Aldehyde & Ketone-All Lectures

CHEMISTRY [1]
LECTURE - I
ALDEHYDE & KETONES
INTRODUCTION compounds because carbonyl group takes parts in
resonance with the lone pair of electrons.
Organic Compounds having  group aree  Structure :
In  compounds C-atom is sp 2 hybridised
called carbonyl compounds and  group is
known as carbonyl or oxo group. It's general formula which forms t wo  bonds with C and H-atom
is Cn H2nO (n = 1, 2, 3......) Carbonyl compounds respectively and one  bond with oxygen atom.
are grouped into two categories. The unhybridised atomic orbital of C-atom and the
parallel 2p orbital of oxygen atom give the  bond
in  group.
(a) Aldehydes : Aldehyde group is   (also known
as formyl group). It is a monovalent group


(b) Ketones : The carbonyl group    is a
The C – C – O and H – C – O bond
Ketonic group when its both the valencies are angles are of 120 .
satisfied by alkyl group. It is a bivalent group.
Due to electro-negativity difference in C & O atoms,
 Ketones Are Further Classified As :
(i) Simple or Symmetrical Ketones : Having two the  group is polar..
 
similar alkyl groups.   Hence aldehydes and Ketones posses dipole
moment.
(ii) Mixed or Unsymmetrical Ketones : Having two
GENERAL METHODS OF PREPARATION
different alkyl groups.  (A) For both Aldehydes and Ketones :
[1] By Oxidation of Alcohols :-
Example : (Ketones) :
Symmetrical Unsymmetrical (a) By K2Cr2O7 / H2SO4 :
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.
(Acetone or Dimethyl ketone) (Ethyl methyl ketone)  (Aldehyde)

2–Propanone 2–Butanone
Special Point :      (Ketone)
        Aldehydes are quite susceptible to further oxidation

In all the compounds given above, lone pair of to acids -
electrons and double bond are conjugate. RCH 2 OH 
 R—CHO 
 R—COOH
Thus oxidation of primary alcohols is made at the
so resonance occurs. These compounds temperature much above the boiling point of
 
aldehyde and thus aldehydes are vapourised out
and prevented from being oxidised.
have   group still they are not carbonyl
[2] ALDEHYDE & KETONE
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
(Isobutylene)
acetone.
(b) Oppenaur Oxidation : [3] By Hydrolysis of Gem Dihalides :-
The oxidation of secondary alcohols to ketones Terminal gem-dihalides on hydrolysis give aldehydes
by heating them with specific reagent : while the non-terminal dihalides give ketone.
[(CH 3) 3CO] 3 Al (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 Terminal gem-dihalide [unstable]
equilibrium can be controlled by the amount of 
 CH 3 CH O
acetone, an excess of which favours the oxidation
Acetaldehyde
of the alcohol.
 
 
+  


       
 
 
2 o Alcohol Acetone

  
  
[4] By Oxidation of Diols :-

Ketone Isopropyl alcohol With periodic acid (HIO 4 ) & lead tetra acetate
(CH3COO) 4 Pb vicinal diols gets oxidised to form
RCH 2 OH + O= =O 


 carbonyl compounds
1 0 Alcohol Quinone R CH CH R' + HIO4
R—CHO + HO— —OH OH OH
 RCHO + R'CHO + HIO 3 + H 2 O
Aldehyde Quinol
R R
Note:- The reaction is the reverse of Meerwein-
R C C R' + HIO4 
Ponndorf -verley reduction.
OH OH
(c) Mild Oxidising Agent :
O O
1o alcohols will get oxidised with CrO3 / Pyridine,
collin's reagent Ag/O 2 at 250 o C R C R + R' C R + HIO3 + H2O
RCH 2 OH + [O]  RCHO + H 2 O [5] By Ozonolysis of Alkenes :-

By this reaction, good yield of aldehyde is possible. This reaction is used to determine the position of
double bond in alkene.
[2] Dehydrogenation of Alcohols :-
CH 3 CH 2 OH 

CH 3 CHO
 
(Acetaldehyde)


  
(Acetone)
CHEMISTRY [3]
[7] By Nef's Reaction :
Nitro alkanes are used in this reaction. The 
 of nitro alkane shows acidic nature.


(Nitro form) (Aci form)
°°nitro alkane



 

[6] From Alkyne :-
(a) Hydration :
With dil H 2 SO 4 & 1% HgSO 4 at 60-80 0 C.
CH  CH + H 2 O  
O 
CHOH] 
[CH 2  
 CH3 C H (Nitro form) (Aci form)
(Tautomerisation) nitro alkane
Other alkynes give ketone :  


    
  



   (Ketone)
R O
R C N  No Reaction
(b) Hydroboration : R O
Reaction with B 2H 6 , 2BH 3 or R 2BH give dialkyl ( nitro alkane)
borane.
[8] By Hydrolysis of Carbonyl Derivatives :
 



 R—CH N—OH  R—CHO + NH 2—OH
(Aldoxime) (Aldehyde) (Hydroxyl amine)
     
R  R
C N OH  C O + NH2 OH

   


 R R
(Ketoxime) (Ketone)
    R OR  R
C  C O + 2ROH
H OR H
(Acetal) (Aldehyde) (Alcohol)
CH 3 —C C—CH 3 + R 2 BH   
R OR  R
CH3 CH C CH3  C  C O + 2ROH
R OR R
BR2 (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    

Alkyl halide (b) CH3 C CH2 C OH 
–CO2
R C HO + (CH 3 ) 2 S + HX O O
 CH3 C CH3
(Aldehyde) (Dimethyl thio ether)
O
X O
  
R CH R 
 R C R (B) For Aldehydes Only :
halide Ketone [1] Reduction of Acyl Halides, Esters and Nitriles:
[10] From Grignard Reagents :- (a) Acyl chlorides can be reduced to aldehydes by
(a) By Cyanides : treating them with lithium-tri-tert-butoxyaluminium
hydride, LiAIH[OC(CH 3 ) 3 ], at – 78°C.
RMgX + R C N R C N MgX 
O O
R R

 R
 
H O/H OH
 R N MgX  R C R + NH3 + Mg
2
Cl H
X
R O
(Ketone) (b) Both esters and nitriles can be reduced to aldehydes
by DIBAL-H. Reduction must be carried out at
(b) By Esters : low temperatures. Hydrolysis of the intermediates
HCHO can't be prepared by this method. gives the aldehyde.
O OMgX
O O
HO
RMgX + H C OR  H C OR  H 2
R 
  
 R
R OR' H
(Alkyl formate) (Hemiacetal)
OH O
R—CN  R
  
–ROH
 H C OR  H C O
H
R R R [2] Rosenmund's Reduction :
(Hemiacetal) (Aldehyde)
Quinoline or sulphur act as a poisoned catalyst,
O OMgX controls the further reduction of aldehyde to
HO
RMgX + R C OR  R C OR  2
alcohols.
R
RCOCl + H 2  RCHO + HCl
(Alkyl Alkanoate)
Pd
RCOCl + H 2   RCHO   RCH 2OH
OH Formaldehyde can not be prepared by this method.
 R C OR  R C O Example :
R R R C2H5COCl + H2  C2H5CHO + HCl
(Hemiacetal) (Ketone)
Propionyl Chloride Propanal
(c) By Acid Chlorides :
[3] Stephen's Reduction :-

R' X Alkyl cyanides are reduced by SnCl 2 and HCl.
R' C Cl + RMgX  C O + Mg
R Cl
O R—C N 
 R—CH NH

[11] From -keto Acids :  RCHO+NH 3
The decarboxylation reaction takes place via
C 2 H 5 —C N 
 C 2 H 5 CH NH
formation of six membered ring transition state.

  C 2 H 5 CHO + NH 3
(a) HCOCH 2 COOH  CH 3 CHO+CO 2

CHEMISTRY [5]
[4] Oxo Reaction or Hydroformylation :- [3] From R 2 CuLi :
In this reaction symmetrical alkene gives aldehyde R 2CuLi + R'COCl  R'COR + RCu + LiCl
while unsymmetrical alkene gives isomeric aldehyde
[4] By Hydrolysis of Aceto Acetic Ester (AAE):
(Chain isomers).
H3O
 CH3 C CH2 C OC2H5 
CH 2 CH 2 +  

C H 3C H 2C H O –C2H5OH
O O
CH 3 —CH CH 2 + CO + H 2   
 
OC H  CH3 C CH2 C OH  CH3 C CH3
–C H OH –CO2
CH 3 CH 2 CH 2 CHO + CH3 CH CH3
O O O
CHO ( - keto acid) (Acetone)
(C) For Ketones Only :
[1] From Grignard's Reagent : H3O
Ex : CH3 C CH C OC2H5 
–C2H5OH
RMgX + R—C N   R C NMgX O CH3 O
R
 

2H 2 O
 OCXH  CH3
 R C O + NH3 + Mg C CH C OH  CH3 C CH2 CH3
–C H OH –CO2
OH
R O CH3 O O
O OMgX (–keto acid) (Butanone)
H2O
RMgX + R C Cl  R C Cl   Other Methods for Aldehyde and Ketone :
R [1] By Dry Distillation of Ca-salts of Carboxylic
OH O Acid :
O
 R C Cl  R C + HCl
R COO O C H
R R R Ca + Ca
R COO O C H
O
O
RMgX + R C NH2  RH+ (RCONH)Mg(X) ; Calcium formate
Ketone doe s not forms. 
 2RCHO + 2CaCO 3
O OMgX
(Also R C R and HCHO formed)
RMgX + R C OR  R C OR O
R H COO
Ca 
 HCHO + CaCO 3
OH O HCO O
HO
OR  R C OR  R C + ROH
2
R COO R

Ca  C O + CaCO3
R R R RCO O R
Calcium-alkanoate Ketone
[2] From Dialkyl Cadmium :
Calcium salts of acids other then formic acid on
RCdR' (dialkyl Cadmium) is a organometal lic
heating together gives ketone
compound.
RCOCl + RCdR'  RCOR' + RCdCl O
This reaction is superior than Grignard Reaction R COO O C R' 
Ca + Ca 
because the ketones formed, further reacts with O C R'
R COO
Grignard reagent to form 3° alcohols.
O
Example :
O
C2H5 CH3 C2H5
CH3COCl + Cd  C O+ Cd 2R C R' + 2CaCO3
C2H5 C2H5 Cl
Ketone
To prepare ethyl methyl ketone Calcium acetate  Physical Properties :
and Calcium propionate are used :  State :
O Only formaldehyde is gas, al l other carbonyl
compounds upto C11 are liquids and C 12 & onwards
CH3 OCO O C CH2CH3
Ca + Ca solid.
CH3 OCO O C CH2CH3
O
 Odour :
Calcium Acetate Calcium propionate Lower aldehydes give unpleasant smell, higher
aldehydes and all ketones have pleasant smell.
CH3

 2 C O + 2CaCO3
C2H5  Solubility :
C 1 to C 3 (formaldehyde, acetaldehyde and
Ethyl methyl ketone
propionaldehyde) and acetone are freely soluble
 
[2] By Thermal Decomposition of Carboxylic Acids: in water due to polarity of C O bond and can
Vapour of carboxylic acids when passed over MnO/ form H—bond with water molecule. C 5 onwards
300 0 C give carbonyl compounds are insoluble in water.

2 HCOOH 

HCHO + H 2 O + CO 2 H
 
CH3 C O H O
2 CH 3 COOH  C O + CO2 + H2O
 CH3 H-bonding
RCOOH + HCOOH 


RCHO + CO2 + H2O 
RCOOH + R'COOH 

RCOR' + CO2 + H2O  Boiling Point
[3] Wacker Process : Boiling point  Molecular weight
Boiling point order is -
In this reaction double bond is not cleaved so same Alcohol > Carbonyl compounds > Alkane
C-atom aldehyde and ketone s are formed. This is because in alcohols intermolecular H-bonding
CH 2 CH 2 + PdCl 2 + H 2 O  is present but in carbonyl compounds H-bonding
doesn't exist, instead dipole-dipole vander waal
CH 3 CHO + Pd + HCl
force of attraction is present.
All other alkenes gives ketone.
Alkanes are non polar.
RCH CH 2 + PdCl 2 + H 2 O     
O  
R C CH3 + Pd + HCl
 Density :
Density of carbonyl compounds is lower than water.
CHEMISTRY [7]
ABHYAAS - I
LEVEL - I
Q.1 The best method for the conversion of ethanol Q.9 Partial oxidation of methane gives-
to ethanal is- (A) HCHO (B) HCOOH
(A) By passing ethanol vapours over Cu at (C) H2 O and CO 2 (D) CO and H2
578 K Q.10 The reaction -
(B) By oxidation with acidic potassium
dichromate CH3COCl + H2  CH3CHO + HCl is
(C) By oxidation with mangenese dioxide at (A) Stephen's reaction
300ºC (B) Rosenmund reaction
(D) By oxidation with acidic KMnO 4 (C) Hoffmann reaction
Q.2 When propyne reacts with 20% H 2 SO 4 & (D) Cannizzaro's reaction
1% HgSO 4 , we get- Q.11 Acetone will be obtained by the ozonolysis
(A) Acetaldehyde (B) Propanaldehyde of-
(C) Acetone (D) Formic acid (A) 1-Butene (B) 2-Butene
Q.3 The product formed by the reaction of propyne (C) Isobutene (D) 2-Butyne
with dil. H2SO4 in the presence of Hg2+ can Q.12 What is the function of BaSO4 in Rosenmund
not be prepared by the following reaction- reactionn -
(A) Dry distillation of calcium ethanoate
(A) To stop further oxidation of aldehyde
(B) By passing vapours of ethanoic acid over (B) To stop further reduction of aldehyde
MnO at 300ºC
(C) Act as a poisonous catalyst
(C) By ozonolysis of 2- Butene (D) It checks the reactivity of pd.
(D) By alkaline hydrolysis of isopropylidene Q.13 The slow partial oxidation of ethyl alcohol is
chloride likely to form-
Q.4 Except acetylene, other alkynes react with (A) CO 2 +H 2 O (B) Acetic acid
H2O to give- (C) CH + H2 O (D) Acetaldehyde
(A) Aldehyde (B) CH 3 CHO Q.14 Reaction of ethyl formate with exce ss of
(C) Ketones (D) Alkanal. CH 3 MgI followed by hydrolysis gives:
Q.5 When CH3 MgI reacts with CH 3 CN and the (A) n-Propyl alcohol (B) Ethanal
product is hydrolysed, we get- (C) Propanal (D) Isopropyl alcohol
(A) Propanal (B) Acetone Q.15 Compound used for preserving dead bodies
(C) Formaldehyde (D) Acetaldehyde is -
Q.6 Ethylidene chloride (CH3CHCl2) on hydrolysis
(A) CH 2 O (40%) (B) CH 3 CHO (10%)
with NaOH gives -
(C) CH 3 OH (25%) (D) C 2 H 5 OH (40%)
(A) CH 3 CHO (B) CH 3 COCH 3
Q.16 Which fo the following forces is correctly
(C) CH 3 CH(OH) 2 (D) C 2 H 5 OH described about boiling point of Aldehydes &
Q.7 (HCOO) 2 Ca + (CH 3 COO) 2 Ca  "A"- ketones -
Product A is– (A) Hydrogen bond
(A) Propanone (B) Methanal (B) Vander wall force
(C) Ethanal (D) One of the above (C) Dipole-dipole attraction
Q.8 When calcium acetate is heated with calcium (D) None of these
formate then, we get- Q.17 Which aldehyde is insoluble in H2O -
(A) Methanol (B) Acetic acid (A) Propanal (B) Ethanal
(C) Acetaldehyde (D) Acetone (C) Butanal (D) Heptanal
Q.18 The general order of reactivity of carbonyl Q.20 Which of the following combinations give t-
compounds for nucleophilic addition reactions butyl alcohol when treated with Grignard
is - reagent-
(A) H2C = O > RCHO > ArCHO (A) CH 3 MgBr + CH 3 COCH 3
> R2 C = O > Ar 2 C =O (B) C 2 H 5 MgBr + CH 3 COCH 3
(B) ArCHO > Ar2C = O > RCHO (C) CH 3 MgBr + (CH 3 ) 3 C. OH
> R 2C = O> H2 C = O (D) CH 3 MgBr + CH 3 CH 2 CHO
(C) Ar 2 C = O > R 2 C =O >ArCHO Q .2 1 Which of the following statements is wrong:
<
> RCHO > H 2 C = O (A) The Polar character of the C=O group
(D) H2C = O > R2C = O > Ar 2C =O gives rise to intermolecular attraction called
> RCHO > ArCHO dipole-dipole attractions.
Q.19 Least reactive towards nucleophilic additon is (B) The lower aldehydes and ketones are
soluble in water.
(C) The boiling points of aldehydes and
(A) CH2 = O (B)  
ketones are lower than those of nonpolar
alkanes of comparable molecular weight
(C)   (D)   (D) Aldehydes and ketones are incapable of
intermolecular hydrogen bonding w it h
themselves.
LEVEL - II
Q .1 Dry distillation of calcium propanoate gives : Q .6 Carbonyl compounds are best purified by :
(A) Propanone (B) Propanal (A) Steam distillation
(C) Butanone (D) Diethyl ketone (B) Hydrolysis of sodium bisulphite adducts
Q .2 Acetone can be prepared by dry distillation of: (C) Fractional crytallisation
(A) Calcium formate & calcium acetate (D) Sublimation
(B) Calcium acetate Q .7 Gem dihalides are obtained by the reaction of:
(C) Calcium propanoate (A) Chlorine on ethanal
(D) Calcium propanoate and calcium formate (B) Chlorine on a keetone
Q .3 Stephen reaction is the reaction involving : (C) PCl 5 on a carbonyl compound
(A) Reduction of alkanoyl chloride with (D) PCl5 on diols
Pd/BaSO 4 Q .8 Ketones can be prepared by the following
(B) Reduction of alkyl isocyanide with sodium methods except :
and alcohol (A) By heating calcium salts of acids
(C) Reduction of alkyl cyanide with SnCl2 and (B) By reducing acid chlorides with hydrgoen
HCl and hydrolysing the intermediate aldimine in the presence of palladium catalyst supported
(D) Reduction of carbonyl compound with zinc on barium sulphate
amalgum and HCl (C) By passing vapours of an acid over
Q .4 Hydration of acetylene in the presence of dilute manganous oxide at 300ºC
sulphuric acid and Hg 2+ ions at 80ºC gives : (D) By passing any alkyne having three or more
(A) Ethanol (B) Ethanal carbon atoms in hot dilute sulphuric acid in
(C) Vinayl alcohol (D) All of these the presence of mercuric ions.
Q .5 CH 3 –CH(OH)–CH 2 (NH 2 ) is a : Q .9 Ketone cannot be prepared by :
(A) a –amino alcohol (A) Ozonolysis of alkenes
(B) an –aminoalcohol (B) Heating of calcium salts of acids
(C) a hydroxy primary amine (C) Epoxidation of alkenes with peracids
(D) a  –hydroxy amine (D) Oxidation of a glycol with periodic acid
CHEMISTRY [9]
Q.10 Oxidation of 2–methylpropane–1,2–diol with Q .1 5 Which of the following will be in gaseous state,
periodic acid gives : if room temperature is 25ºC :
(A) Propionic acid and formaldehyde (A) Actaldehyde (B) Butanone
(B) Acetone and formaldehyde (C) Acetone (D) Formalin
(C) Acetone and acetic acid Q-16 Aldehydes have boiling points lower than those
(D) Acetone and Propionic acid of .................. and higher than those of
Q.11 Oxidation of 1,2–glycols of the general .................. of comparable molecular masses.
OH OH
| |
structure R1—C—C—R1 with periodic acid Q-17 Aldol dondensation proceeds by carbon-carbon
| |
R2 R2 bond fromation between an enolate donor and
a carbonyl acceptor. For each of the following
gives :
aldol products (1 through 4)
(A) A diketone
(B) Two molecules of an aldehyde
(C) A ketone
(D) A diol
Q.12 Which of the following statements is wrong :
(A) The polar character of the C=O group gives
rise to intermolcular attractions called dipole–
dipole attraction
(B) The lower aldehydes and ketones are
match the donor and acceptor compound.
soluble in water
Column – I Column – II
(C) The boiling points of aldehydes and ketones
[Donor] [Acceptor]
are lower than those of nonpolar alkanes of
comparable molecular weights
(D) Aldehydes and ketones are incapable of (A) (p) 
intermolecular hydrogen bonding w ith
themselves
(B) (q)
Q.13 Aldehydic group can occur :
(A) Any where in the carbon chain
(B) In the middle of the carbon test (C) (r)
(C) Only at the second carbon atom of the
chain
(D) Only at the end carbon atom of the carbon (D) (s)
chain
Q.14 When propyne is teated with aqueous sulphuric
acid in the presence of mercuric sulphate, the
major product is :
(A) Propanal
(B) Propyl hydrogen sulphate
(C) Propanol
(D) Acetone
ANSWERS
LEVEL - I
LEVEL - II
   
CHEMISTRY [11]
LECTURE - II
CHEMICAL PROPERTIES CH3 CH3CH2
(IV)(i) C O (ii) C O
Reactions of Both Aldehydes and Ketones : CH3 CH3
Due to strong electronegativity of oxygen, the
mobile  electrons pulled strongly towards oxygen, (CH3)2CH CCl3
leaving the carbon atom deficient of electrons.4 (iii) C O (iv) C O
 
CH3 CH3
  

Sol. (A) I > II > III
Carbon is thus readily attacked by N u . (B) II > I > III > IV
The negatively charged oxygen is at tacked by (C) IV > III > II > I
electron deficient (electrophile) E + .
(D) IV > I > II > III
 bond in carbonyl group is stronger than [Hint : CH 3— is +I group, decreases the intensity
C=C bond in alkanes. of +ve charge on C-atom of C O group.
   
  Cl – is –I group increases the intensity of +ve
   
charge on C-atom of C O group.]
 

 
Reactivity of carbonyl group  Magnitude of +ve Cl
(-I) CH3(+I)
Ex.In Cl C C O and C O , which one
charge   – I group  H
 Cl H
Chloral
Ex.Why carbonyl compound gives nucleophilic addition
reaction (NAR) ? is more reactive ?
  Sol. I is more reactive than II.
Sol. 
CHEMICAL REACTIONS
 
 Carbonyl compounds in general under goes
neucleophilic addition reaction :
.. 
  (A) Nucleophilic Addition Reactions :

[1] Addition of HCN :
Ex.Arrange the following for reactivity in decreasing

order
H CH3 
(I) (i) C O (ii) C O 
H H

CH3
(iii) C O
CH3

(II) (i) (ii)
(iii) (iv) CH 3 CH 2 CHO
(III) (i) (ii) 
(iii) (iv) CCl 3 CHO




 

Na+
[3] Reaction with Ammonia Derivatives :



These are condensation or addition elimination
reaction. These proceeds well in weakly acidic
medium.
NH 3  NH 2 Z (Ammonia derivative)
H
Z  
C O + H2 N Z  C N Z + HO
2
Addition - elimination (Condensation)

Mechanism :
 ..
 
  

 Ammonia Derivatives (NH 2Z) :

3 Z = OH  NH 2 OH (Hydroxyl amine)
Z = NH 2  NH 2 NH 2 (hydrazine)
2
Z = NHC 6 H 5  NH 2 NHC 6 H 5
(Phenyl hydrazine)

NO2 NO2
3
Z = NH NO2  NH2 NH NO2
2, 4–Dinitro phenyl hydrazine (DNP) Brady's reagent

Z = NHCONH 2  NH 2 NHCONH 2
H
Semi Carbazide.
R R
C O + H2 NOH C NOH
H H
(Aldoxime)
[2] Addition of NaHSO 3 :
This reaction is utilized for the separation of carbonyl R R
C O + H2 NNH2 C NNH2
compounds from non - carbonyl compounds. H H
(Hydrazone)
C OH
C O + NaHSO3    R R
C O + H2 NNHC6H5  C NNHC6H5
SO3Na H H
Sodium bi sulphite Bisulphite compound
(Phenyl hydrazone)
(Crystalline) NO2

    Carbonyl compounds. *(Regain) R
C O + H2 NNH NO2 
Mechanism : H
2,4-DNP (Brady's reagent)
NaH SO 3 




NO2





 
R
 C NNH NO2
H
2,4-DNP (Brady's reagent) (2, 4 - dinitro phenyl hydrazone)
CHEMISTRY [13]
R [7] Reaction with Grignard Reagent :
C O + H2 NNHCONH2 
H H H
C O + CH3 Mgl  C OMgl
R H H
 C NNHCONH2 (Semi Carbazone) CH3
H Ethanol ( alcohol)
[4] With Alcohol andHThioalcohol : H HO I
OMgl 
2
CH3CH2OH + Mg
H H H OH
C O + ROH 
R CH 3 CHO + CH 3 Mgl 
H OH H OR OMgl OH
C  C OH
R OR R OR CH3 H2O
C H  CH3 C H + Mg
I
Hemi-acetal Acetal
CH3 CH3
R R OR
C O + 2ROH   C + H2O 2–Propanol ( alcohol)
R R OR OMgl
Ketal CH3
C O + CH3 + Mgl  CH3 C CH3
Tri ethoxy methane [HC(OC 2 H 5 ) 3 ] remove the CH3
water formed during the reaction and so the CH3
reaction proceeds in forward direction. 2–Methyl–2–propanol (3 alcohol)
OMgl OH
R SR I
R
O + 2RSH 
C H2O
CH3  CH3 C CH3 + Mg
C 
H SR OH
H CH3
Thioalcohol Mercaptal [8] Reaction with H 2O :
R SO2R It is a reversible reaction.
C

 OH
H SO2R C O + HO
2

 C
 OH
R
C O + 2RSH 
 (neutral) unstable hydrate
R Ex : W hich compound form more stable hydrate
R SR R SO2R with H 2 O?
C C

 (A) HCHO (B) CH 3 CHO
R SR R SO2R
(C) CH 3 COCH 3 (D) CH 3 COC 2 H 5
Mercaptal (Thio Ketal) Sulphones Compound [Hint : HCHO since it is more reactive towards
All sulphones compounds are hypnotic compounds. this reaction.]
CH3 SO2R CH3 SO2R C2H5 SO2R Ans. (A)
C C C
CH3 SO2R C2H5 SO2R C2H5 SO2R Ex : Which carbonyl compound not gives reversible
reaction with water ?
Sulphonal Trional Tetronal
Sol. Chloral hydrate.
[5] Reaction with Glycol (Group Protection) :
H O CH2 O CH2 Cl Cl HO
C O+  C
H O CH2

O CH2 Cl C CH + H2O  Cl C CH
(neutral) Cyclic acetal/ketal Cl O Cl HO

[6] Reaction with Sodium Alkynide : (Chloral) (Chloral hydrate)
    Stable by intra molecular hydrogen bonding.


ABHYAAS - II
LEVEL - 0
Q.1 What would be the product when acetaldehyde Q.7 The reaction of acetone with CN – is
reacts with HCN and the product is further represented as –
hydrolysed-
In the above reaction, which is the fast step:
(A) 2-Hydroxy propanoic acid
(A) Step (I)
(B) Lactic acid
(B) Step (II)
(C) Both A & B
(C) Step (III)
(D) None of these
(D) All steps take place with equal ease.
Q.2 Reaction of ammonia derivative with carbonyl
Q.8 Arrange [(CH 3 ) 3 C] 2 CO (I), [(CH 3 ) 2 CH] 2 C=O
compound is an example of -
(II), (CH 3 ) 2 C=O (III) and CH 3 CHO (IV) in
(A) Addition and Substitution
order of reactivity towards nucleophilic attack:
(B) Substitution and Elimination
(A) I > II > III > IV
(C) Addition and Elimination
(B) I > III > IV > II
(D) Addition and intramolecular substitution
(C) IV > III > II > I
Q.3 The vapour density of a compound is 29,
(D) II > I > III > IV
which reacts with iodine and NaOH to form
a yellow compound.The compound is- Q.9 Which of the following alkenes is most
(A) CH 3 COOH (B) CH 3 COCH 3 suitable for the preparation butanone by
ozonolysis -
(C) CH 3 CHOHCH 3 (D) CH 3 OH
(A) (B)
Q.4 Stephen reaction is the reaction involving:
(A) Reduction of alkanoyl chloride with
Pd/BaSO 4 . (C) (D)
(B) Reduction of alkyl isocyanide with sodium Q.10 In the reaction

and alcohol. CH 3 CHO + HCN  CH 3 CHOHCN
(C) Reduction of alkyl cyanide with SnCl 2 the product obtained is -
and HCl and hydrolysing the intermediate
(A) a meso compound
aldimine.
(B) a levorotatory compound
(D) Reduction of carbonyl compound with zinc
amalgam and HCl. (C) a dextrorotatory compound
Q.5 Acetone gives test with- (D) a recemic mixture
(A) 2,4 Dinitro phenyl hydrazine Q.11 Consider the following sequence of reactions
(B) Fehling solution 
 A 
1.CH3MgI
 B
CH3C  CH 
H3 O
Hg2  2.H2 O
(C) Schiff's reagent
(D) All The final product (B) is -
Q.6 A ketone reacted with ethyl magnesium (A) CH3C  CCH3
bromide followed by hydrolysis gave a product (B) CH 3 COCH 2 CH 3
which on dehydration gave an alkene. The (C) CH 3 CH 2 CHOHCH 3
alkene on ozonolysis gave diethyl ketone and
(D) (CH3)3 C – OH
acetaldehyde. The ketone is-
Q.12 An alkene C 7 H 14 on reductive ozonolysis
(A) Dimethyl ketone
gives an aldehyde with formula C3H6O and
(B) Ethyl methyl ketone a ketone. The ketone is -
(C) Diethyl ketone (A) 2-butanone (B) 2-pentanone
(D) Ethyl propyl ketone (C) 3-pentanone (D) propanone
CHEMISTRY [15]
Q.13 Identify the compounds A and B in the Q.20 A cyanohydrin of a compound (X) on hydrolysis
following reaction sequence gives an -hydroxy acid which shows optical
 activity after resolution. The compound (X) is
(CH3)2C = O   a 
NaCN H3 O
 b (A) Acetone (B) Formaldehyde
HCl Heat
(A) a = CH 3 CO 2 H, b = (CH 3 CO) 2 O (C) Diethyl ketone (D) Acetaldehyde

(B) a = (CH 3 ) 2 C(OH)CN, Q.21 Which of the following geminal diols is the
b = (CH3)2C(OH)CO2H most unstable ?
(C) a = CH 3 CHO, b = CH 3 CO 2 H
(D) a = (CH3) 2C(OH)CN, b = (CH3)2C = O (A) (B)
Q.14 Necleophilic addition reaction will be most

favoured in -
(C) (D)
(A) CH 3 CHO
(B)    Q.22 The possible number of stereoisomers that may

be produced by the reaction of racemic s-butyl
(C) (CH3) 2 C = O methyl ketone with ethylmagnesium bromide
(D) CH 3 CH 2 CHO and subsequent hydrolysis is
Q.15 The increasing order of the rate of HCN (A) Two (B) Three
addition to compounds a – d is - (C) Four (D) Six
(a) HCHO (b) CH 3 COCH 3 Q.23 Consider the following sequence of reactions.
(c) PhCOCH 3 (d) PhCOPh
Ketone A 
 B 
C
(A) a < b < c < d (B) d < b < c < a 
(C) d < c < b < a (D) d < a < c < b

Q.16 Among the following compounds which one 

will react with acetone to give a product that
contains carbon-nitrogen double bond -
The ketone (A) is
(A) C 6 H 5 NHC 6 H 5 (B) (CH 3 ) 3 N
(A) (B)
(C) (D) C 6 H 5 NHNH 2
N
H
(C) (D)
Q.17 A compound (A), C4H8Cl2, on hydrolysis gives
a pro duct (B) which forms a 2, 4-DNP
derivative but does not reduce Tollens reagent.
Q.24 An organic compound (A), C 5H 10 O, reacts
The compound (A) has the structure
with hydrazine to form a hydrazone derivative
(A) CH 3 CH 2 CHClCH 2 Cl
(B). The hydrazone (B) on being heated with
(B) CH 3 CH 2 CCl 2CH 3 KOH at about 180ºC, gives n-pentane. The
(C) CH 3 CH 2 CH 2 CHCl 2 compound (A) does not respond positively to
(D) CH 3 CHClCHClCH 3 Tollens reagent and to the iodoform test. The
Q.18 The reagent one would choose to transform compound (A) is
CH 3 CH 2 COCl into CH 3 CH 2 COCH 3 is
(A) CH3 MgI (B) (CH 3 ) 2Cd
(C) (CH 3 O) 2 Mg (D) CH3Cl (A) (B)
Q.19 Which of the following compounds does not
react with NaHSO 3 ? (C) (D)
(A) C 6 H 5 CHO (B) C 6 H 5 COCH 3
(C) CH 3 COCH 3 (D) C 2 H 5 COC 2 H 5
Thought Type Question Q.28 Statement-I : The addition of ammonia
Aldehydes and ketons are specially susceptible derivatives on carbonyl compounds is carried in
to nucleophilic addition because carbonyl weakly acidic medium.
group C=O is polar (due to electronegativity Statement-II : In weakly acidic medium attacking
nucleophile is also protonated.
difference between carbon and oxygen).
+ –
C=O Q.29 The increasing order of the rate of HCN addition
to compounds A – D is -
Positive charge on carbon makes it reactive
towards the nucleophile. This addition is [a] HCHO [b] CH 3 COCH 3
catalysed by acid. [c] PhCOCH 3 [d] PhCOCH 3
Reactivity of carbonyl compound towards (A) d < b < c < a (B) d < c < b < a
nucleopilic addition increases with increase in (C) c < d < b < a (D) a < b < c < d
the electron deficiency at carbonyl carbon. Q.30 The formation of cyanohydrin from a ketone is
Thus, (– I.E.) groups increase while (+ I.E.) an example of –
groups decrease the reactivity of carbonyl
compound. (A) Electrophilic addition
Answer the following questions : (B) Nucleophilic addition
Q.25 Which among the following is most reactive to (C) Nucleophilic substitution
give nucleophilic addition ? (D) Electrophilic substitution
(A) FCH 2 CHO (B) CICH 2CHO Q.31 Among the given compounds, the most
(C) BrCH 2 CHO (D) ICH 2 CHO susceptible to nucleophilic attack at the carbonyl
group is -
Q.26 Select the least reactive carbonyl compound for
nucleophilic addition - (A) MeCOCl (B) MeCHO
(C) MeCOOMe (D) MeCOOCOMe
O O
|| || Q.32 Among the following compounds, which will
(A) C 6 H 5 — C — C 6 H 5 (B) C 6 H 5 — C — CH 3 react with acetone to give a product containing
O
>C=N–
O
|| || (A) C 6H 5NH 2 (B) (CH 3) 3N
(C) C 6 H 5 — C — H (D) CH 3 — C — H
(C) C 6H 5NHC 6H 5 (D) C 6H 5NHNH 2
Statement Based Question Q.33 Which of the following will react with water –
Each of the questions given below consist
(A) CHCl 3 (B) Cl 3CCHO
of Statement – I and Statement – II. Use
the following Key to choose the appropriate (C) CCl4 (D) ClCH 2CH 2Cl
answer.
(A) If both Statement-I and Statement-II are
t ru e, and Statem ent -I I is the co rr ect
explanation of Statement-I.
(B) If both Statement-I and Statement-II are
true but Statement-II is not the correct
explanation of Statement-I.
(C) If Statement-I is true but Statement-II is
false.
(D) If Statement-I is false but Statement-II
is true.
Q.27 Statement-I : Corbonyl compounds take part
in nucleophilic addition reactions.
Statement-II : These reactions are initiated by
nucleophilic attack at the electron deficient
carbon atom.
CHEMISTRY [17]
LEVEL - I
Q .1 Carbonyl compounds readily undergo : Q .6 A HCN 2HOH
 B   2–Hydroxy propanoic
(A) Nucleophilic substitutions acid, the compound B is :
(B) Electrophilic addtion reactions (A) CH 3 CHO
(C) Nucleophilic addition reactions (B) Acetaldehyde cyanohydrin
(D) Free radical substitution reactions (C) Formaldehyde cyanohydrine
Q .2 The oximes of which of the following pairs of (D) Acetone
compounds will have the same percentage of Q .7 The structural formula of chloral hydrate is :
nitrogen :
(A) Acetone and acetophenone
OH OH
(B) Propionaldehyde and dimethyl ketone (A) CCl 3 CH (B) HCCl 2 CH
OH OH
(C) Propanal and ethanal (C) CCl 3 CH 2 (OH) (D) None
(D) Methanal and acrolein Q .8 An organic liquid which reduce s tol len’s
Q .3 Which of the following statments is incorrect : reagent gives one semicarbazone derivative in
(A) Carbonyl compounds undergo nucleophilic which 36.47% Nitrogen is present. The liquid
would be :
additions
(A) CH 3 CHO
(B) Carbonyl compounds have large dipole
(B) CH 3 CH 2 CHO
moments
(C) CH 3 – CH –CHO
(C) Acetone is more reactive towards |
CH3
nucleophilic reagents then acetaldehyde
(D) CH 3 CH 2 CH 2 CHO
(D) Carbon atom of the carbonyl group is sp2
Q .9 Acetone on heating with ammonia produces :
hybridised
Q .4 Which of the following cyanohydrins on
hydrolysis gives an optically active acid giving (A) Acetaldimine (B) Diacetone alcohol
iodoform reaction : (C) Diacetone amine (D) Hydrobenzamide
(A) Acetone cyanohydrin Q .1 0 An organic compound C 5H 10 O forms phenyl
hydrazone, gives positive iodoform test and
(B) Propionaldehyde cyanohydrin
u nd ergoe s Wol f-Kishn er react ion to give
(C) Acetaldehyde cyanohydrin isopentane. It is :
(D) Formaldehyde cyanohydrin (A) Pentanol
Q .5 HCN
CH 3– C –CH3  LiAlH4
 A   B, [B] is : (B) Pentan-2-one
O (C) Pentan-3-one
(D) 3-methylbutan-2-one
(A) CH3 – CH – CH – COOH
| | Q .1 1 Which of the following is the mechanism of
OH CH3 represen tat ive re actio ns of carb o ny l
CH3 compounds
| (A) Neucleophilic substitution
(B) CH3 – C – COOH
| (B) Electrophilic substitution
OH
CH3 (C) Neucleophilic addition
| (D) Electrophilic addition
(C) CH3 – C – CH2NH2
| Q .1 2 >C=O + 2RS H  >C(SR) 2 + H 2 O , the
OH
product is called :
(D) CH3 – CH – CN (A) Mercaptan (B) Thioketal
|
CH3 (C) Thiacetal (D) All
Q .1 3 A m ixtur e o f t he sim plest m emb ers o f NaCN 
Q.21 (CH 3) 2 CO   A 
H3O
 B in the above

alkanone and alkanal families is formed on (HCl) 
o zo nolysis o f which of t he follo wing sequence of reactions A and B are :

compounds (A) (CH 3 ) 2 C(OH)CN, (CH 3 ) 2 C(OH)COOH
(A) Propyne (B) Isobutylene (B) (CH 3 ) 2 C(OH)CN, (CH 3 ) 2 C(OH) 2
(C) -Butylene (D) 3-Pentaone (C) (CH 3 ) 2 C(OH)CN, (CH 3 ) 2 CHCOOH
Q.14 The general order of reactivity of carbonyl (D) (CH 3 ) 2 C(OH)CN, (CH 3 ) 2 C=O
compounds for nucleophilic addition reactions Q.22 From which of the following tertiary butyl
alcohol is obtained by the action of methyl
is :
magnesium iodide :
(A) H2C = O > RCHO > ArCHO > R 2C = O
(A) HCHO (B) CH 3 CHO
> Ar 2C = O
(C) CH 3 COCH 3 (D) CO 2
(B) ArCHO > Ar 2C = O > RCHO > R2C = O
Q.23 The products obtained via oxymercuration
> H 2C = O (HgSO 4 + H 2SO 4) of 1–butyne would be :
(C) Ar2C = O > R2C = O > ArCHO > RCHO (A) CH 3 CH 2 COCH 3
> H 2C = O (B) CH 3 CH 2 CH 2 CHO
(D) H2C = O > R2C = O > Ar2C = O > RCHO (C) CH 3 CH 2 CHO + HCHO
> ArCHO (D) CH 3 CH 2 COOH + HCOOH
Q.15 Dry distillation of the mixture of calcium Q.24 Product in following reaction is : CH 3 MgI +
formate and calcium acetate gives : HCHO  Product :
(A) Acetone (B) Acetaldehyde (A) CH 3 CHO (B) CH 3 OH
(C) Formaldehyde (D) Formic acid (C) C 2 H 5 OH (D) CH 3 –O–CH 3
Q.16 Reaction of acetaldehyde with HCN followed Q.25 In the reaction :
by hydrolysis gives a compound which shows: CH3CHO + HCN
(A) Optical isomerism
 –
(B) Geometrical isomerism CH3CH(OH)CN
H / OH
  CH3CH(OH)COOH)
(C) Metamerism an asymmetric centre is generated. The acid

(D) Tautomerism obtained would be :
Q.17 Which of the following reagent reacts (A) 20% D + 80% L–isomer
differently with HCHO, CH 3 CHO and (B) D–isomer
CH 3 COCH 3 : (C) L–isomer
(A) HCN (B) NH 2 NH 2 (D) 50% D + 50% L–isomer
(C) NH 2 OH (D) NH 3 Q.26 The increasing order of the rate of HCN
addition to compounds A - D is -
Q.18 Acetone is prepared by :
[a] HCHO [b] CH 3 COCH 3
(A) Oxidation of n–propyl alcohol
[c] PhCOCH 3 [d] PhCOPh
(B) Pyrolysis of acetic acid
(A)d < b < c < a (B) d < c < b < a
(C) Oxidation of acetaldehyde
(C) c < d < b < a (D) a < b < c < d
(D) Pyrolysis of calcium acetate
Q.27 A carbonyl compound reacts with hydrogen
Q.19 Which compound is soluble in H 2O : cyanide to form cyanohydrin which on
(A) HCHO (B) CH 3 CHO hydrolysis forms a racemic mixture of
(C) CH 3 COCH 3 (D) All -hydroxy acid. The carbonyl compound is -
(A) acetone (B) diethyl ketone
Q.20 CH 3CHO + CH 3 MgBr  Product  H2O
A
(C) formaldehyde (D) acetaldehyde
(A) Primary alcohol (B) Secondary alcohol
(C) Tertiary alcohol (D) Ketone
CHEMISTRY [19]
LEVEL - II
Select the Correct Alternative (Only One Correct Q .7 Which compound is unable to react with
Answer) NaHSO 3 ?
Q.1 Which of the following reacts with water to form (A) CH 3 CHO
very stable product ? (B) CH3 CH OCH3
(A) CH 3 Cl (B) CCl 4
CH3
(C) CCl 3 CHO (D) CH 2 ClCH 2 Cl
Q.2 If 3-hexanone is reacted with NaBH4 followed (C) CH3 C O
by hydrolysis with D 2O, the product will be : CH3
(A) CH 3 CH 2 CH(OH)CH 2 CH 2 CH 3 (D) HCHO
(B) CH 3 CH 2 CD(OH)CH 2 CH 2 CH 3 Q .8 Which of the following compounds gives a
(C) CH 3 CH 2 CH(OD)CH 2 CH 2 CH 3 ketone with grignard reagent
(D) CH 3 CH 2 CD(OD)CH 2 CH 2 CH 3 (A) formaldehyde (B) Ethyl alcohol
Q.3 A carbonyl compound 'A' reacts with hydrogen (C) Methyl cyanide (D) Methyl iodide
cyanide to form a cyanohydrin 'B' which on
hydrolysis gives an optically active alpha hydroxy Select the Correct Alternatives (One or More Then
One Correct Answers)
acid 'C'. 'A' gives a positive iodoform test 'A',
'B' and 'C' are given by the set :- Q.9 Among the given compounds, the most
susceptible to nucleophilic attack at the carbonyl
group is
(A) HCHO ; ;
(A) CH 3 COCl (B) CH 3 CHO
(C) CH 3 COOCH 3 (D) CH 3 COOCOCH 3
(B) CH 3 CHO ;
O
1. (CH3)2CuLi
(C) CH 3 CH 2 CHO ; Q.10 In the reaction  A.
2.H3O
(D) CH The product (A) is :
Q .4 In which of the following reactions aldehydes O

CH3 OH
and ketones are distinguished :
(A) Reaction with phenyl hydrazine
(A) (B)
(B) Reaction with hydroxylamine
CH3
(C) Reaction with semicarbazide
(D) Reaction with silver nirate mixed with O OH
H3C
ammonia
Q.5 Cyanohydrin of the following compound on (C) (D)
hydrolysis gives optically active product :
CH3 CH3
(A) HCHO (B) CH 3 CHO
Fill in the Blanks :
(C) CH 3 COCH 3 (D) All the above
Q.11 To prepare ethanol, CH3MgI is treated with the
Q .6 Which compound gives reaction with 2,4-dinitro
phenyl hydrazine? other reagent ..................
CH3 Q.12 Hydrazone of an aldehyde when heated with

C O CH3
(A) (B) C O sodium ethoxide forms .................. This is
CH3 H
known as .................. reaction.
H
(C) C O (D) All of these
H
Comprehension Based Questions : Subjective Exercise :
Comprehension # 1 Q.18 Give Reasons for the Following :
Aldehyde and ketones are specially susceptible
(a) Ketones are less electrophilic than aldehydes.
to nucleophile addition because carbonyl group
(b) Aldehydes are reducing agents and ketones
C=O is polar (due to electronegativity different
are not.
between carbon and oxygen).
+ –
(c) HBr fails to give addition products with
C=O carbonyl compounds.
Positive charge on carbon makes it reactive Q.19 The formation of cyanohydrin from a ketone is
towards the nucleophile. This addition is
an example of
catalysed by acid. Reactivity of carbonyl
compound towards nucleophilic addition (A) Electrophilic addition
increases with increase in the electron deficiency (B) Nucleophilic addition
at carbonyl carbon. Thus, (–I.E.) group increase (C) Nucleophilic substitution
while (+I.E.) groups decrease the reactivity of
(D) Electrophilic substitution
carbonyl compound.
Q.13 Which of the following is most reactive to give Q.20 An organic compound C3H6O does not give a
nucleophilic addition? precipitate with 2,4-Dinitrophenyl hydrazine
(A) FCH 2 CHO (B) ClCH 2 CHO reagent-
(C) BrCH 2 CHO (D) ICH 2 CHO (A) CH 3 CH 2 CHO
Q.14 Carbonyl compounds show nucleophilic addition (B) CH 3 COCH 3
with : (C) CH 2 =CH–CH 2 OH
(A) HCN (B) NaHSO 3
(D) —OH
(C) (CH 3 OH + HCl) (D) all of these
Q.15 Which among the following carbonyl Q.21 Among the given compounds, the most
compounds is most polar? succeptible to nucleophilic attack at the carbonyl
C2H5 CH3 group is -
(A) C=O (B) C=O
CH3 CH3 (A) MeCOCl (B) MeCHO
CH3 H (C) MeCOOMe (D) MeCOOCOMe
(C) C=O (D) C=O Q.22 The product obtained via oxymercuration
H H
(HgSO 4+H2SO4) of 1-butyne would be -
Q.16 Select the least reactive carbonyl compound for
nucleophilic addition: O
O O (A) CH 3CH 2– C–CH 3
(A) C6H5––C––C6H5 (B) C6H5––C––CH3 (B) CH 3 CH 2 CH 2 CHO
O O (C) CH 3CH 2 CHO + HCHO
(C) C6H5––C––H (D) CH3––C––H (D) CH 3 CH 2 COOH+HCOOH
Q.17 Which among the following isomeric compound Q.23 Which of the following will react with water to
is most reactive? form a stable hydrate -
O (A) CHCl 3 (B) Cl 3 CCHO
(A) CH3––CH––CH
2 2––CH2––C––H
(C) CCl4 (D) ClCH 2 CH 2Cl
O
(B) CH3––CH––CH
2 2––C––CH3
O
(C) CH3––CH––C––CH
2 2––CH3
(D) All are equally reactive

CHEMISTRY [21]
ANSWERS
LEVEL - 0
LEVEL - I
LEVEL - II
Comprehension #1 :
Subjective Exercise :
LECTURE - III
OTHER REACTIONS 1
(b) Transfer of hydride ion H to second molecule
[1] Wittig Reaction :-
of HCHO
Wittig reaction affords an important and useful
method for the synthesis of alkenes by the treatment 
of aldehydes or kentones with 

alkylidenetriphenylphosphorane (Ph 3 P = CR 2 ) or
simply known as phosphorane 
(c) Proton Exchange
   

 

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 In mixed or crossed cannizaro reaction more reactive
as C 6 H 5 Li, BuLi, NaNH 2 , NaH, C 2 H 5 ONa, etc.) aldehyde is oxidised and less reactive
aldelyde is reduced.
  HCHO + C 6 H 5 CHO 

+
HCOONa + C 6H 5C H 2O H
Oxidized Reduced
(So dium formate) (Benzyl alcohol)


H
Ex:CH 3 CHO + HCHO 
C(CH 2 OH) 4 + (HCOO) 2 Ca,
2, 2-Dihydroxy methyl –1, 3–propane diol.(Penta
[2] Cannizaro's Reaction : erythritol)
Those aldehydes which do not contain  -H atom explain mechanism?
give this reaction, with conc. NaOH or KOH; [3] Tischenko Reaction :
Products are Salt of carboxylic acid + alcohol. It is a modified cannizaro reaction. All aldehydes
In this reaction one molecule of carbonyl compounds undergo this reaction in presence of (C2H5O) 3Al,
is oxidised to acid, while other is reduced to alcohol, to form e ster.
such type of reactions are called disproportionation
reaction. (Redox reaction)
2RCHO 

   
HCHO + HCHO  HCOONa + CH 3OH
Ester
Mechanism : (Cannizaro Reaction) Example :
(a) Rapid reversible addition of OH to one molecule  

of HCHO. 
 
 


 
 CH 3 —COOCH 2 CH 3 (Ethyl acetate)

CHEMISTRY [23]
ABHYAAS - III
LEVEL - 0
Q.1 In Cannizzaro reaction- Q.7 Which one of the following on treatement with
50% aqueous sodium hydroxide yields the
(A) Aldehyde is converted into alcohol
correspondnig alcohol and acid
(B) Alcohol is converted into aldehyde
(A) CH3CO CH3 (B) C6H5CH2CHO
(C) Primary amine is converted into isocyanide
(C) C 6 H 5 CHO (D) CH 3 CH 2 CH 2 CHO
(D) Acid is converted into amine
Q.8 In the Cannizzaro reaction 2PhCHO
Q.2 HCHO with conc. alkali forms two compounds.  –
  PhCH 2 OH + PhCOO the slowest
The change in oxidation number would be-
step is
(A) (0 to –2) in both the compounds
(A) The attack of OH– at the carboxyl group
(B) (0 to +2) in both the compounds
(B) The transfer of hydride to the carbonyl
(C) (0 to +2) in one compound and (0 to –
group
2) in the second compound
(C) The abstraction of proton from the
(D) All are correct carboxylic acid
Q.3 For Cannizzaro's reaction. Which is necessary- (D) The deprotonation of PhCH2OH
(A) Presence of  –C
(B) Absence of  –C Q.9 The reaction + conc. NaOH
(C) Presence of  –H
produces
(D) Absence of  –H
Q.4 The reaction,
(A) (B)
2RCHO 

 RCOOCH2 R is called-
Ester
(A) Tishenko reaction
(C) (D)
(B) Knoevangel reaction
(C) Cannizzaro reaction
(D) HVZ reaction D
|
Cannizaro
Q.5 Formaldehyde reacts with 50% aqueous alkali Q.10 2D — C  O  OH    X and Y
reaction
to form: alcohol X and Y are :
(A) A mixture of methanol and sodium
O D
acetate.
|| |
(B) A mixture of ethanol and sodium formate. (A) D — C — O, D — C — OH
|
(C) A mixture of methanol and sodium D
formate.
O D
(D) A resinous mass. || |
(B) D — C — O, D — C — OH
Q.6 Cannizzaro reaction does not take place with- |
H
(A) (CH 3 ) 3 CCHO (B) CHO O D
|| |
(C) H — C — O, D — C — OH
|
(C) CHO (D) CH 3 CHO D
(D) None
O
Passage Based Question Q.13 Mixture of C6H5CHO and HCHO is treated with
Passage : NaOH then cannizzaro’s reaction involves -
Aldehyde without –H atoms on reaction with (A) Oxidation of HCHO
concentrated alkali solut ion undergo an (B) Reduction of HCHO and Oxidation of
oxidation-reduction (disproportionation) C 6 H 5 CHO
reaction. One half of the aldehyde is reduced to
(C) Reduction of C6H5OH
a 1° alcohol and the other is oxidised to a
carboxylic acid. This is known as Cannizzaro (D) Both A & C
reaction.
Statement Based Question
O Each of the questions given below consist of
|| 50 % NaOH
2 – C – H     
 O Statement – I and Statement – II. Use the
||  following Key to choose the appropriate answer.
(no –H) – CH2OH + – C – O – Na
(A) If both Statement- I and Statement- II are
Two steps are involved in this reaction. true, and Statement-II is the correct explanation
(i) Attack of OH ion on the carbonyl group of of Statement– I.
one aldehyde yields an oxyanion. (B) If both Statement-I and Statement-II are
O
true but Statement-II is not the correct
O
|| | explanation of Statement – I.
H–C–H + OH H–C–H (C) If Statement-I is true but Statement-II is
|
OH false.
(oxyanion) (D) If Statement-I is false but Statement-II
(ii) As a result of hydride transfer, the final product is true.
is formed Q . 1 4 Statement-I : Crossed Cannizzaro reaction
bet ween formaldehyde and benzaldehyde
O O
| H || give benzyl alcohol and formate ion.
H–C–H + C=O H – C + CH3O Statement-II : Formaldehyde is a bet ter
| H |
OH OH hydride donar than benzaldehyde .
Proton Q.15 In the Cannizzaro reaction given below, 2Ph–
exchange

O O CHO   Ph–CH 2 OH + PhCO 2 ¯ the

|| – + Na || slowest step is -
H – C – ONa + CH3OH H – C + CH3OH
| (A) the attack of OH¯ at the carbonyl group
O
Intramolecular Cannizzaro’s reaction is also (B) the transfer of hydride to the carbonyl group
possible (C) the abstraction of proton from the carboxylic
CHO NaOH CH 2OH acid
(D) the deprotonation of Ph–CH2OH
CHO COONa
Q.11 The aldehyde which shows Cannizzaro’s
reaction is - CH3
(A) HCHO (B) C 6 H 5CHO Q.16 In the reaction, P is, CO SeO
2 
CH3
(C) CCl 3 –CHO (D) all of these
Q.12 The product formed in the following reaction P + Se + H2O
will be -
CHO NaOH
| product - (A) CH3COCHO (B) CH3COOCH3
CHO
(C) CH3COCH2OH (D) None
CH2OH CH2OH
(A) | (B) |
CH2OH COONa
COONa
(C) | (D) All of these
COONa
CHEMISTRY [25]
LEVEL - I
Q.1 Cannizaro reaction is given by : Q.8 Benzaldehyde can be conveted benzyl alcohol by –
(A) Aldehydes containing alpha hydrogens (A) HCl
(B) Aldehydes not containing alpha hydrogens (B) NaOH
(C) A ketone having alpha hydrogen atoms (C) LiAlH4
(D) Ketones not having alpha hydrogens (D) 2nd and 3rd are correct
Q .2 Acetaldehyde on treatement with aluminium Q .9 Benzyl alcohol from benzaldehyde is obtained
ethoxide gives : in the following reaction –
(A) Ethyl methanoate (B) Ethyl acetate (A) Cannizzaro’s reaction
(C) Ethyl propionate (D) Ethyl formate (B) Kolbe’s reaction
Q .3 Cannizzaro reaction is given by : (C) Wurtz reaction
(A) Aldehydes containing –hydrogen atoms (D) Fitting’s reaction
(B) Aldehydes as well as ketones containing Q.10 The cannizzaro reaction is not given by :
–hydrogen atoms (A) Trimethyl acetaldehyde
(C) Aldehydes not containing –hydrogen (B) Acetaldehyde
atoms (C) Benzaldehyde
(D) Aldehyde containg –hydrogen atoms (D) Formaldehyde
Q .4 Formaldehyde reacts with 50% aqueous alkali Q .1 1 B en z aldehyd e a nd fo r maldehy d e give a
to form : common reaction :
(A) Cannizzaro’s reaction
(A) A mixture of methanol and sodium acetate
(B) Benzoin condensation
(B) A mixture of ethanol and sodium acetate
(C) Claisen condensation
(C) A mixture of methanol and sodium formate
(D) A resinous mass (D) Perkin’s reaction
Q .5 Reaction of acetaldehyde with aluminium Q.12 When CH3COCH3 reacts with Cl2 and NaOH,
ethoxide in the presence of anhydrous AlCl 3 which of the following is formed :
is called : (A) CHCl 3 (B) CCl 4
(A) Cannizzaro’s reaction (C) CCl 2 H 2 (D) CH 3 Cl
(B) Bouveault–Blanc reduction Q.13 Which one of the following undergoes reaction
(C) Tischenko reaction with 50% sodium hydroxide solution to give
(D) Rosenmund reaction the corresponding alcohol and acid?
Q .6 Which of the following substrates show (A) Benzoic acid (B) Benzaldehyde
cannizzaro’s reaction : (C) Butanal (D) Phenol
[a] CH 3 CHO [b] HCHO Q.14 Which one of the following aldehydes gives
[c] CCl 3 CHO [d] C 2 H 5 CHO cannizaro reaction when heated with strong
(A) b and c (B) b, a, c alkali ?
(C) b, c, d (D) a and d (A) Banzaldehyde (B) Propionaldehyde
Q .7 Benzaldehyde is heated with a conc. solution (C) Acetaldehyde (D) Butanal
of KOH to form –
(A) C 6 H 5 CH 2 OH
(B) C 6 H 5 COOH
(C) C 6 H 5 COOK
(D) C 6 H 5 COOK + C 6 H 5 CH 2 OH
LEVEL - II
Select the Correct Alternative (Only One Correct Q.7 Wh ich of the carbonyl groups in
Answer) p-MeOC 6 H 4 COMe and p-NO 2 C 6 H 4 COMe
Q.1 Cannizzaro reaction is not given by : protonates more readily in acid solution and
(A) Trimethylacetaldehyde why?
(B) Acetaldehyde
Q.8 In the Cannizzaro reaction given below
(C) Benzaldehyde

(D) Formaldehyde 2 Ph –CHO   Ph–CH 2OH + PhCO 12
Q.2 In a Cannizaro reaction, the intermediate that the slowest step is-
will be the best hydride donor is : (A) the attack of OH1 at the carbonyl group
(B) the transfer of hydride to the carbonyl group
– – (C) the abstraction of proton from the carboxylic
(A) (B) – acid
(D) the deprotonation of Ph–CH2OH
Q.9 In a Cannizzaro reaction the intermediate which
– – is the best hydride donor is -
–
(C) (D) –
 
Q.3 Benzaldehyde reacts with formaldehyde in the (A) (B)

presence of alkali to form :-
(A) Methyl alcohol and sodium benzoate  
(B) Benzyl alcohol and sodium formate (C)  (D) 
(C) Benzoic acid and ethanol
(D) Formic acid and benzyl alcohol Q.10 Any one of the product formed is :
Q.4 Which one of the following on treatment with
50% aq. NaOH yields the corresponding alcohol
(i)
and acid 
(A) C 6 H 5 CHO (B) CH 3 CH 2 CH 2 CHO

(C) CH 3 COCH 3 (D) C 6 H 5 CH 2 CHO COOH HOOC
Select the Correct Alternatives (One or More Then
(A)
Q.5 In the Cannizzaro reaction given below, COOH HOOC
—
CH2OH CH2OH
2Ph – CHO 
OH
 Ph – CH 2 OH + PhCO 21
(B)
the slowest step is :
CH2OH CH2OH
(A) the attack of 1OH at the carbonyl group
CH2OH COOH
(B) the transfer of hydride to the carbonyl group
(C) the abstraction of proton from the carboxylic (C)
acid
COOH CH2OH
(D) the deprotonation of Ph – CH 2 OH
O
Fill in the Blanks : O
Q.6 Cannizzaro's reaction is followed by those
aldehydes which .................. -hydrogen atom. (D)
O
O
CHEMISTRY [27]
ANSWERS
LEVEL - 0
LEVEL - I
LEVEL - II
– –
+
+
O –
( having –R)
I will be more readily protonated than (II). Alternative protoned (I) is more stabilised by resonance than protonated
(II).
– –
+
In (X) there is extended conjugation and only one charge is involved. In (Y) there is not this extended conjugation
and
the relative close proximity of two positive charges is a destabilising factor. Hence (X) is more stable than (Y).
LECTURE - IV
REACTION WITH HALOGEN e.g., acetone may be brominated in glacial acetic
acid to give monobromoacetone :
(a) Replacement of -H Atoms :
T his reaction is not show n by formaldehyde CH 3 COCH 3 + Br 2  CH 3 COCH 2 Br + HBr
(HCHO), since  -H atoms are absent, as enolisation (43–44%)
does not takes place in HCHO. The halogenation of carbonyl compounds is

–HCl catalysed by acids and bases. Let us consider the
CH2 C H + Cl2  CH2 C H
case of acetone. In alkaline solution,
H O Cl O tribromoacetone and bromoform are isolated. Thus,
Cl the introduction of a second and a third bromine
Cl2 Cl2
atom is more rapid than the first. In aqueous
H
–HCl
CH C H
–HCl
CCl3 C H sodium hydroxide, the rate has been shown to
O Cl O O be independent of the bromine concentration,
Chloral but first order with respect to both acetone and
base i.e.,
Example :
Rate = k [acetone] [OH 1 ]
–3HCl
CH3 C CH3 + 3Cl2  CH3 C CCl3
O O  



   
Tri chloro acetone 
Example :
 
     
 
–3HCl
CH3 CH2 C CH3 + 3Cl2 
O ALDOL CONDENSATION
 CH3 CH2 C CCl3
Two molecules of an aldehyde or a ketone undergo
O condensation in the presence of a base to
Example : yield a -hydroxyaldehyde or a -hydroxyketone.
CCl3 C R + NaOH CHCl3 + NaO C This reaction is called the aldol condensation.
In general Carbonyl compounds which contain
O O
-H atoms undergo aldol condensat ion
Example : with dil. NaOH. Aldol contains both alcoholic
and carbonyl group.
–2HCl
CH3 CH2 C CH2 CH3 + 2Cl2   Mechanism of Aldol Condensation :- It takes
O place in the following two stages :
 CH3 CH2 C CCl2 CH3
(a) Formation of Carbanion
O (b) Combination of carbanion with other aldehyde
(b) Replacement of O-atom of C O Group : molecule.
(a) Formation of Carbanion :
It takes place by PCl 5 or SOCl 2 .
-H atom of C O group are quite acidic which
Cl
C O + PCl 5   C + POCl 3 can be removed easily as proton, by a base.
Cl  
– –
Phosphorus penta chloride OH+ H CH2 C H CH2 C H + H2O
Cl O O
C O+ SOCl 2  C + SO 2 Base Acetaldehyde Carbanion
Cl
Carbanion t hus formed is stable because of
Thionyl chloride
resonance -
(c) Haloform Reactions : –
CH2 C H  CH2 C H
Chlorine or bromine replaces one or more
-hydrogen atoms in aldehydes and ketones, O O–
CHEMISTRY [29]
(b) Combination of carbanion with other aldehyde O
molecule : CH3 CH3
O H C CH C CH3 + O C 
CH3 CH3
–
CH3 C + CH2 C O O
H CH3 HCl gas CH3 CH3
CH + O C  C CH C CH C
Aldehyde (other molecule) CH3 –H2O
CH3 CH3
H O– Phorone
Mixed or Crossed Aldol Condensation :
O CH3 C CH2 CHO

H
H+ H2O

OH H
 
CH3 C CH2 C O 
H
Aldol 
 
OH H O

H C O CH3 CH CH CH
H  –Unsaturated aldehyde
Aldol condensation is possible between : 

1 . Two aldehyde (Same or different) 
2 . Two ketone s (Same or different) H
3 . One aldehyde and one ketone



 
Ex:CH 3 CHO + CH 3 CH 2 CHO  Total 4


products. Write structure of products ?
Simple or Self Condensation :  
Sol. CH3 CH + CH2CHO  (Aldol)
dil
CH3 CH + HCH2CHO 
NaOH
CH3 CH CH CHO
O H
O OH H


 CH 3 —CH CH—CHO
CHO 
–H2O
CH3 CH CH CHO
 
Crotonaldehyde
H CH3 CH2 CH + CH2 CHO  (Aldol)
O H

 CH 3— CH 2— CH CH—CHO



CH3
 
CH3 CH + CH CHO  (Aldol)
O H
CH3

 CH3 CH C CHO
Note:- If in crossed aldol condensation reaction,
CH3
  only one carbonyl compound have –H than total
CH3 CH2 CH + CH CHO  (Aldol) t wo product formed.
O H 
CH3 CH 3CHO + C6H5CHO 

 
 Total 2 product.

 CH3 CH2 CH C CHO  
CH3 CH + CH2 CHO  (Aldol)
 Intramolecular Aldol Condensation : O H
 
 CH 3 —CH CH—CHO

(Crotonaldehyde)

 
C6H5 CH + CH2 CHO  (Aldol)
O H

 1 
 C 6 H 5 —CH CH—CHO
(Cinnamaldehyde)


( – Unsaturated Ketone)

(Aldol)
Here 5 membered ring is more stable than 3
membered ring so above product is formed as
a major product.
CHEMISTRY [31]
ABHYAAS - IV
LEVEL - 0
Q.1 Aldol condensation between the following Q.6 Which of the following statements is correct:
compounds followed by dehydration gives (A) Al l primar y alcohol give iodoform
methyl vinyl ketone-
reaction.
(A) HCHO and CH 3 COCH 3
(B) All secondar y alcohols give iodoform
(B) HCHO and CH 3 CHO
reaction.
(C) Two molecules of CH3 CHO
(C) Ethanol is the only primary alkanol that
(D) Two molecules of CH3 COCH 3
gives positive iodoform test.

Q.2 C 6 H 5 CHO + CH 3 COCH 3   (D) All aldehydes with  hydrogen atoms give
C 6 H 5 CH(OH)CH 2 COCH 3 positive iodoform reaction:
 C 6 H 5 CH = CHCOCH 3 Q.7 How many aldols will be formed by CH3CHO
This reaction is known as: and CH 3 –CH 2 –CHO –
(A) Aldol condensation (A) 2 (B) 3
(B) Cross aldol condensation (C) 4 (D) 1
(C) The Claisen-Schmidt reaction
Q.8 In the reaction sequence:
(D) None of these


CH 3 –CCH   A 
Q.3 CH 3 –– CHO 
 CH 3 CH(OH)CH 2 CHO
B I2 + NaOH  C
In the aldol condensation of acetaldehyde
A, B and C are given by the set:
represented above, which of the following
intermediate species are obtained ? (A) CH 3 CH 2 CHO, CH 3 CH 2 CH 2 Cl, CHI 3

 (B) CH 3 COCH 3 ,   , CHI 3

(A)   (B)  
(C)    (D) All above

(C) CH 3 COCH 3 , CCl 3 -   , CHI 3
Q.4 A carbonyl compound gives a positive

iodoform test but does not reduce Tollen's (D) CH 3 CH 2 CHO, CCl 3 – –CH 2 –CH 3 ,
reagent or Fehling's solut ion. It forms a CHI 3 .
cyanohydrin with HCN, which on hydrolysis
gives a hydroxy acid with a methyl side chain. Q.9 Predict the product ‘B’ in the seuqnece of
The compound is: reaction
(A) Acetaldehyde. (B) Propionaldehyde
 A  B
NaOH
HC = CH 
30%H2 SO4
(C) Acetone (D) Crotonaldehyde. HgSO 4
Q.5 Which of the following statements is wrong:

(A) CH 3 COONa
(A) All methyl ketones give a positive
(B) CH 3 COOH
iodoform test.
(C) CH 3 CHO
(B) Acetaldehyde is the only aldehyde that
gives iodoform test. (D) CH 3 CH(OH)CH 2 CHO
(C) All secondary alcohols give positive
iodoform test.
(D) Any alcohol that can be oxidised to an
acetyl group gives a positive iodoform test.
Q.10 Which of the following is an example of aldol Q.15 The best reagent to convert pent–3–en–2–ol into
condensation ? pent–3–in–2–one is -
(A) C 6 H 5 CHO + HCHO (A) Acidic dichromate
(B) Acidic permanganate

NaOH
 C 6 H 5 CH 2 OH
heat
(C) Pyridinium chloro–chromate
(B) 2CH 3 COOC 2 H 5 (D) Chromic anhydride in glacial acetic acid

  CH 3 COCH 2 COOC 2 H 5 Q.16 Which of the folowing on heating with aqueous
KOH, produces acetaldehyde ?
(C) CH 3 COCH 3 + (CH 3 ) 2 NH
(A) CH 3 COCl (B) CH 3 CH 2 Cl
CH3 CH3 (C) CH 2 ClCH 2 Cl (D) CH 3 CHCl 2
 CH3 – C –– N – CH3 Q.17 The enolic form of acetone contains–
OH (A) 9 sigma bonds, 1 pi bond and 2 lone pairs
(B) 8 sigma bonds, 2 pi bonds and 2 lone pairs
(D) 2CH 3 COCH 3  Ba(OH)2

CH 3 C(OH)(CH 3 )CH 2 COCH 3 (C) 10 sigma bonds, 1 pi bond and 1lone pair
Q.11 The major product obtained from (D) 9 sigma bonds, 2 pi bonds and 1 lone pair
photochemical chlorination of ethylbenzene (in Q.18 Which of the following will give yellow
excess) is hydrolyzed with aqueous KOH and precipitate with I2/NaOH ?
the product is then oxidized with PCC. The (A) ICH 2COCH 2CH 3
final product formed is
(B) CH 3COOCOCH 3
(A) PhCH 2 CHO (B) PhCOCH 3
(C) CH 3CONH 2
(C) PhCHO (D) PhCOOH
Q.12 Which of the following will not undergo aldol (D) CH 3CH(OH)CH 2CH 3
condensation ? Q.19 Which of the following will not undergo aldol
(A) Acetaldehyde condensation –
(B) Propionaldehyde (A) Acetaldehyde
(C) Trideuterio acetaldehyde (B) Propanaldehyde
(D) Benzaldehyde (C) Benzaldehyde
Q.13 Among the following compounds, the one (D) Trideutero acetaldehyde
which can undergo both aldol condensation
Q.20 The enol form of acetone, after treatment with
and Cannizzaro reaction is
(A) (CH 3 ) 2 CHCHO (B) HCHO D2O gives –
(C) C 6 H 5 CHO (D) CH 3CHO
OD O
D2O, H2SO 4 I II
Q.14 C  CH     P the (A) CH3  C  CH2 (B) CD3  C  CD 3
HgSO 4
OH OD
I I
(C) CH2  C  CH2D (D) CD2  C  CD3
principal organic product) where P is:
Q.21 Which of the following has the most acidic
hydrogen -
(A) 3-hexanone
(A) (B)
(B) 2,4-hexanedione
(C) 2,5-hexanedione
(C) (D) (D) 2,3-hexandione

CHEMISTRY [33]
Passage :
Q .2 4 The structure of the product S is –
A carbonyl compound P, which gives positive
io d ofo r m te st , undergo e s re act ion w it h O
MeMgBr followed by dehydration to give an
olefin Q. Ozonolysis fo Q leads to a dicarbonyl
compound R, Which undergoes intramolecular (A) (B)
aldol reaction to give predominantly S. O
Me Me Me
1. MeMgBr3 1. O 1. OH
P  Q  R   
 S
2.H,H O
2
2. Zn,H2O 2. 
O O
3.H2SO4,
Me
(C) (D)
Q .2 2 The structure of the carbonyl compound P
is–
Me Me
Me
(A) (B)
O Me O Me Statement Based Question
O Each of the questions given below consist
of Statement-I and Statement-II. Use the
(C) (D) following Key to choose the appropriate
O Et Me answer.
Q .2 3 The structures of the products Q and R, (A) If both Statement-I and Statement-II are
respectively, are – tru e, an d Stat em en t -I I is the co rr ect
O explanation of Statement-I.
(B) If both Statement-I and Statement-II are
H
(A) Me , COMe true but Statement-II is not the correct
Me explanation of Statement-I.
Me Me Me (C) If Statement-I is true but Statement-II is
false.
O
(D) If Statement-I is false but Statement-II
H is true.
(B) ,
CHO
Me
Me Me Me Q.25 Statement-I : Acetaldehyde undergoe s aldol
condensation with dilute NaOH.
O
Statement-II : Aldehyde which do not contain
H -hydrogen undergoes aldol condensation.
(C) , CHO
Et
Me Me Et
Me O
CH3
(D) , CHO
Me
Me Et
LEVEL - I
Q .1 Aldol condensation is the reaction of : Q .8 C 6 H 5 CHO and HCHO reacts with NaOH to
(A) Formaldehyde and 10% NaOH give :
(B) Acetaldehyde and dil. KOH (A) C 6 H 5 CH 2 OH + HCOONa
(C) Formaldehyde and HCN (B) C 6 H 5 COONa + CH 3 OH
(D) Acetone and chloroform (C) C 6 H 5 COOH + CH 4
Q .2 Acetaldehyde reacts with K2CO 3 to form : (D) None of these
Q .9 Acetone on reaction with bromine in presence
of basic catalyst gives :
OH H OH H
| | | | (A) CH 3 COCH 2 Br (B) CH 3 COCBr 3
(A) CH3–CH2–CH–C=O (B) CH3–CH–CH2–C=O (C) Propane (D) (CH 3 ) 2 C–Br 2
(C) CH3–CH–C–CH3 (D) CH2–CH2–CH–C=O Q.10 Which one of the following aldehyde will not
| || | | form an aldol when treated with dilute NaOH:
OH O OH H
Q .3 Chlorine reacts with acetaldehyde in the (A) CH 3 CHO (B) CH 3 CH 2 CHO

presence of antimony chloride to from : (C) (CH 3 ) 3 CCHO (D) C 6 H 5 CH 2 CHO
(A) CCl 3 –CHO (B) CH 3 COCl Q.11 Formaldehyde when treated with conc. KOH
(C) CH 2 Cl–CHO (D) CHCl 2 –CHO gives :
Q .4 Which of the following aldehydes does not (A) CH 3 CHO (B) C 2 H 4
form iodoform on heat ing with iodine and (C) CH 3 OH, HCOOK (D) CH 3 OH, CH 3 CHO
alkali : Cl C H Cl
Q.12 Acetaldehyde 
2 
SbCl3 A 
6 5
Con. H2SO4
 (B),
(A) Pyruvic aldehyde (B) ICH 2 CHO
(C) Propionaldehyde (D) 2–Hydroxypropanal (B) is :
Q .5 A carbonyl compound gives a positive (A) Chloroform (B) Chloral
iodoform test but doe s not reduce Tollen’s (C) DDT (D) TNB
reagent or Fehling’s solut ion. It forms a Q .1 3 Two molecules of an aldehyde reacts with a
cyanohydrin with HCN, which on hydrolysis concentrated solution of NaOH and produces
gives a hydroxy acid with a methyl side chain. one molecule of an alcohol and acid each,
The compound is : which one is the aldehyde :
(A) Acetaldehyde (B) Propionaldehyde (A) Acetaldehyde
(C) Acetone (D) Crotonaldehyde (B) Formaldehyde
Q .6 Aldehyde not containing –hydrogen atoms (C) Propionaldehyde
reacts with aqueous alkali to form : (D) Butyraldehyde
(A) an  unsaturated aldehyde Q .1 4 What happens on adding concentrated caustic
alkali to an aldehyde containing -hydrogen :
(B) an  unsaturated acid
(A) Resinification
(C) Corresponding alcohol and corresponding
(B) Saccharification
carboxylate anion
(C) Tischenko reaction
(D) Corresponding carboxylic acid
(D) Cannizzaro’s reaction
Q .7 Which of the following carbonyl compounds
Q.15 In the presence of a dilute base C6H5CHO and
exhibits keto–enol isomerism to an appreciable CH3CHO react together to give a product. The
extent : product is :
(A) Acetone (B) Acetylacetone (A) C 6 H 5 CH 3 (B) C 6 H 5 CH 2 CH 2 OH
(C) Acetaldehyde (D) Acetic ester (C) C 6 H 5 CH 2 OH (D) C 6 H 5 CH=CHCHO
CHEMISTRY [35]
Q.16 What is/are the product(s) formed when an Q.22 Which of the following will not undergo aldol
equimolar mixture of benzladehyde and condensation :
formladehyde is heated with concentrated NaOH (A) Acetaldehyde
(A) C 6 H 5 –CH 2 –OH and H–COONa (B) Propanaldehyde
(B) C 6 H 5 –COONa and CH 3 –OH (C) Benzaldehyde
(C) C 6 H 5 –COOH and CH 3 –ONa (D) Trideuteroacetaldehyde
(D) C 6 H 5 –CH 2 –COONa Q.23 Which of the following has the most acidic
Q.17 Which of the following does not give yellow proton :
precipitate with I 2 and NaOH (A) CH 3 COCH 3
(A) C 2 H 5 OH (B) CH 3 CHO
(B) (CH 3 ) 2 C=CH 2
(C) CH 3 COCH 3 (D) HCHO
(C) CH 3 COCH 2 COCH 3
Q.18 Which of the following does not give yellow
(D) (CH 3 CO) 3 CH
precipiate with NaOH + KI ? Q.24 Which of the following compound will undergo
(A) Acetone (B) Acetaldehyde self aldol condensation in the presence of cold
(C) Benzaldehyde (D) Acetophenone dilute alkali :
Q.19 Aldol condensation involving
(A) C 6 H 5 CHO (B) CH 3 CH 2 CHO
CH 3CHO + CH 3 CHO gives the product :
(C) CHC–CHO (D) CH 2 =CH–CHO
(A) CH 3 CHOHCH 2 CHO
Q.25 Which of the following gives aldol
(B) CH 3 COCH 2 CH 3
condensation reaction :
(C) CH 3 CH=CH 2
(A) C 6 H 5 OH
(D) None of these
O
Q.20 Which one of the following gives iodoform test: ||
(B) C6H5 – C – C6H5
(A) Formaldehyde (B) Ethyl alcohol
(C) Benzyl alcohol (D) Benzaldehyde O
||
Q.21 Among the following compounds, which will (C) CH 3CH 2 – C – CH3
react with acetone to give a product containing
> C = N – O
||
(A) C 6 H 5 NH 2 (B) (CH 3 ) 3 N (D) (CH3)3C – C – C6H5
(C) C 6 H 5 NHC 6 H 5 (D) None of these
LEVEL - II
Select the Correct Alternative (Only One Correct Select the Correct Alternatives (One or More Then
Answer) One Correct Answers)
Q.1 The compound that gives a positive iodoform Q.6 Which of the following does not give iodoform
test is :- reaction ?
(A) 1-pentanol (B) 2-pentanone (A) CH 3 CH 2 CH 2 OH (B) CH 3 OH
(C) 3-pentanone (D) pentanal (C) CH 3 CHO (D) PhCOCH 3
Q.2 Which of the following does not undergo aldol Q.7 Which of the possible compound will be formed
condensation ? in the following sequence of reaction.
(A) HCHO (B) CH 3 CHO CH 2 = CH 2 
HBr
 X 
Hydrolysis

 Y
(C) CH 3 COCH 3 (D) CH 3 CH 2 CHO Na CO
Q.3 In the reaction : 
l excess  Z :
2 3
2
(A) C 2 H 5 Br (B) C 2 H 5 OH
O   [X]
1
O + OH / 
(C) CHI 3 (D) CH 3 CHO
[X] will be :- Q.8 CH 3 – CHO  OH
 CH 3 CH(OH)CH 2 CHO
In the aldol condensation of acetaldehyde
OH O OH OH
represented above, which of the following
(A) (B) intermediate species are obtained ?
 
(A) (B) –
O O
OH
(C) (D)  
(C) (D)
Q.4 Predict the product 'B' in the sequence of
reaction Q.9 Cyclohexanone on being heated with NaOH
solution forms
CH  CH 
30% H SO
HgSO
 A 
dil. NaOH
2
 10  C
4
B
4
OH
(A) CH 3 COONa (B) CH 3 COOH (A)
(C) CH 3 CHO (D) CH3–CH–CH2–CHO
OH O
Q.5 Acetaldehyde reacts with NaOH to form :-
(B)
(A)     OH OH
(C)
(B)    
O
(C)   
O
(D)
(D)    
O
CHEMISTRY [37]
Match the Column :- Q.15 Identify A, B and C ?
Q.10 Match the column I with column II.
Column-I

 
 

(A) + HCHO 



Adduct 
H 3O 1

 
 

(B) + (CH 2 ) 2 O 
 Q.16 The enolic form of acetone contains -

(A) 9 sigma bonds, 1 pi bond and 2 lone pairs
H 3O 
Adduct  (B) 8 sigma bonds, 2 pi bond and 2 lone pairs
+ CO 2  (C) 10 sigma bonds, 1 pi bond and 1 lone pairs

(C) 
 (D) 9 sigma bonds, 2 pi bond and 1 lone pairs

Adduct 
H 3O
Q.17 m–chlorobenzaldehyde on reaction with conc.
(D) + Ph–CN 
 KOH at room temperature gives


(A) Potassium m-chlorobenzoate and
Adduct  H 3O
m-hydroxybenzaldehyde
Column-II (B) m-hydroxy benzaldehyde and m-chlorobenzyl
(p) Ketone alcohol
(q) 1ºAlcohol (n + 1) carbon
(C) m-chlorobenzyl alcohol and m-hydroxybenzyl
(r) Acid (n + 1) carbon
alcohol
(s) 1ºAlcohol (n + 2) carbon
(D) Potassium m-chlorobenzoate and
Q.11 A comopound has two isomers (A) and (B) of
m-chlorobenzyl alcohol
formula C 5H 10 O. Isomer (A) on treating with
NaOH (aq.) give 2, 2-demethylpropan-1-ol and Q.18 Which of the following will give yellow
2, 2-dimethylpropanoic acid salt. The isomer (B) precipitate with I 2/NaOH-
on treating with NaOH (aq.) gives 3-hydroxy- (A) ICH 2 COCH 2 CH 2
2-propylheptanal. What are A and B ? (B) CH 3 COOCOCH 3
Q.12 A ketone (A) which undergoes haloform reaction (C) CH 3 CONH 2
gives compound B on reduction. B on heating
(D) CH 3 CH(OH)CH 2 CH 3
with sulphuric acid gives compound C, which
form mono ozonide D. D on hydrolysis in Q.19 Which of the following will not undergo aldol
presence of Zn dust gives only acetaldehyde. condensation -
Identify A, B and C. Write down the reactions (A) Acetaldehyde
involved. (B) Propanaldehyde
Q.13 Complete the following reactions : (C) Benzaldehyde
(D) Trideutero acetaldehyde


 (A) Q.20 The enol form of acetone, after treatment with
D2O gives -
Q.14 The sodium salt of a carboxylic acid, A, was
produced by passing a gas, B, into an aqueous OH OH
solution of caustic alkali at an elevated (A) CH2–C–CH2D (B) CD2=C–CD3
temperature and pressure. A on heating in
OH OD
presence of sodium hydroxide followed by
treatment with sulphuric acid gave a dibasic acid (C) CH2=C–CH2D (D) CD2=C–CD3
C. A sameple of 0.4 g of C on combustion gave Q.21 Which of the following has the most acidic
0.08 g of water and 0.39 g of carbondioxide. hydrogen-
The silver salt of acid weighin 1g on ignition
yielded 0.71 g of silver as residue. Identify A, (A) 3-hexanone (B) 2, 4-hexanedione
(C) 2, 5-hexanedione (D) 2, 3 hexandione
B andC.
Q.22 A mixture of benzaldehyde and formaldehyde Q.28 Compound H is formed by the reaction of
on heating with aqueous NaOH solution gives -
O
(A) benzyl alcohol and sodium formate ||
(B) sodium benzoate and methyl alcohol (A) + PhMgBr
Ph CH3
(C) sodium benzoate and sodium formate
(D) benzyl alcohol and methyl alcohol O
||
Q.23 Complete the following : (B) + PhCH2MgBr
Ph CH3
+ HCHO
O
(C)
|| + PhCH 2 MgBr

KOH
 (A )  (B ) Ph H
Q.24 Complete the following reaction with
O Me
appropriate structure :
(D)
|| +
CH3
Ph H Ph MgBr
O 
 (X)
Q.29 The structure of compound I is
H
Q.25 Suggest appropriate structures for the missing Ph CH3 H3C Ph
compounds. (The number of carbon atoms
(A) (B)
remains the same throughout the reactions). H H
Ph Ph
CH3
Ph CH3 H3C CH3

dil KM nO 4


 (A) 
HIO 4
 (B)
CH3 (C) (D)
H CH2Ph Ph H
OH –
 (C) Q.30 The structures of compounds J, K and L,
Q.26 Carry out the following transformation in not respectively, are
more than three steps. (A) PhCOCH 3, PhCH 2COCH 3 and
H3C O PhCH 2 COO¯K +
H3C (B) PhCHO, PhCH2 CHO and PhCOO¯K +
H
CH3
(C) PhCOCH3, PhCH2CHO and CH3COO¯K +
Q.27 Cyclohexene on ozonolysis followed by reaction (D) PhCHO, PhCOCH3 and PhCOO¯K+
with zinc dust and water gives compound E.
Compound E on further treatment with aqueous Paragraph for Question Nos. 31 to 33
KOH yields compound F. Compound F is A carbonyl compound P, which gives positive
iodoform te st, undergoe s react ion w it h
(A) (B) MeMgBr followed by dehydration to give an
olefin Q. Ozonolysis of Q leads to a dicarbonyl
compound R, which undergoes intramolecular
aldol reaction to give predominantly S.
(C) (D)
P   R 
 Q   S
Paragraph for Question No. 28 to 30 


A tertiary alcohol H upon acid catalysed Q.31 The structure of the carbonyl compound P is
dehydration gives a product I. Ozonolysis of I Me
leads to compounds J and K. Compound J upon (A) (B)
reaction with KOH gives benzyl alcohol and a O Me O Me
compound L, whereas K on reaction with KOH
O O
H3 C
Ph
(C) (D)
gives only M. M = O Et
H Me
Ph
CHEMISTRY [39]
Q.32 The structure of the products Q and R, Q.34 The number of aldol reaction(s) that occurs in
respectively, are the given transformation is
O
 

(A) Me , H
COMe
Me Me Me
Me
(A) 1 (B) 2
O (C) 3 (D) 4
Q.35 After completion of the reactions (I and II), the
(B) , H organic compound(s) in the reaction mixtures
CHO
Me is(are)
Me Me Me
O  
Reaction I : 
(C) , H
Et CHO
Me Me Et  
Reaction II :  
Me O
CH3 O O O
(D) ,
CHO H3 C CH2Br H3 C CBr3 Br3C CBr3
Me Et P Q R
Me
O O
Q.33 The structure of the product S is
Br C BrH 2C CH2Br H3C ONa CHBr3
OP Q R S T U
(A) Reaction I : P and Reaction II : P
(A) (B)
(B) Reaction I : U, acetone and
O
Me Me Reaction II : Q acetone
Me
(C) Reaction I : T, U, acetone and
Reaction II : P
O O
(D) Reaction I : R, acetone and
Me Reaction II : S acetone
(C) (D)
Me Me
ANSWERS
LEVEL - 0
Q.1 (A) Q.2 (C) Q.3 (D) Q.4 (C) Q.5 (C) Q.6 (C) Q.7 (C)
Q.8 (C) Q.9 (D) Q.10 (D) Q.11 (B) Q.12 (D) Q.13 (A) Q.14 (B)
Q.15 (D) Q.16 (D) Q.17 (A) Q.18 (D) Q.19 (C) Q.20 (A) Q.21 (B)
Q.22 (B) Q.23 (A) Q.24 (B) Q.25 (C)
LEVEL - I
Q-1 (B) Q-2 (B) Q-3 (A) Q-4 (C) Q-5 (C) Q-6 (C) Q-7 (B)
Q-8 (A) Q-9 (B) Q-10 (C) Q-11 (C) Q-12 (C) Q-13 (B) Q-14 (A)
Q-15 (D) Q-16 (A) Q-17 (D) Q-18 (C) Q-19 (A) Q-20 (B) Q-21 (A)
Q-22 (C) Q-23 (D) Q-24 (B) Q-25 (C)
LEVEL - II
Q.1 (B) Q.2 (A) Q.3 (D) Q.4 (D) Q.5 (B) Q.6 (A,B) Q.7 (B,C,D)
Q.8 (A,B,C) Q.9 (C)
Match the Column :-

Q.10 (A  q) ; (B  s) ; (C  r) ; (D  p)
Q.11 A = ; B =
O
H3C H3C H3C
Q.12 A = CH3 ; B = CH3 ; C = H3C CH3 ; D = CH3
O OH
O O
O
Q.13
CH3
Q.14 A = HCOOH ; B = CO ; 
Q.15 (A) : ; (B) : ; (C) :
Q.16 (A) Q.17 (D) Q.18 (A) Q.19 (C) Q.20 (C) Q.21 (B) Q.22 (A)
CHEMISTRY [41]
Q.23 A= B = HCOOK
Q.24 KCN + H2SO4  KHSO4 + HCN
CH3
O + HCN  

LiAIH 4
 H
H
O O
Q.25 A = ; B= ; C=
H3C CH3
Q.26 CH 3 CH 2 C  CH  CH 3 CH 2 C  CNa   CH 3 CH 2 C  C—CH 3


Q.27 (A) Q.28 (B) Q.29 (A) Q.30 (D) Q.31 (B) Q.32 (A) Q.33 (B)
Q.34 (C) Q.35 (C)
LECTURE - V
 Claisen Condensation :  Perkin Reaction :
When two molecules of ester undergo a condensation In perkin reaction, condensation has been effected
reaction, the reaction is called Claisen condensation. between aromatic aldehydes and aliphatic acid
T he pro duct of the claisen condensat ion is a anhydride in the presence of sodium or potassium
-keto e ster. salt of the acid corresponding to the anhydride,
  to yield , -unsaturated aromatic acids.
The acid anhydride should have at least two -
O H.
C 6 H 5 CHO + (CH 3 CO) 2 O

AcONa
 C 6H 5— C H = C H — C O O H
170 180  C
  



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 : 
 



 

 

 Intramolecular Claisen Condensation :

 Dieckmann Condensation :
 Knoevenagel Reaction :
The addition of base to a 1,6-diester causes the
die ster to undergo intramolecular claisen Condensation of aldehydes and ketones with
condensation, thereby forming a five membered compounds having active methylene group in the
ring  -keto e ster. An intramolecular claisen presence of basic catalyst to form a, b-unsaturated
condensation is called a Dieckmann condensation. 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.

 
 

 

CHEMISTRY [43]
 Reformatsky Reaction : ion to the carbonyl carbon places this hydrogen in
A similar reaction like the addition of organometallic the alpha position of the nitrile thus rendering it relatively
compounds on carbonyl compounds that acidic. The carbanion, thus generated, attacks the
involves the addition of an organozinc reagent carbonyl carbon of the second aldehyde molecule in
to the carbonyl group of an aldehyde or ketone. a rate-determining step forming an unstable cyanohydrin
This reaction, called Reformatsky reaction, extends of benzoin which immediately breaks down into benzoin
the carbon skeleton of an aldehyde or ketone and hydrogen cyanide.
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 e ster.
O
Zn/C6H6 
O + Br 
O
Aldehyde R
or ketone -bromoester

ZnBr
 + 3
O OH
O O
Zn/C H H3O
O—R O—R 

-hydroxy ester
 Schmidt Reaction :
This is the reaction between a carbonyl compound
and hydrazoic acid in the presence of a strong  Benzilic Acid Rearrangement :
acid concentrated sulphuric acid. Aldehydes give The addition of a strong base to a carbonyl group
a mixture of cyanide and formyl derivatives of results in the formation of an anion. The reversal
primary amines, whereas ketones give amides : of the anionic charge may cause expulsion of
the attached group X, e.g.
RCHO + HN 3 
 RCN + RNHCHO + N 2 

O
RCOR + HN 3 
 RCONHR + N 2
Reaction with primary amine :
 However, in a 1, 2-diketone the group X may
migrate to the adjacent electron-deficient carbonyl
Schiff's Base carbon forming -hydroxy acid.Thus, benzil on
 Benzoin Condensation : treatment with a strong base forms benzilic acid
The benzoin condensation is essentially a (salt), hence the name benzilic acid rearrangement.
dimerisation of two aromatic aldehydes under the 
catalytic influence of cyanide ions to give benzoin

(I).
O
2 C6H5CHO
KCN H3C
OH
(I)
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
ABHYAAS - V
LEVEL - 0
Q.1 An aldehyde isomeric with allyl alcohol gives Q.5 Methyl ethyl ketone can be reduced to
phenyl hydrazone. n-butane by –
Pick out a ketone that too gives a phenyl (A) Meerwein-Ponndorf reduction
hydrazone containing the same percentage (B) Wolff-Kishner reduction
of nitrogen: (C) Mg-Hg, H 2 O
(A) Methyl ethyl ketone (D) HI / red phosphorus at 423 K
(B) Dimethyl ketone Q.6 Ethyl cyanide is allowed to react with
(C) 2– Butanone methylmagnesium iodide and subsequently
(D) 2– Methyl propanone acidified with dilute HCl. The product formed
Q.2 Aldehyde s and ketones form hydrocarbons is -
by: (A) propanone (B) propanal
(A) The Clemmensen reduction (C) butanal (D) butanone
(B) The Cannizzaro reaction Q.7 Benzamide on heating with bromine and
(C) The Rosenmund reduction caustic alkali gives -
(D) Aldol condensation (A) benzene
Q.3 Dr y dist il lat ion of calcium formate and (B) methyl amino and benzene
subsequent treatment with dilute KOH gives (C) aniline
the mixture of: (D) m-Bromo-benzaldehyde
(A) CH 3OH, HCOOK (B)CH3CHO, HCOOK Q.8 Phenylglyoxal, C6H5COCHO, on heating with
(C) HCHO, HCOOK (D) None of the above concentrated NaOH gives
Q.4 Aldehyde not containing -hydrogen atom (A) C 6H 5COONa and CH 3OH
reacts with aqueous alkali to form: (B) C6H 5CH 2OH and HCOONa
(A) An ,  unsaturated aldehyde. (C) C 6 H 5 CHOHCOONa
(B) An ,  unsaturated acid. (D) C6H 5COONa and HCOONa
(C) Corresponding alcohol and corresponding
carboxylate anion.
(D) Corresponding carboxylic acid.
LEVEL - 1
Q.1 C6H5CHO 

NH2OH
 A 
H2O
B , CN
Q.3 ? 
EtOH, H2O
 Benzoin.
What is not true for the compound B –
(A) Gives cannizaro’s reaction The reactant is obtained by dry distillation of the
calcium salts of the following pairs –
(B) Acts as strong reducing agent
(A) C6H5CH2COOH, HCOOH
(C) Gives phenol on reduction
(B) C6H5COOH, HCOOH
(D) Gives optical active compound with HCN
(C) C6H4(OH)COOH, HCOOH
Q.2 Benzaldehyde condenses with acetic anhyderide (D) C6H4(NH2)COOH, HCOOH
to give cinnamic acid in presence of –
Q.4 Hydrobenzamide is formed in the reaction –
(A) Sodium acetate (A) C 6 H 5 COOH + NH 3
(B) Sodium chloride (B) C 6 H 5 CHO + NH 3
(C) Sodium benzoate (C) HCHO + NH 3
(D) Sodium metal (D) CH 3 COCH 3 + NH 3
CHEMISTRY [45]
KMnO
PCl3 Q.12 Replacement of carbonylic oxygen is observed in
Q.5 CH3CHO 

4
A  B
H the reaction :
CH3COONa
  C, [C] is :
(A) C6H5CHO/2H
(A) CH3COOC2H5 (B) CH3COCl (B) C6H5CHO/H2N–NH2

(C) CH3COOH (D) (CH3CO)2O (C) C6H5COOH/PCl5
(D) C6H5CHO/HCN
Alc KOH Br2 Alc. KOH
Q.6 A  B   C 
NaNH2
D Q.13 Use is made of the following reagent to convert
2
benzaldehyde to benzoyl chloride :
Hg NH2OH

dil. H SO
 E   (CH3)2C = NOH (A) Phosphorus pentachloride
2 4
[A] is : (B) Thionyl chloride

(A) CH3CH2Br (B) CH3CH2CH2Br (C) Reaction with chlorine in presence of AlCl3
(C) CH3CHBr2 (D) CH3CH2CHBr2 (D) Reaction with Cl2
Q.7 In the aqueous solution of which of the following Q.14 Benzyl phenyl ketone is :
compounds forms the compounds belonging to (A) C6H5COC6H5
carbo hydrate family on keeping it in the aqueous (B) C6H5–CO–CO–C6H5
solution of barium hydroxide: ( A ) (C) C6H5CH2–CO–C6H5
Benzaldehyde (B) Formaldehyde ( C ) (D) C6H5CH2–CO–CH2–C6H5
Acetaldehye (D) Acetone Q.15 Which aldehyde is used in the manufacture of
Q.8 Oximinoacetone is formed by the reaction of perfumes :
which of the following :
(A) Cinnamaldehyde (B) Benzaldehyde
(A) Propanal + HNO 2
(C) Propionaldehyde (D) Acryaldehyde
(B) Methylamine + Acetone
Q.16 In the metal carbonyls of the general formual
(C) HNO 2 + Propanone M(CO) x , where M = metal and x = 4, then
(D) Acetone + NH 2 OH metals is bonded to:
Q.9 Hypnotic drugs named sulphonals can be (A) Carbon and oxygen
manufactured by which of the foll owing
(B) Carbon
reactions : (C) Oxygen
(A) Carbonyl compound + alcohol (D) CO triple bond
[O]
A   Q.17 Formaldehyde when treated with KOH gives
(B) Carbonyl compound + Thioalcohol methanol and potassium formate. The reaction
[O]
A   is knows as :
(C) Ketone + Phenylhydrazien (A) Perkin reaction
(D) Aldehyde + Baryta water (B) Claisen reaction
Q .1 0 C6H 5CHO + PCl 5, the product is : (C) Cannizzaro reaction
(A) Benzyl chloride (D) Knoevenagel reaction
(B) Benzotrichloride Q.18 The reaction : C 6 H 5 CHO + CH 3 CHO 
(C) Benzal chloride C6H5CH = CH–CHO is known as :
(D) Triphenyl phosphate
(A) Perkin’s reaction
Cl2
Q .1 1 C 6 H 5 CHO   A + HCl (B) Claisen condensation
The product A when reacts with the following (C) Benzoin condenstaion
compounds the reaction is known as Schotten
Baumann reaction
Q.19 CO + NaOH  :
(A) C 6 H 5 NH 2 (B) C 6 H 5 CH 2 OH (A) HCOONa (B) C 2 H 2 O 4
(C) C 6 H 5 OH (D) All of these (C) HCOOH (D) CH 3 COOH
Q.20 Cinnamic acid is formed when C 6 H 5 –CHO Q.24 When m–chlorobenzaldehyde is treated with
condenses with (CH3CO) 2O in presence of : 50% KOH solution, the products obtained is/
(A) Conc. H 2 SO 4 are :
(B) Sodium acetate
OH OH
(C) Sodium metal | |
—CH–CH—
(D) Anhydrous ZnCl 2 (A)
NaOH | |
Q.21 CH 3 COCH 2 COOC 2 H 5  A
H O 2 OH OH
—
[A] is COO CH 2OH
(A) CH 3 COOH (B) CH 3 COCH 3
(B) +
(C) C 2 H 5 CHO (D) None of these
| |
Q.22 Benzaldehyde on reaction with acetophenone OH OH
–
in the presence of sodium hydroxide solution COO CH 2OH
gives :
(C) +
(A) C 6 H 5 CH=CHCOC 6 H 5
| |
(B) C 6 H 5 COCH 2 C 6 H 5 Cl Cl
(C) C 6 H 5 CH=CHC 6 H 5 OH OH
| |
(D) C 6 H 5 CH(OH)COC 6 H 5 —CH–CH—
(D)

Q.23 A 
800ºC
 CH 2 =C=O, Reactant ‘A’ in the | |
Cl Cl
reaction is :
(A) CH 3 CH 2 CHO (B) CH 3 CHO Q.25 2-Butanone is best converted to propanoic acid
(C) CH 3 – C –CH 3 (D) C 2 H 5 OH by
||
O (A) aq. NaOH/NaI/H + (B) aq. NaOH/I2/H +
(C) Tollen’s reagent (D) Fehiling solution
LEVEL - II
Select the Correct Alternative (Only One Correct Q-2 Which one of the following reagents is suitable
Answer) for the conversion of 2-cyclohexenone into
Q-1 In the reaction CH 2 Br + Mg 3-methylcyclohexanone ?

dry ether
 A+ CH 3 CHO  adduct 
H3O


 B.
(A) CH3 MgI (B) (CH3 ) 2CuLi
(C) CH3I2 and Zn (D) CH 3AlCl 2
The product (B) is :
Q-3 The compounds A, B and C in the reaction
(A) CH3CH CH2Br sequence
OH
 


 
(B) CH2CHCH3
are given by the set :-
OH
(A) Iodoform, ethylene, ethyl alcohol
(B) Iodoform, acetylene, acetaldehyde
(C) CH3–CH2 CH2CHCH3 (C) Iodoform, propyne, acetone
OH (D) Iodoform, 2–propanol, propanone
(D) CH2=CH CH2Br
CHEMISTRY [47]
Select the Correct Alternatives (One or More Then Q-7 Which of the following hydrogens will be the most
One Correct Answers) acidic?
Q-4 End products of the following sequence of reaction (d) O
H
is
O CH C CH CH2
CH3  H H H
  

(c) (b) (a)
O (A) a (B) b
A & B are :
(C) c (D) d
I CO2H
Q-8 In the sequence of reactions
I and
(A) I CH3 O
O
I O 
 

(B) I and
the final product (B) is
I O O O
I O OH
(C) I and (A) (B)
I CO2H
O O
I COOK
O
(D) I and
I (C) (D)
O
Ph Fill in the Blanks :

Q-5 Ph 
OH
A. A is : Q-9 When calcium acetate is distilled alone ..................
O
is formed.
OH Ph OH
Comprehension Based Questions :
Ph
(A) (B) Comprehension # 1
O Ph CO
2
Ph Aldehyde, ketone, acid and acid derivatives contain
Ph >C = O group. Aldehyde and ketones gives
nucleophilic addition reactions where as acid and acid
(C) Ph (D) None derivatives gives nucleophilic addition followed by
OH elimination reactions. Nucleophilic addition reactions
O
 followed by elimination of acid derivatives is known
as acyl substitution reaction. This substitution
Q-6 Which of the following statements are correct? reaction takes places by formation of tetrahedral
(A) Benzaldehyde reduces Fehling's solution intermediate.
(B) C6H5CHO + C6H5CHO  NaOH

 -10 For the given reaction
O O
C6 H5CH= CHC 6H5 + O 2 is a Claisen-Schmidt
L + Nu Nu+ L
reaction. R R
(C) pKa (formic acid) is less than pKa (acetic acid) which of these is correct ?
O
(A) L must be better leaving group than Nu
(D) CH CCH + CH CHO 
NaOH


3 3 3 (B) Nu– must be strong enough nucleophile to attack
OH carbonyl carbon
CH3– C – CH2 CHO is an example of aldol (C) Carbonyl carbon must be enough electrophilic to
react with Nu–
CH3
(D) All of these
condensation.
Q-11 Which of the following compounds has very poor Q-15 Which one of the carbonyl compounds is more
leaving group ? reactive towards NaCN/ H + ?
O O O
(A) R (B) R (A) H5C6
H Cl
H
O O
(C) R (D) R H3C
OH OR' (B) O CHO
Q-12 Which one of the following is least reactive compound
for nucleophilic acyl substitution. O
O (C) H3C
O H3C H
(A) H3C (B) NH
O
Cl H3C
(D) NC
H
O
H3C Q-16 Carbonyl compounds gives nucleophilic addtion with
O
NH (A) carbon nucleophile
H3C
(C) NH(D) (B) oxygen nucleophile
(C) Nitrogen nucleophile
O2N (D) All of these
Comprehension # 2 Subjective Exercise :

Aldehydes and ketones are amphoteric. Thus they Q-17 (a) The double bond in aldehydes and ketones is reactive
can act both as acids and bases. Under acidic towards nucleophilic reagents like CN— whereas that
conditions, the carbon of the protonated carbonyl in an alkene is not.
group is much more electrophilic, reacting even with
(b) Alkenes undergo electrophilic addition whereas
weak nucleophilie. Carbonyl compound gives
aldehydes and ketones undergo nucleophilic addition.
nucleophilic addition reaction. In this reaction the
nucleophilic attack proceedes the electrophilic attack.
Q-13 Which of these statements are correct ? Q-18 Complete the following equations giving the
structures of the major organic product.
(A) Carbonyl compound is amphoteric in character
O
(B) Acid catalyst makes the carbonyl carbon more
electrophilic (i) 
SeO 2

(C) basic catalyst makes the nucleophilic attack more
faster. Cl
OEt  ?
base
(D) All of these (ii) O+
O
Q-14 Which of the statements are/is correct ?
Q-19 Complete the following equation :
(A) The rate determining step of addition reaction
is the addition of nucleophile O
CH   ?
( i ) NaNH 2
(B) T he rate-determining step is addtion of (a) H3C + HC ( ii ) H 3 O 
electrophile CH3
(C) The reaction intermeidate of the reaction is
alkoxide ion O Cl
(b) H3C + O
(D) both (A) and (C) CH3 O C2H5

NaNH 2

CHEMISTRY [49]
Q-20 Complete the following equation : Q-27 Compound A (molecular formula C3H8O) is treated
with acidified potassium dichromate to from a product
Hg2  / H  B (molecular formula C3H6O). B forms a shining silver
HC  CH 
NaNH 2
 ? 
CH 3 Br
 ? 
H2 O
?
mirror on warming with ammonical silver nitrate. B
OH when treated with an aqueous solut ion of
I2
 H
 H3C H2NCONHNH2. HCl and sodium acetate gives a
NaOH
CH3 O product C. Identify the structure of C-
H3C (A) CH3CH2CH=NNHCONH2
STORMING SUBJECTIVE EXERCISE (B) CH3–C=NNHCONH2
Q-21 Identify (A) to (D) as reactant, reagent, product as CH3
name of the reaction in following :
(C) CH3–C=NCONHNH2
(i) 3(CH3)2C=O 
 (A) Aldol condensation
HCl
CH3
(ii) CH3COCl + H2 
 (C) Rosenmund's reaction
(B )
(D) CH3CH2CH=NCONHNH2
(iii) (D) 
( i ) NH NH
( ii ) C H ONa
2
 CH3CH2CH3
2
5
2
(iv) (D) 

OBr 1
 CHBr3 + CH3COO1 Q-28
Q-22 Two different Grignard reagents, (X) and (Y) produce

C6H5CH2C(CH3)2OH on reaction with (P) and (Q)
respectively. Give structures of (X), (Y) and (Q). Following statements is/are correct about
mixture :
Q-23 (a) 2-methyl-1,3-cyclohexanedione is more acidic (A) mixture is 3-types of oximes
than cyclohexanone - explain with reason (B) mixture is 2-types of oximes
(b) Explain why HCN will add to the double bond (C) all are optically active
in CH 2 =CHCOOH but not in RCH=CHR (D) one is optically active
Q-29 Complete the following :
Q-24 (a) Convert : PhCHO into PhCH = CHCOPh C 6 H 5 – CHO + CH 3 – COOC 2 H 5
(b) Identify A, B, C and D in the following 

reaction.
Alc.
Q-30 Complete the following :
C7H6O C14H12O2
KCN
[A] [B] O
O CHC6H5
CH3COONa
C9H8O2
Br2
C9H8O2Br2 

[A ] 
 
 
Acetic anhydride
[C] [D]
Q-25 CH3CHO + H2NOH  CH3 –CH = N – OH.
Q-31 Compound 'A' (C 8 H 8 O) on treatment with
The above reaction occurs at - NH 2 OH.HCl given 'B' and 'C'. 'B' and 'C'
(A) pH = 1 (B) pH ~ 4.5 rearrange to give 'D' and 'E', respectively, on
(C) Any value of pH (D) pH = 12 treatment with acid. B, C, D and E are all isomers
Q-26 Among the following compounds, which will of molecular formula (C 8 H 9 NO). When 'D' is
boiled with alcoholic KOH an oil 'F' (C 6H 7 N)
react with acetone to give a product containing
separates out. 'F' reacts rapidly with CH3COCl
>C = N– to give back 'D'. On the other hand, È' on
(A) C 6 H 5 NH 2 (B) (CH 3) 3 N boiling with alkali followed by acidification gives
(C) C6H5NHC6H5 (D) C6H5NHNH2 a white solid 'G' (C7H6O 2). Identify 'A' to 'G'.
Q-32 An organic compound (A), C6H10O, on reaction with Q-36 The structure of the product I is
CH 3 MgBr fol lowed by acid treatment give s
compound (B). The compound (B) on ozonolysis gives (A) Br
Me
compound (C), which in presence of a base give 1-
acetyl cyclopentene (D). The compound (B) on Me
(B)
react ion w it h HBr give s compound (E). Br
Write the strucures of (A), (B), (C) and (E). Show
(C) Br
how (D) is formed from (C). Me
Me Br
Q-33 An organic compound (A) reacts with H2 to give (D)
(B) and (C) successively. On ozonolysis of (A), Q-37 The structures of compounds J and K, respectively,
two aldehydes (D) C2H4O and (E) C2H2O2 and are
formed. On ozonolysis of (B) only propanal is
formed. What are (A) to (E) ? (A) Me COOH and SOCl2
OH
CH COONa (B) Me || and SO2Cl2
Q-34 + X 3  O
(C) Me and SOCl2

COOH
(D) Me COOH and CH3SO2Cl
What is X?
(A) CH 3 COOH (B) BrCH2, COOH Q-38 The structure of product L is

(C) (CH 3CO) 2 O (D) CHO–COOH
Me CHO
Q-35 The smallest ketone and its next homologue are (A)
reacted with NH2OH to form oxime.
(B) Me CHO
(A) Two different oximes are formed
(B) Three different oximes are formed CHO
(C)
(C) Two oximes are optically active Me
(D) All oximes are optically active (D) Me
CHO
Paragraph for Question No. 36 to 38 Q-39 Among P, Q, R and S, t he aromat ic
In the following reaction sequence, products I, compound(s) is / are :
J and L are formed. K represents a reagent.
Cl
 P 
Q
Hex-3-ynal 
 I 
  J
Cl  
 R
K
  Me  L OO

||
O O

 S
(A) P (B) Q
(C) R (D) S
CHEMISTRY [51]
ANSWERS
LEVEL - 0
Q.1 (B) Q.2 (A) Q.3 (A) Q.4 (C) Q.5 (B,D) Q.6 (D) Q.7 (C)
Q.8 (C)
LEVEL - I
Q .1 (C) Q .2 (A) Q .3 (B) Q .4 (B) Q.5 (D) Q.6 (B) Q.7 (B)
Q.8 (C) Q.9 (B) Q.10 (C) Q.11 (D) Q.12 (B) Q.13 (D) Q.14 (C)
Q.15 (B) Q.16 (B) Q.17 (C) Q.18 (B) Q.19 (A) Q.20 (B) Q.21 (B)
Q.22 (A) Q.23 (A) Q.24 (C) Q.25 (B)
LEVEL - II
Q.1 (B) Q.2 (B) Q.3 (B) Q.4 (D) Q.5 (B) Q.6 (C,D) Q.7 (C)
Q.8 (C)
Q-9 acetone
Comprehension #1 :
Q-10 (D) Q-11 (A) Q-12 (B)
Comprehension #2 :
Q-13 (D) Q-14 (D) Q-15 (D) Q-16 (D)
Q-17 (a) The carbonyl group in aldehydes and ketones add on CN— resulting in the fromation of
an anion where the negative charge resides on oxygen. However if a nucleophile adds on
to an alkene the negat ive charge re side s on carbon. Since carbon is much le ss strongly
electron attracting than oxygen, this species is less stable and hence not readily formed.
O–
C
CN
(b) In alkenes the double bond joins two carbon atoms and there is no resultant polarity.
In carbonyl compounds, the carbonyl group is highly polar and the high partial positive
charge on the C atom makes it subsceptible to nucleophilic at tack.
O
O
O OEt
Q-18 (i) ; (ii)
O
Q-19 (a) H3C OH ; (b) O

H3C O
H3C H3C C2H5
O
HC
O OH O
Q-20 HC  C —Na + ; H3C—C  CH ; H3C ; H3C + CHI3
CH3 CH3 ONa
H3C H3C CH3

Q-21 (i) 3 O 
 dryHCl
CHCOCH phorone.
H3C H3C CH3
(ii) CH 3 COCl + H 2 

Pd / BaSO
quinoline
 CH 3 CHO + HCl
4
H3C
CO 
NH 2 NH 2
(iii) C 2 H 5 ONa CH 3 CH 2 CH 3
H3C
O O
Q-22 If X is Ph—CH 2 MgX, then P is CH3 – C – CH3 and if Y is CH 3–MgX, then Q is Ph
CH3
Q-23 (a) 2-methyl-1, 3-cyclohexanedione is more acidic because its enolate ion is stabilized by
an additional resanance structure.
O O O O
CH3 CH3 CH3 CH3
– H
H 

O O O O
Resonance stabilized conjugate base.

(b) In the case of the acid the double bond is activated due to the presence of a –COOH group



       
    


     
    
1
Q-24 (a) CH 3 MgI, H 3 O + , H + /K 2 Cr 2 O 7 , PhCHO/ OH , 
(b) A = C 6 H 5 CHO ; B = PhCH(OH)COPh ;
C = C 6 H 5 CH=CH—COOH ; D = C 6 H 5 CHBr—CHBr—COOH
No reaction
Q-25 (B) Q-26 (A) Q-27 (A) Q-28 (A)

Q-29 C 6 H 5 CH = CHCOOC 2 H 5
CHEMISTRY [53]
C6H5
Q-30 A = C 6H 5CHO, base B=
O
H5C6 – C – CH3 H5C6 – C – CH3
Q-31 A = CH3 ; B= ; C=
N – OH OH – N
H3C– C – NH H5C6– C – NH
D = ; E = ; F = H 5 C 6 – NH 2
O C6H5 CH3
O
O
G = H5C6
OH
CH3 O
O
H
Q-32 A = ; B= ; C = H3C
O
COCH3 CH3
D = ; E = Br
CH3 CH3 CH3

Q-33 A = H3C B = H3C C = H3C
D = H 3 C – CHO E = CHO
CHO
Q-34 (C) Q-35 (B) Q-36 (D) Q-37 (A) Q-38 (C) Q-39 (A, B, C, D)
LECTURE - VI
THE BECKMANN REARRANGENMENT [b] SeO 2 (Selenium Oxide) :
The acid catalysed transformation of a ketoxime to Ketones or aldehydes on oxidation with SeO 2 gives
an N-substituted amide is known as the Beckmann dicarbonyl compounds.
rearrangement. This reaction is possible only in compounds containing
–carbon.
HCHO doesn't show this reaction.

CH3CHO + SeO2 

 CH CHO + SeO H C C H + Se + H2O
O O

Glyoxal

CH3 C CH3 + SeO2 

 O
 CH3 C C H + Se + H2O
O O
Methyl glyoxal (Pyruvaldehyde)
[c] Baeyer's Villiger Oxidation :

Both aldehyde and ketones are oxidized by peroxy
The rearrangement is catalysed by a variety of acids. T his reaction, called the Bae yer-villiger
acidic reagents such as H 3 PO 2 , H 2 SO 4 , SOCl 2 , oxidation, is especially useful with Ketones, because
it converts them to carboxylic esters.
PCl 5 , etc.
For Example, treating acetophenone with a peroxy
OXIDATION REACTIONS acid converts it to the ester phenyl acetate.
[a] By K2Cr 2O 7/H 2SO 4 :
On oxidation with K 2 Cr 2 O 7/H 2SO 4 1° alc. gives
aldehyde, which on further oxidation gives acid
with same C-atom. While, 2 0 alcohol on oxidation
3
gives ketone which on further oxidation gives
acid with less C-atom. Mechanism :
R—CH 2OH 
[O]
 R—CHO 
[O]
 R—COOH H

( alcohol)
:O: H—A :O
+
[O] C6H5 C6H5
CH3CH2CH2 CH CH3 
 H3C H3C
OH H O
:O
:

(2° alcohol) O H—A O O O
+ 
[O] H3C O R
CH3CHCH
2 2 C CH3   R O
5 H
O :OH C6H5 A
:
C H 3C H 2C O O H + C H 3C O O H

(i) 3° alcohol is not oxidised within 2 or 3 minutes. H O :O
:
H H—A
O :O
:
O
(ii) 1° and 2° alcohol converts orange colour of K2Cr2O 7 O O
R O
to green in 2-3 minutes. HC H3C R
C6H5
CHEMISTRY [55]
[b] Clemmensen Reduction :
H
OH :A

H O The reduction of carbonyl groups of aldehydes and
OH O O ketones to methylene groups with amalgamated zinc
O + 
H3C O O and concentrated hydrochloric acid is known as
R
R H3C
C6H5 C6H5 Clemmensen reduction.
COCH3
O Zn–Hg, HCl
Reflux
OC6H5 CH3
H3C
The product of this reaction show that a phenyl group The nature of product depends upon the reducing
has a greater tendency to migrate then a agent used. It can be summarized as.
methyl group. Had this not been the case, the (i) C O  CH2
product would have been C 6 H 5 COOCH 3 and
not CH 3COOC 6 H5. This tendency of a group to Reducing agents are
migrate is called is migratory aptitude. Studies  Red P/HI at 150°C
of the Baeyer-villiger oxidation and other reaction  Zn-Hg/HCl [Clemensen's reduction]
have shown that the migratory aptitude of  NH 2 —NH 2 /C 2 H 5 OH,OH [Wolff Kischner's
groups H > phenyl > 3° alkyl > 2° alkyl 1° alkyl reduction]
> methyl. In all cases, this order is for
groups migrating with their electron pairs, that (ii) C O  CHOH
is, as anions. Reducing agents are
Ex. CH3 C C2H5  ? Per acid  LiAlH 4 (Nicetron brown)
O  Na/C 2 H 5 OH (Bouvalt blank)
 NaH/Benzene (Darzen reaction)
Sol. CH3 C OC2H5
 [(CH 3 ) 2 CHO] 3 Al (Aluminium isopropoxide)
O
 (CH 3 ) 2 CHOH (Isopropyl alcohol)
CH3 Reduction with aluminium isopropoxide is excess
Ex. CH3 C C CH3 
Per acid
? of isopropanol is called MPV (Meerwein
Ponndroff Verley) reduction. Other reducible
CH3 O
groups are not attacked like
CH3
—NO 2 , —CH CH 2 , —C C—.
Sol. CH3 C O C CH3
Example :
CH3 O
CH3 CH3
C O 
 CHOH
REDUCTION CH2 CH CH2 CH
[a] The Wolf Kishner Reduction :
When a ketone or an aldehyde is heated in a REACTIONS GIVEN BY ONLY ALDEHYDES
basic solution of hydrazine, the carbonyl group [1] Polymerisation : It is a reversible process.
is converted to a methylene group this process Formaldehyde :
is called Deoxygenation because an oxygen is
removed from the reactant. The reaction is known (a) 




as the Wolf-kishner Reduction.
Formalin Paraformaldehyde
COCH3 (40% HCHO) n = 6–50
(i) NH2–NH2 Hydrated white crystal
(ii) OH/HOCH2–CH2OH
CH3 Paraformaldehyde is a linear polymer which show
reducing character with Tollen's reagent, Fehling
solution etc.
(b) 

 CH3 CH + NH2 

Poly oxy methylene (n > 100) O H
(c)  ammonia
Meta formaldehyde (Trioxane) 


Cyclic polymer (Trioxy methylene)
Cyclic polymer doesn't show reducingcharacter with

Tollen's reagent etc 3 C H 3— C H N H 
 
(d) 6HCHO  C6H12O 6
 
Formose sugar
A linear polymer (  -acrose)
.
Acetaldehyde :
(a) 3CH3CHO  (CH3CHO) 3
 Reducing Character :
Aldehydes are easily oxidised so they are strong
reducing agents.
(a) Tollen's Reagent :
It oxidises aldehydes. Tollen's reagent is ammonical
silver nitrate solution
(AgNO 3 +NH 4 OH)   [Ag(NH 3 ) 2 ]OH
RCHO+[Ag(NH 3 ) 2 ]OH 
RCOOH + Ag + H 2 O
(b) 4CH3CHO 

 (CH 3CHO) 4 Silver mirror
AgNO 3 + NH 4 OH  AgOH  Ag 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
 Reaction with Ammonia : tartrate + NaOH)
Except formaldehyde, all other aldehydes give addition Fehling solution A + Fehlings solution B(Dark
reactions (HCHO give addition elimination i.e. blue colour of cupric tartrate)
condensation reaction)
RCHO + Cu +2 + OH –
6CH 2O + 4NH3  (CH 2) 6N4 + 6H2O  RCOOH+Cu 2 O
Urotropine (Hexamine) (Cuprous oxide–Red ppt.)
White crystalline solid C u 2+  Cu +
Used in preparation of explosive (Cupric - Blue) (Cuprous - Red ppt.)
Used in treatment of urine infection diseases
CHEMISTRY [57]
(c) Benedict's Solution : (e) Reaction With Schiff's Reagent :
It is a mixture of CuSO 4 + sodium citrate + Na2CO 3 . Schiff's reagent is dil solution of p-roseniline hydrochloride
It provides Cu +2 . or magenta dye.
It is reduced by aldehyde to give red ppt of cuprous Its pink colour is discharged by passing SO 2 gas and
oxide. the colourless solution is called schiff's reagent, Aldehyde
RCHO + Cu 2+ + OH – reacts with this reagent to restore the pink colour.
 RCOOH + Cu 2 O
(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)
ABHYAAS - VI
LEVEL - 0
Q.1 One mole of an organic compound requires Q.9 The conversion

0.5 mole of oxygen to produce an acid. CH 3 CHO ––– OHC –– CHO can be
The compound may be- effected by:
(A) Alcohol (B) Ether (A) CrO 3 (B) SeO 2
(C) Ketone (D) Aldehyde (C) Br 2 /NaOH (D) KMnO 4
Q.10 Match list I with list II and then select the
Q.2 Which is most difficult to oxidise-
correct answer from the codes given below
(A) HCHO (B) CH 3 CHO the lists:
(C) CH 3 COCH 3 (D) CH 3 CH 2 CHO List-I
Q.3 For the reaction RCH = O + 2[H]  RCH2OH (1) RCOR'  RCH 2 R'
the catalyst is-
(A) Ni only (B) Pd. only (2) 

(C) Pt. only (D) Any of the above
Q.4 Aldehydes and ketones can be reduced to (3)   Aluminium isopropoxide
corresponding hydrocarbons by-
 
(A) Refluxing with strong acids
(B) Passing the vapours over PbO 2
(C) Refluxing with zinc amalgam (4) RCHO + Al(OC 2 H 5 ) 3   Ester
(D) Refluxing with strong base List-II
Q.5 The conversion (a) Meerwein-Ponndorf Verley reduction.
CH3CH2CHO ––––– CH3CH2CH2OH (b) Clemmensen reduction
can not be affected by: (c) Tischenko reaction
(d) Wolff-Kishner reaction
(A) NaBH4 (B) Zn/HCl
Codes :
(C) He2/Ni (D) Na + alcohol
1 2 3 4
Q.6 Acetaldehyde oxidises: (A) b d c a
(A) Fehling's solution. (B) d b a c
(B) Ammoniacal AgNO3 solution (C) b d a c
(C) NaOI. (D) a c b d
(D) None of these Q.11 Match List I with list II and then select the
Q.7 Acetaldehyde on warming with fehling solution correct answer from the codes given below
the lists:
gives a red precipitate of:
List-I List-II
(A) Elemental copper
(1) C 6 H 5 CHO (a) Mesitylene
(B) Cuprous oxide
(2) CH 3 COCHO (b) Paraldehyde
(C) Cupric oxide
(3) CH 3 COCH 3 (c) Iodoform reaction
(D) Mixture of all of the above.
(4) CH 3 CHO (d) Cannizzaro reaction
Q.8 Fehling solution is made by mixing two separate
Codes :
solutions. One of which is a solution of copper
1 2 3 4
sulphate only while the other contains:
(A) d c b a
(B) d b c a
(A) NaHCO3 (B) Na2CO 3 (C) a c b d
(C) KNaC4H4O6 (D) KHCO3 (D) d c a b
CHEMISTRY [59]
Q.12 Conversion of acetone into 2,3-dimethylbutane- (A) Mesityl oxide (B) Phoron
2, 3-diol can be achieved by: (A) Zn/Hg/HCl (C) Mesitylene (D) Aldol
(B) Wolff-Kishner reduction
Q.20 Acetaldehyde on treatment with a few drops of
(C) Mg/Hg/H2O concentrated H2SO4 gives
(D) The conversion is not possible. (A) CH3CHOHCH2CHO
Q.13 Both Fehling's solution and Benedict's solution (B) CH3CH = CHCHO
give th is compound when treated w ith
acetaldehyde:
(A) CuO (B) Cu2O (C)
(C) Cu(OH)2 (D) Cu(CO)4

Q.14 If acetaldehyde is treated with Benedict or Fehling
solution, the following change occurs in the
system: (D)
(A) Ag+  Agº (B) Cu+2  Cuº

(C) Cu+2  Cu+ (D) Na+  Naº
Q.21 The most appropriate reagent for the conversion of
Q.15 CH 3 CH=CH-CHO may be reduced to
2-pentanone into butanoic acid is (A) Chromic acid
CH 3 CH=CHCH 2 OH using:
(A) H 2 /Pt
(B) Acidified KMnO4
(B) NaBH 4
(C) Alkaline KMnO4
(C) [(CH 3 ) 2 CHO] 3 Al
(D) Sodium hypochlorite
(D) Zn-Hg/HCl
Q.22 Consider the following sequence of reactions.
Q.16 The compounds A, B and C in the reaction
CH 3 COCH 3 
 A 
 B
sequence  A 

B 

 C
are given by the set – 

 C. The final product (C) is
(A) Iodoform, ethylene, ethyl alcohol (A) (CH 3 ) 2 C(OH)CH 2 COCH 3
(B) Iodoform, acetylene, acetaldehyde (B) (CH3 ) 2 C = CHCOCH3
(C) Iodoform, propyne, acetone. (C) (CH 3 ) 2 CHCH 2 CHOHCH 3
(D) Iodoform, 2-propanol, propanone. (D) (CH3) 2 C = CHCHOHCH 3
Q.17 An organic compound reduce s Tollens Q.23 The reaction of C 6 H 5 CH = CHCHO with
reagent and Fehling's solution. It can be – NaBH4 gives
(A) CH 3 CH 2 CHO
(A) C 6 H 5 CH 2 CH 2 CH 2 OH
(B) C 6 H 5 CHO
(B) C 6 H 5 CH = CHCH 2 OH
(C) CH 3 COCH 2 CH 3
(C) C 6 H 5 CH 2 CH 2 CHO
(D) (CH 3 ) 3 CCOCH 3
(D) C 6 H 5 CH 2 CHOHCH 3
Q.18 Acetaldehyde, on being heated with conc.
H2 SO 4 at 273 K, gives:
(A) Acetic acid (B) Paraldehyde
(C) Metaldehyde (D) None of these
Q.19 On being treated with HCl, acetone gives:
Q.25 Which one of the following is reduced with zinc and
hydrochloric acid to give the corre sponding
 
Q.24 B    A, hydrocarbon ?
(A) Ethyl acetate
(B) Acetic acid
(C) Acetamide
B and C are: (D) Butan-2-one
(A) in all cases
(B) in all cases
(C) in all cases
(D) A: , B: ,C:
LEVEL - I
Q.1 Which of the following alkoxides is used to oxidize PdBaSO4
Q.5 C6H5COCl   Intermediate
e
secondary alcohols to corresponding ketones : H 2
Ca  Salt
(A) Aluminium isopropoxide Oxidation
  Intermediate 
Dry Distillation
 A
(B) Aluminium ethoxide Compound (A) in above reaction sequence is

(C) Aluminium t–butoxide
(D) Sodium ethoxide (A) Benzophenone (B) Benzaldehyde
Q .2 The compounds A, B and C in the reaction (C) Acetophenone (D) Benzoquinone
A B,Pd / H2
sequence RCOOH   RCOCl  
C Pd / BaSO4 (i) SnCl2 / HCl
Q .6 A  H2
  - CHO 
(ii)H2O
B
are given by the set :
(A) Cl 2 , BaSO 4 , RCHO A and B respectively are –
(B) HCl, BaSO 4 , RCOR (A) Benzoyl chloride, benzonitrile
(C) PCl 5 , BaSO 4 , RCHO (B) Benzyl chloride, benzylnitrile
(D) PCl 3 , BaSO 4 , CH 3 CHO (C) Benzal chloride, benzonitrile
Q .3 Acetone is oxidised by selenium dioxide at (D) Benzotrichloride, benzonitrile
room temperature to form : Q .7 Ethyl alcohol an oxidation with K2Cr 2O7 gives:
(A) CH3 COOH and CO 2 (B) Glyoxal
(C) Methylglyoxal (D) Dimethylglyoxal (A) Acetic Acid (B) Acetaldehyde
(C) Formaldehyde (D) Formic acid
Q .4 The compounds A, B and C in the reaction
PCl5 Pd / BaSO4 Conc. H2SO4
CH3 Ag
Q .8 A   B   C 
0ºC
 D in
I2
sequence CO  A 

B
Alkali
CH3 the above reaction A, B, C & D are:
H2SO4 (A) CH 3 COOH, CH 3 COCl, CH 3 CHO,
2
 C are given by the set :
Hg Metaldehyde
(A) Iodoform, ethylene, ethyl alcohol (B) CH 3 COOH, CH 3 COCl, CH 3 CHO,
(B) Iodoform, acetylene, acetaldehyde Paraldehyde
(C) Iodoform, propyne, acetone (C) CH 3 COOH, CH 3 COCl, CH 3 –CH 2 OH,
(D) Iodoform, 2–propanol, propanone Paraldehyde
(D) None of these
CHEMISTRY [61]
Q.9 Formaldehyde on reaction with PCl5 gives : Q.16 Which of the following compounds is formed on
(A) Methyl chloride heating acetone with a weak alkali like baryta
(B) Methylene chloride water :
(C) Chloroformaldehyde (A) Phorone
(B) 3-Methyl-2-penten-2-one
(D) None of these
(C) Mesitylene
Q.10 Compound (A) C 5 H 10 O forms a phenyl
(D) Mesityl oxide
hydrazone and give s negative Tollen’s and
Q.17 Tetramethylethylene glycol is obtained on the
iodoform tests. Compound (A) on reduction
reductio n of which of the foll owing
gives n–pentane. Compound (A) is : compounds by Hg/Mg in benzene
(A) A primary alcohol (B) An aldehyde (A) Butanone (B) Ethanal
(C) A ketone (D) A secondary alcohol (C) Propanal (D) Propanone
Q .1 1 T he ox idat io n o f RCH 2 COCH 3 w it h acidic Q .1 8 [(CH 3) 2 C=CH] 2 C = O is :
potassium dichromate produces : (A) Ketone
(B) Trimer of acetone
(A) A mixture of RCOOH and CH 3 COOH
(C) Unsaturated aldehyde
(B) A mixture of RCH 2COOH and HCOOH
(D) Dimer of acetone
(C) CH 3 COOH only Q .1 9 HCHO and C 6 H 5 CHO can be distinguished
(D) RCOOH only by :
Q .1 2 Which of the following compounds will give (A) Fehling solution (B) Tollen’s reagent
a mixed ketone on oxidation : (C) KMnO 4 (D) All of these
(A) (CH 3 ) 3 COH
Q .2 0 Choose the wrong statement :
(B) CH 3 CH 2 CH 2 OH
(A) Smell of benzaldehyde and mirbane oil is
(C) CH 3 CH 2 CH(OH)CH 3 not different
(D) (CH 3 ) 2 CHCH 2 OH ( B) B enz ald ehy de un dergo e s Tis chenko
Q .1 3 Magenta is : reaction
(A) Alkaline phenolphthalein (C) Benzaldehyde reduces Fehling’s solution
(B) Red litums (D) Dry distillation of calcium benzoate gives
a ketonic compound
(C) p-rosaniline hydrochloride
Q.21 Oxidation of toluene with CrO3 in the presence
(D) Methyl red of (CH 3 CO) 2 O gives a product ‘A’ which on
Q .1 4 Which of the following reactions may be used treatment with aqueous NaOH produces :
for o b taining an unsatu rated ald ehyd e (A) C 6 H 5 CHO (B) (C 6 H5 CO) 2 O
containing mo re car bo n ato ms than the (C) C 6 H 5 COONa (D) 2,4–diacetyl toluene
parent alkanal : Q.22 The suitable reagent for the reduction of
(A) Aldol condensation ketones to hydrocarbons is :
(A) Zn–Hg/HCl (B) HI
(B) Polymerisation
(C) Red P (D) H 2 SO 4
(C) Tischenko reaction
Q.23 Which of the following regents distinguishes
between aldehyde and ketone :
Q .1 5 Which of the following is formed on heating
(A) Fehling soluion (B) H 2SO 4 solution
the representative member of alkanoic acid
(C) NaHSO 3 (D) NH 3
family with manganous oxide at 300º :
Q.24 Acetone is easily oxidized with :
(A) Acetaldehyde
(A) Tollen’s reagent
(B) Ethyl acetate
(B) Fehling solution
(C) Acetone (C) Acidic dichromate solution
(D) Manganous acetate (D) Benedict’s solution
Q.25 Which one of the following reactions is a Q.31 the oxidation of toluene to benzaldehyde by chromyl
method for the conversion of a ketone into a chloride is called :
hydrocarbon ? (A) Cannizzaro reaction
(A) Aldol condensation (B) Wurtz reaction
(B) Reimer–Tiemann reaction (C) Etard reaction
(C) Cannizzaro reaction (D) Reimer–Tiemann reaction
(D) Wolff–Kishner reduction Q.32 Clemensen’s reduction of ketones is carried out in
Q.26 Which of the following does not give brick red :
precipitate with Fehling solution : (A) H2 with Pd catalyst
(A) Acetone (B) Acetladehyde (B) Glycol with KOH
(C) Formalin (D) D–glucose (C) LiAlH4 in water
Q.27 Acetaldehyde and acetone can be distinguished (D) Zn–Hg with HCl
by : Q.33 Reduction of > C = O to CH2 can be carried out
with :
(A) Molisch test (B) Bromoform test
(A) Catalytic reduction
(C) Solubility in water (D) Tollen’s test
(B) Na/C 2 H 5 OH
Q.28 Acetaldehyde cannot show :
(C) Wolf–Kischner reduction
(A) Iodoform test (B) Lucas test
(D) LiAlH 4
(C) Benedict’s test (D) Tollen’s test
Q.34 Formaldehyde reacts with ammonia to give
Q.29 Ketones [R– C –R 1 ] where R = R 1 = alkyl urotropine. The formula of urotropine is :
||
O (A) (CH 2 ) 6 N 4 (B) (CH 2 ) 4 N 3
(C) (CH 2 ) 6 N 6 (D) (CH 2 ) 3 N 3
group.
Q.35 Reduction of aldehydes and ketones to
It can be obtained in one step by :
hydrocarbon take place in the presence of :
(A) Hydrolysis of esters
(A) Zn amalgam and HCl acid
(B) Oxidation of primary alcohol (B) Pd/BaSO 4
(C) Oxidation of secondary alcohol (C) Anhydrous AlCl 3
(D) Reaction of acid halide with alcohols (D) Ni/Pt
Q.30 C2H5CHO and (CH3) 2CO can be distinugished Q.36 Which one of the following is reduced with
by testing with : zinc and hydrochloric acid to give the
corresponding hydrocarbon?
(A) Phenyl hydrazine (B) Hydroxylamine
(A) Butan-2-one (B) Acetic acid
(C) Fehling solution (D) Sodium bisulphite
(C) Acetamide (D) Ethyl acetate
CHEMISTRY [63]
LEVEL - II
Select the Correct Alternative (Only One Correct Q.5 Which of the following reaction leads to the formation
Answer) of secondary alcohol ?
Q.1 In the reaction sequence O
RCOCl + 
H 2 
 A 
B (A) C6H5 C CH3 
 
 O
 C
(B) C6H5 C CH3 
A,B and C are given by the set :
(A) RCHO, RCH(OH)CN, RCH(OH)CH 2 NH 2 (C) 
 
(B) RCHO, RCH(OH)CN, RCH(OH)COOH
(C) RCHO, O

(D) CH3 C CH3 
     
Select the Correct Alternatives (One or More Then
(D) RCHO, R–CH 2 –CN, R–CH 2 –COOH Q.6 Which of the following compound on treatment
Q.2 Oxidation of 2-methyl propane–1,2–diol with with LiAlH 4 will give a product that will give
periodic acid gives :- positive iodoform test?
(A) CH 3 CH 2 CHO
(A) Propionic acid and formaldehyde
(B) CH 3 CH 2 CO 2 CH 3
(B) Acetone and formaldehyde
(C) CH 3 CH 2 OCH 2 CH 3
(C) Acetone and acetic acid
(D) CH 3 COCH 3
(D) Acetone and propionic acid Q.7 Which of the following compounds undergo
Q.3 A carbonyl compound gives a positive iodoform periodic oxidation
test but does not reduce Tollen's reagent or
O
Fehling's solution. It forms a cyanohydrin with
O OCH3 O
HCN, which on hydrolysis gives a hydroxy acid
with a methyl side chain. The compound is :- (A) (B)
OH HO
(A) Acetaldehyde OH OH
(B) Propionaldehyde
OCH3
(C) Acetone CH–CH–CH3
(C) (D)
(D) Crotonaldehyde OH OH
OCH3
Q.4 The major organic product formed from the
following reaction is :– Q.8 In the reaction sequence, [X] is ketone:



[X]     
(A)
[X] will be :-
O O
(B) CH3
(A) (B)
(C) O O
CH3 H3C CH3
(C) (D)
(D)
Q.9 In the given reaction : Q.12 An organic compound with the molecular formula
C3H6O does not respond positively to the silver
; mirror test with Tollens reagent but produces an
oxime. The compound is
(A) CH2= CHCH2OH
(B) CH 3 CH 2 CHO
(C) CH 2 = CHOCH 3
(A) and (B) are :
(D) CH 3 COCH 3
(A) H2C Q.13 2- Methylcyclohexanone is allowed to react with
OH and
metachloroperoxobenzoic acid. The major
product formed in the reaction is
(B) H3C OH and O
O
CHO
O
(C) H2C and (A) (B)
CH3
(D) H3C OH and C O
H3C O
O O
Q.10 When m-Chlorobenzaldehyde is treated with (C) (D)
50% KOH solution, the products obtained is CH3
(are)
COO– Q.14 Urotropine is formed by the action of
(A) .................. with ...................
Q.15 The conversion of acid chlorides into aldehydes
Cl
CH2OH by reduction is termed ..................
(B) Q.16 Aldehyde show reducing properties due to their
ready conversion into ..................
Cl
OH OH Q.17 Two separate solut ions, Fehling's solut ion
CH – CH A(.........) and Fehling's solution B(NaOH
(C) +..........) are at first mixed up together and is
then heated with the aldehyde. A ..................
Cl Cl
OH OH precipitate is formed.
CH – CH Q.18 Tollen's reagent gives .................. with acetaldehyde.
(D)
OH OH Match the Column :-

O Q.19 Match the compounds/ions in Column I with
O
their properties/reactions is Column. II
O
Q.11 The conversion : can be Column -I Column -II
(A) C 6 H 5 CHO (p) gives precipitate with
effected by using the reagent 2,4dinitrophenylhydrazine
(A) H2O, H2SO4 (B) O2 (B) CH3C  CH (q) give preciptitate with
AgNO 3
(C) CN– (r) is a nucleophile
(C)  (D) CrO3, H2SO4 (D) I– (s) is involved in
cyanohydrin formation
CHEMISTRY [65]
Subjective Exercise : Q.27 Under Wolff Kishner reduction conditions, the
Q.20 Identify (A) and (B) in the given sequence of reaction conversion which may be through about is -
– (A) Benzaldehyde into Benzyl alcohol
PhCH2CHO 
SeO
 (A) 
( i )con.OH
2
(ii )H 
 (B)
(B) Cyclohexanol into Cyclohexane
(C) Cyclohexanol into Cyclohexanol
Q.21 (a) Distinguish bet ween PhCOEt and (D) Benzophenone into Diphenylmethane
p-MeC 6 H 4 COMe by a chemical method. Q.28 In the reaction, P is,
(b) Arrage the following in the order of increasing CH3 SeO2
CO P + Se + HO
reactivity towards nucleophilic addition CH3
2
reactions.
(A) CH 3 COCHO (B) CH 3 COOCH 3
(i) CH 3 CHO, C 6 H 5 COC 6 H 5 , (C) CH 3 COCH 2 OH (D) None
CH 3 COC 6 H 5 ,CH 3 COCH 3
(ii) CH 3 CHO, CF 3 CHO, CH 2 = CHCHO Q.29 The appropriate reagent for the following
transformation -
Q.22 Compound X with molecular formula C9H10 O
O
form a semicarbazone and give negative Tollen's CH2CH3
and Iodoform tests. Upon reduction it gives CH3 
n-propyl benzene. Deduce the structure of X. OH
OH
(A) Zn (Hg), HCl (B) NH 2 NH 2 ,OH –
Q.23 Two organic compounds (A) and (B) have same (C) H2 /Ni (D) NaBH4
empirical formula CH2O. Vapour density of (B)
is twice the vapour density of (A). (A) reduces
Fehling solution but does not react with Q.30 
NaHCO 3 . Compound (B) neither reacts with
NaHCO3 nor reduces Fehling solution. What are
(A) and (B) ? Also report an isomer of (B) if it Product formed by P & Q can be differentietod
reacts with NaHCO 3 . by :
(A) 2, 4-DNP
Q.24 A compound C5H10O does not reduce Fehling's
solution, form a phenyl hydrazone, shows the (B) Lucas reagent (ZnCl2+ conc. HCl)
haloform reaction, and can be converted into (C) NaHSO 3
n-pentane by Zn—Hg and conc. HCl. What is (D) Fehlings solution
this comopound ? Q.31 Which of the reagent is used to convert
Q.25 Complete the following reactions : 2–Butanone into propanoic acid -
O (A) NaOH, I2/H (B) Tollen's reagent
 (C) Fehling solution (D) NaOH, NaI/H
+ H3C—CCNa  
NH 3
(i) Low Temp.
O
H O C
 (A) 
dil H SO
(B)  
(– H O )

3 2
Hg 2 
4 2
Q.32 O
( i ) OsO / H O,OH 1
(C) 
4 2
( ii ) HIO
 (D) The above reagent can be synthesise from the
4
following compounds in alkaline medium
Write the structure s of A to D and give the following by acidification -
IUPAC name of (D).
/ Q.26 Hydrogenation of benzoyl chloride in the CHO COOH
(A) (B)
presence of Pd on BaSO4 gives CHO CHO
(A) Benzyl alcohol (B) Benzaldehyde

COOCH3 COOCH3
(C) Benzoic acid (D) Phenol (C) (D)
CH3 COOH
Q.33 An unknown compound of carbon, hydrogen and Paragraph for Questions Nos. 55 to 56
oxygen contains 69.77%C and 11.63% H, and has An acyclic hydrocarbon P, having molecular formula
a molecular weight of 86. It does not reduce Fehling C6H10, gave acetone as the only organic product
solution but forms a bisulphate addition compound through the following sequence of reactions, in the
and gives a positive iodiform test. What are the which Q is an intermediate organic compound.
possible structures ? (i) dil H2SO4/HgSO4

P Q
Q.34 Iodoform is obtained by the reaction of acetone with (C6H10) (ii) NaBH4/ethanol
(iii) dil.acid
hypoiodite but not with iodide. Why ?
(i) conc.H2SO4
(Catalytic amount) O
Q.35 An organic compound 'A' on treatment with ethyl (–H2O)
P Q 2 C
alcohol gives a carboxylic acid 'B' and compound 'C'. (ii) O3 H3C CH3
Hydrolysis of 'C' under acidic conditions gives 'B' and (iii) Zn/H2O
'D'. Oxidation of 'D' with KMnO4 also gives 'B'. 'B'
on heating with Ca(OH)2 gives 'E' (C3H6O). E does Q.38 The structure of compound P is -
not give Tollen's test and does not reduce Fehling's
(A) CH 3CH 2 CH 2CH 2–CC–H
solution but form a 2,4-dinitrophenyl hydrazone.
(B) H 3CH 2CC–CH 2CH 3
Identify (A), (B), (C), (D) and (E).
H3C
Q.36 Statement-1 : Glucose gives a reddish-brown (C) H–C–CC–CH3
precipitate with Fehling’s solution. H3C
because
Statement-2 : Reaction of glucose with H 3C
Fehling’s solution gives CuO and gluconic acid. (D) H3C–C–CC–H
H 3C
(A) Statement-1 is True, Statement-2 is True;
Statement-2 is a correct explanation for Q.39 The structure of the compound Q is -
Statement-1. H3C OH
(B) Statement-1 is True, Statement-2 is True; (A) H–C–C–CH2CH3
Statement-2 is NOT a correct explanation for H3C H
Statement-1.
(C) Statement-1 is True, Statement-2 is False. H3C OH
(D) Statement-1 is False, Statement-2 is True. (B) H3C–C–C–CH3
Q.37 Match the compounds/ion in column I with their H3C H
properties/ reaction in Column II. Indicate your
answer by darkening the appropriate bubbles H3C OH
of the matrix given in the ORS. (C) H–C–CH2CHCH3
Column -I Column -II H3C
(A) C 6 H 5 CHO (p) gives precipitate with OH

2,4dinitrophenylhydrazine (D) CH3CH2CH2CHCH2CH3
(B) CH3C  CH (q) give preciptitate with
AgNO 3
(C) CN– (r) is a nucleophile
(D) I– (s) is involved in
cyanohydrin formation
CHEMISTRY [67]
ANSWERS
LEVEL - 0
LEVEL - I
LEVEL - II
Match the Column :-

   
 C

H5C6 C.CH2.CH3
O
O
CH3 – C – R
O O CH3
Hence this ketone is H3C CH3 or
H3C CH3
O
OH OH CH3 O
CH CH3
CH3 OHC
O
6,7-dioxooctanal
O
. . . . . . .
.
Element % Relative no. of atoms Simplest ratio
O
H3C
CH3.CH2.CH2.C.CH3 H3C CH3
O H3C O
Pentan-2-one 3-methylbutan-2-one
.
1 1

OI
 
OH

O O
H3C O H3C O
. O H3C O H3C
H3C OH CH3
H5C2
O
.
. Match the Column :-    
. .
CHEMISTRY [69]
LECTURE - VII
THE BECKMANN REARRANGENMENT
CH3 CH3
 Reaction of Only Ketones :
CH3 C CH COCH3+ O C CH3 
(1) Reduction : Acetone is reduced by magnesium
amalgam and water to give pinacol.
CH3 O CH3
–H2O
CH3 CH3 COCH + O C CH3  CH3 C CH C CH C CH3
C O+ O C 
CH3 CH3 (Phorone) or 2,6–Dimethyl–2,5–
hepta diene–4–one
CH3 CH3
CH3 Mg Hg
C  CH3 C C CH3 (b) In presence of conc.H 2 SO 4
water
CH3
OH OH CH3
O
Pinacol Conc. H2SO4 Mesitylene
3CH3 C CH3 
condensation
(2) Reaction with Chloroform : Polymerisation H3C CH3
CH3 CH3 OH
C O + CHCl3  C Fe
CH3 CCl3 3CH3 C CH
CH3 Addition Polymerisation
(Chloretone)
(6) Reaction with Ammonia :
OH
OH
aq.NaOH
 CH3 *CH COOH CH3 O
CCl3
(Chloretone) (Lactic acid) CH3 C O + HCH2C CH3
2-Hydroxy propanoic acid HNH2
(3) Reaction with HNO 2 :
O CH3 O
O
–H2O
CH3  CH3 C CH2 C CH3
CH3 C CH3 + O N OH
O HNH NH2
–H2O
N OH  CH3 C CH N OH Diacetone amine
Oximino acetone
(7) Pyrolysis :
(4) Oxidation Reaction : According to popoff's rule
C O group stays with smaller alkyl group. CH2 C O  CH2

C O + CH4
O
H CH3 Ketene
CH3 CH2 C CH3 Acetone
 CH 3 COOH + CH 3 COOH

(5) Condensation Reaction :  HCHO   CO  H 2 

 pyrolysis 
 
(a) In presence of dry HCl - aldol condensation CH 3 CHO  CH 4  CO 

takes place
CH3 O
–H2O
CH3 C O + CH3 C CH3 
O CH3 O
C  CH3 C CH C CH3
Mesityl oxide
TEST FOR HCHO, CH 3 CHO, CH 3 COCH 3
S.No. Test HCHO CH 3CHO CH 3COCH 3
     
  
   
 
  Blue




BENZALDEHYDE (C 6 H 5 CHO)
Oil of bitter almonds
General Method of Preparation :

CHEMISTRY [71]
Chemical properties :
N Z C
 2
Ar

ABHYAAS - VII
LEVEL - 0
  



CHEMISTRY [73]
Statement Based Question
Statement-I :
I
Statement II :
LEVEL - I
CH3
|
O—CH
CH3–CH O
O CH3–CH
CH—O
|
CH3
CH2
O O
H2C CH2
O
CH3
|
CH
O O
CH3–CH CH–CH3
O
CH2
O CH2
H2C O
CH2
List I List II
Codes :
A B C D
CHEMISTRY [75]
O2 NH
  
3
Heat
 
CHEMISTRY [77]
LEVEL - II
CH3–CH2–CH2–Cl (i) O2/

P Q
AlCl3 (ii) HO 
3
O
CH3–CH2–C–H
O
CH3–C–CH3
O
CH3–C–CH3
O
CH3–CH2–C–H
ANSWERS
LEVEL - 0
LEVEL - I
LEVEL - II
CHEMISTRY [79]

Aldehyde & Ketone-All Lectures

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CHEMISTRY [1]

(Acetone or Dimethyl ketone) (Ethyl methyl ketone)  (Aldehyde)

        Aldehydes are quite susceptible to further oxidation

[4] By Oxidation of Diols :-

RCH 2 OH + [O]  RCHO + H 2 O [5] By Ozonolysis of Alkenes :-

RCOOH + HCOOH 

Ex.Arrange the following for reactivity in decreasing

(iii) (iv) CH 3 CH 2 CHO

(III) (i) (ii) 

(iii) (iv) CCl 3 CHO

[3] Reaction with Ammonia Derivatives :

Addition - elimination (Condensation)

 Ammonia Derivatives (NH 2Z) :

Z = NH NO2  NH2 NH NO2

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

(neutral) Cyclic acetal/ketal Cl O Cl HO

(B) Reduction of alkyl isocyanide with sodium Q.10 In the reaction

(A) a = CH 3 CO 2 H, b = (CH 3 CO) 2 O (C) Diethyl ketone (D) Acetaldehyde

Q.14 Necleophilic addition reaction will be most

(B)    Q.22 The possible number of stereoisomers that may

(C) d < c < b < a (D) d < a < c < b

o zo nolysis o f which of t he follo wing sequence of reactions A and B are :

(C) Metamerism an asymmetric centre is generated. The acid

(D) CH The product (A) is :

Q .4 In which of the following reactions aldehydes O

CH3 Q.12 Hydrazone of an aldehyde when heated with

(D) All are equally reactive

Fill in the Blanks :

of aldehydes or kentones with 

(c) Proton Exchange

The wittig reagent, alkylidenetriphenylphosphorane 

  HCHO + C 6 H 5 CHO 

 CH 3 —COOCH 2 CH 3 (Ethyl acetate)

O O CHO   Ph–CH 2 OH + PhCO 2 ¯ the

(A) C 6 H 5 CHO (B) CH 3 CH 2 CH 2 CHO

Fill in the Blanks :

CH3 CH 3CHO + C6H5CHO 

( – Unsaturated Ketone)

 (B) CH 3 COCH 3 ,   , CHI 3

(C)    (D) All above

Q.4 A carbonyl compound gives a positive

Q.5 Which of the following statements is wrong:

(C) (D) (D) 2,3-hexandione

Q .3 Chlorine reacts with acetaldehyde in the (A) CH 3 CHO (B) CH 3 CH 2 CHO

+ CO 2  (C) 10 sigma bonds, 1 pi bond and 1 lone pairs

Match the Column :-

Q.15 (A) : ; (B) : ; (C) :

Q.24 KCN + H2SO4  KHSO4 + HCN

O + HCN  

Q.26 CH 3 CH 2 C  CH  CH 3 CH 2 C  CNa   CH 3 CH 2 C  C—CH 3

 Intramolecular Claisen Condensation :

catalytic influence of cyanide ions to give benzoin

Q.1 C6H5CHO 

(A) CH3COOC2H5 (B) CH3COCl (B) C6H5CHO/H2N–NH2

[A] is : (B) Thionyl chloride

Q-1 In the reaction CH 2 Br + Mg 3-methylcyclohexanone ?

Comprehension # 2 Subjective Exercise :

(iv) (D) 

Q-22 Two different Grignard reagents, (X) and (Y) produce

(C) Me and SOCl2