Aldehydes & Ketones
Aldehydes & Ketones
Aldehydes & Ketones
1.
Introduction
Aldehydes & ketones have general formula CnH2nO and contains >C = O group. Thus aldehydes (RCHO)
and ketones (RCOR) are collectively called as carbonyl compounds. Aldehyde is always at terminal
position while ketone is never at terminal position.
2.
R
120
R
C
..
C=O
..
major
120
R
+
..C O:
..
minor
This polarity confirms that there is nucleophilic addition reaction takes place in carbonyl compound.
The double bond of the carbonyl group has a large dipole moment because oxygen is more electronegative
than carbon.
Carbonyl carbon act as an electrophile (Lewis acid)
Carbonyl oxygen act as a nucleophile (Lewis base)
3.
3.1
By oxidation of alcohols :
[ O]
Aldehydes
Primary alcohols
[ O]
Ketones
Secondary alcohols
3.2
By dehydrogenation of alcohols :
Dehydrogenation means removal of hydrogen and reagent used is heated copper.
Cu / 300 C
Aldehyde (RCH = O)
2 alcohol (R2CHOH)
Cu / 300 C
Ketone (R2C = O)
3 alcohol
3.3
1 alcohol (RCH2OH)
H2
H2
Cu / 300 C
Alkene
H2O
Ozonolysis of alkene :
It is used to get carbonyl compounds from alkene. The reaction is
Zn H2 O
Note : (i) During the cleavage of ozonide Zn is used to check further oxidation of aldehyde into acid.
(ii) By this method we can locate double bond in olefin or exact structrue of hydrocarbon can be determined
by knowing ozonolysis product i.e. by placing double bond at the place of two carbonyl oxygen atoms of two
carbonyl compounds.
(iii) Among the three molecules of carbonyl compounds.
(a) If one molecule contains two carbonyl groups, then hydrocarbon will be alkadiene.
(b) If all the three molecules contain two carbonyl group then hydrocarbon will be cycloalkatriene.
3.4
Wacker process :
Alkenes can directly be oxidised to corresponding aldehydes or ketones by treating them with a solution of
PdCl2 containing a catalytic amount of CuCl2 in presence of air or O2 . Except ethene any higher alkene will
give ketone.
CH2 = CH2 + H2O + PdCl2
CuCl 2
CH3 CH = O + Pd + 2HCl
air or O 2
CuCl 2
+ Pd + 2HCl
air or O 2
Note : During the reaction PdCl2 is reduced to Pd and CuCl2 is reduced to Cu(I)
3.5
Hydration of alkynes :
2O
CH CH H
CH3CHO
Ethyne
H2SO 4 / HgSO 4
Ethanal
R C CH 2
H2 O
3.6
Hydroboration of alkyne :
It is used to get aldehyde from terminal alkyne. Here reagent is (i) diborane (B2H6) (ii) H2O2,OH
(i) B H
2 6
R C C H
R CH2 CH O
(ii) H2 O 2 / OH
3.7
Ex.
(CH3COO)2Ca
+ CaCO3
+ CaCO3
calcium acetate
On dry distillation of calcium salt of acetic acid with calcium salt of formic acid we get a mixture of aldehyde,
ketone and formaldehyde.
3.8
On passing mixture of vapours of fatty acid with formic acid we get a mixture of aldehyde, ketone and
formaldehyde.
JEE(Main + Advanced) Carbonyl Compounds (Aldehydes & Ketones) # 107
3.9
Cl / hv
H O
4.
4.1
Rosenmund's reduction :
Here acid chlorides are reduced to aldehyde with H2 in boiling xylene using palladium as a catalyst supported
on barium sulphate.
PdBaSO 4
+ HCl
Boiling Xylene
Note : (a) Pd Catalyst is poisoned by BaSO4 to check further reduction of aldehyde to alcohol.
(b) Formaldehyde cannot be obtained by this method because HCOCl is unstable at common temperature.
(c) Reaction with acid chloride and dialkyl cadmium we can obtain ketone.
4.2
Stephen's reduction :
SnCl 2 / HCl
RCN
4.3
H2O
RCH = O + NH4Cl
Oxo-process :
It is also called as carbonylation here alkene reacts with water gas at high temperature and pressure in the
presence of cobalt carbonyl catalyst to give aldehyde.
CO H2 / , Pr essure
RCH=CH2 [Co
( CO ) ]
4 2
4.4
Reimer-Teimann Reaction :
By this method phenolic aldehyde is prepared
CHCl3 / KOH
4.5
(Aldehydes)
1. DIBAL H
RCN
RCH=O
2. H2O
4.6
From hydrocarbons :
By oxidation of methyl benzene and its derivative using chromyl chloride (CrO2Cl2)
CHO
CS2
+ CrO2Cl2
H3O
Benzaldehyde
4.7
By oxidation of methyl benzene and its derivative using chromic oxide (CrO3) in
acetic anhydride:
H3O
273 283 K
+ CrO3+(CH3CO)2O
4.8.
By Gatterman-Koch reaction :
Benzene or its derivative CO
,HCl
Benzaldehyde or substituted benzaldehyde
Anhy. AlCl3 / CuCl
CO
,HCl
4.9
By hydrogen cyanide :
Hydrogen cyanide on treating with Grignard reagent followed by double decomposition with water gives
aldehyde via aldimine.
H2O / H
H2O / H
5.
5.1
+ R'2 Cd
5.2
5.3
H2O / H
Note : It is -ketoacid which decarboxylate more readily as it proceeds via six membered cyclic transition-state.
CO
5.4
From nitriles :
Treatment of nitrile with Grignard reagent followed by hydrolysis gives a ketone.
H2O / H
ether
CH3 CH2 C N + C6H5MgBr
H2O / H
H3O
6.
Solubility of aldehydes and ketones decreases rapidly on increasing the length of the alkyl chain.
All aldehydes and ketones are fairly soluble in organic solvents such as ether, methanol, etc.
Lower aldehydes have sharp pungent odours.
As the size of aldehydes increases, the odour becomes less pungent and more fragrant.
7.
Chemical Reactions
7.1
Nucleophile (Nu-) attacks the carbonyl group perpendicular to the plane of sp2 hybridised orbitals of carbonyl
carbon.
In the process, hybridisation of carbon changes from sp2 to sp3.
A tetrahedral alkoxide is formed as intermediate.
Reactivity : Aldehydes are more reactive than ketones in nucleophilic addition reactions.
>
C=O >
H
There are two factors which influence the reactivity of ketone and aldehyde.
(i) Inductive effect
(i) + I effect of alkyl group decrease the amount of charge on C+ (C+ O). in ketones.
(ii) Steric effect also causes the less reactivity of carbonyl group.
(I)
Note : (i) Addition of HCN over aldehyde and ketones gives cyanohydrin.
(ii) Cyanohydrin on acid hydrolysis gives -hydroxy acid.
(iii) Cyanohydrin on treating with NH3(l) followed by acid hydrolysis gives -amino acid.
(iv) In case of ketone cyanohydrin formation is reversible due to bulky group of ketone which hinder the
formation.
(II)
salt on hydrolysis gives carbonyl compounds again, this reaction is used to separate the aldehydes from
mixture.
H2 O
H O
2
(III)
(IV)
Addition of water :
Aldehyde or ketone reacts with water to form gem-diols. Water is a poor nucelophile and therefore adds
relatively slowly to the carbonyl group, but the rate of reaction can be increased by an acid catalyst.
Mechanism:
+
OH
OH
OH
O
+
O
H
|
H
+H
+
RCH
RCH
RCH
RCH + H
+
|
H
OH
O+
H
H
OH
(V)
RCH
+
If Z are
Reagents Name
Products
OH
Hydroxylamine
Oxime
NH2
Hydrazine
Hydrazone
NHC6H5 Phenylhydrazine
NH
NO2
2,4-dinitrophenylhydrazine
(Brady's reagent) or 2,4-DNP
Phenylhydrazone
2,4-dinitrophenylhydrazone
(Solid orange precipitate)
NO2
O
NHCNH2
Semicarbazide
Semicarbazone
(VI)
(a) When formaldehyde is treated with Grignard reagent followed by acid hydrolysis primary alcohol is
obtained.
H
H
H
|
|
|
H2O / H
H C O + RMgBr H C OMgBr H C OH
|
|
R
R
1 alcohol
(b) When aldehyde except formaldehyde is treated with grignard reagent followed by hydrolysis 2 alcohol is
obtained.
H 2O/H
(c) When ketone is treated with grignard reagent followed by acid hydrolysis 3 alcohol is obtained.
7.2
Mechanism :
H2O
Note : (i) Oxime undergoes Beckmann rearrangement to give its isomer amide.
(ii) In this reaction the group which is anti to OH group migrates.
Re arrangemen t
Ex.
Re arrangemen t
7.3
-Hydrogen of aldehydes and ketones are acidic: They undergo a number of reactions due to the acidic
nature of -hydrogen.
Reason for the acidity of -hydrogen: Strong electron-withdrawing effect of the carbonyl group, and
resonance stabilisation of the conjugate base
(I)
CH3CH
||
O
OH
CH2=CH
|
O
CH2CH
||
O
Step-I
CH3CH
||
(RDS)
O
H2O
CH3CHCH2CHO
Step III
|
O
Step-II
CH3CHCH2CHO
|
OH
Heat
CH3CH=CHCHO
Ex.
(a)
H2O
(b) 2CH3COCH3
Propanone
Ba(OH)2
CH3
CH3CCH2CCH3
OH
H2O
4-Hydroxy-4-methylpentan-2-one
(II)
Cross-Aldol condensation :
On using two types of carbonyl compounds both having -hydrogen atoms we get a mixture of four condensed
product because two types of carbonyl compounds will give two type of carbanions which will be nucleophile
for itself and other molecule.
(i ) NaOH
CH3CHO + CH3CH2CHO
(ii )
OH
293 K
Note : On using formaldehyde and acetaldehyde during crossed aldol all the -hydrogen atom of acetaldehyde are
replaced one by one by hydroxymethyl group because of smaller size of formaldehyde to give
trihydroxymethylacetaldehyde which undergoes crossed cannizaro's reaction with formaldehyde to give
tetrahydroxymethyl methane and formate ion as a final product.
(CH2OH)2CHCH=O
(CH2OH)4C + HCOONa+
Ex.
Sol.
C6H5CHO + CH3CHO
(III)
If two carbonyl groups with -hydrogen atoms are present within the same molecule, then we get cyclic , unsaturated aldehyde / ketones via the formation of cyclic--hydroxy aldehyde / ketone in presence of basic
medium.
7.4
Perkin reaction :
When aromatic aldehyde like benzaldehyde is treated with anhydride in the presence of sodium salt of
acid from which anhydride is derived we get , -unsaturated acid.
Mechanism :
Note : By knowing , -unsaturated acid we can get idea about the anhydride used in perkin reaction. This can
be done by keeping 'H' at and OH at -carbon atom followed by breaking , carbon. By this we can
know about acid and it will be anhydride of this acid only.
7.5
Knoevenagel reaction :
It is preparation of , -unsaturated acid with carbonyl compound using malonic ester in the presence of
pyridine base.
Mechanism :
7.6
Reformatsky reaction :
When carbonyl compound and -halogenated ester are heated with zinc followed by treating with water we
get -hydroxyester.
R
C = O + BrZnCHCOOC2H5
C CH COOC2H5
H2O
C CH COOC2H5
OH R
OZnBr
-hydroxyester
7.7
Cannizzaro reaction :
Aldehydes which do not have an -hydrogen atom, undergo self oxidation and reduction (disproportionation)
reaction on treatment with a concentrated alkali.
Ex.
Mechanism :
HC=O
(B)
H
HCO
H C = O + CH3O
OH
H C = O + CH3OH
By this mechanism it is clear that acid corresponds to that carbonyl compound over which
easily as nucleophile.
can attack
Note : It is observed that hydride ion transfer from (I) to Carbonyl compound (B) is rate determining step.
(i)
(ii)
in case (i)
the cases.
will easily go to (A) and in case (ii) it will go to (B) hence acid salt will be formate ion in both
Mechanism :
H
HC=O
OH
HC=O
HC=O
H shift
H C O
H C O
C=O
OH
Ex.
7.8
CH2OH
|
COO (Glycolate ion)
OH
(i) NaOH
(ii) acidification
C6H5
C6H5COH
COOH
7.9
Benzoin Condensation :
During this reaction benzoin is obtained when an ethanolic solution of benzaldehyde is heated with strong
alkali potassium cyanide or sodium cyanide.
Mechanism :
Note : Phosphorus ylides are prepared from alkylhalide and triphenylphosphine in the presence of base like sodium
ethoxide as
Ex.
+ Ph3P = CH2
Reduction to alcohols :
NaBH4 or LiAlH4
Primary alcohols
Aldehydes
or Catalytic hydrogenation
4 or LiAlH4
NaBH
Secondary alcohols
Ketones
or Catalytic hydrogenation
(II)
Clemmensen reduction :
Used to get alkane from carbonyl compounds.
Mechanism :
Note : Generally this reaction is avoid if acid sensitive groups are present in the carbonyl compounds.
(III)
Wolf-Kishner reduction :
Used to get alkane from carbonyl compounds.
Mechanism :
Note : Generally this reaction is avoid if base sensitive groups are present in the carbonyl compounds
(IV)
+ POCl3
(V)
(ii)
Pinacol-Pinacolone rearrangement :
Pinacole is obtained when 2 moles of acetone are heated with divalent active metal magnesium followed by
treating with water.
Mg /
H2O
(Pinacol)
H2O
Haloform reaction :
Acetaldehyde and methylalkyl ketones react rapidly with halogen (Cl2, Br2 or I2) in the presence of alkali to
give haloform and acid salt.
NaOX
+ CHX3
(X = Cl, Br, I)
O
O
||
||
Br / NaOH
R C CH3 2 R C ONa CHBr3 (Bromoform)
O
||
In this reaction CH3 of CH3 C group is converted into haloform as it contains acidic hydrogen atom and
rest-part of alkyl methyl ketone give acid salt having carbon atom corresponding to alkyl ketone.
Preparation of haloform from methylketone involves two steps.
(a) Halogenation
(b) Alkalihydrolysis
O
||
R C CH3
O
||
R C CBr3 (Halogenation)
Br2
O
O
||
||
NaOH
R C CBr3 CHBr3 + R C ONa (Alkalihydrolysis)
O
||
Note : This reaction is used to distinguish the presence of CH3 C group.
(II)
Baeyer-Villiger oxidation :
It is preparation of ester from ketone using peracid.
peracid
Mechanism :
(III)
Oxidation of Aldehydes :
Aldehydes are oxidised to carboxylic acids by common oxidising agents such as KMnO4, HNO3, K2Cr2O7, etc.
[O ]
RCOOH
RCHO
Aldehydes are also oxidised by mild oxidising agents such as Tollens reagent and Fehlings reagent. On the
other hand, ketones are not oxidised by mild oxidising agents.
Ketones are oxidised under vigorous conditions, i.e., by strong oxidising agents and at elevated temperatures.
It involves carbon-carbon bond cleavage.
[ O]
Tollens reagent is weak oxidising agent. It gives Ag mirror test with aldehyde.
R CH = O + 2Ag (NH3 )2 +
Cu(OH)2 +
Equal volume of both the solutions are heated with aldehyde to give red brown precipitate of cuprous oxide
(Cu2O) which confirms the presence of aldehyde.
R CHO + 2CuO RCOOH + Cu2O (Red ppt)
Blue
RCHO + 2Cu2+ +
RCOO +
+ 2H2O
Cu(OH)2 +
(I)
(II)
(III)
(IV)
C6H5 CH = O
(V)
(Benzaldehyde)
oil of bitter almond
OH / H2O
( CH3COOH)
O
||
O C CH3
|
C6H5 CH O C CH3
||
O
CH3
(CH3CO)2O
C6H5 CH3
CrO3
C6H5 CH = N CH N = CH C6H5
C6H5
Hydrobenzamide
CO + HCl / AlCl3
H2 / Pd - BaSO4
boiling xylene
C6H5NH2
O
||
C6H5 C Cl
C6H5 CH = N C6H5
Schiff's base or anils
8.
Act as solvents.
Act as starting materials and reagents for the synthesis of other products.
Formalin (40% solution of formaldehyde)- Used for preserving biological specimens, bakelite, urea ,
formaldehyde glues and other polymers products.
Acetaldehyde used in the manufacture of acetic acid, ethyl acetate, vinyl acetate, polymers and drugs.
Benzaldehyde used in perfumery and in dye industries.
Butyraldehyde, vanillin, camphor, etc., are well known for their odours and flavours.
Acetone and ethyl methyl ketone are common industrial solvents.
9.
Grignard reagent
9.1
CM
or
9.2
Preparation :
Dry and pure
RMgX
RX + Mg Ether
Ether is used as a solvent because it is a Lewis base that donates its lone pair of electrons to electrondeficient magnesium atom, therefore providing stability to the Grignard's reagent (G.R.) by completing the
octet on magnesium atom.
Process : To an etherial solution of alkyl halide Mg metal is added at very low temp. (0 5C). A vigorous
reaction takes place , and a solution of G.R. is obtained. It cannot be evaporated to get it in solid state
because reaction will be explosive. It is stable only in solution state.
Reactivity order with respect to X (For preparation of RMgX)
RX:
Ex.
9.3
If Grignard reagent is regarded as the attacking reagent, then the nucleophilic carbanion of Grignard's reagent
will attack on the other compound taken as substrate.
9.4
Chemical Reactions
(I)
(II)
CH2 CH3
|
MgBr
|
Ex.
Ex.
(III)
+ CH3 CH2 Br
Ph MgX +
and CN , N = O,
ether
(1)
Ex.
(IV)
(1)
H
|
R C OMgX
|
H
(a) R MgX +
ether
(1)
(b) R MgX +
R
|
ether
R C OH
(1)
|
H
2 Alcohol
(c) R MgX +
R
|
ether
R C OMgX
(1)
|
R
H
|
R C OH
|
H
1 Alcohol
R
|
R C OH
|
R
3 Alcohol
R 'MgX
Ex.
R 'MgX
H3 O
(anhydride)
RMgX
(Ester)
R ''MgX
RMgX
R ''MgX
H3 O
H
H
|
|
C O R R C OR R C H
|
||
||
OMgX
O
O
+ R'OMgX
H
|
R CR
|
OMgX
H
|
R C R
|
OH
(V)
Ex.
(VI)
R CH2 CH 2
|
OMgX
CH3
|
S 2
N R CH2 CH OH ;
( 2 )
R CH2 CH2
|
OH
1 Alcohol
having two more C
CH3
|
S 2
N R CH2 C OH
|
CH3
(3)
R O O MgX
( i) O O
(ii) HOH
(VI)
A carboxylic acid is formed on hydrolysis of the adduct formed by passing carbon dioxide in the etherial
solution of a Grignard's reagent.
ether
R C OMgX HOH
R C OH
RMgX + O=C=O (1
)
Mg(OH) X
||
||
O
O
JEE(Main + Advanced) Carbonyl Compounds (Aldehydes & Ketones) # 128
HO
NH3 +
Applications :
G.R. is used to prepare alcohols or phenol from those alkyl halides / aryl halides which do not give normal SN
reactions
Ex.
(i)
(ii)
Sol.
2.
Sol.
( i ) O3
( ii ) Zn / H2 O
3.
Sol.
Since (B) is alcohol and (C) is alkene hence (B) is 3 alcohol only according to question (It is known that
alkene can only be obtained from 3 alcohol when heated with copper). Thus structure of (B) is (CH3)3COH
and its corresponding. alkyl bromide will be (CH3)3CBr (tertiarybutylbromide)
4.
Sol.
Since E is obtained on dry distillation of calcium salt of acetic acid hence E will be
unknowns are
A=
B = CH3 CH = CH2
C=
D = CH3 C C H
. Thus other
5.
Sol.
What will be structure of aromatic C8H8Cl2 (A), which on aqueous alkalihydrolysis gives product (B). (B) gives
positive iodoform test.
Since (B) is showing iodoform test hence it will be methylketone only as it is obtained on aqueous alkali
hydrolysis of (A) which will be non-terminal gem dihalides as
6.
Hence 'A' is
(b)
(c)
(d)
Sol.
(a)
(b)
(c)
(d)
+ CH3MgBr
+ CH3MgBr
+ CH3MgBr
+ CH3MgBr
7.
What will be structure of C4H8O2 which on treating with excess CH3MgBr followed by acidification gives sole
alcohol (A). (A) on treating with sodium hypoiodite solution gives positive iodoform test.
Sol.
Since (A) gives positively iodoform test hence it will be alkanol-2. 2 alcohol can be obtained only when
alkylformate is treated with Grignard's reagent via aldehyde where alkyl part is alkyl part of Grignard's reagent.
(propanol-2). Thus C4H8O2 is either
As Grignard's reagent is CH3MgBr hence 2 alcohol will be
or
Reactions :
(i) CH MgBr
3 CH3CH=O +
H2O / H
Here we get two alcohols propanol-2 and propanol-1. Alkyl part of formic acid ester which gives propanol-2
will be isopropyl only. Thus structure of C4H8O2 is
OH
Ph
8.
C=N
H O
1.PCl / Ether
5
A 3 B + C.
2. H2 O
p-CH3C6H4
A , B , C are
(A) PhCONH-p - CH3C6H4
Sol.
(B) PhCOOH
(C) pCH3C6H4NH2
(A,B,C)
OH
Ph
C=N
p-CH3C6H4
1.PCl / Ether
2. H2 O
H
+
OPCl
Ph
C=N
p-CH3C6H4
9.
(D) PhCHO
Sol.
10.
(ii)
(iii)
Sol.
Witting reaction
(i)
11.
(iii)
Predict Product
(i)
Sol.
(ii)
Product
(ii)
Product
(i)
(ii)
12.
Sol.
Baeyer-villiger oxidation
13.
(1)
(2)
Sol.
(1)
(2)
(a) =
(b) =
(c) =
14.
(A) on treating with (B) in the presence of dry ether gives (C) which on acids hydrolysis gives (D). (D) on
oxidation gives 2,5-dimethylhexan-3-one.
Sol.
A=
B=
or
or
A=
B=
2.
Arrange the following compounds in increasing order of their reactivity in nucleophilic addition reactions.
Ethanal, Propanal, Propanone, Butanone.
3.
Arrange the following compounds in increasing order of their reactivity with HCN :
Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
4.
5.
6.
How will you distinguish between Benzoic acid and Ethyl benzoate?
7.
8.
Show how each of the following compounds can be converted to benzoic acid?
(i) Bromobenzene
(ii) Phenylethene (Styrene)
9.
10.
What is meant by the following terms? Give an example of the reaction in each case?
(i) 2,4-DNP-derivative
(ii) Schiffs base
11.
(b)
1. CrO Cl
2
2
2. H3O
14.
An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular mass of
the compound is 86. It does not reduce Tollens reagent but forms an addition compound with sodium
hydrogensulphite and give positive iodoform test. On vigorous oxidation it gives ethanoic and propanoic acid.
Write the possible structure of the compound.
(b) PhCN + CH3MgBr
MnO,
(a) 2CH3COOH
O3 / Zn
(c)
(d)
Why aldehydes are more reactive than ketones (among isomers) towards nucleophilic addition reaction.
B-2.
Arrange the following compounds in decreasing order of rate of nucleophilic addition with RMgBr.
(I) PhCOCH3
(II) PhCHO
(III) CH3CHO
(IV) CCl3CHO
B-3.
Arrange the following compounds in decreasing orders of nucleophilic addition with semicarbazide
..
..
NH2NHCONH2 i.e., N H2 Z :
(II)
(I)
B-4.
B-5.
(IV)
(b)
(c)
(d) CH3CHO
Arrange the following compounds in decreasing orders of Keq for hydrate formation.
(b)
(a)
B-6.
(III)
(c)
(d)
(b)
B-7.
Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not. Explain why ?
B-8.
Give the structure of the carbonyl compound and amine used to form the following imines.
(a)
B-9.
(b)
Show which alcohol and carbonyl compound react to give each of the following product.
(a)
B-10.
(b)
Ph
(a)
H
C
CH3
+ NaHSO3
(b)
18
D2O
(c) CH3 C CH3
(d)
||
O16
H SO
C=N
4
2
C2H5
OH
(a)
CH3CH2CHO
(b)
PhCH2CHO
(c)
OH /
PhCOCH3
OH /
C-2.
Indicate the starting aldehyde or ketone from which each of the following compounds are formed by an aldol
condensation reaction.
(a) 2Ethyl 3hydroxy hexanal ;
(b) 4Hydroxy4methyl2pentanone
C-3.
When acetone is treated with excess of benzaldehyde in the presence of base, the crossed condensation
add two equivalents of benzaldehyde and expels two equivalent of water and forms [X]. Identify the structure
of [X] when [X] reacts with NH2OH how many stereoisomers are formed.
C-4.
(a)
CH3
|
OH /
CH3 C C H + CH3 C H
||
|
||
O
CH3 O
(b)
OH /
Ph C H + CH3 CH2 C H
||
||
O
O
(c)
Ph C H +
||
O
OH /
C CH3
||
O
C-5.
C-6.
Show which esters would undergo claisen condensation to give the following ketoester.
CH2CH3
|
CH
CH
CH
CCHCOCH
3
2
2
2CH3
(a)
||
||
O
O
(b)
O
||
(c) (CH3)2 CHCH2CCHC OEt
|| |
O CH(CH3)2
Identify the products in the following disproportionation reaction and also mention rate determining step.
+
D-2.
OH
CH3 C H + H C H
Product
||
||
O
O
excess
LiAlH
4
(p)
(q) + (r)
(a)
O
Per acid
(b)
E-2.
CHO
(a)
+ Ag2O
(b)
+ Ag(NH3)2 OH
(d)
HO
HO
CHO
(c)
||
O
+ K2Cr 2O 7 / H2SO 4
CHO
+ KMnO4
(cold, dil.)
Ph
O
||
C6H5
CH3
Br / OH
I2 / KOH
CH3CH2OH
(b)
I2 / KOH
PhCH2COCH3
(c)
I2 / KOH
(Me)3CCOCH3
CH CH CH CH Li
benzene
G-2.
G-3.
Ph C O
3
2
CH3I + Ph3P
2 2
Product.
Compound (X) with molecular formula C9H10O forms a semicarbazone and gives negative Tollens and Iodoform
tests. Upon reduction it gives n-propyl benzene. Deduce the structure of X.
H-2.
Which of the following compounds are suitable solvents for Grignard reagent ?
(a) n-Hexane
(c) CHCl3
(d) Cyclohexane
(e) Benzene
(g)
(h)
(b)
MgBr
+ DOCH3
(c)
H-3.
H-4.
H-5.
Y
CH = CH MgBr
X
propene.
2
H-6.
Draw the organic products you would expect to obtained from the following reactions (after hydrolysis).
(a)
(b)
(c)
(1) Ether
A-2.
(D) butaone
A-3.
A-4.
KMnO / H
4
(A) CH3CH2OH
(C) CH3
A-5.
Cu /
(B) CH3CH2OH
Cu /
OH
(D)
Cu /
A-6.
Arrange the following compounds in decreasing orders of rate of exchange of O18 with H2O18
(X) CCl3CHO
(Y) CH3CHO
(Z) CH3COCH3
(W) CF3CHO
(A) W > Z > X > Y
B-2.
Which of the following compound has the largest equilibrium constant for the addition of water ?
(A)
(B)
(C)
(D)
JEE(Main + Advanced) Carbonyl Compounds (Aldehydes & Ketones) # 140
B-3.
B-4.
(A)
(B)
(C)
(D)
NH2 NH2
(A)
B-5.
(B)
(C)
(D)
(C)
(D)
O16
||
D2O18
CH3 C H
D
The intermediate is :
(A)
B-6.
(B)
Aromatic carbonyl compounds having molecular formula C8H8O react with NH2OH how many oximes can be
formed :
(A) 8
(B) 10
(C) 12
(D) 6
CH2OH
B-7.
CH3O
H
H
H
OH
OCH3
[ X]
CH2OH
Compound (X) in the above reaction.
(A)
(B)
(C)
(D)
B-8.
The correct order of reactivity of PhMgBr with following compounds will be.
(C6H5)2CO,
CH3 CH = O ,
(CH3)2 C = O
(1)
(2)
(3)
(C) 3 > 2 > 1
The cyanohydrin of a carbonyl compound on hydrolysis gives lactic acid. The carbonyl compound is
(C) CH3COCH3
(D) CH3COCH2CH3
(A) HCHO
(B) CH3CHO
(D) PhCHO
(X) is the product of cross aldol condensation between benzaldehyde (C6H5CHO) and acetone What is its
structure ?
(A)
(B) C6H5CH=C(CH3)2
(C) C6H5COCH2C=(CH3)2
C-3.
In which of the following compounds the methylene hydrogens are the most acidic ?
(B) CH3CH2COOC2H5
(C) CH3CH2CH(COOC2H5)2
(D) CH3COCH2CN.
(A) CH3COCH2CH3
C-4.
HBr
(1) CH3COONa
B
A
PhCHO + (CH3CO)2O
(2) hydrolysis,
The product B is :
(A) PhCH = CHCH2Br
C-5.
(B)
C-6.*
(A)
(B)
(C)
(D)
(A)
(B)
(C)
(D)
(B)
(C)
(D) CH3CHO.
D-2.
NaOH
A + B.
In the reaction, (CH3)3CCHO + HCHO
heat
KOH
D-3.
D-4.
D-5.
(A)
(B)
+ CH3OH
(C)
In the cannizzaro's reaction the intermediate that will be the best hydride donar ?
(A)
(B)
(C)
(D)
heat
+ conc. NaOH
?
(A)
(B)
(C)
(D)
D-6.
Product is
(A)
(B)
(C)
(D)
LiAlH 4
[X], Product (X) in this reaction is :
E-1.
OH /
(A)
(B)
(C)
(D)
(X)
E-2.*
(Y)
KMnO 4 / OH
(Z)
(A)
E-3.
(B)
(C)
(D)
(A)
E-4.
(B) Ph C CH
||
O
(C) PhCH(Me)OCOOMe
2-Methyhlcyclohexanone is allowed to react with metachloroperbenzoic acid. The major product in the reaction is
(A)
(B)
(C)
(D)
E-5.
E-6.
(D) LiAlH4
(B) ZnHg/HCl
(D) NaBH4.
F-1.
Br / H
2 Major Product is :
(A)
(B)
(C)
O
F-2.
D
D
(A)
(B)
(C)
(D)
F-4.*
D O / OH
2
excess
(A)
D O / OH
2
(B)
D O / OH
2
(C)
(D)
F-5.*
D O / OH
2
(A)
(B)
(C)
(D)
(X)
C6H5CHO + CH3NO2
heat
G-2.
(A)
(B)
(D)
(A)
G-3.
(B)
(C)
PhCH2COOEt +
(A)
(D)
(B)
Product B is :
(A) PhCH2COOH (B) PhCH2COOEt (C)
(1) 2 / OH
( 2)H
EtO
(P) (Q) (R)
G-4.*
(A)
G-5.
(B)
(D)
+ (C6H5)3P = CHCH3
G-6.
(A)
G-7.*
(C)
(B)
(C)
(D)
(B)
(C)
(D)
(D) none
(C) Both
C6H5COOH + CH3MgI ?
(A) C6H5COOMgI
(B) CH4
ether
+ Mg
H-2.
(A)
(B)
( i)
Et 2O
+ (CH3)2CH Mg Br
( ii ) H O
H-3.
(C)
1 CH MgX
1 CH MgX
HOCH2CH2COCH2CH2CO2Et 3
P 3
Q 3
R
a : EtO C CH2 CH2 C CH2 CH2OMgX
||
||
O
O
CH3
|
b : EtO C CH2 CH2 C CH2CH2OMgX
||
|
O
OMgX
c : CH3 C CH2 CH2 C CH2 CH2 OMgX
||
||
O
O
CH3
|
d : CH3 C CH2 CH2 C CH2 CH2 OMgX
|
||
OMgX
O
which is/are correct.
(A) P is a
(B) Q is c
H-5.
H-7.
(D) Q is b
? The product is :
(A)
H-6.
(C) R is not d
(B)
(C)
(C) (CD3)3 CD
O
||
Zn Hg / HCl
Ph MgBr + (CH3 )2 CH C Cl [X]
[Y]
1 mole
Identify strucutre of [Y].
(A) Ph CH2 CH CH3
CH3
|
(C) Ph C CH3
|
CH3
(D)
|
CH3
|
CH3
H-8.
(A)
H-9.
1. CH3MgBr (excess)
(B)
(C)
(D)
A compound X (C5H12O4) upon treatment with CH3MgX gives 4 mole of methane. Identify the structure of (X).
(A)
H-10.
2. H
(B)
CH3CH2CH2CH2CH2Br
(C)
(D)
Identify Z
(A)
(B)
(C)
(D)
CH MgBr
H-11.
3 (A)
1( eq.)
(B)
(A)
H-12.
(C)
(D)
How many functional group produced CH4 gas by the reaction of compound (I) with CH3MgBr.
(I)
(A) 3
(B) 4
(C) 5
(D) 6
1.
Statement-1 : Aldehyde and ketone undergo nucleophilic addition reaction with carbon nucleophile and
underog nucleophilic addition-elimination reaction with nitrogen Nucleophile.
Statement-2 : Addition of nucleophile on aldehyde and ketone form tetrahedral intermediate, in case of
tetrahedral intermediate of nitrogen nucleophile non bonding electrons are present on nitrogen which cause
water molecule to eliminate while in case of carbon and hydrogen nucleophile non bonding electron are not
present.
2.
Statement-1 : The rate of addition reaction of alcohol on aldehyde can be increased by adding small amount
of base.
Statement-2 : Addition of alcohols to an aldehyde form acetal.
3.
Statement-1 :
Compound II is more reactive towards nucleophilic addition reaction.
Statement-2 : Cyclic ketones are more reactive than acyclic ketone due to less steric hinderance and
compact structure of cyclic ketone.
4.
5.
7.
8._
9.
10.
Statement-1 : Acetal are easily coverted to parent carbonyl compound. This easy interconverision make
acetal attractive as protecting group to prevent carbonyl compound.
Statement-2 : Acetal are easily hydrolysed in acidic as well as basic medium.
11.
Statement-1 : Acetaldehyde react with nitromethane in presence of dil. NaOH to give 1-nitro-2-propanol.
Statement-2 : The hydrogen atom of acetaldehyde are more acidic than nitromethane.
Statement-1 : The addition of ammonia derivative to a carbonyl compound is carried out in weakly acidic
medium.
Statement-2 : In weakly acidic medium attacking nucleophile is also protonated.
Statement-1 : HCHO is always oxidized in the crossed cannizzaro reaction.
Statement-2 : HCHO is the most reactive aldehyde, it exist in aqueous OH solution as the conjugate base
12.
13.
of its hydrate
, there is also a statistical factor because HCHO has two aldehydic hydrogen
available for transfer while in other aldehyde hydrate anion has only one such hydrogen atom.
+ HO NH2
(a)
(b)
H
+ NH2 NH2
(d)
2.
When semicarbazide reacts with a ketone (or aldehyde) to form semicarbazone. Only one nitrogen atom of
semicarbazide acts as a nucleophile and attack the carbonyl carbon of the ketone. The product of the
reaction consequently is R2C=NNHCONH2 rather than R2C=NCONHNH2. What factor account for the fact
that two nitrogen atoms of semicarbazide are relatively non nucleophilic ?
3.
Cyclopropanone exists as the hydrate in water but 2-hydroxy ethanal does not exist as its hemiacetal
expalin why ?
4.
(a)
||
O
O
CH2 - Br
(c)
CH2 - Ph
5.
(a) Cis-1, 2-Cyclopentanediol reacts with acetone in the presence of dry HCl to yield compound K, C8H14O2,
which is resistant to boiling alkali, but which is readily converted into the starting material by aqueous acids.
What is structure of K ?
(b) Trans-1, 2-Cyclopentanediol does not form an analogous compound. Explain why ?
6.
(a)
(b)
7.
Predict the product from claisen condensation of the following pair of esters.
+
(b)
(c)
8.
EtO
(a)
EtO
2. H2O /
Write the components which on crossed claisen condensation could be used to prepare the following esters.
(a)
9.
1. EtO
(b)
(c)
CH COONa
3
CHO + CH3 C O C CH3
OHC
||
O
||
O
excess
CN
(b)
CH3CHO + CH2
/
+ CH3COCH2COOEt EtONa
(c)
10.
Pyridine /
CN
EtOH
(a)
(b)
(c)
OH /
OH /
OH /
EtO
11.
12.
CDO
(a)
OH /
OMe
CHO
(b)
OMe
CHO
OH /
NO2
13.
OH
H
OH
PhCOCHBr2
C
A B
The compound 'C' is :
14.
Product is :
+ CHO
(ii) H3O
|
COOH
15.
16.
The compound C4H8CI2 (A) on hydrolysis gives a compound C4H8O, (B). The compound (B) reacts with
hydroxylamine and gives a negative test with Tollens reagent. What are (A) and (B) Support your answer
with proper reasoning and give the equations of reactions.
17.
An alcohol (A), 0.22 gm of this alcohol librates 56 ml of CH4 at STP on reaction with CH3MgBr. Write the
molecular formula of alcohol which satisfy these conditions.
18.
An organic compound which have molecular formula C4H4O3, gives 3 mole of CH4 gas on treatment with
methyl magnesium bromide. Give structure of the compound.
19.
C10H21Br
( X)
Cl
2
Y Give 5 types of structural monochloro product
Y has only 1 and 2 carbon atoms and X is 1 alkyl halide. Give structure of X & Y.
20.
(b)
(c)
1.
Products
Products obtained in the reaction is(A) Diastereomer
(B) Racemic mixture
2.
CHD 2MgI
Conc.H2SO 4
Y
CH2O X
H3 O
3.
OH
|
(A) CHD CH2 OH , CHO CHO
(i) CH CHO
dry ether
B.
A 3
+ Mg
(ii) H3O
product B is :
4.
(A)
(B)
(C)
(D)
(1)
( 2)
( )
CH2 OH
(A) (1) |
H (2) Mg /
CH2 OH
CH2 OH
(B) (1) |
H (2) Mg /
CH2 OH
(3) H C O H / H+
||
O
(3) CH3 C O Et / H+
||
O
CH2 OH
+
(C) (1) |
H (2) Mg / THF (3) CH3 C O Et / H
||
CH2 OH
O
CH2 OH
(D) (1) |
H (2) Mg / THF (3) H C O H / H+
||
CH2 OH
O
5.
(X)
(Y)
(Y) is
(B)
(A)
(C)
6.
Product is
(A)
7.
(D)
(B)
(C)
(D)
and
(B) PhCH2CHO,
and
(C)
(D)
8.
and
and
(i) CH3CH2MgBr
Cu,
(ii) H O
3 (X) (Y)
Ph CH CH C H
||
O
(i) KCN / H SO
2
4
Product is
9.
10.
(ii) LiAlH4
CH2 NH CH3
2
4
Heat
B.
+ H2NOH
A
Heat
11.
(A)
and
(B)
(C)
and
(D)
and
and
Compound (X) C9H10O gives yellow coloured ppt with 2,4 DNP but does not give red coloured ppt with
Fehlings solution. (X) on treatment with NH2OH/H+ gives compound (Y) C9H11NO. (Y) when treated with PCl5
gives isomeric compound (Z). (Z) on hydrolysis gives propanoic acid and aniline. What will be the correct
structure of (X), (Y) and (Z) ?
(X)
(Y)
(Z)
(A)
(B)
(C)
(D)
12.
Product
(A)
(B)
(C)
(D)
13.
(A)
14.
(A)
(B)
(B)
(C)
(D)
(B)
(C)
(D)
(B)
(A)
15.
O
CH3
||
|
KOH, H2O
CH3 CCH2CCHO
Product (C H O) :
7 10
|
CH3
(A)
(B)
(C)
(D)
16.
17.
(A)
(B)
(C)
(D)
(A)
+ CH3COOC2H5
(B)
+ CH3 C OC2H5
||
O
(C)
+ C2H5O C OC2H5
||
O
(D)
18.
(X) Identify.
(A)
(B)
OH/
Product is.
COOH
O
(A)
20.
(B) Ph CH
(C)
Ph CH
(D)
OH
+
OH
(A) LiAlH4
21.
(D)
CHO
O
19.
(C)
(B) Na / C2H5OH
(C) H2 / Ni
(D) CH2 = O /
Conc. NaOH
(A) I, II, IV
(B) III, IV
(C) II, V
(D) I, V
(i ) CH ( COOC H ) / Pyridine
5 2
2 2
(P) is
(ii) H O,
22.
(A)
(B)
(C)
(D)
23.
(mixture of alkenes)
24.
(i) CO2
SOCl2
(i) (C6H5CH2 )2 CuLi
Mg / Ether
[A]
[B]
[C]
[D]
(ii) H2O / H
(i)
(A)
(B)
(C)
(D)
NaBH
4
( i ) CH3MgBr (1 mole )
[A] [B]
25.
C OCH3
O
Identify the structure of [B] in following sequence of reactions.
(A)
(B)
(C)
(D)
26.
Followed
Cl CH2 C OEt + 2CH3MgI product.
by H2O
||
O
CH3
|
(B) Cl CH2 C OEt
|
OH
CH3
|
(A) HO CH2 C CH3
|
OH
27.
29.
Mg
Y
2CH2 = CH CH2 Cl X (CH2 = CH CH2)2CH OH + CH3 CH2 OH
Ether
Followed by H2O
In the above chemical reaction, Y may be
CH3
|
(D) Cl CH2 C CH3
|
OH
(D) Ethanoylchloride
Et O
2
The reaction,
BrCH2CH2CH2Br + Mg
produces mainly.
(A) CH3CH2CH3
(B) BrMgCH2CH2CH2MgBr
(C)
(A)
O
O
||
||
H
H3 C C (CH2 )2 C CH3
(B)
(C)
(D)
(A) CH3CH
CH CHO
3 KCN + HCl
OH ( very fast )
CH CH O
H2O/H+
(B) (hydrate) 3
( fast )
Me
OH
CN
30.
CH
CN
hydrate
HCN / OH
CH3MgBr
Adduct formation
(C) Cyanohydrin C2H5CHO
slow
fast
(D) All of these
31.
Products.
KCN / H O
H O ,
NH ,
3
3
2
(A)
KCN / NH Cl
H O ,
3
(B) 4
HCN / NaOH
(C)
Br / CH COOH
33.
SOCl
H O,
2
NH3
NH
CrO / H
2
3
3
3
(D)
In the given reaction which one of the following statement is correct
35.
(X)
(Y)
(B) Y is
(C) Z is
(Z)
(D) Z is CH3COOH
A compound (A) C5H10O forms a phenyl hydrozone and gives negative tollen's and positive iodoform test
compound can be :
(A)
(B)
(C)
(D)
36.
( 2 ) H3 O
O
O
||
||
(1) H O / H
(C) CH 3 C CH2 CH 2 C OC 2H 5 2
( 2 ) NaOH( cao )
(D)
37.
3
2
3
(A) C6H5-CH=O
CH COOC H / OH
3
25
(C) C6H5-CH=O
38.
CH (COOC H )
2
2 5 2
(B) C6H5-CH=O
Pyridine
(D) C6H5-CH=O
(ii) H2O / H /
(A)
(B)
(C)
(D)
Column II
( i ) OH
(A) MeCO(CH2)4COMe
(ii ) H /
(p)
(B) (CH2)4
OEt
(q)
CH COO
(C) PhCHO +
OH
(D) PhCOCOPh
2.
Column-I
Aldol product
Column-II
Reactant required
(A)
(p)
(B)
(q) HCHO
(C)
(r) PhCHO
(D) PhCH=CHCHO
(s) CH3CHO
3.
Column-I
Column-II
(A)
(p) 1, 4-addition
(B)
(q) Tautomerism
4.
Column-I
Column-II
(A)
(B)
(C)
(r) Dehydration
(D)
(p) Alkanone
(q) Ester
(r) 1 Alcohol
(s) Dithionic acid
PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
Aldehydes and Ketones reacts with NH2OH to form Aldoximes and Ketoximes respectively. Configuration of
these can be determined by Beckmann rearrangement as that group migrates which is anti w.r.t OH.
1.
C
OH
H2O
R' C N R
R'C N R
(II )
( III )
|
OH2
OH
..
C
R'
..
R'
R'C NH R
||
O
H O
H SO4
2 Ph NH2 +
[X] 2
(B)
(C)
(D)
(C) III
(D) IV
(C)
(D)
(1) H SO
2
4
NH2OH
(A) (B).
3.
( 2) hydrolysis
(A)
(B)
Comprehension # 2
Carbonyl compound which contains H gives aldol condenation reaction in presence of alkaline medium.
The reaction between two molecules of acetaldehyde take place as follows in presence of base.
4.
(C) O2N
CHO
(D) C6H5CH2CHO
5.
6.
Product
(C)
(D)
Comprehension # 3
The conversion of aldehyde having no alpha hydrogen to a mixture of carboxylic acid and primary alcohol is
known as cannizzaro reaction. The most important feature of this reaction is the conjugate base of hydrate
of aldehyde.
7.
8.
(A) CH3OH +
(B) HCOONa +
(C) HCOONa +
(D) HCOONa +
Comprehension # 4
Perkin reaction is the condensation reaction between aromatic aldehyde and aliphatic acid anhydride in the
presence of sodium or potasium salt of the acid of the corresponding anhydride to yield , unsaturated
aromatic acid.
PhCHO + (CH3CO)2O
PhCH=CHCOOH + CH3COOH
Mechanism
CH3COONa
CH3COO + Na
CH3COO +
CH3COOH +
H2 O /
Product is
9.
(A)
(B)
(C)
(D)
(i ) H O /
10.
(ii) H
(A)
11.
(B)
(C)
+ (CH3CH2CO)2O
(D)
H2 O /
Product is
(A)
(B)
(C)
(D)
Comprehension # 5
Ester having -hydrogen on treatment with a strong base eg. C2H5ONa undergoes self condensation to
produce -keto esters.This is called claisen condensation.
C2H5O + H CH2COOC2H5
C2H5OH +
12.
(A)
+ C2H5OH
(C)
(B)
+ C2H5OH
13.
+ C2H5OH
product is
(A)
(B)
(C)
14.
(A)
(B)
(C)
(D)
COOH
Comprehension # 6
Study following mechanism of haloform reaction.
H
|
R C C H + HO || |
O H
RCCH
|| |
O H
X
|
R C C H (1) HO, (2) I 2
|| |
C
O H
II
b
X
f
CHX3 R C O R C OH + -CX3
||
||
O
O
HOe
X
|
R C C X
|| |
O X
X
|
RCC X
|| |
O H
- d
(1) HO
(2) I2
15.
16.
(B) b
(C) c
(D) f
O
C CH3
(C) CH3 C CH2 CH2 C
||
||
O
O
17.
(D)
(C) d
(D) b
Comprehension # 7
PhCOOH + CHI3
yellow ppt.
18.
19.
(C)
(D) PhCCPh
(A)
20.
(B)
(B)
(C)
(D)
Comprehension-8
Observe the following experiment
21.
22.
23.
(C)
(D)
If the liquid Q is H C OC 2H5 then the product R can be (P can be any other halide)
||
O
(A)
(B)
If R is
(A)
, CH3
(C) CH3
CH3,
(C)
OC2H5
(D)
(D)
, CH3Cl
Identify (A), (B), (C), (D) and (E) in the following schemes and write their structures :
HgSO / H2 SO 4
NaNH 2
A
C
B 4
Br / CCl 4
2
NH2NHCONH 2
D
N aOD / D 2 O ( excess )
E
Major Product is
2.
3.
4.
(A)
(B)
(C)
(D)
CH MgBr
P. The product P will be
Ethylester 3
excess
(B)
(C)
[JEE-2003, 3/84]
(D)
The order or reactivity of phenyl magnesium bromide with the following compounds is : [JEE-2004, 3/84]
(ii) H / H2O
(A)
(B) Ph H
(C)
[JEE-2005, 3/60]
(D)
6.
O
||
(A) CH2 C O H
|
Br
7.
O O
|| ||
(B) H C C O H
10.
(C) NaOH, I2 /
Cyclohexene on ozonolysis followed by reaction with zinc dust and water gives compound E. Compound E
on further treatment with aqueous KOH yields compound F. Compound F is :
[JEE 2007, 3/162]
(A)
9.
O
||
(C) CH3 C O H
8.
, X can be :
CHO
CHO
(B)
(C)
COOH
CO2H
(D)
CO2H
Match the compounds/ions in Column I with their properties/reactions in Column II. [JEE 2007, 8/162]
Column I
Column II
(A)
C6H5CHO
(p)
gives precipitate with 2,4 dinitrophenylhydrazine.
(B)
CH3C CH
(q)
gives precipitate with AgNO3 .
(C)
CN
(r)
is a nucleophile.
(D)
(s)
is involved in cyanohydrin formation.
In the following reaction sequence, the correct structures of E, F and G are
[E]
[F] + [G]
F=
G = CHI3
(C) E =
F=
G = CHI3
(B) E =
F=
G = CHI3
(D) E =
F=
G = CH3
M=
11.
(A)
+ PhMgBr
(B)
(C)
+ PhCH2MgBr
(D)
+ PhCH2MgBr
12.
(A)
13.
(B)
(C)
(D)
Hex-3-ynal
14.
15.
[JEE-2008, 4/163]
(A)
(B)
(C)
(D)
and SOCl2
(C)
16.
[JEE-2008, 4/163]
(B)
and SOCl2
(D)
and CH3SO2Cl
[JEE-2008, 4/163]
(A)
(B)
(C)
(D)
1. O3
1. MeMgBr
S
R
P Q
2. H , H2O
3. H2SO4 ,
17.
2.
2. Zn, H2O
(A)
(B)
(C)
(D)
18.
(A)
(C)
19.
(B)
(D)
(B)
(C)
(D)
Match each of the compounds given in Column I with the reaction(s), that they can undergo, given in column
II.
[JEE-2009, 8/
160]
Column I
21.
(A)
20.
Column II
(A)
(p)
Nucleophilic substitution
(B)
(q)
Elimination
(C)
(r)
Nucleophilic addition
(D)
(s)
(t)
Dehydrogenation
In the scheme given below, the total number of intramolecular aldol condensation products formed from 'Y' is:
[JEE 2010, 3/163]
1. O
3
2. Zn, H2O
1. NaOH( aq)
2. heat
22.
(A)
(C)
23.
24.
and
(B)
and
(D)
The compound R is :
and
and
(A)
(B)
(C)
(D)
The compound S is :
(A)
(B)
(C)
(D)
25.
Match the reactions in column I with appropriate type of steps/reactive intermediate involved in these reactions
as given in column II
Column I
Column II
[JEE 2011]
(A)
aq NaOH
CH MgI
(B)
H SO
4
2
(C)
(r) Dehydration
H SO
4
2
(D)
(t) Carbanion
Comprehension (Q. 26 to 27)
An acyclic hydrocarbon P, having molecular formula C6H10, gave acetone as the only organic product through
the following sequence of reactions, in which Q is an intermediate organic compound.
[JEE 2011]
26.
27.
28.
(B) H3CH2CCCCH2CH3
[JEE 2011]
(C)
(D)
[JEE 2011]
(A)
(B)
(C)
(D)
The number of aldol reaction (s) that occurs in the given transformation is :
CH3CHO + 4HCHO
(A) 1
(B) 2
(C) 3
(D) 4
29.
The compound that undergoes decarboxlylation most readily under mild condition is [IIT-JEE 2012, 3/136]
(A)
30.
(B)
(C)
(D)
95% H SO
CN
2
4
H
CH3CH2COCH3 G
Heat
(A)
(B)
(C)
(D)
J (C9H8O2) gives effervescence on treatment with NaHCO3 and positive Baeyer's test
31.
The compound K is
(A)
32.
(B)
(D)
The compound is
(B)
(A)
33.
(C)
(C)
(D)
After completion of the reactions (I and II), the organic compound(s) in the reaction mixtures is (are)
[JEE (Advance) 2013, 3/360]
O
H3C
O
CH2Br
H3C
O
CBr3 Br3C
CBr3 BrH2C
P
Q
R
(A) Reaction I : P and Reaction II : P
(B) Reaction I : U, acetone and Reaction II : Q, acetone
(C) Reaction I : T, U, acetone and Reaction II : P
(D) Reaction I : R, acetone and Reaction II : S, acetone
O
ONa CHBr3
CH2Br H3C
2.
O
||
(1)
[AIEEE-2002]
OH
CH3
O
||
O
||
(2)
(3)
OH
3.
[AIEEE-2002]
(4)
OH
OH
[AIEEE-2002]
(4) C H bond
4.
Which one of the following is reduced with Zn, Hg and HCl acid to give the corresponding hydrocarbon?
[AIEEE-2004]
(1) Ethyl acetate
(2) Butan-2-one
(3) Acetamide
(4) Acetic acid
5.
Which one of the following undergoes reaction with 50% sodium hydroxide solution to give the corresponding
alcohol and acid ?
[AIEEE-2004]
(1) Phenol
(2) Benzoic acid
(3) Butanal
(4) Benzaldehyde
6.
Acetyl bromide reacts with excess of CH3MgI followed by treatment with a saturated solution of NH4Cl gives
[AIEEE-2004]
(1) Acetone
(2) Acetamide
(3) 2-Methyl-2-propanol (4) Acetyl iodide
7.
8.
Reaction of cyclohexanone with dimethylamine in the presence of catalytic amount of an acid forms a
compound if water during the reaction is continuously removed. The compound formed is generally known as
[AIEEE-2005]
(1) an amine
(2) an imine
(3) an enamine
(4) a Schiff's base
9.
10.
[AIEEE-2006]
[AIEEE-2007, 3/120]
P 2
H O
HCHO
B
A Ether
CH3CH2OH
C 2 D. The compound D is
Mg
(2) propanal
(3) butanal
In the following sequence of reactions, the alkene affords the compound 'B'
O3
H2O
CH3 CH CHCH3
A B .The compound B is
Zn
(1) CH3COCH3
12.
(2) CH3CH2COCH3
(3) CH3CHO
(1) CH3CCCH3
(2)
(4) CH3CH2CHO
[AIEEE-2008]
(3) CH
(4) CH3CH=CH2
13.
[AIEEE-2009, 4/144]
..
:O H
2Ph CHO PhCH2OH + PhCO2
the slowest step is :
(1) the transfer of hydride to the carbonyl group
14.
Trichloroacetaldehyde was subjected to Cannizzaro's reaction by using NaOH. The mixture of the products
contains sodium trichloroacetate ion and another compound. The other compound is :
[AIEEE 2011, 4/120]
(1) 2, 2, 2Trichloroethanol
(2) Trichloromethanol
(3) 2, 2, 2Trichloropropanol
(4) Chloroform
15.
Ozonolysis of an organic compound 'A' produces acetone and propionaldehyde in equimolar mixture. Identify
'A' from the following compounds :
[AIEEE 2011, 4/120]
(1) 1-Pentene
(2) 2-Pentene
(3) 2-Methyl-2-pentene
(4) 2-Methyl-1-pentene
16.
17.
In the given transformation, which the following is the most appropriate reagent ?
Re agent
(1) NH2NH2, O H
(2) ZnHg/HCl
(4) NaBH4
A organic compound (A) which has a characteristic odour, on treatment with NaOH form two compound (B)
and (C). Compound (B) has the molecular formula C7H8O which on oxidation gives back compound (A).
Compound (C) is the sodium salt of an acid. (C) when heated with sodalime yields an aromatic hydrocarbon
(D). Deduce the structures of (A), (B), (C) and (D).
[CBSE 1999]
2.
3.
[CBSE 2000]
4.
[CBSE 2002]
5.
[CBSE 2002]
6.
[CBSE 2003]
7.
8.
CH3CHO + HCN
H3 C CH CN
|
OH
Predict the products of and ballance the following reactions :
C6H5CHO + KOH (conc.)
[CBSE 2004]
[CBSE 2005]
9.
An organic compound A contains 69.77% carbon, 11.63% hydrogen and the rest it oxygen. The molecular
mass of the compound is 86. It does not reduce Tollen's reagent but forms an addition product with sodium
hydrogen sulphite and gives positive iodoform test. On vigorous oxidation it gives ethanoic and propanoic
acids. Write the possible structure of the compound A.
[CBSE 2008]
10.
11.
12.
Illustrate the following name reactions by giving a chemical equation in each case : [ CBSE 2010, 1 Mark]
Cannizaros reaction
13.
14.
15.
16.
17.
18.
19.
Arrange the following compounds in an increasing order of their reactivity in nucleophilic addition reactions :
ethanal, propanal, propanone, butanone.
[ CBSE 2012, 1 Mark]
20.
Illustrate the following name reactions giving suitable example in each case :
22.
23.
24
Conc .KOH
(i) 2H C H
||
O
(ii)
(b) Give simple chemical tests to distinguish between Ethanal and propanal :
The electron density at the carbonyl carbon increases with the increase in the +I effect. As a result, the
chances of attack by a nucleophile decrease. Hence, the increasing order of the reactivities of the given
carbonyl compounds in nucleophilic addition reactions is:
Butanone < Propanone < Propanal < Ethanal
3.
The +I effect is more in ketone than in aldehyde. Hence, acetophenone is the least reactive in nucleophilic
addition reactions. Among aldehydes, the +I effect is the highest in p-tolualdehyde because of the presence
of the electron-donating CH3 group and the lowest in p-nitrobezaldehyde because of the presence of the
electron-withdrawing -NO2 group. Hence, the increasing order of the reactivities of the given compounds is:
Acetophenone < p-tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde
4.
The molecular masses of the given compounds are in the range 44 to 46. CH3CH2OH undergoes extensive
intermolecular H-bonding, resulting in the association of molecules. Therefore, it has the highest boiling
point. CH3CHO is more polar than CH3COCH3 and so CH3CHO has stronger intermolecular dipole - dipole
attraction than CH3COCH3 CH3CH2CH3 has only weak van der Waals force. Thus, the arrangement of the
given compounds in the increasing order of their boiling points is given by:
CH3CH2CH3 < CH3COCH3 < CH3CHO < CH3CH2OH
5.
Propanal
Propanoate ion
Tollen's reagent
Silver mirror
6.
Sodium acetate
Benzoic acid and Ethyl benzoate can be distinguished by sodium bicarbonate test.
Sodium bicarbonate test :
Acids react with NaHCO3 to produce brisk effervescence due to the evolution of CO2 gas.
Benzoic acid being an acid responds to this test, but ethylbenzoate does not.
C6H5COOH + NaHCO3 C6H5COONa + CO2+ H2O
Benzoic acid
Sodium benzoate
7.
8.
(i)
Sodium
methanoate
9.
H3O
O CO
Mg
dry ice
Ether
KMnO4 KOH
(ii)
Iodoform
(yellow ppt)
H O
+ HCOOK
Semicarbazones are derivatives of aldehydes and ketones produced by the condensation reaction between
a ketone or aldehyde and semicarbazide.
Semicarbazones are useful for identification and characterization of aldehydes and ketones.
10.
(i) 2, 4-DNP-derivative :
2, 4-dinitrophenylhydrazones are 2, 4-DNP-derivatives, which are produced when aldehydes or ketones react
with 2, 4-dinitrophenylhydrazine in a weakly acidic medium.
NO2
C == O + H2 NNH
NO2
NO2
2, 4-Dinitrophenylhydrazine
C == NNH
NO2 + H2O
2, 4-Dinitrophenylhydrazone
To identify and characterize aldehydes and ketones, 2, 4-DNP derivatives are used.
(ii) Schiffs base :
Aldehydes and ketones on treatment with primary aliphatic or aromatic amines in the presence of trace of an
acid yields a Schiffs base.
Trace of H
11.
H O
1. CrO Cl
2
2
(b)
12.
+ CdCl2
2. CS 2
H O
Ph MgBr
(i)
Hydrolysis
Dry ether
O
||
CO
CH O
(ii)
+ 2 [Ag(NH3)2 ] + 3OH
Tollen's
reagent
Cyclohexane
carbaldehyde
+ 2 Ag + 4NH3 + 2H2O
Cyclohexane
carboxylate ion
Silver
mirror
Zn / Hg HCl
(iii)
13.
( Clemmensen
reduction )
(i) On treatment with dilute alkali, ethanal produces 3-hydroxybutanal gives butane-1, 3-diol on reduction.
dil. NaOH
NaBH
CH3CHO
(Re duction)
Ethanal
(ii) On treatment with dilute alkali, ethanal produces 3-hydroxybutanal gives bute-2-enal on heating.
dil. NaOH
CH3CHO
H2O
Ethanal
(iii) When treated with Tollens reagent, But-2-enal produced in the above reaction produces but-2-enoic
acid.
[ Ag(NH ) ] OH
2
3
Tollen's reagent
14.
Cannizzaro reaction :
The self oxidation-reduction (disproportionation) reaction of aldehydes having no -hydrogens on treatment
with concentrated alkalis is known as the Cannizzaro reaction. In this reaction, two molecules of aldehydes
participate where one is reduced to alcohol and the other is oxidized to carboxylic acid.
+ conc. KOH CH3OH + HCOOK
Hydride transfer is the rate determing step.
15.
% of carbon = 69.77 %
% of hydrogen = 11.63 %
% of oxygen = {100 - (69.77 + 11.63)}% = 18.6 %
69.77 11.63 18.6
:
:
12
1
16
= 5.81 : 11.63 : 1.16
= 5 : 10 : 1
Therefore, the empirical formula of the compound is C5H10O.
Now, the empirical formula mass of the compound = 5 12 + 10 1 + 1 16 = 86.
Molecular mass of the compound = 86
Therefore, the molecular formula of the compound is given by C5H10O.
Hence, the given compound is pentan-2-one.
C:H:O =
EXERCISE - 1
PART - I
(b)
+ NH3 + Mg(OH)I
A-1.
(a)
(c)
(d)
B-1.
The reactivity of carbonyl group towards nucleophilic reagent depends upon the extent of positive charge
present on the carbon. In ketones two alkyl group attach to the carbon reduce the positive charge on the
carbonyl carbon due to their electron repelling nature while in aldehyde the positive charge on carbonyl
carbon is reduced to lesser extent because only one alkyl group is present.
Also, In ketones steric hinderance is more than aldehyde.
B-2.
B-3.
B-4.
d>b>c>a
B-5.
c>b>a>d
B-6.
(a)
(b)
or KCN / dil.H2SO 4
( 2) H2O / H
B-7.
B-8.
(a)
B-9.
(a) CH3CHO +
B-10.
C-1.
+ CH3CHO
(b)
Ph
|
CH3
C-2.
(a) CH3CH2CH2CHO ;
C-3.
[X] =
C-4.
CH3
|
(a) CH3 C CH CH C H ;
|
||
CH3
O
(c) PhCOCH=C
CH3
(b) CH3COCH3
, Four stereoisomers are formed.
O
||
(b) Ph CH C C H ;
|
CH3
(c) Ph CH CH C
||
O
C-5.
C-6.
D-1.
(P) =
D-2.
CH2 OH
|
HO CH2 C CH2 OH + HCOONa+
|
CH2 OH
E-1.
(a)
(Q) = DCH2OH
(p)
, (q)
(b)
COOH
|
E-2.
(a)
(b)
||
O
COOH
|
(c)
F-1.
Ph
O
||
Br
C6H5
CH3
F-2.
(a)
(b)
(c)
G-1.
Ph2C = CH2
Br
(d)
O
||
C6H5
Ph
CH3
|
OH
OH
, (Diastereomer).
CHI3 + HCOONa
CHI3 + PhCH2COONa
CHI3 + (Me)3CCOONa
G-2l.
G-3.
H-1.
b, f, g, h
H-2.
(a) CH3 D +
H-3.
C2H5
|
(i) C2H5MgBr
CH3 C C2H5
CH3 C CH2CH3
|
( 2) H3O
||
OH
(c)
|
CH3
3-Methylpentan-3-ol
H-4.
(i)
(ii) CH3CH2CH2OH
H-5.
X = CH2=CHBr, Y = CH3Br
H-6.
(a)
(b)
(c)
PART - II
A-1.
(A)
A-2.
(A)
A-3.
(C)
A-4.
(C)
A-5.
(A)
A-6.
(A)
B-1.
(B)
B-2.
(C)
B-3.
(D)
B-4.
(A)
B-5.
(B)
B-6.
(B)
B-7.
(B)
B-8.
(B)
B-9.
(B)
C-1.
(D)
C-2.
(A)
C-3.
(D)
C-4.
(B)
C-5.
(D)
C-6.*
(A,B,D)
D-1.
(D)
D-2.
(A)
D-3.
(A)
D-4.
(C)
D-5.
(C)
D-6.
(B)
E-1.
(A)
E-2.*
(A,B,C)
E-3.
(A)
E-4.
(C)
E-5.
(A)
E-6.
(B)
F-1.
(A)
F-2.
(C)
F-3.*
(A,B,C)
F-4.*
(A,B,C)
F-5.*
(A,C)
G-1.
(C)
G-2.
(B)
G-3.
(A)
G-4.*
(A,C,D)
G-5.
(C)
G-6.
(B)
G-7.* (A,B,C)
H-1.
(C)
H-2.
(B)
H-3.
(C)
H-4.*_ (A,C,D)
H-5.
(A)
H-6.
(A)
H-7.
(A)
H-8.
(B)
H-9.
H-10.
(A)
H-11.
(A)
H-12.
(B)
(C)
PART - III
1.
(A)
2.
(D)
3.
(A)
4.
(B)
5.
(A)
6.
(A)
7.
(D)
8._
(E)
9.
(A)
10.
(C)
11.
(C)
12.
(C)
13.
(A)
EXERCISE - 2
PART - I
1.
2.
(a)
(b)
(c)
N NH Ph
||
(d) Ph C Ph
Two nitrogen atoms of semicarbazide that are adjacent to the (C=O) group have their lone pair present in
conjugation so nucleophilicity decreases.
H O
3.
In cyclopropanone angle strain decreases after addition of water, while cyclic hemiacetal structure of
2-hydroxy ethanal will develope angle strain.
H2O
HOCH2CHO
Hemiacetal
(Not form due to angle strain)
4.
CH2 OH
|
H
CH2 OH
(a)
(i) LiAlH
(ii) H
CH2 OH
|
H
CH2 OH
(i) HC C Na
HC C CH2 CH2 C CH3
(ii) H
||
O
O
CH2 - Br
(c)
CH2 OH
|
H
CH2 OH
(i) PhMgBr
CH2Br
CH2 - Ph
(ii) H2O
5.
(a)
(b) The OH groups in the trans isomer are too far apart to form cyclic structure.
6.
(a) 4
(b) 0
7.
(a)
8.
(b)
(c) CH3CH2COOH
+ Ph CH2 C OCH3
||
O
(b)
CN
9.
(a)
HOOCCH=HC
CH=CHCOOH
(b)
CH3CH = C
CN
(c)
10.
(a)
(b)
(c)
11.
CH2OH
CHOH
12.
(a)
(b)
OMe
13.
PhCH(OH)COOH
JEE(Main + Advanced) Carbonyl Compounds (Aldehydes & Ketones) # 188
14.
HO CH2 COONa.
16.
A = CH3CCI2CH2CH3, B = CH3COCH2CH3.
17.
C5H11OH
18.
O OH
|| |
HO C C C CH
|
H
19.
X = CH3(CH2)8CH2Br ; Y = CH3(CH2)8CH3
20.
(a)
15.
CH3
|
Ph C C C CH3
|
OH
CH3
|
Ph C CH3
|
OH
(b)
(c)
Followed
+ 2CH3MgBr
by H2O
PART - II
1.
(A)
2.
(C)
3.
(B)
4.
(C)
5.
(B)
6.
(B)
7.
(D)
8.
(B)
9.
(A)
10.
(D)
11.
(B)
12.
(A)
13.
(B)
14.
(B)
15.
(C)
16.
(A)
17.
(C)
18.
(C)
19.
(B)
20.
(D)
21.
(C)
22.
(A)
23.
(D)
24.
(A)
25.
(C)
26.
(D)
27.
(A)
28.
(C)
29.
(B)
30.
(A,C)
31.
(B,C,D)
32.
(A,B,C)
33.
(A,B,C,D)
34.
(A, B,C)
35.
(A),D)
36.
(A,B,D)
37.
(A,B,D)
38.
(A,B,C)
1.
3.
5.
PART - III
PART - IV
1.
(A)
2.
(B)
3.
(A)
4.
(D)
5.
(D)
6.
(D)
7.
(B)
8.
(C)
9.
(A)
10.
(A)
11.
(A)
12.
(A)
13.
(D)
14.
(A)
15.
(A)
16.
(C)
17.
(B)
18.
(B)
19.
(C)
20.
(C)
21.
(C)
22.
(A)
23.
(B)
6.
(D)
EXERCISE - 3
PART - I
1.
(A) =
(B) =
(D) =
(E) =
(C) =
2.
(B)
3.
(A)
4.
7.
(C)
8.
(A)
9.
10.
(C)
11.
(B)
12.
(A)
13.
(D)
14.
(D)
15.
(A)
16.
(C)
17.
(B)
18.
(A)
19.
(B)
20.
22.
(B)
23.
(A)
24.
(D)
25.
26.
(D)
27.
(B)
28.
(C)
29.
(B)
31.
(C)
32.
(A)
33.
(C)
1.
(4)
2.
(2)
3.
(3)
4.
(2)
5.
(4)
7.
(1)
6.
(3)
8.
(3)
9.
(4)
10.
(1)
11.
(3)
12.
(3)
13.
(1)
14.
(1)
15.
(3)
16.
(4)
17.
(1)
30.
(C)
5.
(B)
21.
(A)
PART - II
PART - III
1.
The molecular formula of the compound is C7H8O therefore, it is an aromatic compound. Since on heating
with NaOH it yields an alcohol, therefore, it is nothing but benzaldehyde and the alcohol is benzyl alcohol.
+ C6H5COONa
Since (C) is a sodium salt of an acid and gives a hydrocarbon (D) on heating with soda lime therefore, (C) is
sodium benzoate and (D) is benzene as illustrated below :
2.
(A)
(B)
(C)
(D)
3.
I2 / OH
PhCOCH3
CHI3 + Ph COO Na
4.
HCHO
5.
(i)
formaldehy de
H2NNHCONH2
HO
2
HCN NNHCONH2
formaldehy de
semicarbazone
semicarbaz ide
(ii)
6.
CH3
CH3
|
|
H2O / H
CH3 C O CH3MgBr CH3 C OMgBr
|
CH3
CH3
|
H
H C OH
|
CN
7.
CH3
|
O
H C O
|
CN
8.
Benzaldehyde
9.
Pot. benzoate
Benzyl alcohol
A = C5 H10 O
Oxidation
CH3COOH + CH3CH2COOH
CH3
CH3 MgBr
10.
C=O
CH3
H2O/H+
(ii)
CH3
CH3
OH
CH3
2 - methylpropan-2-ol
Methyl magnesium
bromide
11.
(i)
12.
Cannizaros reaction : When aldehyde having no -hydrogen reacts in presence of conc. NaOH, sodium
salt of acid and alcohol is formed.
50% NaOH
Wolff-Kishner reduction : When aldehydes and ketones are reduced with hydrazine and KOH, hydrocarbons
are formed.
KOH
NH2 NH2
CH3 CH3 N2
CH3CH N NH2
CH3 C O
glycol
Ethanal
hydrazone
|
H
14.
(i) Cannizzaro reaction : Aldehydes which do not contain an -hydrogen atom, when treated with
concentrated alkali solution undergo self oxidation - reduction. As a result, one molecule of the aldehyde is
reduced to the corresponding alcohol which is oxidised to the corresponding carboxylic acid. This reaction is
called Cannizzaro reaction.
2C 6H5 CHO NaOH C 6H5 CH2OH C 6H5 COONa
Benzaldehyde ( 50%)
Benzyl alcohol
Sod. benzoate
(ii) Clemmensen Reduction : When aldehydes and ketones are reduced with Zn(Hg) and conc. HCl,
hydrocarbons are formed.
Zn(Hg)
Zn(Hg)
CH CH CH + H O
+ 4[H] conc
3
2
3
2
. HCl
15.
(i) Fehling solution test : Warm each compound with few drops of Fehling solution. Propanal gives a red
precipate of cuprous oxide.
2
CH2CH2 CHO 2
5OH
Cu
red ppt.
(ii) Iodoform Test : Warm each compound with iodine and sodium hydroxide solution on a water bath.
Acetophenone (C6H5COCH3) gives yellow precipitate of iodoform Benzaldehyde doe not give this test.
16.
17.
(i) Cannizzaro reaction : Aldehydes which do not contain an -hydrogen atom, when treated with
concentrated alkali solution undergo self oxidation - reduction. As a result, one molecule of the aldehyde
is reduced to the corresponding alcohol which is oxidised to the corresponding carboxylic acid. This
reaction is called Cannizzaro reaction.
2C 6H5 CHO NaOH C 6H5 CH2OH C 6H5 COONa
Benzaldehyde ( 50%)
Benzyl alcohol
Sod. benzoate
18.
19.
20.
(i) Clemmensen reduction = When aldehydes and ketones are reduced with Zn (Hg) and
conc. HCI, hydrocarbons are formed.
Zn(Hg)
CH3CHO + 4[H] CH3 CH3 + H2O
HCl
21.
Add I2 and NaOH = Pentan-2one will give yellow ppt. of iodoform whereas pentan 3 one will not react.
CH3
22.
CH3CHO + CH3MgX
H2O
CH3
CH3CHOMgX
H2O
CH3CHOH + Mg(OH)X
Propan-2-ol
23.
(iii) 2CH3CHO
Ethanal
24
(i)
H
H
C=O +
H
H
H
C=O + Conc. KOH
HCOH + H C
H
Formaldehyde
Methanol
OK
Potassium formate
O2N
(ii)
CHO
Benzaldehyde
HNO3/H2SO4
273-283 K
CHO
m-Nitrobenzaldehdye
(b) Ethanal gives iodoform test but propanal can not give iodoform test
CH3
|
acid
+ HO CH2 C CH2 OH
|
CH3
( excess)
(A)
2.
(B)
(C)
(D)
(A)
(B)
(C)
(D)
Conc. OH
y
x
3.
excess /
(A)
4.
(B)
(C)
(D)
5.
Under Wolf Kishner reduction conditions, the conversions which may be brought about is ?
(A) Benzaldehyde into Benzyl alcohol
(B) Cyclohexanol into Cyclohexane
(C) Cyclohexanone into Cyclohexanol
(D) Benzophenone into Diphenylmethane
6.
(B) Benzaldehyde
(D) Phenol
7.
Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is :
(A) MeCOCl
(B) MeCHO
(C) MeCOOMe
(D) MeCOOCOMe
8.
An organic compound C3H6O does not give a precipitate with 2, 4-dinitrophenyl hydrazine reagent also does
not react with metallic sodium it could be :
(A) CH3CH2CHO
(B) CH3COCH3
(C) CH2=CHCH2OH
(D) CH2=CHOCH3
9.
10.
(A) C6H5CH=CHCOOH
(B)
(C)
(D)
(X)
(B)
(C)
(D)
Al(OEt )3
(B)
11.
A and B are :
(A)
(B)
(C) Both a and b
(D)
12.
, [X] is :
(A) 2 Mole
13.
(B)
Among the following compounds which one will react with acetone to give a product that contains carbonnitrogen double bond ?
(B) (CH3)3 N
(A) C H N HC H
6 5
6 5
14.
(C)
(C)
(D) C6H5 N H N H2 .
O=CH O=CH
C 2H 5 N H 2 +
acid
CH3
H3C
CH2
C2H5
|
+N
..
(A)
CH
H5C2N
N
..
(B)
HC
(C)
NC2H 5
CH
(D)
CH3
CH3
15.
H3C
CH3
(A)
16.
(B)
(C)
(D)
A compound (X) on treatment with SOCl2 produces another compound (Y). The latter on hydrolysis yields a
mixture of benzoic acid and methylamine. The compound (X) is :
(A)
(B)
(C)
(D)
17.
product formed is :
(B)
(A)
18.
(C)
(D)
X
X can be :
19
(A)
(B)
(C)
(D)
20.
21.
(A)
(B)
(C)
Which of the following reaction will give -keto aldehyde as the final product ?
(A)
(B)
(C)
An organic compound X on treatment with acidified K2Cr2O7 gives compound Y which reacts with I2 and
sodium carbonate to form Triiodomethane. The compound X can be :
O
(A) CH3OH
(B) CH3CCH3
(C) CH3CHO
(D) CH3CH(OH)CH3 .
22.
(B)
Compound (B) is :
(A)
23.
(B)
(D)
Arrange the following compound in decreasing order of Keq for hydrate formation.
KCN,EtOH
Product is :
H O
24.
25.
(C)
(A)
(B)
(C)
(D)
(A)
(B)
(C)
(D)
26.
HO
(A) 1
27.
(B) 8
(C) 4
(D) 2
OH
28.
(A)
(B)
(C)
(D)
29.
A mixture of benzaldehyde and formaldehyde on heating with aqueous NaOH solution gives :
(A) Benzyl alcohol and sodium formate
(B) Sodium benzoate and methyl alcohol
(C) Sodium benzoate and sodium formate (D) Benzyl alcohol and methyl alcohol
30.
31.
H O
HCN
3 Product
(A) K2Cr2O7 / H
(C) CrO3 / H, Zn-Hg/ Con. HCl
(B) N2H4 / OH
(D) CrO3 / H, N2H4 / OH,
33.
OH
(A)
OH
(B) PhCHO +
OH
(D)
34.
Which of the following is possible combination to prepare 1 -phenyl 1,3 butadiene from Wittig reaction ?
(A)
+ Ph3 P = CH CH = CH2
(C)
35.
+ Ph3P = CH CH = CH2
(B)
(D)
36.
(A) R =
CH3
(B) S =
O
O
CH3
(C) Q =
37.
Among the following compounds, which will react with acetone to give a product containing > C = N :
[JEE-98, 3M]
(A) C6H5NH2
(B) (CH3)3N
(C) C6H5NHC6H5
(D) C6H5NHNH2
2.
(A) on hydration gives (B) which gives positive iodoform test. Also (A) gives white precipitate with Tollen's
reagent. (B) is also obtained from acetyl chloride on treating with benzene in the presence of anhydrous AlCl3
3.
An alkene C6H12 after ozonolysis yielded two products. One of these gave a positive iodoform reaction but a
negative Tollen's test. The other gave a positive Tollen's test but negative iodoform test. The structure of C6H12 is.
4.
The calcium salt of an acid A (C6H10O4) on dry distillation produced B (C5H8O). When B is reacted with Bromine
solution in acetic acid, C (C5H7OBr) is obtained. C is reacted with anhydrous acidic glycol (HOCH2CH2OH)
solution and PhMgBr is added to this solution carefully and then its is subjected to dilute HCl solution then
compound D (C11H12O) is formed. D reacted with hydroxylamine hydrochloride to give E and F having
molecular formula (C11H13NO). E on heating with small amount of H2SO4 produced G which on hydrolysis
produced H. F under the same treatment yields I and J compounds respectively. E, F, G and I all are
isomeric and have molecular formula (C11H13NO). H have two hydrogen atom while J have only one
hydrogen atom. Identify compounds A to J. H on reaction with SOCl2 followed by treatment with anhydrous
AlCl3 gives the following compound X.
X=
5.
(1) B H
Mg / Et O
(1) Ph CHO
HCl, ZnCl2
2 6
B
D
C 2 CH3CH2CH2MgCl
A
( 2) H3O ,
( 2) H2O2 / OH
6.
An organic compound (A) C4H9Cl on reaction with aqueous KOH gives (B). (A) on reaction with alcoholic
KOH gives (C) which is also formed on passing the vapours of (B) over heated copper. The compound (C)
readily decolourise bromine water. Ozonolysis of (C) gives two compounds (D) and (E). Compound (D) reacts
with NH2OH to give (F) and compound (E) reacts with NaOH to give an alcohol (G) and sodium salt (H) of an
acid. (D) can also be prepared from propyne on treatment with water in presence of Hg+2 and H2SO4. Indentify
(A) to (H) with proper reasoning.
7.
An organic compound (A) contains 40% carbon and 67% Hydrogen. Its vapour density is 15. (A) on reaction
with a concentrated solution of KOH gives two compound (B) and (C). When (B) is oxidised original compound
(A) is obtained. When C is treated with concentrated HCl, it gives a compound (D) which reduces ammonical.
AgNO3 solution and also gives effervescences with sodium bicarbonate solution. Write structure (A), (B), (C)
and (D).
8.
(H3O )
HCN
Alkaline hydrolysis
A
B
CH3CH=CHCHO
OH
9.
10.
An organic compound (A) C9H10O reacts with NH2OH to give two isomers B & C with same moleculer formula
C9H10ON.The compound B and C isomerizes to D and E respectively on treating with small amount of H2SO4.
Compound (F) C8H8O2 is formed either by (A) on treating with I2/KOH followed by acidification or by acid
hydrolysis of (D). Hydrolysis of (E) gives orthomethylaniline. identify the structure from (A) to (E).
11.
Compound A to D do not gives tollens test however compound C does. Give the structure of A to D.
HOCH CH OH
Mg / Et 2O
2
2
(C H O Br)
(C6H11MgO2Br)
4-bromobutanal HA
6 11 2
CH3OH,HA
(C7H14O2)
(C6H12O2)
[Solomon]
12.
Acetophenone on reaction with hydroxylamine hydrochloride can produce two isomeric oximes. Write structure
of the oximes.
13.
Complete the following giving the structures of the principal organic products.
+ Ph3P = CH2 E
(a)
(c)
14.
(d)
How many asymmetric cabon atoms are created during the complete reduction of benzil (PhCOCOPh) with
LiAlH4 ? Also write the number of possible stereoisomer of the possible product.
MeMgBr
15.
16.
(b)
+ (COOEt)2 + EtONa
17.
An aldehyde (A) (C11H8O), which does not undergo self aldol condensation, gives benzaldehyde and two
mole of (B) on ozonolysis. Compound (B), on oxidation with silver ion, gives oxalic acid. Identify the compound
(A) and (B).
[JEE-98, 2M]
18.
[JEE-98, 2M]
3
C H CH = CHCHO
C6H5CH(OH)C CH
6 5
19.
(i) LiAlH
4
B
(ii) H ,
20.
Compound A (C8H8O) on treatment with NH2OH . HCl gives B and C . B and C rearrange to give D and
E respectively on treatment with acid . B , C , D , and E are all isomers of molecular formula C8H9NO
. When D is boiled with alcoholic KOH , an oil F (C6H7N) separates out . F reacts rapidly with CH3COCl to
give back D . E on boiling with alkali , followed by acidification gives a white solid G (C7H6O2) Identify A
to G.
21.
Carry out the following transformation in not more than three steps :
O
||
CH3 CH2 C C H CH3 CH2 CH2 C CH3
22.
23.
24.
Two different Grignard reagents, (X) and (Y) produce C6H5CH2C(CH3)2OH on reaction with (P) and (Q)
respectively. Give structures of (X), (Y), (P) and (Q).
H
A
Base
25.
An organic compound (A), C8H4O3, in dry benzene in the presence of anhydrous AlCl3 gives compound (B).
The compound (B) on treatment with PCl5, followed by reaction with H2 / Pd(BaSO4) gives compound (C),
which on reaction with hydrazine gives a cyclised compound (D) (C14H10N2). Identify (A), (B), (C) and (D).
Explain the formation of (D) from (C).
26.
An organic compound A, C6H10O, on reaction with CH3MgBr followed by acid treatment gives compound B.
The compound B on ozonolysis gives compound C, which in presence of a base gives 1-acetyl cyclopentene
D. The compound B on reaction with HBr gives compound E. Write the structures of A, B, C and E. Show
how D is formed from C.
27.
Na Hg / HCl
HNO / H SO
2
4
3
B 3
C
2
H / Pd / C
2
E D
PART - I
1.
(A)
2.
(B)
3.
(C)
4.
(D)
5.
(D)
6.
(B)
7.
(A)
8.
(D)
9.
(D)
10.
(B)
11.
(A)
12.
(B)
13.
(D)
14.
(A)
15.
(A)
16.
(A)
17.
(C)
18.
(D)
19
(D)
20.
(A)
21.
(D)
22.
(A)
23.
(A)
24.
(A)
25.
(C)
26.
(D)
27.
(B)
28.
(D)
29.
(A)
30.
(C)
31.
(A,D)
32.
(C,D)
33.
(A,B,C)
34.
(A,B)
35. (A,B,C,D)
36.
(A,B,C,D)
37.
(A,D)
PART - II
1.
A = Propyne
B=
C=
D = CH3 C C CH3
(aldol product)
E=
F=
G =
2.
(A) C6H5 C C H
3.
4.
(B)
or
(A)
(B)
NH OH / HCl
(D)
(C)
+
(E)
H SO
(F)
HO
4
2
(E)
Br / CH COOH
23
(H)
H SO
H O
2 H2N CH2 CH2 CH2 CH COOH
|
Ph
4
2
(F)
(I)
(J)
5.
(B) CH3CH2CH2OH
(C) CH3CH2CH2Cl
6.
(A)
(B)
(C)
(E) HCHO,
(F)
, (G) CH3OH,
(A) 2HCHO,
8.
10.
(C) HCOONa,
(D) HCOOH
Br
|
(B) C 6H5 C CH2 CH2 CH2 Br
|
CH3
(C)
(D)
(A)
(B)
(C)
CH3
O
(D)
11.
(D)
(H) HCOONa
7.
9.
(B) CH3OH,
(E) CH3 C NH
(A)
(B)
(C)
(D)
HCl
H2O
12.
It shows two isomers which are geometrical isomers to each other and represented as follow :
(i)
C6H5
CH3
C=N
(ii)
C6H5
CH3
OH
OH
C=N
Syn-methyl anti-Syn-phenyl
Ketoxime
Presence of acid
or
PCl5
or Acid anhydride
Presence of acid
or PCl5
or
O
||
CH3 C NH C 6H5
N phenyl acetamide
O
||
C 6H5 NH C CH3
Acid anhydride
N phenyl acetamide
Therefore both isomers give different product with different configturation.
13.
(a)
CH2 + Ph3P=O
(b)
(c)
14.
(d)
*
*
Ph CH CH Ph
|
|
OH OH
two chiral C atoms ; total 3 isomers :
15.
16.
17.
Ozonolysis
A =
CHO
CHO
|
|
COOH
COOH
Two moles
B =
18.
CHO
COOH
Ag O
|
oxalic acid
2 |
COOH
COOH
(B)
OH
|
H3O
C 6H5 CH C CH
H2O
OH
O
C6H5 C H C CH C6H5 CH = C = C H
C6H5 CH = C = CHOH
C6H5 CH = CH CHO
( C6H5CHO )
(A)
Base
19.
(i ) LiAlH
Rearrangement
20.
So compound are
A=
B=
C=
O
||
D = CH3 C NH C 6H5
O
||
E = C 6H5 C NH CH3
F = C6H5 NH2
O
||
G = C 6H 5 C O H
21.
O
||
BH3 / THF
CH3 X
Na
CH3CH2C CNa
CH3CH2C CH
CH3 CH2CH2CCH3
CH3CH2C CCH3
H2O 2 , OH
O
||
CH3 CH2CH2CCH3
22.
(P)
(Q)
CH3
|
CH3 C CH2 C 6H5
|
OH
CH3
|
CH3 C CH2 C 6H5
|
OH
23.
24.
(A)
(Beckmann's rearrangement)
Base
Tautomerism
25.
(A)
26.
A=
(B)
(C)
(D)
,B=
O
||
CH2 CH2 CH3
27.
A = Cl
B=
Cl
D=
C=
'A'
E=