 C O
Ca C O + CaCO3
CH2 CH2 C O
Cycopentanone
O
6
4. From fatty acids: Formic acid alone oxidation gives formaldehyde in presence of MnO/573 K. Acids
other than formic acid gives ketones whereas a mixture of formic acid gives ketones whereas a
mixture of formic acid and any other acid gives aldehydes other than formaldehyde.
MnO/573
H  CO OH  HCOO  H   H  CHO  CO 2  H 2O
CH 3  CO OH  HCOO H 
 CH 3  CHO  CO 2  H 2O
CH3 CO OH + HOOC CH3 CH3 C CH3 + CO2 + H2O
5. From hydrocarbons :
(a) Hydration of alkynes
In presence of 1% HgSO4 and 20% dil.H2SO4 alkynes add a molecule of water to form aldehydes or
ketones. By this method only ethyne form ethanal, but all other alkynes form ketones. Formaldehyde
can not be prepared by this method. In this addition, first an intermediate compound is formed which
tautomerised to form aldehydes or ketones.
H
2+ +
Hg /H
CH CH + H OH CH2 CH 
Tautomerism
OH  
 CH3 C O
CH3 C CH2 CH3 C CH3

CH3 C CH + H2O
OH
CH3 CH2 CH C CH3 CH3 CH2 CH2 C CH3

CH3 CH2 C C CH3
OH O
O
OH
C CH2 CH3
C C CH3 C CH CH3

+ H2O 
7
(b) Hydroboration-oxidation of alkynes : [HBO]
Non terminal alkynes on HBO form ketones while terminal alkynes form aldehydes. But unsymmetrical
non-terminal alkynes form ketones in which keto group stay with smaller alkyl group.
CH3
H2O2
B2H6 B
1. 6CH3 C C CH3 2 CH3 CH C NaOH
THF 3

Tautomerises
CH3   CH C CH3
6CH3 CH2 C  6 CH3
O OH
Anenol
+ CH3 CH2 C CH2 CH3

(1) B2 H 6 /THF C CH2 CH2 CH3
2. CH 3  C  C  CH 2  CH 3 
(2) NaOH /H 2O 2
 CH3
(Major) O
(Minor)
(1)B2 H 6 /THF
3. CH 3  C  CH 
(2) NaOH  H 2 O2
CH 3  CH 2  CHO
Aldehydes can also be prepared from terminal alkynes by using sterically hindred boranes like bis (1,
2 dimethyl propyl) borane known as disimyl borane in place of B 2H6.
(1)R 2 BH
CH3 C CH 
(2)H O /OH 
 CH 3  CH 2  CHO
2 2
(c) By ozonolysis of alkenes

Alkenes on reductive ozonolysis form aldehydes and ketones.
CH 2 Cl 2
Eg : CH2 + O3  CH2 O CH2 
Zn /H 2O
2H CHO + H2O2
CH2 O O
CH3 CH3
CH3 CH3 O CH3
C C 2 C O + H2O2
C C Ozonolysis
  CH3 CH3
CH3 CH3
CH3 O O
8
Note:
By this method we can locate the position of double bonds, estimate the number of double bond, and
elucidate the structure of hydrocarbon. If one molecule contain two carbonyl groups, then hydrocarbon
will be alkadiene. If all compounds contain two carbonyl group then hydrocarbon will be cycloalkatriene.
It is used for the prepartion of aliphatic carbonyl compounds.
(d) Oxidation of alkenes - Wacker process
Alkenes are oxidised to aldehydes and ketones in presence of air using PdCl2 containing CuCl2.
CuCl 2
CH 2  CH 2  H 2 O  PdCl2 
O2
 CH 3  CHO  Pd  2HCl
CH3 CH CH2 + H2O + PdCl2 CH3 C CH3 + Pd + 2HCl
Only ethene form ethanal while higher alkenes will give ketones. In this reaction PdCl2 reduced to Pd.
The function of CuCl2 is to oxidise Pd to PdCl2 and CuCl2 is reduced to Cu2Cl2 which itself, reoxidised
to CuCl2. CuCl2 is called supporting catalyst in this reaction.
6. From dihalides
Terminal geminal dihalides on alkaline hydrolysis form aldehydes while non-terminal geminal dihalide
form ketones.
OH
2KOH CH
CH3 CHCl2 CH3
-2KCl 
 CH 3  CHO
 H 2O
OH
Cl CH3 O
CH3 C CH3 

2KOH
 CH3 C OH 
 CH3 C CH3
2KCl  H2O
CH3 OH
OH
CH3 CHCl2 CHO
CH
2Cl2 KOH OH

38K
   

9
7. Rosenmund reduction
Acid chlorides are easily reduced to the corresponding aldehydes by H2 in presence of Pd-supported
over BaSO4 in boiling xylene.
O
Pd BaSO4/S
R C Cl + H2 R CHO + HCl
Xylene
O
Pd BaSO4/S
CH3 C Cl + H2 CH3 CHO + HCl
Xylene
COCl CHO
Pd BaSO4/S
+ H2 + HCl form 3° alcohol. This is because C Mg
Xylene
bond is more polar than C Cd
8. From nitriles and esters

When an ethereal solution of a nitrile is reduced with SnCl2 and HCl at room temperature, aldimine
hydrochloride is precipitated which on hydrolysis with H2O gives aldehydes.
SnCl2  2HCl 
 SnCl 4  2[H]
H 2 O/ 
CH 3  C  N  2  H   HCl 
 CH 3  CH  NH.HCl   CH 3  CHO  NH 4Cl
Ethanal dimine hydrochloride
CHO
CH NHHCl
H2O/
C N + 2(H) + HCl + NH4Cl
This is called Stephens reduction. But nitriles can be selectively reduced by diisobutyl aluminium
hydride [DIBAL-H] to aldehydes.
(1)DIBAL  H
R  C  N 
(2)H 2 O/ 
 R  CHO  NH 3 . It is also used to reduce unsaturated nitriles to unsaturated
aldehydes and esters to aldehydes and alcohol.
10
DIBAL  H
CH 3  CH  CH  CH 2  CN   CH 3  CH  CH  CH 2CHO
CH 3   CH 2 9  COOC2 H5 
 CH 3   CH 2 9  CHO C2 H 5OH
Ethyl undeeonoate UNDECANAL
Aldehydes are also prepared by the action of R–MgX on orthoformic esters.
OC2H5
OC2H5
CH3 MgBr + H C OC2H5 Dry ether
CH3 CH H3O+ OH
CH3 CHO + 2C2H5
OC2H5 OC2H5
1. Formaldehyde cannot be prepared by the method since HCOCl is unstable gas at room temperautre.
2. BaSO4/S/quinoline acts as a catalytic poison.
3. If Pd/Li[AlH4] or Na[BH4] used for reduction final product will be an alcohol.
Similarly acid chlorides can be converted into aldehydes by Lithium tri-tert-butoxy aluminium hydride
at 296 K.
O
LiAlH(O  t  Bu)3
R C Cl 
in ether at
 R  CHO
This reducing agent is less reactive Li[AlH4] because the electron withdrawing t-Butoxy group stabilizes
the negatively charged aluminium ion. Ketones cannot be prepared by Rosenmund reduction.
But ketones can be prepared by the action of dialkyl cadmium on an acid chloride in ether medium.
O O
/ /
2R C Cl + R2Cd 2R C R + CdCl2
O O
2CH3 C Cl + (C2H5)2Cd 2CH3 C C2H5 + CdCl2
COCl COCH3
2 + (CH3)2Cd 
2 + CdCl2
Grignard reagents cannot be used in place of R2Cd because RMgX is more reactive than R2Cd to
ketones that further with RMgX. Both aliphatic and aromatic ketones can be prepared by the action of
RMgX on an alkyl or aryl nitrile followed by acid hydrolysis of intermediate addition product.
11
NMgBr
H3O+
dryether
CH 3  CH 2  MgBr  CH 3  C  N  CH3 CH2 C CH3
NH3 + Mg(OH)Br + CH3 CH2 C CH3
NMgBr
MgBr C
Dry
C2H5 H3 O 
+ CH3  CH 2  C  N 
 ether  
OH
C
C2H5 + NH3 + Mg
Br
If instead of alkyl or aryl nitrites, HCN is used in the above reaction, aldehydes will be formed.
CH3
OH
+
H C N + CH3 MgBr H H3 O+ CHO + NH3 + Mg
C NMgBr CH3
Br
9. From aromatic hydrocarbon:

1. Toluene can be oxidised to Benzaldehyde in presence of CrO 2Cl2 in CS2 or CCl4. The brown chromium
complex is separated and decomposed with dil.acid form benzaldehyde.
OCrCl2OH
CH3 CH CHO
OCrCl2OH
2CrO 2 Cl 2

CCl4 /CS2
 H3O+
This called Etard’s reaction. Similarly m-xylene on oxidation form m-Tolualdehyde.

Benzaldehyde is also prepared by the oxidation of toluene in presence of CrO3 in AC2O[(CH3)2CO]
12
OCOCH3
CH3 CH CHO
OCOCH3
CrO3 / Ac 2O

283K
 H3O+ + 2CH3COOH
Benzaldehyde to benzoic acid is avoided by trapping the aldehyde as gem-diacetate which cannot be
furtehr oxidised.
Gattermann-Koch reaction: When a mixture of CO and HCl gas is passed through a solution of
benzene or toluene in nitrobenzne at 323 K in presence of AlCl3 and CuCl, benzaldehyde is formed.
CO  HCl 
 HCOCl(unstable gas)
CHO
AlCl 3 /CuCl
+ HOCl   + HCl
This is also called Gattermann-Koch formaylation or aldehyde synthesis reaction.

But in Gattermann aldehyde synthesis or Gattermann formylation instead of CO in the above
reaction, here HCN is used.
CH NHHCl CHO
AlCl3
+ HCN + HCl   H3O+ + NH4Cl
Benzylchloride on oxidation in presence of Pb(NO3)2 or Cu in a current of CO2 produces benzaldehyde.
CH2Cl
2 + Pb(NO3)2 
 2C6 H 5 CH 2 ONO 2  PbO 2
O
C6H5 CH O N 
 C6 H 5 CHO  HNO 2
O
H
13
10. Reimer-Tiemann reaction : Treatment of phenol with CHCl3 and aqueous NaOH or KOH at 340 K
followed by hydrolysis form 2-hydroxybenzaldehyde or salicylaldehyde.
ONa
OH ONa OH
CHCl2 OH
CH CHO
NaOH 2NaOH  H2O
+ CHCl3    

340 K 2NaCl OH 
ONa
CHO
Dil.HCl

A small amount of p-hydroxy Benzaldehyde is also formed. This is an electrophilic substitution

Cl
reaction in which the electrophile is C (dichloro carbene)
Cl
11. Friedel - Crafs acylation reaction

It is one of the most convenient method used for the preparation of aromatic ketone in which the keto
group is attached to the aromatic ring. It involves the treatment of aromatic hydrocarbon wit acid
halide in presence of AlCl3.
Anhydrous AlCl3
+ CH3 – COCl  COCH3 + HCl
O
Anhydrous AlCl3
+ C6 H 5 COCl  C + HCl
2 + Cl Phosgene
CO  Cl 
Anhydrous AlCl3
C + 2HCl
This is an electrophilic substitution reaction.
14
12. Oxo process : It is also called carbonylation. In this reaction terminal alkene reacts with water gas
at high temperature and pressure in presence of cobalt carbonyl catalyst to form aldehyde.
  CO  CO  
4 2
R  CH  CH 2  CO  H 2 
high P
 R  CH 2  CH 2  CHO  R CH CH3
CHO
13. By acid hydrolysis of  -keto ester:-
O O
 CO2 C CH3
CH3 C CH2 H 3O
COOC2H5   CH3 C CH2 COOH CH3
 C2 H5 OH 
O
It is the  -ketoacid Decarboxylate more easily through the formation of six membered cyclic transition
state intermediate.
H
H
O O O O
C CH2 C O CH3 C C O
CH3 CO2
CH2
O OH
CH3 C 
Tautomerism
CH3  
 CH3 C CH2
14. By the oxidation of syn vicinal diols with LTA (CH3COO)4Pb (Lead tetra acetate) or NaIO4 form
aldehydes.
R CH CH R/ 
Pb CH 3COO 4
 R  CHO  RCHO
OH OH
Anti vicinal diols donot give this reaction because cyclic intermediate is not formed.
R R
O
R/ C OH R/ C O
I O
+ IO 4 
 /
R/ C OH R C O O
R R
15
15. Physical properties of aldehydes and ketones
The first member of the aldehyde series, formaldehyde, is a gas at room temperature, while the next
ten members are colourless volatile liquids. Ketones upto eleven carbon atoms are colourless volatile
liquids. But higher members are solids. But aqueous solution of formaldehyde is called formalin;
Which is 40% H–CHO, 8% CH3OH and 52% H2O, Used as a preservative for anatomical specimens.
On long storage it undergoes trimerisation and polymerisation form solid particles.
CH2
O O
Polymerisation
Trimerisation nCH 2O    CH 2O n
3CH 2 O 

CH2 CH2 Paraformaldehyde
O
Trioxine
O
CH CH CH3
Similarly 3CH 3  CHO 

O O
CH
CH3
Paraldehyde used as a hypnotic medicine
4CH 3  CHO 
 CH3 CH O CH CH3
O
O
CH3 CH O CH CH3
Metaldehyde
Lower aldehydes have unpleasant odour but higher members have fruity smell. Aromatic aldehydes
and ketones possess pleasant smell. They are almost solids and liquids.
Solubility - Lower aliphatic aldehydes and ketones are soluble in H2O due to formation of H-bonding
with water but it decrease with increase in molar mass. Aromatic aldehydes and ketones are insoluble
in H2O but soluble in organic solvents.
Boiling points : The boiling points of aldehydes and ketones are higher than those of ethers and
hydrocarbons of comparable molar masses due to dipole-dipole interactions. (Vander Waals force of
attraction) but lower than those of corresponding alcohols and acids due to the absence of H-bonding.
Among isomeric aldehydes and ketones, ketones have slightly higher boiling points due to slightly
higher dipole moments because of the +I effect of the two alkyl groups.
16
Reactivity of aldehydes and ketones: They mainly undergoes nucleophilic addition reactions because
the intermediate anion formed is more stable than cation as the less stable sp2 hybridised carbonyl
carbon is transformed into more stable sp3 hybridised carbon, which then picks up a proton either
from a solvent or from the reagent to complete the addition.
Nu Nu
R
slow step E+ C OE
C O + Nu R C O R
Fast
R (Anion)
R R
If the attacking nucleophile is weak, the nucleophilic addition reactions are usually carried out in weakly
acidic medium. This is because the carbonyl group gets protonated, by resonance which increases
the positive charge on teh carbonyl carbon and thereby makes it more electrophilic. As a result weak
nucleophiles adds to the carbonyl group easily.
Nu
C O+H +
C OH C OH Nu C
OH
In general aldehydes are more reactive than ketones due to the following reasons. The relative
reactivities of aliphatic aldehydes and ketones depends upon the following factors.
1. +I effect of alkyl groups : Greater the number of alkyl groups attached to the carbonyl group, higher
is the electron density on the carbonyl carbon and hence lower is its reactivity towards nucleophilic
O
addition reactions. Thus reactivity order decreases as H–CHO > CH3 – CHO > CH3 C CH3.
CH3
CH3
Similarly H – CHO > CH3 – CHO > CH CHO > CH3C CHO
CH3
CH3
2. Steric effects : As the number and size of the alkyl groups attached to the carboxyl carbon increases,
the attack of the nucleophile on the carbonyl group becomes more and more difficult due to steric
hindrance. Hence the reactivity decreases as
H  CHO  CH 3  CHO  CH3 COCH3  CH 3  CO  CH 2  CH 3 > pentan-3-one > Di-isopropyl

ketone.
In general aromatic aldehydes and ketones are less reactive than aliphatic analogues. This is due to
+R effect of the benzene ring which reduces nucleophility of the carbonyl carbon as below.
17
H C O
C O H C O
H C O H C O H
CHO COCH3
O
Thus reactivity order of follows > > C
Again, the presence of electron donating groups in the benzene ring decreases the electrophilicity of
the carbonyl carbon and hence decreases the reactivity of aldehydes and ketones while the presence
of electron withdrawing groups increases the reactivity of aldehydes and ketones towards nucleophilic
addition. Hence the order of reactivity is
CHO CHO CHO CHO CHO CHO

CHO
> > > > > >
NO2 CN Cl CH3 OCH3 OH
Some important nucleophilic addition reactions are:

1. Addition of HCN : - Aldehydes and ketones react with HCN to from cyanohydydrins very slowly
because HCN is a weak acid. Hence it is catalysed at pH = 9 - 10 in presence of a base.
OH 


HCN 
 H 2 O  CN

OH
C O + HCN C
CN
OH
R C O + HCN R C CN
H H
Cyanohydrin
18
–
Addition of CN is a slow step and hence it is a nucleophilic addition. These cyanohydrins are good
synthetic reagents used for the synthesis of substituted acids.
H H
H
H3O+
CH3 C O + HCN CH3 C CN CH3 C COOH
OH OH
Lactic acid
CN
H C O H C OH
+ HCN 

Mandelic acid
This type of synthesis of an optically active compound from an optically inactive compound without
recourse to resolution is called Asymmetric synthesis.
2. Addition of NaHSO3 : Most of the aldehydes and aliphatic methyl ketones, aromatic aldehydes like
benzaldehyde react with a saturated solution of NaHSO3 to form white crystalline products. Higher
ketones and other aromatic compounds do not react due to steric effect.
H
R OH
R C O + NaHSO3 C
H SO3Na
R R OH
C O + NaHSO3 C
R SO3Na
R
These bisulphite addition products are further hydrolysed to give back pure aldehydes and ketones.
R OH R
C C O + SO2 + HCl + H2O
+ HCl 

H SO3Na H
 This property is used in the separation and purification of aldehydes and ketones.
19
3. Addition of Grignard reagents: Formaldehyde react with RMgX form 1° alcohols. All other aldehydes
form 2° alcohols but ketones under similar condition form 3° alcohols.
H H H
OH
H3O+ OH + Mg
H C O +R MgX H C O MgX H C
X
R R
H H
H
C OMgX C OH
C O + RMgX 

R R
CH3 CH3 CH3
C O + RMgX 
 C OMgX C OH
R R
But  or  - Halogenated carbonyl compound on treatment with RMgX form a five or six membered
cyclic ether.
O
Intramolecular
CH3 C CH2 CH2 CH Br + RMgX 
SN reaction

  
C CH2 CH2 CH2 CH3

CH3
R O
OMgX Br
Cyclic ether
4. Addition of water : Aldehydes and ketones react with H2O to form 1, 1 diols or gemdiols or hydrates
which are unstable to be isolated.
OH
C O +H OH C
OH
20
The reaction is reversible and position of equilibrium depends upon steric and electroni factors. The
tendency to form hydrate decrease with steric hindrance and increase with the presence of electron
withdrawing substituents.
H
Cl Cl
O

 
Cl C C O + H 2O Cl C CH
O
Eg : Cl Cl
Chloral H
Chloral hydrate
This hydrate is stabilized by intramolecular H-bonding.
CH CHO
For Eg : CH3 form hydrate in low yield but benzaldehyde with the same amount of
CH3
steric hindrance does not. This is because the +R effect of the benzene ring reduces the positive
charge at the carbonyl carbon and thereby opposes the hydrate formation.
5. u: Aldehydes react with one equivalent of monohydric alcohols in the presence of dry HCl gas to form
alkoxy alcohol intermediate called hemiacetals which further react with another molecule of alcohol to
form gem-dialkoxy alkane called acetals:
OR/ OR/

R OH
R  CHO  
R C 
H  
R OH
R C H + H2O
dry HCl H
H
OR/
Hemi acetal
Acetal
OC2H5 OC2H5
H

C2 H5 OH
CH3 C H 
C2 H5 OH
 C H + H2O
CH3 C O 
H
 
H
 CH3
H OC2H5
Ketones do not react with monohydric alcohols but with dihydric alcohols under similar condition form
cyclic ketals.
21
R O CH 2
R HO CH 2
C + H2O
C O+ 
dil.HCl

HO CH 2 R O CH 2
R
CH3 CH3
HO CH2 O CH2
C  C
O+ 
H or
 
 + H2O
PTS O CH2
HO CH2 CH3 CH3
The function of dry HCl is to protonates the oxygen of the carbonyl compounds and hence increses
the electrophilicity of the carbonyl carbon facilitating the nucleophilic attack. These acetals and ketals
are hydrolysed to give back original aldehydes and ketones. Hence they are used to protect these
groups in organic synthesis. Like alcohols, alkane dithiol reacts with aldehydes and ketones in presence
of BF3, HCl etc form cyclic thioacetals and ketals.
CH3 CH3
HS CH2 S CH2
C O+ BF3  Ether
  C
HS CH2 CH3 S CH2
CH3
Diethyldimethyl mercaptol
6. Reaction with Ammonia and its derivatives:

Aldehydes and ketones react with a number of ammonia derivatives like NH 2OH, NH2–NH2,
C6 H 5  NHNH 2 , O2N NH NH2 (2, 4-DNPH) (Called Brady’s reagent) and
NO2
NH C NH2 in weakly acidic medium (pH = 3.5) to form compounds containing C N

NH2
O
groups called Schiff’s base or azomethines.

C O + H2 N
H (pH  3.5)
OH  C N OH oximes
 H2 O

H
C O + H2 N NH2 
 H2O
 C N NH2 Hydrazone
22
C O + H2 N NH 
 H2O
 C N NH Phenyl hydrazone
C O + H2N NH NO   C N NH NO2

 H2O
NO2
NO2
C O + H2N NHCO NH2   C N NHCO NH2

H O 2
Semicarbazide
All these derivatives are crystalline solids with sharp M.P. and hence used for the identification of
aldehydes and ketones. These derivatives when hydrolysed by dil.acids to regenerate original aldehydes
and ketones. Hence these are used for purification of carbonyl compounds.
If pH is less than 3.5, these ammonia derivatives will be converted into ammonium salt, which is an
electrophile and hence nucleophilic addition will not occur.
NH2 Z 
pH  3.5
 NH3 Z (Electrophile)
+ H+
Ammonium salt
If pH > 3.5, the carbonyl group will not get protonation. ie the positive charge on the carbonyl carbon
will not increase and hence the reaction will not occur. Hence, an optinum pH of 3.5 should be
maintained.
In case of semicarbazide the –NH2 group attached to the C directly is not involved in resonance
O
and hence is available for nucleophilic attack on carbonyl gorup.
Reaction with NH3:
H–CHO react with NH3 to form hexamethylene tetramine or urotropine used as a urinary antiseptic.
  CH 2 6 N 4  6H 2 O
6CH 2O  4NH 3 
Urotropine
23
NO2
CH2 N
CH2 CH2
N (RDX)
CH2 Nitration
CH2 

at elevated temperature
2N N N NO2 [Research development explosive]
N N
used as most Cydonite
CH2 powerful explosive
Urotropine
Other aldehydes react with NH3 to form amino alcohols which lose a molecule of H2O to form adimines.
CH3 OH H
CH3
C O C
+H NH2 
 H2O
 CH3 C NH
H NH2
H Acetaldimine
But benzaldehyde reacts with NH3 form a complex product called hydrobenzamide.
H H
H
C6H5 C O H2 N H C6H5 C N H
+ +O C C6H5 

 C
3H 2 O
C6H5 C O H2N H C6H5 C N C6H5
H H
Hydrobenzamide
While acetone react with NH3 to form diacetone amine.
CH3 CH2 C CH3

CH3 CH3 OH + H CH2 C CH3
 C
C 
 H2 O

C O + NH3 O CH3 NH2
CH3 CH3 NH2
Diacetone amine
24
Reaction with 1° amines :

Carbonyl compounds react with 1° amines in presence of acid form Schiff’s base or azomethines.
The most stable Schiff’s base is obtained from aromatic aldehyde with Aromatic 1° amine.
H H
H+ C6H5 C N C6H5
C6H5 C O + H2N
H2O Benzal aniline
Reaction with 2° amines :

Carbonyl compounds contain at least one  -Hydrogen react with 2° amine in presence of (PTS)  p-
toluene sulphonic acid. to form ,  unsaturated amines called enamines.
PTS C C N
CH C O + HN 
 H2O

Enamine
Among these the most stable enamines are those which derived from cyclic ketones and cyclic 2°
amines like pyrrolidine, piperidine etc.
O + HN PTS
  N
 H2O
Enamine
H
H PTS
  N
O OH + HN  H2O
Enamine
Ketones react with chloroform in presence of alkali form chloretone used as a hypnotic medicine.
CH3 CH3 OH
OH  C
C O + CHCl3  
CH3 CCl3
CH3
Carbonyl compounds react with PCl5 to form gem dihalides:
CH3 Cl
CH3
PCl C
Eg : C O 
5
 + POCl3
H Cl
H
25
CH3
CH3 Cl
C + POCl3
C O + PCl5 

CH3 CH3 Cl
Acetone when heated with con : H2SO4; Mesitylene is formed.
CH3
O
con:H 2SO4
3CH3 C CH3  
CH3 CH3
C6H5 – CHO react with Cl2 at low temperature form Benzoyl chloride.
COCl
CHO + Cl2 + HCl
But acetophenone react with Br2 in ether medium at 273 K form phenacyl bromide.
O O
C CH3 + Br2 C CH2 Br + HBr
Electrophilic substitution
Since CHO, C CH3 groups etc are deactivating or m-directing, during electrophilic substitution
reaction, benzaldehyde gives m-substituted derivatives.
26
CHO
Br2
Br
CHO CHO Low yield due to partial oxidation
Eg : Nitration
NO2
CHO
Sulphonation
SO3H
Oxidation of aldehydes and ketones

Aldehydes act as a reducing agents since they can be easily oxidised to corresponding acids.
R  CHO  (O) 
 R  COOH
Aldehydes reduce Tollen’s reagent (Ammoniacal Silver Nitrate Solution) to metallic silver. This is also
called silver mirror test.
R  CHO  Ag 2 O 
 R  COOH  2Ag
Fehling solution test : A mixture of alkaline CuSO4 and sodium potassium tartarate (Rochelle salt) is
called Fehling solution. Aliphatic aldehyde reduce Fehling solution while aromatic aldehydes do not
due to +R effect of benzene ring, they are weak reducing agent.
2 1
R  CHO  Cu O  
 R  COOH  Cu 2 O
Blue Re d
 This test is used to distinguish between aliphatic and aromatic aldehydes. Aldehydes can also be
Br2 / H 2 O
oxidised by Br–H2O to acids. R  CHO   R  COOH
Benedict solution test:

A mixture of alkaline CuSO4 and sodium citrate is called Benedict solution. Chemical reaction is
R CH C R/
similar to those of Fehling test.  -Hydroxy ketones do not contain an aldehyde
OH O
group, like aldehydes they reduce Tollen’s, Fehling and Benedict solutions.
27
R CH C R/ 
Tollens
 R  COOH  R COOH
OH O
But ketones do not undergo oxidation because they are less reactive than aldehydes. Tollen’s, Fehling
and Benedict solutions do not react with ketones. Hence they are used to distinguish between them.
Ketones on oxidation with con:HNO3 form mixture acids. During this C–C bond fission occur in such
a way that keto group will stay with smaller alkyl group. This is popoff’s rule.
CH2 HNO3 CH3 COOH + CH3 CH2 COOH

CH3 C CH2 CH3
Holoform reaction:
Acetaldehyde and all methyl ketones react with excess of Cl2, Br2 or I2 in presence of alkali produce
haloform.
NaOH / I2
CH 3  CHO   CHI3  H  COONa
CH3 C NaOH / Br2

CH3   CHBr3  CH 3  COONa
CH3 C CH2 CH3 

NaOH /I 2
 CHI3 + CH3 – CH2 – COONa

 
In this reaction OX  hypohalite is involved in the oxidation of carbonyl compounds. It is used to
distinguish between methyl ketones from other ketones. It is also used to oxidise ,  -unsaturated
methyl ketones to ,  -unsaturated acids without affecting the double bond.
O
CH3 COOH
CH3 C CH3
C C
C C NaOX
  + CHX3
H CH3
H CH3
28
Aldehydes and ketones with a methyl or methylene group adjacent to the carbonyl groups are oxidised
by SeO2 to  -dicarbonyl compounds.
SeO2
Eg : CH 3  CHO   CHO
CHO
O O
C CH3 
2
 CH3
SeO C CHO
CH3
H
O
 H
SeO2
O   O
 H
H
In this oxidation reactivity of CH2 group is more than CH3 group.

Oxidation with HIO4
It oxidises,  -dialdehyde,  -diketones,  -ketoalcohols,  -ketoaldehydes glycerol, aldoses and 2-
ketoses.
HIO 4
CHO   H-COOH +H - COOH
CHO
CHO 
 H–COOH + HCHO
CH2OH
HIO4
R C C R/ R COOH + R/COOH
O O
HIO4
CH2OH (CHOH)4 CHO H CHO + 5H COOH
Reduction of carbonyl compound

Aldehydes are reduced in to 1° alcohols while ketones into 2° alcohols in presence of Ni, Pd, Pt,
Li[AlH4], Na(BH4), Na-C2H5OH etc.
29
R
H 2 / Ni
C O   R–CH2OH
R R
C O 
 CH OH
R R
Reduction by Na–C2H5OH is called Bouveault-Blanc reduction. Neither Li[AlH4] or Na[BH4] reduces

isolated double bonds. But in case of ,  -unsaturated aldehydes and ketones, Li[AlH4] reduces only
C O group leaving C C intact, while by Na[BH4] reduces both C O and
C C forming a mixture of saturated and unsaturated alcohols in which one reduction group
product predominates over the other.

Li  AlH 
Eg : CH 3  CH  CH  CHO  4
by ether
 CH 3  CH  CH 2  CH 2 OH
CH3 CH2 CH2 CH2OH

Na[BH 4 ]
40%
CH 3  CH  CH  CHO  
CH3 CH CH CH2OH
60%
While reduction, unsaturated alcohol by H2/Ni produce saturated alcohol.

Ni/ H 2
CH 3  CH  CH  CHO   CH 3  CH 2  CH 2  CH 2  OH
O OH O OH
H 2 / Ni Na[BH4]
 
O OH
Na[BH 4 ]
C   C
H
Dicyclohexyl ketone Dicyclohexyl methanol
30
O
Li(AlH4 ) CH2OH + C2H 5OH
C CH2 CH2 COOC2H5 CH3 CH CH2 CH2
CH3
Na[BH4] OH
CH 3 CH CH2 CH2 COOC2H5
OH
However if an    unsaturated part is bonded to aromatic nucleus reduction by Li[AlH4] produce

saturated alcohol.
Li[AlH4]
CH CH CHO CH2 CH2 CH2OH
Cinnamaldehyde
Reduction to pinacols : Acetone is reduced to pinacols by Mg-Hg/H2O.
CH3 CH3
Pinacol
2CH3 CO CH3 CH3 C C CH3
OH OH
This pinacol when heated in presence of acidic reagent produce pinacolone. This is called pinacol-
pinacolone rearrangement.
CH3 CH3 CH3


C C
H
CH3   CH3 C C CH3
CH3 H O 2
OH OH O CH3
Pinacolone
Mechanism
CH3 CH3 CH3 CH3
CH3 C C CH3 + H+ CH3 C C CH3 H2 O

OH OH OH OH2
Oxonium ion
31
CH3 CH3
CH3
1,2-CH3 C CH3
CH3 C C CH3 CH3 C
+
OH CH3 O H
H+
CH3
CH3 C C CH3
O CH3
CLEMMENSEN AND WOLFF KISHNER REDUCTION
The carbonyl group of aldehydes and ketones to methylene

CH2 group to form hydrocarbon
by the following methods.
C O + 4[H] CH2 + H2O
Reduction using Zn - Hg/HCl is called Clemmensen reduction while with NH2 – NH2, KOH and
CH2 CH2 is called Wolff-Kishner reduction.
OH OH
CH3 C O CH2 CH3
Zn-Hg/HCl
+ 4[H] + H2O
Clemmenson KOH, NH2-NH2
CH2 OH
Wolff Kishner
CH2 OH
32
Mechanism of Clemmenson reduction
 2Zn 2   4e 
2Zn 
H+ C OH CH3 C OH + 2e-
CH3 C O CH3
CH3 CH3
CH3
OH2 2H+ C OH
C CH3
CH3 CH H2O CH3
CH3 CH3 CH3
2e-
H+ CH2 CH3
CH3 CH CH3
CH3
Reduction with HI and Red P :

Carbonyl compounds are reduced into corresponding hydrocarbons by HI and Red P at 423 K.
R  CHO  4HI 
 R  CH 3  H 2O  I 2
R C O + 4HI 
 R  CH 2  R  H 2 O  I 2
The function of Red ‘P’ is to remove I2 as PI3, otherwise iodination will takes place.
2P  3I 2 
 2PI3
Carbonyl compounds can also be reduced to hydrocarbons by first converting them to mercaptols
and mercaptols followed by reduction with Raney Ni
S CH2 Raney Ni
dil. HCl C CH2 + HS CH2
C O + HS CH2
H2 O S CH2
HS CH2 CH2
HS
33
Clemmensen reduction and reduction with con : HI and Red P cannto be used for carbonyl compounds
containing acid sensitive groups like –OH, Wolff-Kishner method is suitable.
KOH, NH2 NH2

CH2 OH
COCH3 CH2 CH3
CH2 OH
Eg :
HO OH
Condensation reactions:
1. Aldol condensation reaction : Carbonyl compounds having one or more  -Hydrogen when heated
in presence of dil. NaOH, KOH, Na2CO3, Ba(OH)2 etc to form  -hydroxy aldehyde or ketones called
aldol or ketol, which when heated in presence of dilute acid undergo dehydration to give    unsaturated
aldehydes or ketones. This is called aldol condensation.
H H H
H
dil. NaOH CH3 C C CHO
CH3 C O + CH3 C O
Aldol
OH H
+
H2O H
Crotonaldehyde CH3 CH CH CHO
Similarly,
CH3 CH3 CH3 OH

Ba(OH)2 C
C O + C O
CH3 CH2 COCH3
CH3 CH3
+
H2O H
CH3
O C O O
CH3 CH3 CH3
C CH C CH C CH3
C CH C CH3
CH3 CH3
Phorone CH3
Mesityl oxide MEO
34
Mechanism
Base catalysed alcohol condensation occurs through carbanion or enolate anion formation while acid-
catalysed aldol condensation through enol form of carbonyl compound. These   H atoms are weakly
acidic due to –I effect of C O group. Reactivity increases due to electron withdrawing group
while decreases by electron donating group. Thus nitro ethanol react more faster than ethanal.
CHO CH2 CHO

CH2 CHO + OH CH2
H2O Enolate
H
Which then induces its negative charge to the carbonyl carbon of second molecule to form anion and
it exchanges a proton with H2O form aldol.
H H

Slow step
CHO   
H2 O
CHO  

CH3 C O + CH2  CH3 C CH2  OH
H H
H+
CH3 CH CH CHO CH3 C C CHO
H2O
OH OH
Similarly, Examples:-
O O
dil. NaOH
1. 2 C CH3 C CH C
CH3
35
O O
dil. NaOH
2. 2  
Crossed Aldol condensation

Aldol condensation between two different aldehydes or ketones or between one aldehyde and one
ketone is called crossed aldol condensation, which give four different products and are difficult to
separate them.
dil.NaOH
CH 3  CH 2  CHO  CH 3  CHO   (1) CH3 CH CH2 CHO
OH
(2) CH3 CH2 CH CH CHO
OH CH3
CH2 CH CH2 CHO

(3) CH3
OH
(4) CH3 CH CH CHO
OH CH3
But if one of the aldehydes or ketones does not possess  -Hydrogen atoms only one product is
formed.
Examples:
H
OH
(1) CH3 C O+H CHO CH2 CH CHO
C CH3 + H CHO CH3 CO CH CH2

(2) CH3
H
OH CH CHO
(3) C O + H2 CH CHO CH
36
Such a base catalysed aldol condensation between an aromatic aldehyde and an aliphatic aldehyde
or ketone is called Claisen-Schmidt Condensation reaction.
Intra molecular aldol condensation
If a compound contains two aldehyde or keto groups or one aldehyde and one keto group at 1, 6 or 1,
7 position with respect to each other, then the enolate ion of one carbonyl group can add to the
carbonyl group of the other to form an aldol which loses H 2O to form ,  -unsaturated aldehyde or
ketone.
OH
CHO CH2 CH2
Eg: CH2 CH2 C
dil. NaOH
CH2 CH H
CH2 CH2 CHO
CHO
+
H2O H
CH2 CH2
C H
CH2 C
Perkin Condensation
Aromatic aldehydes react with aliphatic acid anhydrides having   H atom in presence of sod: salt of
same acid, followed by hydrolysis gives ,  -unsaturated acid.
H O O
CH 3COONa
C O + H2 CH C O C CH3 
H O O
H2 O
C CH C O C CH3
CH CH COOH + CH3COOH
37
Benzoin condensation
When Benzaldehyde heated in presence of alcoholic aqueous KCN or NaCN,  -Hydroxy ketone or
benzoin formed.
O H
2 C alc.KCN
H 
 C C
OH O
Mechanism
O O O
C + CN C H + C
H CN H
O OH O OH OH O
C C C C C C
H CN H CN H
Benzoin
Similarly
O OH
2 alc.KCN
  C C
O CHO O O
Furfural H
Knoevenagel condensation reaction : Condensations of aldehyde and ketones with compounds

having active methylene group in the presence of base catalyst to form ,  unsaturated compunds
is called Knoevenagel condensation reaction.
38
H
OOR
Pyridine
C O + H2(COOR)2 C6H5 CH C
OOR
(1) H2O/H+
(2) / CO2
COOH

CH CH COOH C6H5 CH C
CO2 COOH
Cinnamic acid
Beckmann rearrangement: The conversion of ketoximes into N-substituted amides in presence of

acidic catalyst like H2SO4, SOCl2, PCl5, BF3, PPA (Polyphosphoric acid) etc is called Beckmann’s
O
R OH
H2SO4
C N R C NHR/ or R/CONHR
rearrangement.
R/
It is to be noted that during this rearrangement it is the trans or anti group w.r.to OH group is migrated.
Hence it is used to distinguish between geometrical isomers of oximes.
39
Mechanism:-
R OH R OH2
C N H+ C N
R/ R/
H2O
H2O
R C N R R C N R/
OH2
H+
R NR/ R C NHR/
C
OH O
This rearrangement is highly stereospecific ie a specific stereoisomer gives a specific amide.

Tischenko reaction :
It is the modified form of Cannizzaro’s reaction. all aldehydes with or without  -hydrogen atoms
undergo Cannizarro’s reaction in presence of Al(OC 2H5)3. The acid and alcohol further react each
other to form ester is called Tischenko reaction.
Al(OC2H5)3 CH3 C OC2H5 + H2O

2CH3 CHO CH3 COOH + HOC2H5
H2O
Reformatsky reaction :
 -Bromoesters react with aldehydes and ketones in presence of zinc dust to form addition product
which on hydrolysis to form  -hydroxy esters. This is called Reformatsky reaction.
dry ether
Br  CH 2 COOC2 H 5  Zn   BrZn  CH 2 COOC 2 H 5
40
CH3 CH3 OZnBr

 
C O + BrZn CH2COOC2H5 C
CH2COOC2H5
CH3 CH3
H OH
OH CH3
OH
Zn + C
Br CH3 CH2COOC2H5
Cannizzaro’s reaction:
Aldehydes having no   H atoms when heated in presence of strong base like NaOH or KOH undergo
self oxidation reduction or disproportionation to form a mixture of acid salt and alcohol. Since in this
reaction one molecule of an aldehyde is reduced at the expense of the other which is oxidised.
con:NaOH
2H  CHO   H  COONa  CH 3OH
2 CHO COONa + HO CH2
CH3 CH3 CH3
2 CH3 C CHO CH3 C COONa + CH3 C CH2OH
CH3 CH3 CH3
2 con:NaOH
CHO   +
O O COONa O CH2OH
Furfural
Mechanism :
The rapid addition of OH– to one molecule of aldehyde results in the formation of hydroxy alkoxide ion
which transfer a hydride ion to the second moleucle of aldehyde and since if is a slow step process it
is called rate determining step. (II order w.r.to aldehyde and I order w.r.to base). In the final step, the
acid and the alkoxide ion exchange a proton to acid anion and alcohol for attain stability.
41
H O H
Fast
C6H5 C O + OH C6H5 C OH + C O
H
Slow step R.D.S.
O O
C O C O + CH2 OH
It has been seen that the rate of reaction depends on the nucleophilic attack on the carbonyl carbon.
 the factors which reduce the positive charge on the carbonyl carbon retard the reaction and the
reaction may not occur.
CH3
Eg : N CHO (p-dimethyl amino benzaldehyde)does not undergo Cannizzaro’s
CH3
reaction and sterically hindered aldehydes also do not undergo this reaction.
Crossed Cannizzaro’s reaction
Two different aldehydes having no   H atom when heated with con: NaOH, most reactive aldehyde
oxidised to form acid while the least one reduced into alcohol. This is called Crossed Cannizzaro’s
reaction.
NaOH
CH3O CHO + H CHO CH3O CH2OH + HCOONa
For example : CH3 – CHO with excess H–CHO form penta erythritol (Tetramethylolmethane).
42
CH2OH
H CHO H CHO
Crossed aldol CHO CH CHO
CH2 CHO + HCHO   CH2
H CH2 OH CH2OH
CH2 OH
CH2 OH
Crossed Cannizzaro's
 HO CH2 C CHO
HO CH2 C CH2OH + H COONa NaOH
CH2OH
CH2 OH
Intramolecular Cannozzaro’s reaction:

Dialdehydes which do not contain  -hydrogens undergo intramolecular Cannizzaro’s reaction in
presence of strong alkali.
con:NaOH
HCO   COONa 
HCl
COOH
HCO CH2OH CH2OH

Glyoxal Glycollic acid
In certain cases intramolecular Cannizzaro’s reaction product upon acidification followed by dehydration
from lactones.
CH2OH
CHO OH dil.HCl
 
CH2
NaOH
COOH
 
CHO COONa
CH2
O Phthalide
C
43
But isobutanal having one   H atom undergo Cannizzaro’s reaction when heated with con: NaOH
at high temperature.
H H H
2CH3 C NaOH
CHO   CH3 C COONa + CH3 C CH2OH
470K
CH3 CH3 CH3
This is due to +I effect of methyl group, the carbanions of these aldehydes are not stable and hence
instead of undergoing aldol condensation it will undergo Cannizzaro reaction.
Similarly CCl3 – CHO (chloral) is also not having  -atom doesn’t undergo Cannizzaro reaction. But it
undergoes haloform reaction.
O
OH CCl3 C O H CCl3 + HCOOH CHCl3 + HCOO
CCl3 C O
H H
1-phenyl glyoxal when boiled with NaOH undergoes intramolecular crossed Cannizzaro reaction.
O H
NaOH
C CHO C COONa
OH
The reactivity of an aldehyde towards’ Cannizzaro reaction depends upon the following two factors.
1. Ease of attach of OH– in first fast step which requires a less sterically hindered carbonyl carbon.
2. Ease of hydride ion transfer : Electron donating group facilitate the attack of hydride ion.
Example
OH COO + O2N CH2OH

CH3O CHO + O2N CHO CH3O
The +R effect of –OCH3 through resonance facilitate the release of H– ion and electron withdrawed by
NO2 through resonance increases the electropositive character of carbonyl carbon at para position
and thereby increases the affinity for H– ion
44
Wittig reaction
The reaction between an aldehyde or ketone with a phosphorus ylide to give a substituted alkene is
called Wittig reaction and the phosphorus ylide is called Wittig reagent. A molecule that bears no
overall charge but has a negatively charged carobn atom bonded to a positively charge hetero atom is
called an ylide.
+ dry ether O
C O + CH2 C CH2 + (C6H5)3 P
P (C6H5)3
CH CH2
C6H5 C O + CH2 P (C6H5)3 + (C6H5)3P O
H Styrene
Methylene triphenyl phosphorane
O CH2
+ CH2 P(C6H5)3 
 + (C6H5)3P O
Mechanism
(C6H5)3
P
O CH2
O CH2
+ CH2 P(C6H5)3 + (C6H5)3P O



Triphenyl phosphine oxide
45
46

Aldehyde Ketone Notes

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Aldehyde Ketone Notes

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Brilliant STUDY CENTRE LT.

22 (RES) (ONLINE CLASS NOTESA)

Structure and Nomenclature

CH3 CH CHO Isobutyl or 2-methyl propene

3-Methyl cyclohexane carbaldehyde

CH2 CH CH2 Propane-1, 2, 3-Tricarbaldehyde

CHO CHO CHO

CH3 C CH3 Acetone or propanone

CH3 C CH2 CH3 But-2-one

CH3 C CH2 C CH3 Pent-2, 4-Dione

C CH2 CH3 1-Phenyl propanone

CH3 C CH2 CHO 3-oxo butanal

CH2 = CH – CHO Acrolein or Acraldehyde prop-2-enal

PREPARATION OF ALDEHYDES AND KETONES

, PDC pyridiniumdichromate Collius reagent.

This oxidation occurs through hydride transfer from 2° alcohol to acetone.

CH3 CO OH + HOOC CH3 CH3 C CH3 + CO2 + H2O

CH3 C CH2 CH3 C CH3

CH3 CH2 CH C CH3 CH3 CH2 CH2 C CH3

+ CH3 CH2 C CH2 CH3

(c) By ozonolysis of alkenes

CH3 CH CH2 + H2O + PdCl2 CH3 C CH3 + Pd + 2HCl

CH3 C CH3 

bond is more polar than C Cd

8. From nitriles and esters

Aldehydes are also prepared by the action of R–MgX on orthoformic esters.

2CH3 C Cl + (C2H5)2Cd 2CH3 C C2H5 + CdCl2

NH3 + Mg(OH)Br + CH3 CH2 C CH3

9. From aromatic hydrocarbon:

This called Etard’s reaction. Similarly m-xylene on oxidation form m-Tolualdehyde.

This is also called Gattermann-Koch formaylation or aldehyde synthesis reaction.

Benzylchloride on oxidation in presence of Pb(NO3)2 or Cu in a current of CO2 produces benzaldehyde.

A small amount of p-hydroxy Benzaldehyde is also formed. This is an electrophilic substitution

11. Friedel - Crafs acylation reaction

This is an electrophilic substitution reaction.

H  CHO  CH 3  CHO  CH3 COCH3  CH 3  CO  CH 2  CH 3 > pentan-3-one > Di-isopropyl

Thus reactivity order of follows > > C

CHO CHO CHO CHO CHO CHO

> > > > > >

NO2 CN Cl CH3 OCH3 OH

Some important nucleophilic addition reactions are:

CH3 CH3 CH3

C CH2 CH2 CH2 CH3

This hydrate is stabilized by intramolecular H-bonding.

6. Reaction with Ammonia and its derivatives:

C6 H 5  NHNH 2 , O2N NH NH2 (2, 4-DNPH) (Called Brady’s reagent) and

NH C NH2 in weakly acidic medium (pH = 3.5) to form compounds containing C N

C O + H2N NH NO   C N NH NO2

C O + H2N NHCO NH2   C N NHCO NH2

While acetone react with NH3 to form diacetone amine.

CH3 CH2 C CH3

Reaction with 1° amines :

Reaction with 2° amines :

Carbonyl compounds react with PCl5 to form gem dihalides:

Acetone when heated with con : H2SO4; Mesitylene is formed.

CHO + Cl2 + HCl

C CH3 + Br2 C CH2 Br + HBr

Oxidation of aldehydes and ketones

Benedict solution test:

CH2 HNO3 CH3 COOH + CH3 CH2 COOH

CH3 C NaOH / Br2

CH3 C CH2 CH3 

In this oxidation reactivity of CH2 group is more than CH3 group.