ALDEHYDES AND KETONES

 Intro duct ion :

Organic Compounds having C O group are called carbonyl compounds and C O group is known
wn
as carbonyl or oxo group. It's general formula is C n H 2n O (n = 1, 2, 3......) Carbonyl compounds are
grouped into two categories.

O
(a) Aldehydes : Aldehyde group is C H (also known as formyl group). It is a monovalent group

(b) Ketones : The carbonyl group ( C O) is a Ketonic group when its both the valencies are satisfied
by alkyl group. It is a bivalent group.

 Ketones are further classified as :

R
(i) Simple or Symmetrical ketones : Having two similar alkyl groups. C O
R
R
(ii) Mixed or unsymmetrical ketones : Having two different alkyl groups. C O
R'
Example : (Ketones) : S y m m e t r i c a l Unsymmetrical

CH3 CH3CH2
C O C O
CH3 CH3
(Acetone or Dimethyl ketone) (Ethyl methyl ketone)
2–Propanone 2–Butanone

O O O O
Special Point : .. .. .. ..
C OH, C X, C NH2, C OR,
In all the compounds given above, lone pair of electrons and double bond are conjugate.

O O
..
C Z so resonance occurs. These compounds have C group still they are not carbonyl compounds

because carbonyl group takes parts in resonance with the lone pair of electrons.

 Str ucture :

In C O compounds C-atom is sp2 hybridised which forms two  bonds with C and H-atom respectively
and one  bond with oxygen atom. The unhybridised atomic orbital of C-atom and the parallel 2p orbital
of oxygen atom give the  bond in C O group.

C sp 2

C  O The C—C—O and H—C—O bond angles are of 120°.

C

Due to electro-negativity difference in C & O atoms, the C O group is polar..

 
C O Hence aldehydes and Ketones posses dipole moment.
 General Met ho ds of Preparat ion :

(A) For both Aldehydes and Ketones :

(1) By Oxidation of Alcohols :

(a) By K 2 Cr 2 O 7 / H 2 SO 4 :
Oxidation of primary alcohols gives aldehyde and oxidation of secondary alcohols gives Ketones.
Here, (K 2 Cr 2 O 7 / H 2 SO 4 ) is a strong oxidising agent.
[O ]
RCH 2 OH 
K 2 Cr2 O 7 / H 2 SO 4 ( dil.) 
 RCHO (Aldehyde)

[O]
R CH R 
K 2 Cr2 O7 / H 2 SO 4
 R C R (Ketone)
OH O
Aldehydes are quite susceptible to further oxidation to acids -
[O] [O]
R CH 2 O H   R—CHO   R—COOH
Thus oxidation of primary alcohols is made at the temperature much above the boiling point of
aldehyde and thus aldehydes are vapourised out and prevented from being oxidised.
 Note : Aldehydes can be prepared from 1° alcohol,secondary alcohols can be oxidized to ketones, by oxidation
with pyridinium chlorchromate (PCC) in CH 2 Cl 2 solvent, pyridinium dichromate (PDC) and with
Jones reagent(CrO 3 +H 2 SO 4 ) in acetone.

(b) Oppenaur Oxidation :

The oxidation of secondary alcohols to ketones by heating them with specific reagent : [(CH3)3CO]3Al
(Aluminium-t-butoxide) in presence of acetone. Primary alcohols may also be oxidized to aldehydes
if ketones is replaced by a better hydrogen acceptor, e.g. p-benzoquinone. The equilibrium can be
controlled by the amount of acetone, an excess of which favours the oxidation of the alcohol.

R CH3 [(CH 3 )3 CO ]3 Al R CH3

CHOH + 
C O  


 C O+ CH OH
R CH3 R CH3

2 O Alcohol Acetone Ketone Isopropyl alcohol

[(CH 3 )3 CO ]3 Al
RCH 2 OH + O O 
 


 R—CHO + HO— —OH

1 0 Alcohol Quinone Aldehyde Quinol

 Note : The reaction is the reverse of Meerwein-Ponndorf -verley reduction.

(c) Mild Oxidising Agent :

o o
1 alcohols wi ll get oxidised with CrO 3 / Pyridi ne, colli n's reagent Ag / O 2 at 250 C
RCH 2 OH + [O]  RCHO + H 2 O
By this reaction, good yield of aldehyde is possible.
(2) Dehydrogenat ion of alcohols :
Cu
CH 3 CH 2 O H 
300 C  CH 3 C H O (Acetaldehyde)

O
Cu
CH3 CHCH3 
300 C  CH3 C CH3 (Acetone)

OH
 CH3 CH2
Cu
CH3 C OH 
300 C  CH3 C + H2O (Isobutylene)
CH3 CH3

(3) By Hydrolysis of gem dihalide s :

Terminal gem-dihalides on hydrolysis give aldehydes while the non-terminal dihalides give ketone.
Cl OH
CH3CH KOH(aq )
  CH3CH 
2

H O CH 3 C H O
Cl OH
Terminal gem-dihalide [unstable] Acetaldehyde

Cl OH
O
CH3 C CH3 KOH(aq )

 CH3 C CH3 

H 2 O
CH3 C CH3
Cl OH
Acetone
unstable

(4) By Oxidation of diols :

With periodic acid (HIO 4 ) & lead tetra acetate (CH 3COO) 4 Pb vicinal diols gets oxidised to form carbonyl
compounds

R CH CH R' + HIO4  RCHO + R'CHO + HIO 3 + H 2 O

OH OH

R R O O
R C C R' + HIO4  R C R + R' C R + HIO3 + H2O
OH OH

(5) By Ozonolysis of alkenes :

This reaction is used to determine the position of double bond in alkene.

O O
2 –H O
RCH CH2 + O3  RCH CH2 
Zn
RCHO + HCHO
Ozone O
Ozonide

O O
–H2O
R C CH2 + O3  R C CH2  R C O + HCHO
Zn

R R O R

Un b r a n ch e d a l k e n e  ald ehyd e

B r a n ch e d a l k en e  ketone
(6) From Alkyne :
(a) Hydrat ion : With di l H 2 SO 4 & 1% HgSO 4 at 60-80 0 C.
O
CH CH + H 2 O  [CH 2 CHOH ] CH3 C H
(Tautomerisation)
 Other alkynes give ketone :

CH3C CH + H2O  CH3 C CH2 CH3 C CH3

OH O
(enol)
(b) Hydroborat ion : React ion with B 2 H 6 , 2BH 3 or R 2 BH give dialkyl borane.

1 – a l k y n e g iv es  a ld e h y d e
o th e r a l k y n e  k et o n e

H2O2 Tautomerism
R C CH + R2BH R CH CHBR2 
–
RCH CHOH R CH2 C H + R2BOH
OH
O
H 2 O2
CH 3 —C C—CH 3 + R 2 BH    CH3 CH C CH3 
OH –


BR2

R2BOH+CH3 

CH C CH3  CH3 CH2 C CH3 +R2BOH
OH O

(7) By Nef's reaction :

Nitro alkanes are used in this reaction. The  of nitro alkane shows acidic nature.
 
O OH O Na 
NaOH HO
R CH2 N R CH N  R CH N  R CHO + N2O + H2O + NaOH
3

O O O
(Nitro form) (Aci form) (Aldehyde)
1° nitro alkane

R O R OH R O Na  R
NaOH HO
CH N C N  C N  C 3
O + N2O + H2O + NaOH
R O R O R O R

(Nitro form) (Aci form) (Ketone)

2° nitro alkane
R O
R C N NaOH
  No Reaction
R O
(3° nitro alkane)

(8) By hydrolysis of carbonyl derivat ive s :


R—CH N—OH H2O / H R—CHO + NH 2 —OH
 
(Aldoxime) (Aldehyde) (Hydroxyl amine)
R R
C N OH 
H2 O / H
  C O + NH2 OH
R R
(Ketoxime) (Ketone)
R OR R
C 

H 2O / H
 C O + 2ROH
H OR H
(Acetal) (Aldehyde) (Alcohol)
R OR R
C 

H 2O / H
 C O + 2ROH
R OR R
(Ketal) (Ketone) (Alcohol)
(9) By oxidation of alkyl halides:

Oxidation takes place by (CH 3 ) 2 S O dimethyl sulphoxide (DMSO).

R—CH 2 —X + (CH 3 ) 2 S O   R C H O + (CH 3 ) 2 S + HX
Alkyl halide (Aldehyde) (Dimethyl thio ether)

X O
 CH 3  2 S  O
R CH R  
 R C R
2° halide Ketone
( 1 0 ) From Grignard reagent s :

(a) By Cyanides :

H O/H OH
RMgX + R C N R C 2
N MgX  R C R + NH3 + Mg
X
R O
(Ketone)
(b) By Esters : HCHO can't be prepared by this method.

O OMgX OH
–ROH H2O
RMgX + H C OR  H C OR  H C OR  H C O
R R R
(Alkyl formate) (Hemiacetal) (Aldehyde)

O OMgX OH
HO
RMgX + R C OR  R C OR  R C OR  R C O 2

R R R
(Alkyl Alkanoate) (Hemiacetal) (Ketone)
(c) By acid chlorides :

R' X
R' C 
Cl + RMgX  C O + Mg
R Cl
O
( 1 1 ) From  -keto acids :

The decarboxylation reaction takes place via formation of six membered ring transition state.

(a) HCOCH 2 COOH 
110  C
 CH 3 CHO+CO 2


 

(b) CH3 C CH2 C OH  CH3 C CH3
–CO2
O O O
(B) For Aldehydes only :
(1) Reduction of acyl halides, esters and nitriles :
(a) Acyl chlorides can be reduced to aldehydes by treating them with lithium-tri-tert-butoxyaluminium
hydride, LiAIH[OC(CH 3 ) 3 ], at – 78°C.
O O
R R
( i ) LAH ( t BuO )3 , 78  C
 ( ii ) H 2 O
Cl H
 (b) Both esters and nitriles can be reduced to aldehydes by DIBAL-H. Reduction must be carried out
at low temperatures. Hydrolysis of the intermediates gives the aldehyde.

O O
R  R
(i ) DIBAL H,hexane, 78  C
 (ii ) H 2 O
OR' H

O
(i ) DIBAL H,hexane, 78  C
 R
R—CN  (ii ) H 2 O

H
(2) Rosenmund's reduct ion :
Quinoline or sulphur act as a poisoned catalyst, controls the further reduction of aldehyde to alcohols.

Pd / BaSO 4
RCOCl + H 2 
Quinoline or sulphur
 RCHO + HCl
Pd
RCOCl + H 2   R C H O  R CH 2 O H
Formaldehyde can not be prepared by this method.

Pd / BaSO 4
Example : C2 H 5 COCl + H 2 
Quinoline or sulphur
 C 2 H 5 CHO + HCl
Propionyl Chloride Propanal
(3) Stephen's reduct ion :
Alkyl cyanides are reduced by SnCl 2 and HCl.

R—C N SnCl2 / HCl R—CH NH H3O  RCHO+NH 3

   

H3O 
C 2H 5— C N SnCl2 / HCl C 2 H 5 CH NH   C 2 H 5 CHO + NH 3
 
(4) Oxo react ion or hydroformylat ion :
In this reaction symmetrical alkene gives 1 0 aldehyde while unsymmetrical alkene gives isomeric aldehyde
(Chain isomers).
Co
CH 2 CH 2 + CO  H   C H 3C H 2C H O
2 150 C
Water gas

Co
CH 3 —CH CH 2 + CO + H 2 
150 C
 CH 3 CH 2 CH 2 CHO + CH3 CH CH3

CHO
(C) For Ketones only :
(1) From Grignard's reagent :

2H 2 O X
RMgX + R—C N  R C NMgX   R C O + NH3 + Mg
OH
R R

O OMgX OH O
HO
RMgX + R C Cl  R C Cl  R C Cl  R C + HCl 2

R R R
O

RMgX + R C NH2  RH+ (RCONH)Mg(X) ; Ketone doe s not forms.

 O OMgX OH O
HO
RMgX + R C OR  R C OR  R C OR  R C + ROH 2

R R R
(2) From dialkyl Cadmium :
RCdR' (dialkyl Cadmium) is a organometallic compound.
RCOCl + RCdR'  RCOR' + RCdCl
This reaction is superior than Grignard Reaction because the ketones formed, further reacts with Grignard
reagent to form 3° alcohols.

C2H5 CH3 C2H5

Example : CH3COCl + Cd  C O+ Cd
C2H5 C2H5 Cl
(3) From R 2 CuLi :
R 2 CuLi + R'COCl  R'COR + RCu + LiCl
(4) By hydrolysis of Aceto Acet ic Ester (A AE) :
 
H3O 
CH3 C CH2 C OC2H5  CH3 C CH2 C OH  CH3 C CH3
–C2H5OH –CO2
O O O O O
( - keto acid) (Acetone)

 
H3O 
Ex : CH3 C CH C OC2H5  CH3 C CH C OH  CH3 C CH2 CH3
–C2H5OH –CO2
O CH3 O O CH3 O O
(–keto acid) (Butanone)

 Other methods for aldehyde and ketone :

(1) By dry distillation of Ca-salts of carboxylic acid :

O
R COO O C H
Ca + Ca 
 2RCHO + 2CaCO 3
R COO O C H
O
Calcium formate (Also R C R and HCHO formed)
O

H COO
Ca 
 HCHO + CaCO 3
HCO O

R COO R
Ca  C O + CaCO3

RCO O R
Calcium-alkanoate Ketone
Calcium salts of acids other then formic acid on heating together gives ketone
O
O
R COO O C R' 
Ca + Ca  2R C R' + 2CaCO3
R COO O C R'
Ketone
O
 To prepare ethyl methyl ketone Calcium acetate and Calcium propionate are used :
O
CH3
CH3 OCO O C CH2CH3  2 C O + 2CaCO3
Ca + Ca  C2H5
CH3 OCO O C CH2CH3
O
Calcium Acetate Calcium propionate Ethyl methyl ketone

(2) By T hermal decomposit ion of carboxylic acids :

Vapour of carboxylic acids when passed over MnO/300 0 C give carbonyl compounds
MnO
2 HCOOH 
300 C  HCHO + H 2 O + CO 2

CH3
2 CH 3 COOH MnO
 C O + CO2 + H2O
300 C  CH3

MnO
RCOOH + HCOOH 
300 C  RCHO + CO 2 + H 2 O

MnO
RCOOH + R'COOH 
300 C  RCOR' + CO 2 + H 2 O

(3) Wacker process :

In this reaction double bond is not cleaved so same C-atom aldehyde and ketones are formed.
CH 2 CuCl2
CH 2 + PdCl 2 + H 2 O  CH 3 CHO + Pd + HCl

All other alkenes gives ketone.

O
RCH CH 2 + PdCl 2 + H 2 O  CuCl2
 R C CH3 + Pd + HCl

 Physical Proper t ie s :
 State :
Only formaldehyde is gas, all other carbonyl compounds upto C 11 are liquids and C 12 & onwards solid.
 Odour :
Lower aldehydes give unpleasant smell, higher aldehydes and all ketones have pleasant smell.
 Solubility :
C 1 to C 3 (formaldehyde, acetaldehyde and propionaldehyde) and acetone are freely soluble in water
 
due to polarity of C O bond and can form H—bond with water molecule. C 5 onwards are insoluble
i n water.

H
1
  So lub ility 
C O H O Molecular weight
H-bonding
 Boiling point : Boiling point  Molecular weight
Boiling point order is - Alcohol > Carbonyl compounds > Alkane
This is because in alcohols intermolecular H-bonding is present but in carbonyl compounds H-bonding
doesn't exist, instead dipole-dipole vander waal force of at traction is present. Alkanes are non polar.
   
C O C O
 Densit y : Densit y of carbonyl compounds is lower than water.

 Chemical Proper t ie s :

Reactions of both aldehydes and ketones :

Due to strong electronegativity of oxygen, the mobile  electrons pulled strongly towards oxygen,
leaving the carbon atom deficient of electrons.
 
C O       C O

Carbon is thus readily attacked by N u . The negatively charged oxygen is attacked by electron deficient
(electrophile) E + .

C O bond in carbonyl group is stronger than C=C bond in alkanes.

C O Bond energy is 84.0 K Cals C C Bond energy is 83.1 K Cals

C O Bond energy is 178 K Cals C C Bond energy is 146 K Cals

1
React iv it y of carbonyl group   Magnitude of +ve charge  – I group   
+ I group
Ex : Why carbonyl compound gives nucleophilic addition reaction (NAR) ?

 
E
C OE  No Reaction
  Carbocation (Less stable due to incomplete octet)
C O  C O
Sol. .. 
Nu  E
C O  C OE
Nu Nu
Anion (More stable due to complete octet)

Ex. Arrange the following for reactivity in decreasing order

H CH3 CH3
(I) (i) C O (ii) C O (iii) C O
H H CH3

(II) (i) ClCH 2 CHO (ii) NO 2 CH 2 CHO (iii) CH 3 CHO (iv) CH 3 CH 2 CHO

(III) (i) CH 3 CHO (ii) ClCH 2 CHO (iii) HCCl 2 CHO (iv) CCl 3 CHO

CH3 CH3CH2 (CH3)2CH CCl3

(IV) (i) C O (ii) C O (iii) C O (iv) C O
CH3 CH3 CH3 CH3
S o l . (A) I > II > III (B) II > I > III > IV (C) IV > III > II > I (D) IV > I > II > III

[Hint : CH 3 — is +I group, decrease s the i ntensit y of +ve charge on C-atom of C O group.

Cl – is –I group i ncreases the i ntensit y of +ve charge on C-atom of C O group.]

Cl
(-I) CH3(+I)
Ex. In Cl C C O and
C O , which one is more reactive ?
Cl H H
Chloral
S o l . I is more reactive than II.
 Chemical Reactions :
Carbonyl compounds in general under goes neucleophilic addition reaction :
(A) Nucleoph i lic addit ion react ions :
(1) Addition of HCN :

H2O
Partial hydrolysis
C OH
CONH2
-Hydroxy amide

H3O
C O + HCN  C OH Complete
C OH
hydrolysis
CN COOH
(Cyanohydrin) -Hydroxy acid
Ni/H2
C OH
CH2NH2
-Amino alcohol

H2O H
Partial hydrolysis C OH
H
CONH2
Glyconamide

H H 
C O + HCN  C OH H3O H
H C OH
H Complete
H
CN hydrolysis
COOH
(Formaldehyde cyanohydrin)
Glycolic acid

Ni/H2 H
C OH
H
CH2NH2
2-Amino ethanol

CH3
H2O C OH
Partial hydrolysis H
CONH2
Lactamide (2-Hydroxy propanamide)
CH3 CH3
C O + HCN  * OH
C H3O
 CH3
H H C OH
Complete
CN hydrolysis H
Acetaldehyde Cyanohydrin COOH
*(Racemic mixture) Lactic acid (2- Hydroxy propanoic acid)
Ni/H2
CH3
C OH
H
CH2NH2
1-Amino – 2-Propanol
(2) Addition of NaHSO 3 :
This reaction is utilized for the separation of carbonyl compounds from non - carbonyl compounds.

H3O
C O + NaHSO3    C OH      Carbonyl compounds. *(Regain)

SO3Na

Sodium bi sulphite Bisulphite compound

(Crystalline)

Mechanism : NaHSO3 


 Na   HSO 3

HSO 3 

 H   SO 32

OH
C
SO


3

C O + SO
–2
Slow
O H+
 Na+
3  C  Fast
SO3
OH
C
SO3Na

(3) Reaction with ammonia derivatives :

These are condensation or addition elimination reaction. These proceeds well in weakly acidic medium.
NH3  NH 2 Z (Ammonia derivative)

C O + H2 N Z H C N Z + H2O

Z 

Addition - elimination (Condensation)

Mechanism :

 .. IMPE 
–H O
 –H
C OH + NH2Z C OH C OH2 
2
C NHZ C NZ

NH2Z NHZ

 Ammonia derivatives (NH 2 Z) :

Z = OH  NH 2 OH (Hydroxyl amine)
Z = NH 2  NH 2 NH 2 (hydrazine)
Z = NHC 6 H 5  NH 2 NHC 6 H 5 (Phenyl hydrazine)

NO2 NO2
Z =
NH NO2  NH2 NH NO2

2, 4–Dinitro phenyl hydrazine (DNP) Brady's reagent.

Z = NHCONH 2  NH 2 NHCONH 2
Semi Carbazide.
R R
C O + H2 NOH C NOH (Aldoxime)
H H
 R R
C O + H2 NNH2 C NNH2 (Hydrazone)
H H

R R
C O + H2 NNHC6H5  C NNHC6H5 (Phenyl hydrazone)
H H

NO2 NO2
R R
C O + H2 NNH NO2  C NNH NO2
H H
2,4-DNP (Brady's reagent) (2, 4 - dinitro phenyl hydrazone)

R R
C O + H2 NNHCONH2  C NNHCONH2 (Semi Carbazone)
H H

(4) With alcohol and thioalcohol :

H H OH H OR
C HCl ( g )
O + ROH  C ROH
  C
 HCl ( g )
R R OR R OR
Hemi-acetal Acetal

R R OR
C O + 2ROH HCl ( g ) C + H2O


R R OR
Ketal
Tri ethoxy methane [HC(OC 2 H 5 ) 3 ] remove the water formed during the react ion and so the react ion
proceeds in forward direction.

R SR R SO2R
R HCl ( g ) C C
C O + 2RSH 
H2O
 
[O]
H SR H SO2R
H
Thioalcohol Mercaptal

R SR R SO2R
R HCl ( g ) C C
C O + 2RSH 
 H2O 
[O]
R SR R SO2R
R
Mercaptal (Thio Ketal) Sulphones Compound
All sulphones compounds are hypnotic compounds.

CH3 SO2R CH3 SO2R C2H5 SO2R

C C C
CH3 SO2R C2H5 SO2R C2H5 SO2R

Sulphonal Trional Tetronal

(5) React ion w it h glycol (group protect ion) :

H O CH2 O CH2
C O+ HCl ( g )
  C
H2O
H O CH2 O CH2

(neutral) Cyclic acetal / ketal

(6) Reaction with sodium alkynide :

   Acid
C O + HC CNa  C ONa  C OH
Sodium Alkynide
C CH C CH
Acetylinic alcohol

(7) React ion w it h Grignard reagent :

H H HO I
C O + CH3 Mgl  C 2
OMgl CH3CH2OH + Mg
H H OH
CH3

Ethanol (1° alcohol)

OMgl OH
OH
HO
CH 3 CHO + CH 3 Mgl   CH3 C H CH3 2
C H + Mg
I
CH3 CH3

2–Propanol (2° alcohol)

OMgl OH
CH3 HO I
C O + CH3 + Mgl  CH3 C CH3  CH3 2
C CH3 + Mg
CH3 OH
CH3 CH3

2–Methyl–2–propanol (3° alcohol)

(8) Reaction with H 2 O : It is a reversible reaction.

Weak acid
 OH
C O + HO
2 
 H2 O
 C
OH

(neutral) unstable hydrate

Ex : W hich compound form more stable hydrate w ith H 2 O?
(A) HCHO (B) CH 3 CHO (C) CH 3 COCH 3 (D) CH 3 COC 2 H 5
[Hint : HCHO since it is more reactive towards this reaction.]
A n s . (A)
Ex : Which carbonyl compound not gives reversible reaction with water ?
S o l . Chloral hydrate.

Cl Cl HO
Cl C CH + H2O  Cl C CH
Cl O Cl HO

(Chloral) (Chloral hydrate)

Stable by intra molecular hydrogen bonding.
(B) Other Reactions :
(1) Wittig Reaction :
Wit tig reaction affords an impor tant and useful method for the synthesis of alkenes by the treatment
of aldehydes or kentones with alkylidenetriphenylphosphorane (Ph3P = CR2) or simply known as phosphorane

Ph Ph Ph Ph Ph Ph
P + CH2 + P
Ph CH2 Ph O Ph Ph O
(1-phenylvinyl) benzene triphenylphosphine oxide

The wittig reagent, alkylidenetriphenylphosphorane (ylide), is prepared by treating trialkyl or triarylphosphine

usually the latter with an alkyl halide in either soultion. The resulting phosphonium salt is treated with
strong base (such as C 6 H 5 Li, BuLi, NaNH 2 , NaH, C 2 H 5 ONa, etc.)

Ph Ph
Ph Ph Ph
  
 C6H5 Li
P + H3C—Br Ph P CH3 Br Ph P CH2 Ph P CH2 + C6H6 + LiBr

Ph Ph Ph Ph
(I) (II)

(2) Ca nnizaro's react ion :

Those aldehydes which do not contain  -H atom give this reaction, with conc. NaOH or KOH; Products
are Salt of carboxylic acid + alcohol.
In this reaction one molecule of carbonyl compounds is oxidised to acid, while other is reduced to
alcohol, such type of reactions are called disproportionation reaction. (Redox reaction)

Conc.
HCHO + HCHO   HCOONa + CH 3 OH
NaOH

Mechanism : (Cannizaro reaction)

(a) Rapid reversible addition of OH to one molecule of HCHO.

OH
OH
H C H H C H
O O

(b) Transfer of hydride ion H to second molecule of HCHO


OH O OH O
H C H +C H  H C+ H C H
O H O O


Formic Methoxide
acid ion
Proton exchange
 (c) Proton exchange


H C OH + CH3O  HCOO    + CH 3 OH
O
HCOO   + Na   HCOONa

When molecules are same  Simple cannizaro reaction

Two different molecules  Mixed cannizaro reaction.

In mixed or crossed cannizaro reaction more reactive aldehyde is oxidised and less reactive aldelyde
is reduced.

HCHO + C 6 H 5 CHO NaOH HCOONa + C 6H5C H 2O H

 
Oxidized Reduced
(Sodium formate) (Benzyl alcohol)
Ca(OH )2
Ex : CH 3 CHO + HCHO   C(CH 2 OH) 4
 + (HCOO) 2 Ca, explain mechanism ?
2, 2-Dihydroxy methyl –1, 3–propane diol.(Penta erythritol)
(3) Tischenko react ion :
It is a modified cannizaro reaction. All aldehydes undergo this reaction in presence of (C 2 H 5 O) 3 Al, to
form e ster.
O
( R 'O)3 Al
2RCHO   
 RCH2 O C R
Ester

CH 3 COOH  CH 3 CH 2 OH
Example : CH 3 CHO  CH 3 CHO ( C 2 H 5 O )3 Al
    
Esterification 
CH 3 —COOCH 2 CH 3 (Ethyl acetate)
(4) Reaction With Halogen :
(a) Replacement of -H atoms :
This reaction is not shown by formaldehyde (HCHO), since  -H atoms are absent, as enolisation
does not takes place in HCHO.
Cl

–HCl Cl2 Cl2
CH2 C H + Cl2  CH2 C H
–HCl
CH C H
–HCl
CCl3 C H
H O Cl O Cl O O
Chloral

Example : CH3 C –3HCl

CH3 + 3Cl2  CH3 C CCl3

O O
Tri chloro acetone

–3HCl
Example : CH3 CH2 C CH3 + 3Cl2  CH3 CH2 C CCl3

O O

Example : CCl3 C R + NaOH CHCl3 + NaO C

O O
 –2HCl
Example : CH3 CH2 C CH2 CH3 + 2Cl2  CH3 CH2 C CCl2 CH3
O O

(b) Replacement of O-atom of C O group : It take s place by PCl 5 or SOCl 2 .

Cl
C O + PCl 5  C + POCl 3
Cl
Phosphorus penta chloride

Cl
C O+ SOCl 2  C + SO 2
Cl
Thionyl chloride
(c) Haloform react ions :
Chlorine or bromine replaces one or more -hydrogen atoms in aldehydes and ketones, e.g.,
acetone may be brominated in glacial acetic acid to give monobromoacetone :

CH 3 COCH 3 + Br 2  CH 3 COCH 2 Br + HBr (43–44%)

The halogenation of carbonyl compounds is catalysed by acids and bases. Let us consider the
case of acetone. In alkaline solution, tribromoacetone and bromoform are isolated. T hus, the
introduction of a second and a third bromine atom is more rapid than the first. In aqueous sodium
hydroxide, the rate has been shown to be independent of the bromine concentration, but first
order with respect to both acetone and base i.e.,
Rate = k [acetone] [OH  ]

O O
Br2
CH3COCH3+ OH
Slow
H2O + CH3—CCH2

CH3C=CH2 CH3COCH2Br + Br
fast

(5) Aldol Condensation :

Two molecules of an aldehyde or a ketone undergo condensat ion in the presence of a base to yield
a -hydroxyaldehyde or a -hydroxyketone. This reaction is called the aldol condensation. In general
Carbonyl compounds which contain -H atoms undergo aldol condensation with dil. NaOH. Aldol contains
both alcoholic and carbonyl group.
 Mechanism of aldol condensation : It takes place in the following two stages :
(a) Format ion of Carbanion
(b) Combination of carbanion with other aldehyde molecule.
(a) Format ion of Carba nion :
-H atom of C O group are quite acidic which can be removed easily as proton, by a base.

–   –
OH+ H CH2 C H CH2 C H + H2O
O O
Base Acetaldehyde Carbanion
Carbanion thus formed is stable because of resonance -

–
CH2 C H  CH2 C H
O O–
 (b ) Combination of carbanion with other aldehyde molecule :

O H O–
–
CH3 C + CH2 C O CH3 C CH2 CHO
H H

H+ H2O
Aldehyde
(other molecule)
OH H O

CH3 C CH2 C O CH3 CH CH CH
H  –Unsaturated aldehyde
Aldol

Aldol condensation is possible between :

1. Two aldehyde (Same or different)
2. Two ketone s (Same or different)
3. One aldehyde and one ketone

Id en t ica l ca r b o n y l co m p o u n d s  S im p l e o r s e l f a l d o l co n d e n s a t io n .
D iffe r e n t ca r b o n y l co m p o u n d s  M ix e d o r cr o s s e d a l d o l co n d en s a t io n .

Simple or Self condensation :

dil 
CH3 CH + HCH2CHO 
NaOH
CH3 CH CH CHO 
–H O
CH3 CH CH CHO
2

O OH H Crotonaldehyde

CH3 O CH3

CH3 C CH3 + H CH2 C CH3  CH3 C CH2 C  CH3 C CH COCH3 + H2O
O O OH CH3
diacetone alcohol Mesityl oxide or
4–Methyl– 3–pentene– 2–one

O O
CH3 CH3 HCl gas CH3 CH3
C CH C CH3 + O C  C CH C CH C
–H2O
CH3 CH3 CH3 CH3
Phorone
Mixed or Crossed aldol Condensat ion :

Week (2) simple

CH3CH + CH3 C CH3 Total (4) products
Base
(2) mixed
O O

 OH 
CH3 CH + CH2 COCH3  CH3 CH CH2 COCH3  CH3 CH CH COCH3
Week base –H2O

O H OH
(Aldol)
 CH3 CH3 CH3
 
OH 
CH3 C + CH2 CHO  CH3 C CH2 CHO  CH3 C CH CHO
Week base –H2O

O H OH
(Aldol)

OH 
Ex : CH 3 CHO + CH 3 CH 2 CHO 
( WB )  Total 4 product s. Write structure of products ?

  OH 
S o l . CH3 CH + CHCHO
2   (Aldol) 
–H 2 O  CH 3 —CH CH—CHO

O H

 

CH3 CH2 CH + CH2 OH
CHO   (Aldol) 
–H 2 O  CH 3 —CH 2 —CH CH—CHO

O H

CH3 CH3
  OH 
CH3 CH + CH CHO   (Aldol) 
–H 2 O  CH3 CH C CHO

O H

CH3 CH3
  OH 
CH3 CH2  (Aldol)
CH + CH CHO  
–H 2 O  CH3 CH2 CH C CHO

O H

 Intramolecular aldol condensation :

OH 
CH3 C CH2 CH2 C CH3  CH3 C CH2 CH2 C CH2
(–H2O)

O O O O
O H3C O  H3C O
H3C  H
  
–H2O HO O

( – Unsaturated Ketone) (Aldol)

Here 5 membered ring is more stable than 3 membered ring so above product is formed as a major
product.
Note :
 If in crossed aldol condensation reaction , only one carbonyl compound have –H than total two product
for med.

OH
CH 3 CHO + C 6 H 5 CHO  Total 2 product.
 WB 

  
CH3 OH
CH + CH2 CHO   (Aldol) 
–H 2 O 
CH 3 —CH CH—CHO

O H
(Crotonaldehyde)
 
 
C6H5 OH
CH + CH2 CHO   (Aldol) 
–H 2 O  C 6 H 5 —CH CH—CHO

O H
(Cinnamaldehyde)
(6) Claisen condensation :
When two molecules of ester undergo a condensation reaction, the reaction is called Claisen condensation.
The product of the claisen condensation is a -keto e ster.

CH3
CH3CH2ONa
 O + H3C
OC2H5
2H3C H3C C2H5
OH
O O O
-keto ester

After nucleophilic attack, the aldol addition and the Claisen condensation differ. In the claisen condensation,
the negat ively charged oxygen reforms the carbon oxygen -bond and eliminates the OR group.

 Mixed claisen condensation :

O O
O O

O (i) CH3CH2O O CH3

CH3 + H3C O CH3 (ii) H
H3C
-keto ester
(7) Intramolecular claisen condensation :
Dieckma nn condensat ion : T he addit ion of base to a 1,6-die ster cause s the diester to undergo
intramolecular claisen condensation, thereby forming a five membered ring -keto ester. An intramolecular
claisen condensation is called a Dieckmann condensation.

(i) CH3O
(ii) H + CHOH
3

O O H3C
CH3

O
O
CH3
O (i) CH3O OCH3
+ H3C—OH
(ii) H
O O

OCH3

(8) Perki n react ion :

In perkin reaction, condensation has been effected between aromatic aldehydes and aliphatic acid anhydride
in the presence of sodium or potassium salt of the acid corresponding to the anhydride, to yield ,
-unsaturated aromatic acids.
 The acid anhydride should have at least two -H.
AcONa
C 6 H 5 CHO + (CH 3 CO) 2 O   C 6 H 5 —CH=CH—COOH
170 180  C

(CH3CO)2O, AcONa O

O O
O OH
3-(-furyl) acrylic acid

O
OH
(CH3CO)2O, AcONa
O  O

O O
phthalic anhydride phthalyl acetic acid

(9) Knoevenagel Reaction :

Condensation of aldehydes and ketones with compounds having active methylene group in the presence
of basic catalyst to form a, b-unsaturated compounds is called Knoevenagel Reaction. The basic catalyst
may be ammonia or its derivative. Thus 1°, 2°, 3° amines i.e., aniline, di-or tri - alkyl amines, pyridine
or piperidine are used.

O O
O H5C6 O H5C6 O
C6H5CHO + R Pyridine R (i) H2O
Piperidine (ii) , –CO2
O O OH
O R O R 
Malonic Ester Cinnamic acid

( 1 0 ) Reformat sky React ion :

A similar reaction like the addition of organometallic compounds on carbonyl compounds that involves
the addition of an organozinc reagent to the carbonyl group of an aldehyde or ketone. This reaction,
called Reformatsky reaction, extends the carbon skeleton of an aldehyde or ketone and yileds b-hydroxy
esters. It involves treating an aldehyde or ketone with an -bromo ester in the presence of zinc metal;
the solvent most often used is benzene. The initial product is a zinc alkoxide, which must be hydrolysed
to yield the -hydroxy ester.
ZnBr
O OH
O O O
Zn/C6H6 
H3O
O + Br
O O—R O—R
Aldehyde R
or ketone -bromoester -hydroxy ester

( 1 1 ) Schmidt Reaction :

This is the reaction between a carbonyl compound and hydrazoic acid in the presence of a strong acid
concentrated sulphuric acid. Aldehyde s give a mixture of cyanide and formyl derivat ives of primar y
amines, whereas ketones give amides :
 2 4H SO
RCHO + HN 3  RCN + RNHCHO + N 2

2 4H SO
RCOR + HN 3  RCONHR + N 2

Reaction with primary amine : C O + H2 NR  C NR + H2O

Schiff's Base
( 1 2 ) Benzoin condensation :
The benzoin condensation is essentially a dimerisation of two aromatic aldehydes under the catalytic
influence of cyanide ions to give benzoin (I).

2 C6H5CHO
KCN H3C
OH
H5C6
(I)
The hydrogen atom attached to the carbonyl group of aldehyde is not active enough to be removed
easily but the addition of the cyanide ion to the carbonyl carbon places this hydrogen in the alpha
position of the nitrile thus rendering it relatively acidic. The carbanion, thus generated, attacks the
carbonyl carbon of the second aldehyde molecule in a rate-determining step forming an unstable cyanohydrin
of benzoin which immediately breaks down into benzoin and hydrogen cyanide.
OH OH

O O
 proton exchange
H5C6 + CN H5C6 CN 
H5C6 CN H5C6 C 
H N
H

  O
OH O OH O O OH
H3C 
Slow
H5C6  + C6H5 H3C CH3 H3C CH3 OH + CN

CN H CN H CN H H5C6

( 1 3 ) Benzi lic acid rear ra ngement :

The addition of a strong base to a carbonyl group results in the formation of an anion. The reversal
of the anionic charge may cause expulsion of the at tached group X, e.g.

X 
X O
HO 
O O
OH
OH
However, in a 1, 2-diketone the group X may migrate to the adjacent electron-deficient carbonyl carbon
formi ng -hydroxy acid.
Thus, benzi l on treatment with a strong base forms benzilic acid (salt), hence the name benzilic acid
rearrangement.

O OH
O O O
C6H5 NaOH H5C6 H5C6
H5C6 
OH ONa
O H5C6 H5C6
benzil sodium salt of benzilic acid
( 1 4 ) T he Beckma nn rear ra ngenment :
The acid catalysed transformation of a ketoxime to an N-substituted amide is known as the Beckmann
rearrangement.
–H2O
C=O + H2N—OH C=N—OH
Oxime

H
R R 
 O—H
H –H2O R'—C H2O
N N R'
R' OH R' OH2 N—R
 N—R
O—H O
–H R'
R'
N—R NH—R

The rearrangement is catalysed by a variety of acidic reagents such as H 3 PO 2 , H 2 SO 4 , SOCl 2 ,

PCl 5, etc.
(C) Oxidat ion React ions :
(a) By K 2 Cr 2 O 7 /H 2 SO 4 :
On oxidation with K 2 Cr 2 O 7 /H 2 SO 4 1° alc. gives aldehyde, which on further oxidation gives acid
with same C-atom. While, 20 alcohol on oxidation gives ketone which on further oxidation gives acid
with less C-atom.

R—CH 2 OH [O] R—CH O [O] R—COOH

   

(1° alcohol)

[O] [O]
CH3CH2CH2 CH CH3   CH3CH2CH2 C CH3   CH 3 CH 2 COOH+CH 3 COOH

OH O
(2° alcohol)

(i) 3° alcohol is not oxidised within 2 or 3 minutes.

(ii) 1° and 2° alcohol converts orange colour of K 2 Cr 2 O 7 to green in 2-3 minutes.
(b) SeO 2 (Selenium Oxide) :
Ketones or aldehydes on oxidation with SeO 2 gives dicarbonyl compounds. This reaction is possible
only in compounds containing –carbon.
HCHO doesn't show this reaction.

CH3CHO + SeO2  H C C H + Se + H2O

O O
Glyoxal

CH3 C CH3 + SeO2  CH3 C C H + Se + H2O

O O O
Methyl glyoxal (Pyruvaldehyde)
 (c) Bae yer's Vi l liger oxidat ion :
Both aldehyde and ketones are oxidized by peroxy acids. This reaction, called the Baeyer-villiger
oxidation, is especially useful with Ketones, because it converts them to carboxylic esters. For
example, treating acetophenone with a peroxy acid converts it to the ester phenyl acetate.
O

O R O
H5C6—O
H5C6 OH
O
CH3 H3C
phenyl acetate
Mechanism :

H H O
:O

:

:O: H—A :O O O
+ 
H3C O R
H3C C6H5 H3C C6H5 R O
H
:OH C6H5 A

:H
OH :A

H O

:
OH O H :O H—A

:
O + 
O :O
O O O
H3C R O
R H3C H3C R
C6H5 C6H5 C6H5

H3C OC6H5
The product of this reaction show that a phenyl group has a greater tendency to migrate then a methyl
group. Had this not been the case, the product would have been C 6H 5COOCH 3 and not CH 3COOC 6H 5 .
This tendency of a group to migrate is called is migratory aptitude. Studies of the Baeyer-villiger oxidation
and other reaction have shown that the migratory aptitude of groups H > phenyl > 3° alkyl > 2° alkyl
1° alkyl > methyl. In all cases, this order is for groups migrating with their electron pairs, that is, as anions.

Per acid
Ex. CH3 C C2H5  ?
O

S o l . CH3 C OC2H5
O

CH3
Per acid
Ex. CH3 C C CH3  ?
CH3 O

CH3
S o l . CH3 C O C CH3
CH3 O
(D) Reduction :
(a) T he wolf kishner reduct ion :
When a ketone or an aldehyde is heated in a basic solution of hydrazine, the carbonyl group
is converted to a methylene group this process is called Deoxygenation because an oxygen is
removed from the reactant. T he react ion is know n as the Wolf-kishner Reduct ion.

COCH3
(i) NH2–NH2
(ii) OH/HOCH2–CH2OH
CH3

(b) Clemmensen Reduction :

The reduction of carbonyl groups of aldehydes and ketones to methylene groups with amalgamated
zinc and concentrated hydrochloric acid is known as Clemmensen reduction.

COCH3
Zn–Hg, HCl
Reflux
CH3
The nature of product depends upon the reducing agent used. It can be summarized as.

(i) C O  CH2 Reducing agents are

 Red P/HI at 150°C

 Zn-Hg/HCl [Clemensen's reduction]
 NH 2—NH2/C 2H 5OH,OH  [Wolff Kischner's reduction]

(ii) C O  CHOH Reducing agents are

 LiAlH 4 (Nicetron brown)

 Na/C 2 H 5 OH (Bouvalt blank)
 NaH/Benzene (Darzen reaction)
 [(CH 3 ) 2 CHO] 3 Al (Aluminium isopropoxide)
 (CH 3 ) 2 CHOH (Isopropyl alcohol)
Reduction w ith aluminium isopropoxide is excess of isopropanol is called MPV (Meerwei n Ponndroff
Verle y) reduction. Other reducible groups are not at tacked like —NO 2 , —CH CH 2 , —C C—.

Example : CH3 MPV Re duction CH3

C O  
 CHOH
CH2 CH CH2 CH

(E) Reactions given by only aldehydes :

(1) Polymerisation : It is a reversible process.
Formaldehyde :
Evaporation
(a) 
nHCHO  
 (CH 2 O) n , H 2 O Paraformaldehyde is a li near polymer


Formali n Paraformaldehyde which show reducing character with

(40% HCHO) n = 6–50 Tollen's reagent, Fehling solution etc.
Hydrated white crystal
 Conc.

nHCHO 
H SO  
(b) (CH 2 O) n H 2 O
2 4

Poly oxy methylene

n > 100

Allowed to s tan d
(c) 3HCHO   (CH 2 O ) 3
at room temp. CH2
Meta formaldehyde (Trioxane) O O
Cyclic polymer (Trioxy methylene)
H2C CH2
Cyclic polymer doesn't show reducing
O
character with Tollen's reagent etc.

Ca  OH 2
(d) 6HCHO   C 6 H 12 O 6
or Ba  OH 2

Formose sugar
A linear polymer (  -acrose)
Acetaldehyde :

CH2
CH
O O
Conc. H 2 SO 4
(a) 3 C H 3C H O 
 (CH 3 CHO) 3 H3C HC CH CH3
Room temp.
O
Para acetaldehyde
Paraldehyde (cyclic polymer)
Pleasent smelling liquid
Hypnotic compound

CH3 CH3
O
conc. H 2 SO 4 O O
(b) 4 C H 3C H O 
0 C  (CH 3 CHO) 4
O
CH3 CH3
Meta aldehyde
White crystalline solid.
Cyclic polymer
Used as solid fuel or killing snails

(4) Reaction with ammonia :

Except formaldehyde, all other aldehydes give addition reactions (HCHO give addition elimination i.e.
condensation reaction)
 Condensation
6CH 2 O + 4NH 3   (CH ) N + 6 H 2O
Re action 2 6 4

Urotropine (Hexamine)
White crystalline solid
Used in preparation of explosive
Used in treatment of urine infection diseases

Addition Conc. H 2 SO 4
CH3 CH + NH2  CH3 CH NH2   CH3—CH NH
Re action H2O

O H OH Acetaldimine
Acetaldehyde used in preparation
ammonia of cyclic polymer

CH3

CH
HN NH
3 H 2O . 3H2O
3 C H 3— C H NH    HC CH
Trimerisation
H3C N CH3

H
Trimethyl hexahydro Triazine trihydrate

(5) Reducing character :

Aldehydes are easily oxidised so they are strong reducing agents.
(a) Tol len's reagent :
It oxidises aldehyde s. Tollen's reagent is ammonical si lver nitrate solut ion
( A g NO 3+ NH 4O H )      [Ag(NH 3 ) 2 ]O H
RCHO+[Ag(NH 3 ) 2 ]OH  RCOOH + Ag + H 2 O
Silver mirror
AgNO 3 + NH 4 OH      A g O H  A g 2 O
RCHO + Ag 2 O      RCOOH + Ag  (Silver mirror)
(b) Fehling's solution :
It is a mixture of CuSO 4 , NaOH and sodium potassium tartrate.
Fehling solution A– (aq.) solution of CuSO 4
Fehling solution B– Roschelle salt (Sodium potassium tartrate + NaOH)
Fehling solution A + Fehlings solution B(Dark blue colour of cupric tartrate)
RCHO + Cu +2 + OH–  RCOOH + Cu2O
(Cuprous oxide–Red ppt.)
C u 2+  Cu +
(Cupric - Blue) (Cuprous - Red ppt.)
(c) Benedict's solution :
It is a mixture of CuSO 4 + sodium citrate + Na 2 CO 3 . It provides Cu +2 . It is reduced by aldehyde
to give red ppt of cuprous oxide.
–
RCHO + Cu 2+ + OH  RCOOH + Cu2O
(Cuprous oxide–Red ppt.)
 (d) Mercuric chloride :
HgCl 2 is a corrosive sublimate. It is reduced by aldehyde to give white ppt of mercurous chloride
(Calonal) which further react with aldehyde to give black ppt of Hg.
RCHO + HgCl 2 + H 2 O  RCOOH + Hg 2 Cl 2 + HCl
(calomal)
RCHO + Hg 2 Cl 2 + H 2 O  RCOOH + Hg + HCl
(black ppt)
(e) React ion w it h sch iff's reagent :
Schiff's reagent is dil solution of p-roseniline hydrochloride or magenta dye.
Its pi nk colour is discharged by passi ng SO 2 gas and the colourle ss solut ion is called schiff's
reagent, Aldehyde reacts w ith this reagent to re store the pi nk colour.
(F) Reaction of only ketones :
(1) Reduction : Acetone is reduced by magnesium amalgam and water to give pinacol.

CH3 CH3
CH3 CH3 Mg Hg
C O+ O C  CH3 C C CH3
water
CH3 CH3
OH OH

Pi nacol
(2) React ion w it h chloroform :

OH
CH3 CH3 OH
C O + CHCl3  C aq.NaOH
 CH3 *CH COOH
CH3 CCl3
CH3
(Chloretone) (Lactic acid)
2-Hydroxy propanoic acid

(3) Reaction with HNO 2 :

O O
–H2O
CH3 C CH3 + O N OH  CH3 C CH N OH
Oximino acetone
(4) Oxidation reaction : According to popoff's rule C O group stays w ith smaller alkyl group.
O
CH3 CH2 C CH3  CH 3 COOH + CH 3 COOH

(5) Condensat ion react ion :

(a) In presence of dry HCl - aldol condensation takes place

CH3 O CH3 O
–H2O
CH3 C O + CH3 C CH3  CH3 C CH C CH3

Mesityl oxide

CH3 CH3 CH3 O CH3

–H2O
CH3 C CH COCH3+ O C CH3  CH3 C CH C CH C CH3
(Phorone) or 2,6–Dimethyl–2,5–
hepta diene–4–one
 (b) In presence of conc.H 2 SO 4
CH3
O
3CH3 C
Conc. H2SO4
CH3  Mesitylene
condensation
Polymerisation H3C CH3

Fe
3CH3 C CH
Addition Polymerisation
(6) Reaction with ammonia :
CH3 O CH3 O
–H2O
CH3 C O + HCH2C CH3  CH3 C CH2 C CH3
HNH2 NH2
Diacetone amine
(7) Pyrolysis :


CH2 C O  CH2 C O + CH4  HCHO  
 CO  H 2 

 pyrolysis 
H CH3 Ketene  

CH 3 CHO  CH 4  CO 
Acetone

TEST FOR HCHO, CH 3 CHO, CH 3 COCH 3

S.No. Te s t HCHO C H 3C H O C H 3C O C H 3

1. Legel's test :Na [Fe(NO)(CN) 3 ] – Red Red

sodium nitroprusite (alk.)

Only methyl C O

compound gives this test

2. Iodoform te st – – –
(I 2 + NaOH) – yellow ppt yellow ppt

OH

3. Pyragallol OH white ppt. – –

OH

4. Orthonitro benzaldehyde – – Bl ue
5. Tollen's reagent - Silver mirror Silver mirror –
Fehling's reagent - Red ppt Red ppt –
Mercuric chloride - Black ppt Black ppt –
Schiff's reagent - Pink colour Pink colour –
6. DNP O r an g e O r an g e O r an g e
colour colour colour
 BENZALDEHYDE (C 6 H 5 CHO)
Oil of bitter almonds
General Met ho d of Preparat ion :

CO/ HCl + AlCl3

C6H6 * (Gattermann-kosch reaction)
CrO2Cl2
C6HCH
5 3
* (Etard reaction)
Pd/BaSO4
C6HCOCl
5
* (Rosenmund reaction)
(i) SnCl2/HCl (ii) H2O
C6HCN
5
* (Stephen's reaction)
(HCOO)2Ca/
(C6HCOO)
5 2 Ca
aq. KOH C6HCHO
5
C6HCHCl
5 2
[O]
C6HCHOH
5 2
(CH2)6N4
C6HCHCl
5 2
(i) HCOOC2H5 (ii) H2O
C6HMgBr
5
(i) HCN/HCl (ii) H2O
C6H6 (Gattermann)
AlCl3

Chemical proper t ie s :

(Similar) (different)
C6H5CH(OH)CN C6HCOCl
5
HCN 170°/Cl2

NaHSO3 2NH3 C6H5 CH N

C6H5CH(OH)SO3Na CH C6H5
2C6H5CHO
C6H5 CH N
NH2 Z 2C6H5CHO
C6H5CH N Z C6H5 CH C C6H5 Benzoin
alc.KCN
OH O
Red P + HI
C6H5CH3
(CH3CO)2O,CH3COONa
C6H5 CH CH COOH
Oxidation Perkin
C6H5COOH
H2CH NO2
HO–
C6H5 CH CH NO2
PCl5 C6H5CHO Nitrostyrene
C6H5CHCl2
Br
(i) Zn+CH2COOC2H5
Tollen Cinnamic acid
Silver mirror test (ii) H2O
reagent Reformatsky reaction

C6H5COONa + C6H5CH2 OH NaOH

HNO3/H2SO4
Cannizaro reaction m – nitrobenzaldehyde
C6H5CH N Ar Ar NH2
Fuming H2SO4
Schiff's base m–formyl benzene
sulphonic acid
Schiff's
Pink colour Cl2/FeCl3
reagent Chloro benzaldehyde

C6H5COOCH2C6H5 AlCl3

Tischenko reachion Al(OR)3

CH3 C CH3
OH C6H5MgBr O

C6HCH
5 CH C CH3
H2O
C6H5 CH C6H5 OH
O
 SOLVED EXA MPLES

Ex 1. What is A in the following reaction ?

Cl O
O
t  BuOK
+ O 
t  BuOH
 A
H5C2

O O O
H3C
O
O OH
–

C2H5 C2H5
(A) (B) (C) O (D)
O
C2H5

Ex 2. is the final product obtained when one of the following is reacted with base :
CH3

O O O O
(A) H3C CH3 (B) H3C CH3

O O O O
(C) H3C (D) H3C CH3
CH3

O
O O
Alkali
 
Sol. H3C CH3 

CH3

O
O
CH3 C – OH

Ex 3. C C H
  (A)
CH3 H
The product (A) in the given reaction would be :

O O O OH
C C
CO
=
–

(A) CH3 C OH (B)

C–C–H
H CH3
H3C CH3

O
=

O OH C–H
=

H
–

(C) CH3 C (D) C=C

– –

C H CH3
CH3
CH3
 H
O
O O O
CH3 C – OH +
H
CH3 –H
+ H3C OH
C C C C–C–O–H C=C
Sol. CH3 H CH3 –CO2 H3C H
H enol
unstable unstable

H
H3C O
C–C
H3C H

Ex 4. End product of the following sequence of reactions is :

3 CH MgBr
4 2 4 CO / H O 
Ag 2 O HgSO / H SO
CHCH  2 3
   
 
 

O O O O
(A) H3C (B) HO O (C) H3C (D) H O
OH
O O
OH OH

Sol. CHCH + CH3MgBr CHC–MgBr


CO2/H3O

–COOH is (EWG) CH C COOH

HgSO4/H2SO4

OHC–CH–COOH
2

Ag2O

HOOC–CH2–COOH

 (B)
Ex 5. In which of the following substrates, rate of Benzoin condensation will be maximum ?

(A) O2N CHO (B) H3C CHO

(C) HO CHO (D) NH2 CHO

:
:

:O :O: :O–H
:

O
:
:

O O
– –
=

– =
:

   
:
:


Sol. 
N C + CN 
N C–H 
N C:
: :
: :

:O :O
::

:O H CN CN
:
(I) (II) (III)

Benzoin condensation is due to stability of intermediate (III) when negative charge on C extensively delocalised
in benzene ring, nitro and CN group. In all other cases, such dispersal is not extensively possible. On
the other hand, NO2– is also creating a positive charge center on carbonyl carbon, making it more susceptible
to nucleophilic attack of CN –.
Ex 6. This intermediate is converted into product in the wittig reaction :

Ph3 P O

R–C C–R1 O=P – Ph3 + R–C = C–R1

–
–
–
–R1 R2 R1 R2

Out of following which statements are correct ?

(A) C–O bond is weaker as compared to P–O bond
(B) Lone pair of oxygen atom participate in p–d bonding with phosphorous atom
(C) C–P bond is weaker as compare to C–C bond
(D) C–C bond is weaker as compare to C–O bond
Sol. (A), (B), (C)
Ex 7. Consider the following sequence :

CH3
O
H
O O 
O

OH CH 3 CHO

Step I 
Step II
 H3C O
H3C O H3C O H2O Step III

CH3
O O H
CH—CH3 OH


Step IV

H3C O H3C O
Which of following statements are correct for above reaction sequence ?
(A) Step I is acid-base reaction (B) Step II is nucleophilic addition reaction
(C) Step III is acid base reaction (D) Step IV is elimination reaction
Sol. (A), (B), (C), (D)
Ex 8. Which of the following oxidation reaction can be carried out with chromic acid in aqueous acetone at
5–10°C.
O
=

(A) CH3(CH2)3C C–CH–CH3  CH3(CH2)3C C–C–CH3

–

OH
(B) CH 3 (CH 2 ) 3 CH=CH–CH 2 OH  CH 3 (CH 2 ) 3 CH=CH–CHO
(C) C 6 H 5 CH 3  C 6 H 5 COOH
(D) CH 3 (CH 2 ) 3 CH 2 OH  CH 3 (CH 2 ) 3 CHO
Sol. (A), (B), (C), (D)

O
SeO 2
Ex 9. CH3 – C – CH3   A ; A will :

(A) Reduce Tollen's reagent (B) Give iodoform test

(C) Form oxime (D) Give Cannizaro reaction
Sol. SeO 2 oxidises –  – CH 2 – a w.r.t. keto group
 (A), (B), (C) and (D)
 NaOH
Ex 10. 3HCHO + CH 3 CHO  
 A. A found can

(A) Reduce Tollen's reagent (B) Give Cannizaro reaction

(C) React with Na (D) Give green colour with Cr 2 O 72–/H +
Sol. A is by aldol condensation

CH2OH
HOH2C – C – CHO
CH2OH

 (A), (B), (C) and (D)

Mg / Hg
Ex 11. 2CH3 – C – CH3 
H
 Product, product in the reaction is :
O

CH3 CH3
(A) H3C – C – C – CH3 (B) CH3 – C – O – C – CH3
OH OH O O

(C) CH3 – CH – CH – CH3 (D) None of these

OH OH

CH3 CH3
Mg / Hg
Sol. (A) 2CH 3 – CO – CH 3 
 H3C – C – C – CH3
H2O

OH OH
(Pinacol)

Ex 12. Benzaldehyde on reaction with acetophenone in the presence of sodium hydroxide solution gives :
(A) C 6 H 5 CH = CHCOC 6 H 5 (B) C 6 H 5 COCH 2 C 6 H 5
(C) C 6 H 5 CH = CHC 6 H 5 (D) C 6 H 5 CH(OH)COC 6 H 5

O
NaOH
Sol. (A) C 6 H 5 CHO + CH 3 COC 6 H 5 
 C6H5 – CH = CH – C – C6H5
H2O

Ex 13. Product in following reaction is :

CH 3 MgI + HCHO  Product
(A) CH 3 CHO (B) CH 3 OH (C) C 2 H 5 OH (D) CH 3 – O – CH 3

OH
Sol. (C) H – CHO + CH 3 MgI  CH 3 – CH 2 – OH + Mg
I