1720767882044

AIM : FREE EDUCATION TO ALL APUL
CHAPTER
Organic Compounds
28 Containing Oxygen-II
Chapter Highlights
General methods of preparation, correlation of physical properties with their structures. Chemical properties
and uses of Aldehydes, Ketones, Carboxylic acids and their derivatives, Benzaldehyde and Benzoic acid; their
important methods of preparation and reactions. Acidity of carboxylic acids, effect of substituents on the acidity
of carboxylic acid and various levels of multiple-choice questions.
ALDEHYDES, KETONES, ACIDS AND ACID DERIVATIVES
ALDEHYDES AND KETONES • If R and R′ are different alkyl or aryl groups, the
ketone is said to be a mixed ketone, for example ace-
+δ π −δ tophenone (CH3COC6H5).
120º C σ
O
sp2 • Aldehydes are named as alkanal as follows:
R 1. CH3CHO Ethanal
• These have a C = O = O group (Carbonyl
R' 2. CH3CHClCH2CHO 3-Chloro-butanal
group) and a general formula of Cn H2n O so these 3. CHO–CH2–CH2–CHO Butan-1, 4-dial
are called as carbonyl compounds.
CHO But 3-en 1-al
The formula of an aldehyde is 4.
H
CHO 2-Hydroxy cyclohexene 1-carbonal
| 5.
R–C=O OH or Carboxaldehyde
(where R=H or any alkyl or aryl group) 1
5 3 2
For a Ketone the formula is 4
6. O O
R
OH OH
C=O
R' 2, 4 Di-hydroxy pent 2-en 1, 5 di-al
(where R and R′ may be same or different alkyl or CHO CHO
aryl groups) Hexan 2, 3, 5 tri carboxalde
7. –hyde
• If R and R′ represent the same alkyl or aryl groups,
the ketone is a simple ketone as in the case of acetone CHO
(CH3COCH3).
28.2 Chapter 28
• Ketones are named as alkanones as shown below: By Wacker method

CuCl2
1. CH3COCH3 Propanone-2 or Propan 2-one CH2 = CH2 + H2O + PdCl2 CH3CHO + 2HCl + Pd
2. CH3COCH2COCH3 Penta-2, 4-dione CuCl2
CH3 – CH = CH2 + H2O + PdCl2
3. CH2COCHBrCH3 3-Bromo-butan-2-one CH3 – C – CH3 + 2HCl + Pd
||
O
O
OH 3-Amino 2-hydroxy Acetone
4.
NH cyclohex 2-en 1-one
2 By the hydration of alkynes (Kucherov’s Reaction)
O Hg2+, dil. H2SO4
O RC≡CH + H2O RC=CHOH
4 CH3 333 K
5 6 8 Tautomerization
5. 2 RCH2CHO
1 3 7
OH Examples,
5-Hydroxy 7-Methyl oct 3-en 2, 6 di-one
Hg2+, dil. H2SO4
1. HC≡CH + H2O CH2=CHOH
Isomerism Shown by Aldehydes and 333 K
Ethyne
Ketones Tautomerization
CH3CHO
• R–CHO can show functional isomerism and chain Acetaldehyde
isomerism. Hg, dil. H2SO4

• R–CO–R can show functional isomerism and meta- 2. CH3C≡CH + H2O
333 K
merism. For example, in the case of C4H8O
O OH
1. CH3CH2CH2CHO and (CH3)2CHCHO are chain
|| |
isomers. Tautomerization
CH3–C–CH3 CH3–C=CH2
2. CH3COCH2CH3 is the functional isomer to both of
these. By hydrolysis of gem dihalides
RCHX2 + 2KOH (aq) RCH(OH)2
General Methods of Preparation –2KX
– H 2O
for both R–CHO and R–CO–R 1,1-Dihaloalkane
By ozonolysis of alkenes Alkenes on ozonolysis and RCHO

followed by hydrolysis give aldehydes and ketones. Examples,
Examples, 1. CH3CHCl2+ 2KOH (aq) CH3CH(OH)2
–2KCl
O3/CCl4 O CH2 1,1-Dichloroethane
1. CH2=CH2 O
196 K CH3CHO – H2O
O CH2
Ethylene ozonide Acetaldehyde
2. (CH3)2C.Cl2 + 2KOH (aq) –2KCl
(CH3)2C(OH)2
2HCHO Zn/H2O 2, 2-Dichloroetheane
Formaldehyde – ZnO CH3–CO–CH3 – H 2O
Acetone
O
O3/CCl4 By dehydrogenation of alcohols Here the vapours of
2. (CH3)2C=CHCH3 (CH3)2 C CHCH3
alcohol are passed over copper at 300oC as follows:
2-methyl but-2-ene
Cu/300oC
O O 1. R–CH2OH R–CHO + H2
Ozonide
Zn/H2O
CH3CHO + CH3COCH3 Cu/300oC
– ZnO 2. (R)2 CHOH R–CO–R + H2
Acetaldehyde Acetone
AIM : FREE EDUCATION Organic
TO ALL APUL
Compounds Containing Oxygen-II 28.3
By oxidation of alcohols • Tertiary alcohol: A Tertiary alcohol gives ketone

on oxidation under extreme conditions only.
• Primary alcohol: A primary alcohol gives aldehyde
on oxidation by using acidic K2Cr2O7 or pyridinium CH3 CH3
4 [O]
chlorochromate (CrO3 . C5H5N . HCl) etc. CH3 C OH Conc. HNO C =O
3
H CH3 CH 3
—CO2
| —H2O
K Cr O / H SO
R–C–OH + [O] 2 2 7 2 4
| From diols
H • CH2–OH
1° alcohol HIO4
| 2HCHO + HIO3 + H2O
Periodic acid
O OH CH2–OH Formaldehyde
|| | Glycol
R–C–H R–C–OH
–H2O This reaction is called Criegee’s Reaction.
|
H CH2–OH
(CH3COO)4Pb
• This reaction can also be carried out by using CrO3 | 2HCHO + CH3COOH
Lead tetracetate
– pyridine/CH2Cl2. Here due to absence of H2O alde- CH2–OH in benzene Formaldehyde
hydrate is not formed so for their oxidation is not Glycol + (CH3COO)2Pb
possible.
CrO3-pyridine HIO4
C2H5–OH + [O] H3C – CHO
CH2Cl2, –H2O Aldehdyde (Ethanal) CH3—CH—OH 2CH3CHO + HIO3 + H2O
Ethyl alcohol —
PCC CH3—CH—OH
CH2=CH–CH2OH CH2 = CH–CHO
CH2Cl2
CH3 HIO4 CH3
Here raction does not occur at (=) bond also.
C—OH C=O + HCHO
CrO3–Pyridine is called Sarett’s Reagent or Sarett–
—
CH3 CH3 + HIO3 + H2O

Collin’s Reagent. CH2OH
• Secondary alcohols: A secondary alcohol gives
ketone on oxidation by using acidic K2Cr2O7 under From amines
extreme conditions. [O]
1. RCH2NH2 Alk. KMnO4
R–CH=NH
(R)2 CHOH–[O] K2Cr2O7 / H7SO4
2° alcohol H 2O
R–CHO + NH3 + H2O

[O]
2. (R)2CHNH2 Alk. KMnO4
(R)2 . C=NH
O OH
|| |
H2O
R–C–R –H2O
R–C–OH
|
R R–CO–R + NH3 + H2O
Example,
OH By decarboxylation of calcium salts of
Ň carboxylic acids
K2Cr2O7 / H7SO4
CH3− C−H + [O]
Ň R−COO OOCH Δ
CH3 Ca + Ca 2 R−CHO
R−COO OOCH +
Isopropanol 2 CaCO3Ļ
O O
Œ OH R−COO
—
—
CH3 ∆
CH3−C−CH3 C Ca R−C−R + CaCO3Ļ
−H 2 O CH3 OH R−COO
Acetone
28.4 Chapter 28
∆ Rosenmund’s reaction Aldehydes can be prepared by

(HCOO)2 Ca HCHO + CaCO3 passing H2 gas through a boiling solution of acid chlo-
Calcium formate Formaldehyde Calcium carbonate
ride in xylene in the presence of catalyst Pd supported by
∆
BaSO4.
(CH3COO)2 Ca CH3–CO–CH3 + CaCO3
• Here the catalyst is poisoned by sulphur or quinoline
Calcium acetate Acetone
to avoid further reduction of aldehydes into alcohols.
∆
(CH3COO)2 Ca + Ca(OOCH)2 2CH3CHO
O O
Calcium acetate Calcium formate + 2CaCO3 || Pd/BaSO4 ||
R–C–Cl sulphur R–C–H + HCl
By catalytic decomposition of fatty acids When vapours
Acid chloride Aldehyde
of fatty acids are passed over heated alumina or thoria or
magnous oxide, carbonyl compounds are formed. Example,
Al2O3
RCOOH + HCOOH 400°C
RCHO + H2O + CO2 O O
Al2O3 || Pd/BaSO4 ||
CH3COOH + HCOOH 400°C
CH3CHO + H2O + CO2 H3C–C–Cl H3C–C–H + HCl
sulphur
Acid chloride Acetaldehyde
MnO
2CH3COOH 500°C CH3COCH3 + H2O + CO2
Lithium tri-ter butoxyaluminium hydride or SnH2 can also
Acetic acid Acetone
be used here.
Preparations for Aldehydes only Preparation for Ketones only

From organo metallics
From Grignard reagent Grignard reagent gives alde-
1. From Dialkyl cadmium
hyde only with HCN as follow:
dry ether
HC ≡ N + RMgI HRC=NMgI O O
Hydrogen || ∆ ||
Cyanide 2H2O 2R–C–Cl + Cd(R′ )2 Dry ether 2R–C–R′ + CdCl2
RCHO + NH3 + Mg.OH.I Dialkyl
H+
Aldehyde Cadmium
2. From Grignard reagent

From Stephen’s reduction
(i) From Grignard Reagent and Acid Chlorides
Sn/HCl
R–C≡N + 2[H] R–CH=NH R– CO – Cl + R′MgX R – CO – R + XMgCl
H2O/H+
Alkane nitrile RCHO + NH3 Example,
Aldehyde CH3 – CO – Cl + CH3MgCl CH3COCH3
Example, + MgCl2
Sn/HCl
H3C–C≡ N + 2[H] H3C–CH=NH (ii) From Cyanide and Grignard Reagent
Ethane nitrile Imine
H2O/H+ H
CH3CHO + NH3 R'−MgX R O H2 OH
2H2O
R⎯C≡N C=N−MgX
Acetaldehyde R'
From Alkenes by oxo method
CoH(CO)4 100°C R−C−R´ + NH3 + MgX(OH)
—
—
C=C + CO + H2 under pressure

O
C C CHO 3. From Dialkyl cuprutes

O
e.g., CH2 CH3 ||
|| CoH(CO)4 100°C | R–C–Cl + (R′)2CuLi
CH2 + CO + H2 under pressure CH2–CHO Ether
RCOR′ + LiCl + R′.Cu
TO ALL APUL
By acylation of alkenes Chemical Properties

R–C–Cl + H2C=CHR′
|| Reactions due to carbonyl group
O Nucleophilic addition reaction Both aldehydes and
R′ ketones undergo nucleophilic addition reactions due to the
| presence of carbonyl group. This reaction is shown below.
R–C–CH2–CH–Cl
|| +δ
O Nu
Nu
−
−
– HCl R–C–CH=CH–R′ C=O C −δ C−O
|| O
Transition state Nu
O
+
• It is an example of Markovnikov’s addition initiated E

C−OE
by R–C+=O [acylium cation].
Nu
Physical Properties
• The reactivity for nucleophilic addition reaction
• Formaldehyde is a gas while other aldehydes are col-
of a carbonyl compound depends upon the mag-
ourless, volatile liquids up to compounds with car-
nitude of positive charge present on the carbon
bon number 10. Higher members are solids.
atom of carbonyl group that is, the reactivity is
• Lower aldehydes have an unpleasant smell while increased by electron attracting groups like –
higher aldehydes and ketones have a pleasant smell. NO2, – CX 3 and decreased by electron releasing
• The lower aldehydes and ketones are soluble groups like methyl, alkoxy groups.
in water due to H-bonding, the solubility then
• Reactivity for nucleophilic addition reaction for car-
decreases after 5 carbon-atom members. Aromatic
bonyl compounds decreases as follows:
aldehydes and ketones are insoluble in water.
• Ketones and aldehydes are polar compounds so they (i) HCHO > CH3CHO > CH3CH2CHO > CH3COCH3 >
have higher boiling points than those of non polar
CH3COC2H5>C2H5COC2H5>….(CH3)3C.CO.C (CH3)3
compounds with same molecular weight like alkanes
or alkenes. (ii)
dipolar attractions CH2−CHO > CH2−CHO > CH2−CHO > CH2−CHO
—
+δ −δ +δ −δ +δ −δ NO2 CX3 X
C=O C=O C=O
• These have lower boiling points than alcohols

R
and acids due to lack of intermolecular Hydrogen > CH2−CHO > C=O
bonding.
—
R
O R
OH O
(iii) φ–CHO > φ–COCH3 > φ–COφ
> > >
B.Pin Kelvin 371 329 322 309
(a) Reaction with HCN: Carbonyl compounds react
• These are slightly acidic in nature (as alcohols) due with HCN or NaCN and diluted H 2SO4 to give
to the resonance of enolate ion. cyanohydrins which on hydrolysis give hydroxy
Example, acids.
O O NaCN + H2SO4 HCN + NaHSO4
|| || –
– HCN + H2O CN + H3O+
CH3–C–H CH2 – CH
–
O CN
−
−
+
H
| C=O C−O C − OH
CH2 = C–H CN
CN
28.6 Chapter 28
Example, • In case of hindered ketones like (CH3)3C–

H H CO–C(CH3)3 the reaction is not possible due to the
| | steric hindrance caused by bulky methyl groups.
CH3 – C = O + HCN CH3 – C – CN
Acetaldehyde | (c) Addition of Grignard reagent: Here alcohols are
OH
Acetaldehyde cyanohydrin
formed as follows.
R'
H
C = O + R'MgX C
| H+/H2O
CH3–C–COOH OMgBr
| H2O
OH
Lactic acid
C − OH
Lactic acid on oxidn and dehydration gives Pyruvic R'
acid and Acrylic acid respectively.
• Here all aldehydes give secondary alcohols except
O
|| formaldehyde which gives primary alcohol.
CH3—CH.OH—COOH (O) CH3—C—COOH R R R
Δ Pyruvic acid C = O + RMgBr C
con. H2SO4 H H OMgBr
H2O
CH2=CH—COOH
Acrylic acid
R
CH ⎯ OH + BrMgOH
R'
Secondary alcohol
(b) Addition of sodium bi-sulphite: Carbonyl compounds
react with saturated aqueous solution of sodium • All ketones give tertiary alcohols.
bisulphite to give their solid, crystalline bisulphite R R'
derivatives. R
C = O + RMgBr C
OH H H OMgBr
C = O + NaHSO3 C
SO3Na R
Bisulphite H2O
C ⎯ OH + BrMgOH
R'
Example, R
Tertiary alcohol
H H
| | (d) Reaction with H2O
R–C= O + NaHSO3 R–C–SO3Na
| C=O + H. OH C
OH OH
Sodium bisulphite salt unstable products
R R
| |
R – C = O + NaHSO3 R – C – SO3Na
|
C=O + H 2O
OH
Sodium bisulphite salt
• Chloral hydrate is stable due to intramolecular
Hydrogen bonding in its butterfly like structure.
TO ALL APUL
Cl H O (a) Reaction with NH3 derivatives
—
Cl CH PH=3.5
— C=O + H2N – X C–N–X
Cl O
Cl OH H
H
H-bonding
O H−O O−H
H-bonding C =N – X + H2O
O O O O
H2O Here X–may be –OH, –NH2 , –NH ∅ etc.
H • On reaction with hydroxylamine (NH2OH )
—
O O oximes are formed.
O
H2O R PH=3.5
R
O C=O + H2N–OH C =N–OH
= + H2O
O R'
O O — R' Oxime
Indane H
1, 2, 3, trione Ninhydrin • On reaction with hydrazine (NH2 NH2 ) hydra-
zones are formed.
R PH=3.5
R
(e) Addition with alcohols: Here acetals and ketals are C =O
= + H2N–NH2 C =N–NH
= + H2O
2
formed. R' R'
Hydrazone
C = O + 2 HOR
• On reaction with semicarbazides (H2 NNH.CONH2 )
semicarbazones are formed.
R
dry HCl OR C = O + H2N. NH – C – NH2 Ph = 3.5
C + H 2O R' ||
OR R O
Acetal
C = N. NH – C – NH2 + H2O
CH3 CH3 O−CH2 R' ||
HO–CH2
e.g.,
—
C=O + C O
CH3 HO–CH2 CH3 O−CH2 Semicarbazones
In case of Semicarbozide the –NH2 and –NH groups

R
(f ) Reaction with thiols (R–SH ): Here, thio acetal and attached to C = O group do not participate in the reac-
thio ketals are formed. R'
tion as lp e– on them are delocalised due to resonance
SR as follows.
C = O + 2H−S−R C
O O
SR
—
—
—
Thio Acetals or Ketals NH2—NH—C—NH2 NH2—NH—C=NH2

CH3 HS−CH2 CH3 S−CH2
e.g., HCl
—
C=O + C
CH3 HS−CH2 CH3 S−CH2 O
—
Substitution reactions In such reactions the oxygen NH2—NH=C—NH2

atom of carbonyl group is substituted by other groups for
example It means these groups are on favourable for
Nucleophillic attack.
28.8 Chapter 28
• On reaction with phenyl hydrazine (NH2.NH.C6 H5 ) R R OH

phenyl hydrazones are formed. H2/ Ni or Pt or Pd
R C=O C
R R
LiAlH4 or NaBH4
C ==O + H2N.NH.C6H 5 C =N.NH.C
= H + H2O R H
6 5
R' R' 2° alcohol
Phenyl hydrazones
• On reaction with 2, 4 dinitro phenyl hydrazine R
(Brady’s reagent) it gives bright orange or yel- In case a (=) bond is present along with a C =O=
R R' only
group NaBH4 is better to be used as it reduces
low precipitate so it is used to identify C == O R
compounds. R' C =O
= gp. While LiAlH4 reduces both (=) bond and
R'
R
2 C =O
= gp.
R'
C = O + H2N•NH NO2
R–CH=CH–CH2OH
NaBH4
R—CH=CH—CHO
NO2
− H2O LiAlH4
C = N•NH NO2
R—CH2—CH2—CH2OH
2, 4 Dinitro phenyl hydrazones
(Orange or yellow ppt.)
(b) Reduction into alkanes: Carbonyl compounds on
(b) Reaction with primary amines: reduction by HI in presence of red phosphorus give
R R OH alkanes.
C = O +H 2NR C R
H C == O + 4 HI Red Phosphorus CH2 + 2I2 + H2O
H NH R R'
− H2O (c) Clemmensen reduction: It involves reduction of car-
bonyl compounds by zinc amalgam and conc. HCl
R − CH = N − R
Aldimine (Schiff bases)
into alkanes.
Zn-Hg/HCl
R R OH RCHO + 4[H] R – CH3 + H2O
C = O + H2NR C Alkane
R R NH R
R R
− H2O Zn-Hg / HCl
C = O + 4 [H] CH2 + H2O
R R
R
C = NR (d ) Wolff–Kishner reduction: It involves reduction of
R
Ketimine carbonyl compounds with hydrazine hydrate and
KOH in ethylene glycol at 453–473 K or strong bases
(c) Reaction with PCl5 like NaNH2, KNH2 into alcohols.
NH2.NH2
C = O + PCl5 C R–CH=O R–CH=NNH2
–H2O
Cl Hydrazone
Reduction Reactions KOH, glycol

R–CH3 + N2 453 – 473 K
(a) Reduction into alcohols: carbonyl compounds on
catalytic reduction and reduction with complex metal
hydrides give alcohols as follows R R
NH2.NH2
C=O −H2O C = NNH2
R R OH R R
H2/ Ni or Pt or Pd
C=O LiAlH4 or NaBH4
C
H H H KOH, glycol
R–CH2–R + N2
1° alcohol 453–473 K
TO ALL APUL
Name Reactions Crossed aldol condensation Aldol condensation between

two different aldehydes or ketones or between one aldehyde
Aldol condensation It is given by those aldehydes and and one ketone is called crossed aldol condensation.
ketones which contain α-H-atoms in presence of dilute
alkali like NaOH, Ba(OH)2 to give β-hydroxy carbonyl Example,
compounds (aldol or ketol) which on further heating dil. NaOH
gives α, β-unsaturated carbonyl compounds. It is possible CH3CHO + HCHO
+
between two same or different carboxyl compounds but at H
least one must have α-H-atoms. It involves formation of a CH2=CH–CHO HOCH2–CH2–CHO
H2O
carbanion. Acrolein 3 hydroxypropanal
Example,
H OH
| | dil
2CH3–C=O
dil. NaOH
CH3–C–CH2–CHO C6H5CHO + H–CH2−CHO C6H5−CH−CH2−CHO
base
—
Acetaldehyde | OH
H Δ
3-hydroxybutanal (Aldol) −H2O
C6H5−CH =CH−CHO
H+
Cinnamaldehyde
∆ or
– H 2O 3-Phenyl Prop 2-en-1-al
CH3CH = CHCHO Claisen–Schmidt condensation A base catalysed
But-2-en- 1-al
(Crotonaldehyde) condensation of an aromatic aldehyde and an aliphatic
Aldol condensation can also take place in the presence aldehyde or ketone having α-H-atom is known as Claisen-
of an acid. Schmidt condensation or Claisen reaction.
Example, For example,
CH3 Dil. NaOH, 273 K
HCl C6H5CH = O + CH3 – CHO
C = O + H3 CHCOCH3 − H2O
Benzaldehyde
CH3 Acetone
Acetone [C6H5– CHOH – CH2–CHO]
Aldol
–H2O
CH3 C6H5 – CH = CH – CHO
Cinnamaldehyde
C = CHCOCH3
CH3 Mesityloxide dil. NaOH
C6H5CHO + CH3COOC2H5
CH3COCH3
C6H5
CH3 CH3 |
C = CHCOCH = C CH
CH3 CH3
Phorone ||
• If the reaction is carried out in presence of Ba(OH)2 CH
the major product is mesityl oxide but with HCl it is |
phorone. COO
• Formaldehyde undergoes condensation in presence |
of Ba(OH)2 or Ca(OH)2 to form formose. C2H5
Ba(OH)2 Ethyl Cinnamate
HCHO + HCHO CH2CHO
| Cannizzaro reaction This reaction is given by only
OH those aldehydes which do not contain α hydrogen atoms. It
More HCHO CH2OH(CHOH)4CHO is a disproportionation reaction. In which rate determining
Ba(OH)2 step is H shift.
Formose
28.10 AIM : FREE EDUCATION TO ALL APUL
Chapter 28
For example Intramolecular Cannizzaro reaction Here, dispropor-

tionation reaction occurs within the same molecule.
(1) Example,
O CHO–CHO + NaOH CH2OH
|| Glyoxal |
2H–C–H + NaOH CH3OH + HCOONa COONa
Formaldehyde
O
NaOH
(2) 2C6H5CHO + NaOH C6H5CH2OH C—CHO CH.OH—COONa
Benzaldehyde Benzyl alcohol
+ C6H5COONa Tischenko reaction It is the modified form of Cannizzaro
Sod. Benzoate reaction as any aldehyde can take part in it. Here, in the
presence of aluminium ethoxide aldehydes form esters as
(3) CHO COONa CH2OH shown below.
NaOH
—
Al(OC2H5)3
+
COOH COONa COONa 2CH3CHO [CH3COOH + CH3CH2OH]

Acetic acid Ethyl alcohol
(4) CH3 CH3

NaOH –H2O
CH−CHO CH−CH2OH
CH3 CH3
2-Methyl propanol CH3COOCH2CH3
Ethyl acetate
CH3
+ CH−COONa Perkin condensation Here, aromatic aldehydes react
CH3
with aliphatic acid anhydrides (having minimum two α-hy-
drpgen atoms) in the presence of sodium salt of the same
In this case α-Carbanion is less stable and attack of this acid as base, to form condensation products which upon
carbanion to the carboxyl carbon is difficult due to sderic hydrolysis give α, β-unsaturated acids.
linderance which means Aldol condensation is not feasible. Example,
Crossed Cannizzaro reaction It occurs between two dif- C6H5–CH=O + H2 CHCO–O–COCH3
ferent aldehydes. Here, the smaller aldehyde get oxidized Benzaldehyde Acetic anhydride
while the larger aldehyde get reduced into an alcohol.
– H2O
Example, [C6H5CH=CH–CO–O–COCH3]
453 K
C6H5CHO + HCHO + NaOH Condensation product CH3COONa
Benzaldehyde Formaldehyde (50 %) H2O
C6H5–CH2–OH + HCOONa C6H5CH=CHCOOH + CH3COOH
Benzyl alcohol Sodium formate Cinnamic acid Acetic acid
CHO CH2OH Wittig reaction The reaction between an aldehyde or a

ketone with a phosphorus ylide (a molecule that bears no
NaOH overall charge but has a negatively charged carbon atom
+ HCHO + HCOONa bonded to a positively charged heteroatom is called an
ylide) to give a substituted alkene is called Wittig reaction.
OCH3 OCH3 It involves carbene as a reaction intermediate.
R – + Dry ether or THF
NaOH
+ HCHO + HCOONa C = O + :C H2= P (C6H5)3
CHO CH2OH R'
O O Aldehyde Phosphorus ylide
farfural aldehyde farfural alcohol
NaOH R
(CH3)3C.CHO + HCHO (CH3)3C.CH2OH C = CH2 + (C6H5 )3P = O
+ R'
HCOONa Substituted Triphenyl phosphine
alkene oxide
TO Compounds
ALL APUL
Containing Oxygen-II 28.11
Example, e.g., R–CH2–CHO

(O)
R–C–CHO
Dry ether SeO2
(CH3)2 C=O + CH3CH=P(C6H5)3 ||
Ethylenetriphenyl O
phosphorane (O)
R–C–CH2–R R–C–C–R
SeO2
(CH3)2 C = CH–CH3 + (C6H5)3PO || || ||
2-methylbut-2-ene
O O O
Reformatsky reaction α-Bromoesters react with alde- Reactions Shown only by Aldehydes
hydes and ketones in the presence of zinc dust to form
addition product which upon mild hydrolysis give β-hy- Reducing properties
droxyesters. This reaction is known as Reformatsky reac- Aldehydes and not ketones exhibit reducing properties.
tion. For example,
Dry ether Reaction with Schiff’s reagent Schiff’s reagent is a
Br– CH2COOC2H5 + Zn dilute solution of rosaniline hydrochloride in water.
Ethyl bromoacetate The magenta or pink colour of this solution is dis-
charged by passing SO2 gas through it.
BrZn – CH2COOC2H5 R – CHO + Schiff’s reagent Pink colour
Organozinc compound Salicyldehyde fails to show this reaction due to chelation.
CH3 Reaction with tollen’s reagent Ammonical solution of
Dry ether
C = O + BrZn−CH2COOC2H5 silver nitrate is called Tollen’s reagent.
H ’
AgNO3 + NH4OH NH4NO3 + AgOH
–
CH3 OZnBr AgOH + 2NH4OH [Ag(NH3)2]+ OH + 2H2O
C Tollen’s reagent
Diammine silver (I)
H CH2 COOC2H5 Hydroxide
CH3 RCHO + 2[Ag(NH3)2]OH

Dry ether
OH Aldehyde Tollen’s reagent
C RCOOH + H2O + 4NH3 + 2Ag ↓
− Zn(OH)Br
H CH2 COOC2H5 Carboxylic acid silver mirror
β-hydroxy ester Or
Knoevenagel condensation In this reaction, carbonyl RCHO + Ag2O RCOOH + 2Ag↓
compounds undergo condensation with diethyl malonate
• It is also known as silver mirror test for aldehydes.
to give α, β-unsaturated acids.
Pyridine • This test is also given by unsaturated aldehydes,
RCH = O + H2 C(COOC2H5 )2 –H2O however double bond is not effected here.
Aldehyde Diethyl malonate
For example,
RCH = C(COOC2H5 )2 CH2 = CH – CHO + Ag2O

+
H /H2O CH2 = CH – COOH + 2Ag ↓
Hydrolysis
RCH = C(COOH)2 Reaction with Fehling’s solution Fehling’s solution is
∆ copper sulphate solution and alkaline solution of sodium
RCH=CHCOOH
–CO2 potassium tartrate (Rochelle salt).
α, β-unsaturated acid
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
• If R is methyl, then crotonic acid is formed and if R ∆
Cu(OH)2 CuO + H2O
is phenyl then cinnamic acid is formed. RCHO + 2CuO Cu2O ↓ + RCOOH
Aldehyde Cuprous oxide Carboxylic
Oxidation with SeO2
(Red ppt.) acid
Carbonyl
R compounds having a–CH3 or –CH2 –gp attached or
–
with the C = O gp. Under go oxidation with SeO2 to give RCHO + 2Cu+2 + 3OH RCOO + 2Cu+ + H2O
R' Red ppt.
α-di Carbonyl compounds.
Chapter 28
• This test is not shown by benzaldehyde as aromatic Example,

aldehydes are very weak reductants. CH3 OH
CH3 ether Δ
Reaction with Benedict’s solution It is a solution of C = O + NH3 C
CuSO4, sodium citrate and Na2CO3. When heated with an H H NH2
Aldehyde Acetaldehyde
aldehyde, a reddish brown ppt. of Cu2O is formed. ammonia
–
RCHO + 2Cu+2 + 3OH
–
CH3
RCOO + 3H2O + Cu2O↓ Heat
C = NH − H2O
(red ppt.) H
• This test is given by aliphatic aldehydes only. Acetaldimine
Reaction with Bromine water Aldehydes decolourise • Aliphatic ketones also form complexes with ammo-
bromine water (red).
nia called ketonic amines. For example, acetone and
RCHO + Br2 + H2O RCOOH + 2HBr ammonia give rise to diacetoneamine.
H3C CH3 + H.NH2 + HCH2 COCH2

FA C T TO R E M E M B E R
C
α-Hydroxy ketone can also reduce these reagents like
R–CHO. O
e.g., H3C NH2
O H2O + C
||
Ag2O H3C CH2COCH3
CH3–CH–C–CH3 2CH3COOH Di acetone amine
| T.R
+ 2Ag ↓
OH Silver mirror Reaction with alcohol
H
|
HCl
Reaction with ammonia Formaldehyde forms a stable R–CHO + HOR′ R–C–OR′
complex with ammonia which is known as urotropine. |
OH
6HCHO + 4NH3 (CH2)6N4 + 6H2O Hemi Acetal
Urotropine or H
Hexa methylene tetra amine | R′OH
N R–C–OR′
|
CH2 CH2 OR
CH2
Acetal
N⎯CH2 N
• Acetals are only stable in basic medium but undergo
CH2⎯N⎯CH2 hydrolysis in acidic medium to give original alde-
hydes again.
• It is very effective in curing urinary infections and
a rthritis 1. Polymerization of aldehydes
∆, conc. H2SO4
• All other aldehydes react with ammonia in presence n–HCHO (CH2O)n .H2O
of ether to give adducts which upon heating give Aq. Solution Polyoxymethylene or
aldimines. Para formaldehyde
TO Compounds
ALL APUL
∆, conc. H2SO4 Beckmann’s rearrangement Here ketoximes are

3HCHO (HCHO)3 converted into N-substituted amides with the help of
Meta formaldehyde H2SO4, PCl5, SOCl2.
or
R +
O CH2 C=O + H2N − OH H
CH2 O R −H2O
O CH2 R
Trioxane C = N OH
Ca(OH)2 R
6CH2O (HCHO)6
Meerwein–Ponndorf–Verley reduction (MPV
Formose
Reduction) Here, ketones are reduced into secondary
∆, conc. H2SO4
3CH3CHO (CH3CHO)3 alcohols.
Paraldehyde (Hypnotic) It opposite of Oppenauer oxidation
CH3 R CH3 ((CH3)2CHO)3Al
C= O + CHOH
O CH R CH3
CH3 CH O
O CH R CH3
CH OH + C=O
CH3 R CH3
∆, conc. H2SO4 O
4CH3CHO (CH3CHO)4
Metaldehyde CH3 ((CH3)2CHO)3Al
or + CHOH
CH3
CH3 – CH – O – CH – CH3
| | OH
O O
| CH3
| + C=O
CH3 – CH – O – CH – CH3 CH3
Reactions Shown by Ketones Only Oxidation of ketone During such oxidation reactions,
Baeyer–Villiger oxidation It involves the oxida- the keto group stays with the smaller alkyl group (Popoff’s
tion of aliphatic ketones into esters and that of cyclic rule).
ketones into esters by treatment with peroxyacids such Example,
as peracetic acid, perbenzoic acid, trifluoroperacetic [O]
acid. CH3COCH2CH2CH3
2-Pentanone
O O
|| || CH3COOH + CH3CH2COOH
Perbenzoic acid
R–C–R R – C – OR Acetic acid Propionic acid
Ketone Ester
O
O HNO3
Perbenzoic acid || CH3COOH
oxidn
e.g., C6H5COCH3 C6H5–O–C–CH3 +
Phenylacetate CH3−CH2−CH2−COOH
Pentan 2-one
+
Perbenzoic acid CH3CH2−COOH + HCOOH
CH3–CO–CH3 CH3–O–C–CH3
||
O [O]
Methylacetate
In case of Un-symmetrical ketones the prefered order H2O + CO2
of migration is 3° > 2° 1° > methyl.
Chapter 28
Reduction of ketone into pinacol (diol) When Methods of Preparation

ketones are reduced by Mg/Hg in neutral or alkaline
medium pinacols are formed. From toluene
Example, 1. By Etard’s reaction or oxidation by chromyl
chloride
CH3 CH3
| | Mg – Hg/H2O
H3C – C + C – CH3 + 2[H] O CrCl2OH
CH3 CH
|| || O CrCl2OH
O O 2CrO2Cl2
Acetone −H2O
CH3 CH3
| | CHO
H3C – C – C–CH3
| |
OH OH
2, 3-Dimethylbutane-2, 3-diol (pinacol)
CH2−CH3 CH2−CHO
Pyrolysis of ketones Here ketenes are formed.
Example, 1[O]
CrO2Cl2, C2H5OH
∆
CH3COCH3 973 K
CH2 = C = O + CH4
ketene Oxidation by chromic oxide Toluene on oxidation by
chromic oxide in acetic anhydride followed by hydrolysis
Reaction with nitrous acid Here isonitroso derivatives gives benzaldehyde.
are formed.
Example, CH3
(CH3CO)2O OOC.CH3
CH3COCH3 + HNO2 CH3COCH = NOH + H2O
CH
Oximino acetone or
CrO3
isonitroso acetone OOC.CH3
Reaction with sodamide Here sodium derivatives are
formed.
Example, NaOH CHO +2CH3COONa
ether
CH3COCH3 + NaNH2 CH3COCH2Na + NH3
Oxidation by air Toluene on oxidation by air in presence
Reaction with chloroform of V2O5 at 350oC gives benzaldehyde.
CH3 CH3 CHO

KOH
C=O + CHCI3
CH3 V2O5
CH3 + O2
OH 350°C
C
CH3 CCl 3 Here MnO2, oxide of Zr, Mo can also be used as catalysts.
Chloretone (Hypnotic) By the hydrolysis of benzal chloride
BENZALDEHYDE
Cl
CHO Ca(OH)2
CH
Cl
OH
It is present in bitter almonds in the form of its glycoside CH CHO
H2O
amygdalin also known as oil of bitter almonds. OH
TO Compounds
ALL APUL
From benzyl chloride By Gattermann–Koch reaction

Pb(NO3)2 AlCl3
CH2 Cl + H 2O H + CO + HCl
Benzyl chloride
COCl + HCl
[O]
CH2 OH CHO
HNO3
Here CO+HCl is used for formylation as HCOCl is
Benzyl alcohol + H2 O unstable.
From Styrene Ozonolysis of styrene followed by
From distillation of mixture of calcium benzoate and
hydrolysis gives benzaldehyde
calcium formate
O3/CCl4
COO OOCH C6H5CH = CH2
H2O/Zn
Ca + Ca Δ
C6H5CHO + HCHO + H2O2
COO OOCH
By Vilsmeyer Reaction
Calcirum bensoate Calcium formate (CH3)2NH + HCOOH
CHO
POCl3
CHO + 2CaCO3
Physical Properties
By Rosenmund reduction
Pd /BaSO4 • It is a colourless liquid with a boiling point of 179oC
COCI + 2 [H]
and smells like bitter almonds.
COCl + HCl • It is insoluble in water but soluble in organic solvents.

• It is steam volatile and heavier than water.
• Here Pd/BaSO4 are poisoned by ‘Sulphur or quino-
line’ to avoid further reduction. Chemical Properties
• Here lithium tri tert. butoxy aluminium hydride can Reactions due to –CHO group Here benzaldehyde
also be used at –78oC. shows similarities with aliphatic aldehydes.
1. Oxidation by acidic KMnO4 or K2Cr2O7
By Stephen’s reaction
[O]
CHO + HCl HNO3
COOH
SnCl2+HCl
C N + 2[H] ether Benzoic acid
H2O 2. Reaction with Schiff’s reagent It gives pink colour

CH = NH.HCl with schiff’s reagent. The pink colour disappears on
passing SO2 through it.
Aldimine Hydrochloride
3. Reaction with fehling solution
CHO + NH 4Cl
No reaction with Fehling solution occurs here as it is
not enough powerful reducing agent to reduce it due
Gatterman aldehyde reaction to +R effect of Benzene Ring.
AlCl3
H + HCN + HCl 4. Reaction with Tollen’s reagent
Δ
HOH CHO + Ag2O
CH = NH HCl
Aldimine Hydrochloride
COOH + 2Ag
CHO + NH 4Cl Silver mirror
(Black)
Chapter 28
5. Reduction (a) Reaction with HCN

Na + alc.
or LiAlH4
(a) CHO CH2OH CHO + HCN
HI/P
(b) CHO CH3 H
Zn − Hg C OH
+ HCl
(c) CHO CH3 CN
Clemmenson
Reduction Cyano hydrin of benzaldehyde
NH2NH2 (Optically active)
and C2H5ONa
(d) CHO CH3
Wolff Kishner (b) Reaction with RMgX
Reduction
6. Nucleophilic addition reactions: Aromatic Carbonyl CHO + CH3 MgX
Compounds are less reactive for nucleophillic addi-
tion reactions than aliphatic ones as the +ve effect on
H H
R benzene ring increases electron density at C-atom of H+
C == O group which makes addition of Nu– difficult. C OMgX C OH
R'
O O O O CH3 CH3
Phenyl ethanol
C⎯R C⎯R C⎯R C⎯R
(c) Reaction with NaHSO3
CHO + NaHSO3
The presence of electron withdrawing groups on OH

benzene ring increases reactivity. CH
CHO CHO SO3Na
Benzaldehyde sodium bisulphate
NO2
(A white solid)
I > NO2 7. Substitution reactions
(a) Reaction with PCl5
CHO COCH3
CHO + PCl5
> >
Cl
NO2 NO2
CH + POCl 3
CHO CHO CHO Cl
Benzal chloride
II > > (b) Reaction with hydroxylamine
NO2 CX3 X CHO + H2N . OH

Hydroxylamine
CHO CHO CHO
C H
> > > + H2 O
N OH
R OR Benzaldoxime
TO Compounds
ALL APUL
(c) Reaction with hydrazine 2. Nitration

CHO CHO
CHO + H2N − NH2
Hydrazine HNO3 + H2O
NO2
CH N.NH2 + H2O m-nitrobenzalddehyde
Benzaldehyde Hydrazone 3. Sulphonation
(d) Reaction with semicarbazide CHO CHO
CHO + H 2 N.NH CONH 2 H2SO4 + H2O

Semicarbazide SO3H
m-formyl benzene sulphonic acid
PhCH = N.NHCONH 2 + H2 O 4. Reaction with chlorine
Benzaldehyde semi Carbazone
0°C
CHO + Cl2
(e) Reaction with phenyl hydrazine
CHO + H2N.NH COCl +HCl
Phenyl Hydrazine Benzoyl chloride
5. Reaction with ammonia

CH = N.NH
Benzaldehyde phenyl hydrazone CHO H2NH + OHC
+
(f ) Reaction with 2, 4 dinitro phenyl hydrazine
CHO H2NH
NO2
CHO + H2N.NH NO2 −H2O CH N

NO2 CH
−3H2O
CH NO2 CH N
N.NH
Hydrobenzamide
Benzaldehyde 2, 4 dinitro phenyl hydrazone 6. Cannizzaro’s reaction
(orange or yellow ppt).
CHO + KOH
Benzaldehyde vs Aliphatic Aldehydes 2
Despite similarities in their structures benzaldehyde and
CH2OH + COOH
aliphatic aldehydes differ in the manner they react as
discussed below. Benzyl alcohol Potassium benzoate
Electrophillic substitution In benzaldehyde the –CHO CHO + HCHO + KOH

group is a ring deactivating, meta-directing group so the
rate of electrophilic substitution will be slower than that of CH2OH + HCOOK
benzene. Aliphatic Aldehydes do not show these reactions
Benzyl alcohol Potassium formate
1. Halogenation
7. Condensation with aniline
CHO
CHO CHO + H2N
Cl 2 + HCl
FeCl 3 CH=N +H2O
Cl
m-chlorobenzalddehye
Schiff’s base or Benzilidine
Chapter 28
Perkin reaction Benzaldehyde, on reaction with Tischenko reaction It is a modified form of cannizzaro
acetic anhydride in presence of sodium acetate gives α, reaction.
β-unsaturated acid (cinnamic acid). C2H5O(Al)
2 CHO
(CH3CO)2O
CHO CH3COONa, 180° C
COOCH2
CH = CHCOOH + CH 3COOH
Benzyl benzonate
Cinnamic acid
The reaction takes place through the formation of a Benzoin condensation Benzaldehyde on refluxing with
carbanion and in the reaction α-H atoms of anhydride are aqueous alcoholic KCN forms benzoin as follows
involved.
O
Reformatsky reaction Here benzaldehyde reacts with
Aq. Alc
zinc and α-halogenated ester to first produce a β-hydroxy CHO + H C KCN,
ester and then a α, β-unsaturated ester.
H H O
C + Zn + Br CH2COOR C C
−Bromo Ester
O OH
H Benzoin
H+ • Benzoin can be readily oxidized into benzyl.
C CH2COOR
[O]
O Zn Br CH C HNO3
H OH O
Δ
C CH2COOR −H2 O OH
(i) KOH
OH C C C
(ii) H+
CH CH COOR O O COOH
Benzyl Benzilic acid
Knoevenagel reaction Here, benzaldehyde reacts with
malonic ester or malonic acid in presence of base like Claisen–Schmidt reaction or claisen condensation Here,
pyridine to give α, β-unsaturated acid that is, cinnamic benzaldehyde undergoes condensation with another com-
acid. pound having α-hydrogen atom in presence of alkali to
COOR form α, β-unsaturated compounds.
CHO + H2C dil NaOH
COOR CHO + H2CHCHO
Malonic ester Acetaldehyde
COOR + 2
&+ & CH = CHCHO +H 2O
&225 Cinnamaldehyde
&22+
&+ & CHO + H2CHCOCH3
KOH
&22+ •
Acetone
CH = CHCOOH
CH = CHCOCH3 +H2O
Cinnamic acid
Benzilidine acetone
CHO CH=C−COOH
(CH3CH2CO)2O
—
I2, KOH
CH3CH2COONa CH3 • CH = CHCOCH3
α-Methyl Cinnmic acid
TO Compounds
ALL APUL
CARBOXYLIC ACIDS
CH = CHCOOH • Organic compounds having carboxylic group
Cinnamic acid
O
NaOC2H5
• CHO + H 2CH−COOC2H5 ||
Ethyl acetate (–C–OH) are called carboxylic acids.
• The name carboxyl is derived from carbonyl
R
CH = CHCOOC2H5 +H2O = O and hydroxyl ( –OH).
C=
Ethyl cinnamate R'
• Monocarboxylic acids of aliphatic series are com-
Reaction with dimethyl aniline Benzaldehyde reacts with monly known as fatty acids.
N-N-dimethyl aniline in presence of conc. H2SO4 or ZnCl2
to give malachite green. • The general formula of monocarboxylic acid is
CnH2n O2 or CnH2n+1 COOH
H N (CH3)2 • These are known as alkanoic acids. For example,
1. CH3COOH Ethanoic acid.
CHO + + 2. CH3CH2CH2COOH Butanoic acid
H N (CH3)2 3. (CH3)2CHCOOH 2-Methyl propanoic acid
4. CH3–CH2–CH=CH–COOH Pent-2-ene-1-oic acid
or 2-Pentenoic acid
N (CH3)2 5. C6H5– CH=CH–COOH
3-Phenyl prop 2-en 1-oic acid.
CH +H2O
6. COOH
N (CH3)2 |
CH=CH–CHO
Malachite green 4-oxo but 2-enoic acid.
(Tetramethyl diamino-triphenyl methane) • Some acids are given common names according
to the sources from which they are obtained. As in
FA C T TO R E M E M B E R the case of HCOOH formic acid [source is formica
(red ant)] C3H7COOH butyric acid [source is rancid
CH2CH3 butter]
COCH3
• Citric acid is obtained from citrus plant.
NH2.NH2
Base Isomerism Shown by Acids
Acids may show chain isomerism and functional isomer-
OH OH ism with esters, hydroxy carbonyl compounds and hydroxy
As In Case of Clemmansen reduction acid may cause dehy-
oxiranes or cyclic ethers.
In the case of C2H4O2, the various arrangement possible
dration so wolffkishner reduction is used.
are,
COR CH2R
1. CH3–COOH
Zn−Hg/HCl 2. HCOOCH3
or 3. CHO
HI/Red ‘P’
|
X X CH2–OH
It is not favorable to use wolffkishner reduction here as base 4. CH2 CH OH
causes dehydrohalogenation here.
O
Chapter 28
Acids also show optical and geomatrical isomerisms. By the hydrolysis of cyanides (R–CN) Cyanides on
Me hydrolysis by dilute HCl give acids as follows:
e.g., Et *
COOH Valeric Acid (optically active) R – C ≡ N + 2H2O R – COOH + NH3↑
H
Example,
H–C–COOH H–C–COOH
HCl
|| and || CH3 – C ≡ N + 2H2O CH3COOH + NH3 ↑
H–C–COOH HOOC–C–H
If hydrolysis is done by H2O2 amide is the final product.
Maleic acid cis Fumeric acid (trans)
From Grignard reagent and carbon dioxide
FA C T TO R E M E M B E R Grignard reagent on reaction with carbon dioxide followed
 R – COOH + NaHCO3 Effervesence of CO2
by hydrolysis gives acids as follows
Aq [Test of RCOOH] O
 Boiling point of R-COOH > R–OH or R–CHO ||
R − MgX + CO2 R − C − O MgX
or R–COOR′ H.OH
As acids have more extent of Hydrogen bonding,
X
 HCOOH Dimer in vapour or gas phase R − COOH + Mg
Liquid phase OH
For Example,
Polymer O
 HCOOH is a very powerful reducing agent and it reduces ||
Tollen’s reagent, Fehling solution and HgCl2. CH3MgX + CO2 CH3 − C − O MgX
liquid Dry H.OH
 Polymer CH3COOH Dimer
Phase benzene X
CH3COOH + Mg
OH
General Method of Preparation R–Li also gives R–COOH with CO2 as follows.
By the hydrolysis of acid derivatives Acid derivatives
O
can be easily hydrolyzed into acids by using dilute acids CO2 − ⊕
or dilute alkalines as follows R⎯Li R⎯C⎯OLi
Dry ether
R⎯Li
O
|| OLi
+ R⎯C⎯OLi
• R–C–Cl + H2O R–COOH + HCl H3O
Acid chloride
R
NaOH H2O R OH
R–COCl R–COONa R–COOH C R⎯C⎯R
–NaCl −H2O
R OH
O O (O)
|| R − COOH
R–C–NH2 + H2O R–COOH + NH3
Amide
From the Hydrolysis of Haloforms Haloforms undergo
hydrolysis to give acids as follows:
O
||
X OH
• R–C–OR’ + H2O R–COOH + R’-OH 3Na.OH
Ester R−C X −3NaX
R−C OH
X OH
R − CO NaOH
− 2H 2O R − COOH
O + H2O 2R − COOH
R − CO − 2H 2O R − COONa
Acid anhydride
• Here in place of NaOH, KOH can also be used.
TO Compounds
ALL APUL
By oxidation of carbonyl compounds Carbonyl com- O

pounds undergo oxidation into acids by using oxidizing ||
agent like acidic K2Cr2O7 or KMnO4 as follows R – C – NH2 + HNO2 R – COOH + N2+ H2O
R–CHO + [O] R–COOH Example,
Example,
O
CH3CHO + [O] CH3COOH ||
C6H5– C– NH2 + HNO2 C6H5COOH + N2+ H2O
R O
[O]
C=O Vigrously
R − C − OH + R’ − COOH Koch reaction Here alkenes are heated with carbon
R’ monoxide and water at high temperature and pressure to
give acids
• During oxidation of ketones the carobnyl group goes H3PO4
R – CH = CH2 + CO + H2O 350oC
with smaller alkyl group according to Popoff ’s rule.
R – CH2 – CH2 – COOH
Example,
Example,
CH3 O H3PO4
[O] CH3 – CH = CH2 + CO + H2O
C=O 2CH3 − C − OH 350oC
Vigrously
C2H5 CH3 – CH2 – CH2 – COOH
Butanoic acid
From dicarboxylic acid or esters + (CH3)2CHCOOH
2-Methyl propanoic acid
COOR
R − X + Na CH −NaX From R–ONa with CO Sodium alkoxide on
COOR reaction with carbon monoxide followed by reaction
with HCl gives acids
COOR
H.OH ∆
R − CH −R’ − OH R – ONa + CO R – COONa
NaOH
COOR HCl R – COOH
COOH
−CO2
R − CH2 − COOH Example,
R − CH
∆
COOH C2H5ONa + CO C2H5COONa
NaOH
Example, Sod. ethoxide
COOC2H5 HCl
C2H5COOH
C2H5Cl + Na CH − NaCl In case of HCOOH preparation CO and NaOH is used.
COOC2H5
Sodium malonate ∆ HQ
CO + NaOH HCOONa HCOOH
473 K –NaCl
COOC2H5
H.OH
C2H5 − CH From higher alkanes Higher alkanes like hexane,
−C2H5OH
heptane undergo oxidation to give acids as follows:
COOC2H5
∆, 120oC
COOH 2R – CH3 + 3O2 Mn acetate or stearate 2R – COOH + 2H2O
−CO2
C2H5 − CH C2H5 − CH2 − COOH
COOH Butanoic acid Example,
∆, 120oC
2C6H13– CH3 + 3O2 Mn acetate or stearate
From amide (R–CONH2) Amides on reaction with
Normal heptane
nitrous acid give acids as follows:
Chapter 28
2C6H13 – COOH + 2H2O Physical Properties

Heptanoic acid
Physical state Acids with C1 – C3 carbon atoms are
pungent smelling, colourless liquids and with C4 – C9 are
From alkenes Alkenes on oxidative cleavage by hot rotten butter smelling colourless liquids.
alkaline KMnO4 give acids as follows:
Solubility Lower acids with C1 to C4 carbon atom are
O O completely soluble in H2O due to intermolecular hydrogen
| | || || bonding with water, however, the solubility decreases with
hot [O]
–C=C– Alk. KMnO4
– C – OH + – C – OH the increase of molecular weight.
This trend is shown below:
Example, HCOOH > CH3COOH > C2H5COOH > C3H7COOH >
• Acids get dimerise i.e., exits as cyclic dimmers due
Hot [O]
CH3 – CH = CH – CH3 Alk. KMnO4 2CH3COOH to hydrogen bonding
O H O
• If the double bond is at terminal position formic acid R C
C R
is formed which further oxidizes into CO2 and H2O. O H
O
CH3–CH=CH2 Hot
CH3COOH + HCOOH Example, acetic acid exists as a dimer in benzene.
KMnO4
Boiling point The boiling points of acids are compa-
H2O + CO2 rably more than the corresponding alcohols, carbonyl
(O) compounds or acid derivatives due to higher extent of
hydrogen bonding.
From alkynes Alkynes on ozonolysis followed by • Boiling point of acids ∝ Molecular weight
hydrolysis give acids as follows
Example,
1. O3/CCl4 HCOOH < CH3COOH < C2H5COOH < C3H7COOH
R – C ≡ C – R’ 2. H2O <…..
R – COOH + R’ – COOH
Melting point The melting point of an acid with even
Example,
number of carbon atoms is more than and acid having next
1. O3 /CCl4
CH3 – C ≡ C – C2H5 CH3COOH odd number of carbon atoms. It is known as oscillation
2. H2O effect.
Pentyne-2 + C2H5COOH
• Melting point will increase as shown in the following
By Haloform reaction Methyl Ketones on oxidation by Example,
NaXO or X2/NaOH give acids as follows
C4H9COOH > C5H11COOH > …..
NaIO
R–CH2–CH2–C–CH3 R–CH2–CH2– • The – COOH group and alkyl group in acids with
|| or I2/NaOH–CHI3 COONa even number of carbons, lie on opposite sides and
O
H3O+ hence provide a closer packing in the lattice and have
R–CH2–CH2–COOH
high melting points.
NaIO O Chemical Properties

or ONa
I2/NaOH Reactions due to –COOH group
OH −CHI3
Butan 2-01 H3O+ Salt formation Acid reacts with sodium, sodium hydroxide,
sodium bicarbonate, sodium carbonate to form acid salts.
O Na
OH R–COOH R–COONa
NaOH , NaHCO3
Propanoic acid or Na2CO3
TO Compounds
ALL APUL
Example, R – COOH + N3H ∆

R – NH2 + N2 + CO2
Na Conc. H2SO4
Hydrazoic Acid
CH3COOH CH3COONa
NaOH Example,
Here CO2 evolved is from NaHCO3 or Na2CO3 and not ∆
C2H5COOH + N3H C2H5NH2 + N2 + CO2
Conc. H2SO4
of R–COOH. Hydrazoic Acid Ethyl amine
14 14
e.g., C6H5COOH + NaHCO3 C6H5 COONa + CO2 Decarboxylation Acids undergo decarboxylation with
+ H2O soda lime to give alkane.
∆ CaO
R – COOH NaOH R – COONa
1. Reaction with PCl5 or SOCl2 – H2O + NaOH
R – H + Na2CO3
R – COOH + PCl5 R – COCl + HCl + POCl3 Example,
Example, NaOH ∆ CaO
CH3COOH CH3COONa
CH3COOH + PCl5 CH3COCl + HCl + POCl3 –H2O + NaOH
CH4 + Na2CO3
Pyridine CaO,∆
R–COOH + SOCl2 R–COCl + SO2 + HCl HCOONa + NaOH Na2CO3 + H2
Example, Dehydration Acids undergo dehydration with P2O5 or
Pyridine con. H2SO4 to give acid anhydrides.
CH3COOH + SOCl2 CH3COCl + SO2 + HCl
Ester formation or esterification Acid on reaction with R − COOH R − CO
Δ
alcohols or diazomethane in presence of dilute acid or base + P2O5 O
gives esters as follows: R − COOH R − CO
Dil.
R – COOH + HOR R – COOR’ + H2O CH3 − COOH CH3CO
Acid Δ
Example, + P2O5 O + H2O
Dil. CH3CO
CH3COOH + HOC2H5 CH3COOC2H5 + H2O CH3 − COOH
Acid
R – COOH + CH2.N2 Dil.

R – COOCH3 + NH3 Reduction Acids can be reduced into alcohols with the
HCI help of LiAlH4
Example,
dil HCl O
C2H5COOH + CH2.N2 C2H5COOCH3 + NH3
Methyl propanoate || LiAlH4
R – C – OH + 4[H] R – CH2OH + H2O
FA C T TO R E M E M B E R Oxidation or burning Except formic acid, all other mono
 For ester formation reactivity decreases as follows: carboxylic acids are highly resistant to oxidation. They can
 In case of alcohols: primary > secondary > tertiary be oxidized only by prolong heating using strong oxidizing
alcohol agents and get converted to CO2 and H2O.
 In case of acids: HCOOH > CH3COOH > C2H5COOH O
> ........ ||
Δ
R–C–OH CO2 + H2O
O2
Reaction with NH3 Acid reacts with ammonia to give
Example,
ammonium salt which on heating gives amide as shown:
NH3 ∆ O
R – COOH RCOONH4 R – CONH2 ||
–H2O
Example, CH3–C–OH Δ CO2 + H2O
NH3 ∆ O2
CH3COOH CH3COONH4 –H2O Reaction with urea Acid reacts with urea to give amides.
CH3CONH2 R – COOH + NH2CONH2 R – CONH2 + NH3 + CO2
Acetamide
Schmidt reaction Acid reacts with hydrazoic acid in Example,
presence of conc. H2SO4 to give a primary amine. CH3COOH + NH2CONH2 CH3CONH2 + NH3 + CO2
Chapter 28
Heating effect of acid salts When calcium salts of 2KMnO4 + 3H2SO4 + 5CH2O K2SO4
acids are heated ketones are formed, while, when calcium + 3MnSO4 + 5CO2 + 8H2O
formate is heated an aldehyde is formed.
∆ Reaction with organometallics Acids react with organo
(R – COO)2Ca + (R’COO)2Ca metallics to give alkanes.
R – CO – R + R’ – CO – R’ + R – COR’
R’ – CH2MgX + R – COOH
Example, R’ – CH3 + R – COOMgX
HCOO Example,
Δ
Ca HCHO + CaCO3
HCOO CH3CH2MgX + CH3COOH
Calcium formate CH3 – CH3 + CH3COOMgX
CH3COO
Δ R – COOH + R’Li R’ – H + R – COOLi
Ca CH3COCH3
CH3COO
Calcium acetate Example,
HCOONa COONa COOH CH3 COOH + C2H5Li C2H6 + CH3COOLi
∆ H2SO4
+ | |
HCOONa COONa COOH Distinction Test Between R–COOH and Phenol:
Oxalic acid NaHCO3
R–COOH R–COONa + H2O + CO2
Hell–Volhard Zelinsky reaction Carboxylic acids having Effervescence
α-hydrogen atoms react with chlorine or bromine in FeCl3
presence of catalysts like red phosphorous, iron to give
(R–COO)3 Fe
α-chloro or bromo substituted acids.
Buff Coloured Precipitate.
Br2 or Cl2
R – CH2 – COOH R – CH – COOH OH
P |
Br or Cl NaHCO3
No Reaction or
Br2 Effervescence
Example, (I) CH3–CH2–COOH CH3–CH–COOH
P
|Br2/P FeCl3
Br (C6H5O)3 Fe
CH3CHBr2–COOH Blue or Violet
Cl2 Colouration
(II) COOH COOH
BENZOIC ACID
Cl
Reducing properties of HCOOH Formic acid shows COOH
reducing properties and reduces Tollen’s reagent,
Fehling’s solution, mercuric chloride and KMnO4.
Ag2O
HCOOH Tollen reagent H2O + CO2 + 2Ag ↓ It is present in nature in combined state as esters in Balsam
Silver mirror
and in the urine of horse as benzoyl glycine (Hippuric acid).
2CuO
HCOOH Fehling solution
H2O + CO2 + Cu2O ↓ Methods of Preparation
Red ppt. 1. By the hydrolysis of cyanobenzene
2HgCl2 H+
HCOOH 2HCl + CO2 + Hg2Cl2 ↓ C N + 2H2O
Hg2Cl2
HCOOH 2HCl + CO2 + 2Hg ↓
COOH + NH 3
Black
TO Compounds
ALL APUL
2. By the hydrolysis of benzamide [O]

CH2OH CHO
H+
CONH2 + H2O [O]
COOH
COOH + NH 3 By the hydrolysis of benzo trichloride
Cl OH
3. By the hydrolysis of benzoyl chloride 3 KOH
C Cl C OH
Cl −3KCl OH
H+
COCl + H2O Benzo trichloride
COOH + HCl −+ 2 COOH
• From Grignard Reagent

4. By the hydrolysis of ethyl benzoate
Mg Br + O = C = O
+
H
COOC2H5 + H2O
COOMg Br H2 O
COOH + C2H5OH Br
COOH + Mg
5. By the hydrolysis of benzoic anhydride OH
• From Freidal-Craft Reaction
CO H COCl COOH
H+
O + 2H 2 O COCl2 H 2O
Excess
CO Anhy.
AlCl3
In Benzene is in exceses Benzo phenone is formed.

COOH
2
Chemical Properties
By oxidation reactions Toluene on oxidation by alkaline
KMnO4 or CrO3 gives benzoic acid. Electrophilic substitution In benzoic acid the –COOH
group is ring deactivating and meta directing so rate
CH3 3[O]
COOH of electrophilic substitution will be slower than in
−H 2O
benzene.
Any Alkyl group attached to benzene ring can be oxidised (a) Halogenation
into –COOH group if it has α-H-atom. e.g. COOH
COOH
CH3
C2H5 COOH CH COOH Cl2
CH3 Fe
+ HCl
3[O] 3[O]
, Cl
−H2O −H2O
m-chlorobenzonic acid
(b) Nitration
CH3 3[O] COOH
−H2O COOH
CH3 COOH
COOH
Phthalic acid Δ HNO3
H2SO4
+ H2O
• Benzyl alcohol on oxidation by acidic or alkaline
NO2
KMnO4 gives benzoic acid. m-nitrobenzonic acid
Chapter 28
(c) Sulphonation
COCl + POCl3 + HCl
COOH
COOH
Δ
H2SO4 (e) Anhydride formation or dehydration
+ H2O
SO3
COOH
SO3H Δ
+
m-sulphonic benzonic acid
COOH
6. Reactions due to –COOH groups
(a) Salt formation

CO
COOH + NaOH O + H2O
CO
COONa + H 2O
Sodium benzoate (f) Decarboxylation
• COOH + NaHCO3 COOH Soda lime

+ CO2
NaOH
+
CaO
COONa + H2O + CO2 (g) Reaction with diazomethane

Sodium benzoate
COOH + CH2N2
(b) Ester formation
Diazomethane
+
H
COOH + HOR COOCH3 + N2
Methyl benzoate
COOR + H 2O (h) Schmidt reaction

Conc.
COOH + N3H H2SO4
(c) Reaction with NH3 Hydrazoic acid
COOH + NH3
NH2 + N2 + CO2
warm (i) Reduction

COONH4 −H 2O
CONH2
LiAlH4
Ammonium benzoate Benzamide COOH CH2OH + H2O
4[H]
(d) Reaction with SOCl2 or PCl5 DICARBOXYLIC ACID

These acids have two carboxylic groups with a general
COOH + SOCl2 formula CnH2n (COOH)2
Examples,
COCl + HCl + SO 2 • Oxalic acid
Benzoyl chloride
Ethan-1, 2-dioic acid
COOH
• COOH + PCl3
COOH
TO Compounds
ALL APUL
• Malonic acid Physical Properties

Propan-1, 3-dioic acid
• It is a colourless crystalline solid with a melting point
COOH
of 374.5 K in hydrated form and 463 K in anhydrous
CH2
form.
COOH
• It is soluble in water and alcohol but insoluble in ether.
• Succinic acid
Butan-1, 4-dioic acid
Chemical Properties
CH2COOH
1. Salt formation
CH2COOH
COOH COONa
NaOH
• Adipic acid | + NaOH |
COOH COOH
Hexan-1, 6-dioic acid
CH2CH2COOH 2. Reaction with PCl5 or SOCl2
CH2CH2COOH COOH COCl
| + 2PCl5 | + 2POCl3
COOH COOH COCl + HCl
OXALIC ACID | Oxalyl chloride
COOH
3. Ester formation
Method of Preparation COOH COOC2H5
C2H5OH
| + C2H5OH |
1. Lab method: When sucrose or molasses is oxidized
COOH COOH
by conc. HNO3 in presence of V2O5, oxalic acid is
COOC2H5
formed.
|
HNO3 COOC2H5
C12H22O11 + 18[O] COOH
V2O5
| + 5H2O Diethyl oxalate
COOH
4. Reaction with ammonia
2. From glycol
COOH COOH COONH4
CH2OH NH3
NH3
+ 4[O] acidic
+ 5H2O | |
K2Cr2O7 COOH COOH
CH2OH COOH
COONH4
3. From cyanogen |
COONH4
C N COOH Ammonium oxalate
+ 4H2O 2HCl COONH4 CONH2
C N COOH ∆
| |
cyanogens +2NH4Cl –2H2O
COONH4 CONH2
Oxamide
Manufacture On a large scale oxalic acid is prepared
as follows: 5. Oxidation
200oC
CO + NaOH HCOONa 2KMnO4 + 3H2SO4 + 5 H2C2O4
8−10 atm
purple
HCOONa COONa COOH K2SO4 + 2MnSO4 + 10 CO2 + 8H2O
Δ H2SO4
+ │ │ Colourless
HCOONa COONa −Na2SO4 COOH
Chapter 28
6. Reduction
Dehydration
COOH CH2OH
4[H] CH2CONH2 CH2CO
| | + H2O ∆ O + H2O
Zn/H2SO4
COOH COOH CH2CONH2 P2 O5 CH2CO
Glycolic acid Succinic anhydride
7. Electrolytic reduction
COOH 6[H]
CH2OH CHO
2| –H2O | + | MALONIC ACID
COOH COOH COOH
Glycolic acid Glyoxalic acid COOH
8. Reaction with glycol CH2
O OH HO COOH
O O
+
−2H 2O Method of preparation
O OH HO O O
Ethylene oxalate Cl2 KCN
CH3COOH CH2COOH CH2COOH
9. Test of oxalic acid P
| |
NaHCO3 Cl CN
Oxalic acid Efferences of CO2
CaCl2 COOH
2H2O
Oxalic acid white ppt. of Calcium oxalate CH2
−NH3
Hot KMnO4 COOH
Oxalic acid decolourize
Properties
Other Important Acids
Reaction with aldehyde Here an α, β-unsaturated acid is
Succinic Acid formed.
CH2COOH
| H COOH Pyridine
CH2COOH C = O + CH2
Butan-1, 4-dioic acid R COOH
COOH
Preparation
R− CH = C −CO 2
Br2 COOH
C2H4 CH2Br CH2CN H2O
NaCN
| | R – CH = CH – COOH
CH2Br CH2CN
• When R is CH3 the acid is crotonic acid and when it
CH2COOH
| is phenyl the acid is cinnamic acid.
CH2COOH
H HO
Properties | |
∆
Reaction with ammonia O = C–C–C=O O=C=C=C=O
P2O5
| | carbon suboxide
CH2COOH CH2COONH4 OH H + 2H2O
NH3
| |
CH2COOH CH2COONH4 LACTIC ACID
CH2CONH2 CH2CO It is a kind of hydroxy acids
−NH 3 NH
CH2CONH2 CH2CO CH3.CH.OH–COOH
Succinamide Succinimide 2-hydroxy propanoic acid
TO Compounds
ALL APUL
Method of preparation CH2Cl CH2Cl CH2CN

OH | | OH | OH
KCN KCN Hydro
HCN CO C C
CH3CHO CH3 − CH aq. −lysis
| | CN | CN
CN CH2Cl CH2Cl CH2CN
OH
H2O CH2COOH
CH3 − CH
OH
COOH C
COOH
Properties CH2COOH
1. Oxidation reactions Citric acid
KMnO4
CH3.CH.OH– COOH CH3CHO Heating effect on α, β, γ hydroxy acids
HI α–hydroxy acid An α-hydroxy acid on heating forms
CH3.CH.OH– COOH CH3CH2COOH
lactide.
Dil H2SO4
CH3.CH.OH– COOH CH3CHO Example,
+ HCOOH OH HOOC
CH3.CH.OH– COOH CH3 CH + CH CH3
Fe2+ /H2O2 or Ag2O −2H 2O
CH.CO.COOH COOH HO
Pyruvic acid
2. Tartaric Acid
O
CH.OHCOOH
| O C
CH.OHCOOH CH3 CH CH CH3
3. Synthesis of tartaric acid C O
C + H2 CH CH2 Br2 O
CH CH2 β–hydroxy acid β–hydroxy acids on heating forms α, β
CH2Br CH2CN CH2COOH unsaturated acids.
KCN 4H2O
CH2Br CH2CN CH2COOH R– CH – CH – COOH
| | ∆ β α
Br2 Red P
BrCHCOOH OH H R– CH = CH – COOH
| AgOH –H O 2
BrCHCOOH
CHOH COOH γ–hydroxy acid γ-hydroxy acids on heating forms
|
CHOH COOH Lactones.
4. From glyoxal Δ
CH2 − CH2 − CH2 − C = O CH2 CH2 CH2 C O
OH −H2O
CHO CH OH OH
HCN CN O
OH Hydrolysis
CHO CH
CN ACID DERIVATIVES
CHOHCOOH A few examples of acid derivatives are as follows:
• Acid halide, RCOCl
CHOHCOOH
Example, CH3COCl
5. Synthesis of citric acid from glycerol
• Acid anhydride R–CO–O–CO–R
CH2OH CH2Cl Example, (CH3CO)2O
| HCI
| Dil H2SO4
CHOH A. Acid
CHOH • Acid ester, ROOR’
| | [O]
CH2OH CH2Cl Example, CH3COOC2H5
Chapter 28
• Acid amide, RCONH2 These are named as alkanoyl chlorides

Example, CH3CONH2 Examples,
Following is the order of reactivity towards hydroly- 1. CH3COCl Ethanoyl chloride
sis and nucleophilic substitition:
2. CH3 – CH – CH2 – C – Cl
Acid halide > acid anhydride > acid ester > acid
| ||
amide Br O
3-Bromo butanoyl chloride
Nucleophillic Substitution Reaction
O 3. COCl
R O
Nu
C |
R—C—Z
Slow
Z Nu CH2 – CH2 – CH2 – COCl
−Z Pent-1, 4-dioyl chloride
fast
step
COCl
R—C—Nu
4.
O
Here Z X, OCOR, OR, NH2 Benzoyl
Chloride
As these leaving group have basicity order as follows
– – Methods of Preparation
Cl– < R–COO– < R–O– < NH2
From acids Acids on heating with PCl5 or PCl3 or SOCl2
Hence the order of Reactivity is R–COCl > (RCO)2O > give acid chlorides as follows
R–COOR > R–CONH2
∆
COCl RCOOH + PCl5 RCOCl + POCl3 + HCl
R⎯COCl > ∆
3RCOOH + PCl3 3RCOCl + H3PO3
∆
Due to + R effect RCOOH + SOCl2 RCOCl + SO2 + HCl
of Benzene Rine
Here SOCl2 that is, thionyl chloride is the best
Reactivity α Electron with drowing Gps
reagent as the gaseous byproducts are easily separated by
pyridine.
COCl COCl COCl COCl 1. From ester
RCOOR’ + PCl5 RCOCl + POCl3 + R’Cl
> > > > Example,
CH3COOC2H5 + PCl5 CH3COCl
NO2 CX3 X R Ethyl acetate + POCl3+ C2H5Cl
From acid anhydride
COCl COCl COCl RCO
O + PCl5 2RCOCl + POCl3
RCO
> > > RCO
O + PCl5 2RCOCl + POCl3
RCO
X R OR Industrial method Acid chlorides are prepared on large
scale as follows:
PCI3
ACID HALIDES 3RCOONa 3RCOCl + Na3PO3
∆
O Examples,
|| PCI3
3CH3COONa 3CH3COCl + Na3PO3
(R – C – Cl) ∆
TO Compounds
ALL APUL
• 2RCOONa
PCI3
3RCOCl + NaPO3 + NaCl O
∆ ||
Example, C2H5 – C – OC2H5 + C2H5Cl
POCl3 Ethyl Propanoate
2CH3COONa 3CH3COCl + NaPO3 + NaCl
∆
∆ Reaction with ammonia Acid chlorides react with
• (RCOO)2Ca + SO2Cl2 2RCOCl + CaSO4 ammonia to form amides.
Example, RCOCl + NH3 RCONH2 + HCl
∆ Example,
(CH3COO)2Ca + SO2Cl2 2CH3COCl + CaSO4
CH3COCl + NH3 CH3CONH2 + HCl
Physical Properties
Reaction with acid salts or formation of acid anhy-
• These are mostly colourless liquids, for example ace- dride Acid chlorides react with acid salts to give acid
tyl chloride is a colourless liquid with a pungent smell. anhydrides
• Acetyl chloride has a boiling point of 325 K. ∆ RCO
RCOCl + RCOONa O
• Acetyl chloride is insoluble in water but soluble in –NaCl RCO
organic solvents like acetone, ether. Example,
• Acetyl chloride reacts with moist air to form fumes CH3CO
∆
of HCl. CH3COCl + CH3COONa O+
–NaCl
CH3CO
Chemical properties Sodium acetate Acetic anhydride
• Acid chlorides are most reactive among the acid Acetylation CH3COCl is used for the acetylation of
– –OH group, NH2 group to find their number and location.
derivative as Cl is highly electronegative and it
reduces the electron density greatly at – C+ – O– so it OH + ClCOCH3
is very easily attacked by a nucleophile.
R–CH–COCl > R–CH–COCl > R–CHCOCl OCOCH3 + HCl
| | |
NO2 CN X Phenyl acetate
1. Hydrolysis NH2 + ClCOCH3

RCOCl + H2O RCOOH + HCl
Aniline
For example
CH3COCl + H2O CH3COOH + HCl NHCOCH3 + HCl
Reaction with Alcohol Acid chlorides react with alco- Acetanilide
hols to form esters. The reaction is called alcoholysis.
OH (CH3CO)2O OCOCH3
RCOCl + HOR’ RCOOR’ + HCl COOH CH3COCI COOH
Example,
Salicylic acid Acetyl salicylic acid
CH3COCl + HOC2H5 CH3COOC2H5 + HCl Aspirin [Pain killer]
Formation of ester Acid chlorides react with ethers to 2. Reaction with sodium peroxide
give esters as follows
CH3COCl Na O CH3CO O
O O + + + 2NaCl
|| || CH3COCl Na O CH3CO O
ZnCl2 Acetyl peroxide
R– C – Cl + R’– O – R’ R–C– OR’ + R’Cl
Example,
Reduction Reactions
O
(a) Rosenmund’s reduction
|| ZnCl2
C2H5 – C – Cl + C2H5 – O – C2H5 Acid chlorides are reduced by palladium/BaSO4
Diethyl ether poisoned by sulphur or quinoline to avoid further
Chapter 28
reduction of carbonyl compounds (aldehyde) into Example,

alcohols. O O
Pd/BaSO4 || ||
RCOCl + 2H RCHO + HCl
CH3 – C – Cl + NH2NH2 CH3 – C – NHNH2
Example,
H2 (f) Reaction with Grignard reagent: Acid chlorides react
CH3COCl CH3CHO + HCl
Pd/BaSO4 with grignard reagent to give ketones which further
COCl CHO react with grignard reagent to give tertiary alcohols
H2 O
Pd/BaSO4 + HCl ||
RCOCl + XMgR’ R – C – R’ + MgXCl
It is not suitable for HCHO prepration as HCOCl is (g) Reaction with KCN
unstable.
KCN 2H2O
RCOCl RCOCN
(b) Reaction with LiAlH4 –KCL –NH3
O
Here alcohols are formed. ||
4[H] R – C – COOH
RCOCl R – CH2 – OH
LiAlH4
Example, Example,
4[H]
CH3COCl CH3 – CH2 – OH KCN 2H2O
LiAlH4 CH3COCl CH3COCN
–KCL – NH3
(c) Reaction with primary amine O
RCOCl + H.NH.R R – CO – NHR + HCl ||
CH3 – C – COOH
Example,
Pyruvic acid
CH3COCl + H.NH.CH3 CH3 – CO – NHCH3 + HCl (2-oxo propanoic acid)
N-methyl acetamide
(h) Reaction with diazomethane
(d) Reaction with secondary amine
CH3COCl + 2 CH2N2 CH3COCHN2
RCOCl + HNR2 R – CO – NR2 + HCl Diazo −CH3Cl
Example, Methane −N2
CH3COCl + H.N(CH3)2 CH3 – CO – N(CH3)2 + HCl Ag2O/Δ
N, N-dimethyl acetamide
CH3 C CH N≡N Wolf
Rearrangement
(e) Reaction with hydrazine and hydroxyl amine O
O O
|| ||
R – C – Cl + NH2OH R – C – NHOH + HCl CH3 CH = C = O + N2
Hydroxyl amine
Δ H 2O
Example,
O O CH3 CH2 COOH
|| ||
CH3 – C – Cl + NH2OH CH3 – C – NHOH + HCl
Acetyl hydroxyl amine Acid Anhydride
(Hydro oxamic acid )
RCO
O O O
|| || RCO
R – C – Cl + NH2NH2 R – C – NHNH2 + HCl
Hydrazine Acetylhydrazine These are named as alkanoic anhydrides.
TO Compounds
ALL APUL
Examples, ∆O2
CH3CHO CH3CO3H
Catalyst
1. (CH3CO)2O Ethanoic anhydride
2. (C2H5CO)2O Propanoic anhydride CH3CHO
3. (C6H5CO)2O Benzoic anhydride (CH3CO)2O + H2O
4. CH3 CH2 CO Reaction with acetone and acetic acid In this reaction,
Ethanoic
first a ketene is formed which then reacts with acetone to
O propanoic
give acetic anhydride as follows:
CH3 C anhydride
aluminium phosphate
CH3COOH
O AlPO4 /700oC
CH2 = C = O + H2O
Methods of Preparation Ketene
1. Lab method ∆
CH3COCH3 CH2 = C = O + CH4
O O CH3COOH + CH2 = C = O (CH3CO)2O
|| ||
Pyridine From sodium acetate and sulphur dichloride
R–C–Cl + R–C–O–H
C5H5N 8CH3COONa + SCl2 + 2Cl2
O 4(CH3CO)2O + 6NaCl + Na2SO4
R C From acetylene When acetylene is passed through glacial
O + C5H5N+HCl– acetic acid in presence of mercuric sulphate followed by
R' CO Pyridine hydrogen chloride distillation acetic anhydride is formed as follows.
Example, CH 2CH3COOH CH3
O O HgSO4
CH CH(OOC.CH3)2
|| || CH3
Pyridine CH3CO
CH3 – C – Cl + CH3 – C – O – H + O
C5H5N
CHO CH3CO
O
CH3 C Physical Properties
O + C5H5N+HCl–
CH3 C Pyridine hydrogen chloride
• Acetic anhydride is a colourless liquid having a pun-
gent smell.
O
2. By the dehydration of alcohols • Acetic anhydride has a boiling point of 139.5oC.
RCOONa Δ
RCO • Acetic anhydride is partially soluble in water but
+ −NaCl
O
RCOOCl RCO readily soluble in solvents like ether, alcohol
Example, Chemical Properties
CH3 COOH Δ
CH3CO 1. Hydrolysis
+ O
−H2O RCO
CH3COOH CH3CO O + R’ OH RCOOR’ + RCOOH
3. Manufacture RCO
RCOONa RCO RCO
+ Δ
O O ++ NaOH RCOOH + RCOONa
RCOOCl
−NaCl
RCO RCO
Example, RCO Dry HCl
O RCOCl + RCOOH
CH3CO RCO
CH3COONa Δ
+ O 2. Reaction with alcohol or alcoholysis
CH3COCI CH3CO Acid anhydrides on reaction with alcohols give esters as
From acetaldehyde Acetaldehyde is converted into follows:
acetic anhydride by air oxidation at 50–70oC in presence RCO
of catalysts like cobalt acetate, copper acetate. O ++ PCl5 2RCOCl + POCl3
RCO
Chapter 28
Example, C6H5OCOCH3 + CH3COOH

CH3 RCO Phenyl acetate
O ++ C2H5OH
CH3 RCO 2. C6H5NH2 + (CH3CO)2O
CH3COOC2H5 + CH3COOH Aniline
Ethyl acetate C6H5NHCOCH3 + CH3COOH
3. Reaction with PCl5 Acetanilide
RCO
O ++ PCl5 2RCOCl + POCl3 3. CHO CHO
RCO | |
5(CH3CO)2O
Example, (CHOH)4 (CHOCOCH3)4
–5CH3COOH
| |
(CH3CO)2O + PCl5 2CH3COCl + POCl3
CH2OH CH2OCOCH3
4. Reaction with ammonia Glucose penta acetate
RCO Freidal craft reaction Benzene when treated with acetic
O ++ NH3 2RCONH2 + H2O
RCO anhydride in presence of anhydrous AlCl3 acetophenone is
obtained.
CH3CO AlCl3
CH3CO + O
O + NH3 2CH3CONH2 + H2O CH3CO
CH3CO or COCH3
CH3COONH2 + CH3COONH4
+ CH3COOH
5. Reaction with chlorine
Acetophenone
(CH3CO)2O + Cl2 CH3COCl
Reaction with acetaldehyde Acetic anhydride reacts with
+ CH2 – COOH acetaldehyde to give ethylidene diacetate
|
(CH3CO)2O + CH3CHO CH3 – CH.(OOC.CH3)2
Cl
Ethylidene diacetate
Chloroacetic acid
Amides
Reduction An acid anhydride on reduction by LiAlH4
O
gives alcohol.
||
RCO LiAlH4 (R – C – NH2)
O+ 2RCH2OH + H2O
RCO Amides are named as alkanamides.
Examples,
Example,
1. CH3CONH2 Ethanamide
LiAlH4
(CH3CO)2O C2H5OH 2. CH3CHCONH2 2-Hydroxy propanamide
Ether
|
Acetylation It reacts with compounds having active OH
hydrogen atom like aniline, phenol and the active hydrogen
3. CH3CHCONHCH3
atom gets substituted by CH3–CO–group. It is better to use
than R–COCl as it reacts less violently. |
CN
• This reaction conforms the number of –OH or –NH2
N-methyl 3-Cyano propanamide
groups. For example, in glycerol after acetylation
glycerol triacetate is formed that is, glycerol has CONH2
4.
3 –OH groups on different carbon atoms.
Examples, CN
OH
1. C6H5OH + (CH3CO)2O 2-cyano 3-hydroxy cyclo hexene
Phenol 1-Carbamide.
TO Compounds
ALL APUL
3 1 Example,
5 N
4 2 CH3COOC2H5 + NH3 CH3CONH2 + C2H5OH
5.
OH 2. By the reaction between glacial acetic acid and urea
N-ethyl N-methyl
∆
4-hydroxy pent 2-en CH3COOH + NH2CONH2
1-amide Urea
CH3CONH2 + CO2 + NH3
O
CH3
C N
6. CH3 Physical Properties
N, N di methyl benzamide • Formamide is colourless liquid while Acetamide is a
colourless crystalline solid
Methods of Preparation
• Acetamide has a melting point of 82oC and a boiling
By partial hydrolysis of cyanides Cyanides on partial point of 222oC.
hydrolysis by alkaline H2O2 give amides.
H2O2 + NaOH
• Acetamide is soluble in water and alcohol.
R – CN + H2O RCONH2
Alk. • Acetamide can exist as a dimer because of hydrogen
Example, bonding and have highest B.P among acid derivatives
H2O2 + NaOH of comparable molecular weights.
CH3CH2CN + H2O CH3CH2CONH2
Alk.
Propanamide Chemical Properties
H2O2 + NaOH
Amphoteric nature Due to amphoteric nature amides
C6H5CN + H2O C6H5CONH2 can react both with acid and bases to give salts as follows:
Alk.
HCl
From acids Acids react with ammonia to give acid RCONH2 RCONH2.HCl
amides as follows: Amide hydrogen
∆ chloride Stable in aq. solution
RCOOH + NH3 RCOONH4
RCONH2 + H2O 2RCONH2
HgO
(RCONH2)2Hg + H2O
Example, Mercuric amide
∆
CH3COOH + NH3 CH3COONH4 Na
RCONH2 RCONH.Na + ½ H2
CH3CONH2 + H2O Ether
Sodium alkanamide
Acetamide
1. From acid derivatives Hydrolysis It can be hydrolyzed by water, acid or bases,
however, the rate of hydrolysis decreases as follows:
RCOCl + NH3 RCONH2 + HCl Bases > acid > H2O
Example, Hydrolysis
H+
CH3COCl + NH3 CH3CONH2 + HCl RCONH2 + H2O RCOOH + NH3
RCO
O ++ 2NH3 2RCONH2 + H2O Example,
RCO H+
CH3CONH2 + H2O CH3COOH + NH3
Example,
CH3CO Dehydration: Amides can undergo dehydration by P2O5,
O ++ 2NH3 2CH3CONH2 + H2O POCl3, SOCl2 to give cyanides as follows:
CH3CO
P2O5/SOCl2/POCl3
RCOOR’ + NH3 RCONH2 + R’OH RCONH2 RCN
∆ – H2O
Chapter 28
Example, • In this reaction one carbon atom is lost as carbonate

P2O5 /SOCl2/POCl3
CH3CONH2 CH3CN ion or potassium carbonate
∆ – H2O
RCONH2 + Br2 + 4KOH RNH2 + K2CO3
Reaction with nitrous acid (HNO2) Amides react with + 2KBr + 2H2O
nitrous acid (NaNO2 + HCl or HNO2) to give acids. Mechanism
RCONH2 HNO2 RCOOH + N2 + H2O RCONH2 + Br2 RCONHBr + HBr
HBr + KOH KBr + H2O
Example,
HNO2 RCONHBr + KOH RNCO + KBr + H2O
CH3CONH2 CH3COOH + N2 + H2O
RNCO + 2KOH RNH2 + K2CO3
Reduction Amides can be reduced with LiAlH4, Isocyanate
Na/Alcohol into amines as follows: O
LiAlH4 ||
RCONH2 + 4H RCH2NH2 + H2O
Ether • Here R – C – N is the reaction intermediate
Example,
LiAlH4 O Intramolecular
CH3CONH2 + 4H CH3CH2NH2 + H2O rearrangement
Ether R−C−N R−N=C=O
Ethyl amine
Acyl nitrile Isocyanate
Reaction with PCl5 Amides react with PCl5 and give
cyanides as follows: Example,
(Br2 + KOH)
PCl5
C2H5CONH2 C2H5NH2
RCONH2 RCCl2NH2 + POCl3 C2H5CONH2 + Br2 C2H5CONHBr + HBr
HBr + KOH KBr + H2O
∆
C2H5CONHBr + KOH C2H5NCO + KBr + H2O
R – CN + 2HCl C2H5NCO + 2KOH C2H5NH2 + K2CO3
Example, C2H5CONH2 + Br2 + 4KOH C2H5NH2
CH3CONH2 PCl5 CH3CCl2NH2 + POCl3 + K2CO3 + 2KBr + 2H2O
Esters
∆ O
||
CH3–CN + 2HCI
R – C – OR’
Reaction with alcohol (R–OH) Amides react with alco- Esters are named as alkyl alkanoates.
hols to give esters. For example,
hot HCOOCH3 Methyl methanoate
RCONH2 + R’–OH
70oC CH3COOCH3 Methyl ethanoate
R – C – OR’ + NH4Cl CH3CH2COOC2H5 Ethyl Propanoate
|| CH3COCH2COOC2H5 Ethyl-3-keto butanoate
O O
||
Example,
hot C6H5–C–OC2H5
CH3CONH2 + C2H5 OH
70oC Ethyl benzoate
CH3 – C – OC2H5 + NH4Cl C6H5–CH=CH–COOC2H5
|| Ethyl 3-phenyl prop 2-enoate
O COOC2H5
Ethyl acetate
CH2
Hoffmann’s bromamide reaction Here amides are heated
COOC2H5
with bromine and caustic soda to give primary amines that
is, conversion of –CONH2 into –NH2 group. Diethyl propan 1,3
di-oate
TO Compounds
ALL APUL
Isomerism shown by esters Esters are functional (III) Removal of a H+ and a H2O Molecule:
isomers of acids and among themselves, they show meta-
merism. This can be explained taking C3H6O2 as an exam- OH OH
I.M.P.E
: :
ple, which has following isomers: R C O R R C O R
1. CH3–CH2–COOH OH H OH2
−H2O
2. CH3–COOCH3
O
3. HCOOC2H5 OH
−H+
1. Some Facts about Esters R C OR R C OR
• Esters are neutral and pleasant smelling liquids. Ester Protonated Ester
• Esters do not give effervecence of CO2 with aqueous From acid anhydride Acid anhydrides react with alcohols
sodium bicarbonate (distinguishing test from acids). to give esters as follows:
• On hydrolysis, an ester gives an acid and an alcohol. RCO
• On reduction with LiAlH4, an ester gives two moles O ++ R’OH RCOOR’ + RCOOH
of alcohol. RCO
• Higher esters are used as flavouring agents. Example,
CH3CO
Methods of Preparation O ++ C2H5OH
CH3CO
By the reaction acid and alcohols When an acid react CH3COOC2H5 + CH3COOH
with an alcohol in presence of concentrated H2SO4 or HCl Ethyl acetate
gas an ester is formed as follows: From acid chlorides
conc. RCOCl + HOR’ RCOOR’ + HCl

RCOOH + HOR’ RCOOR’ + H2O
H2SO4
Example, Example,
conc.
(I) CH3COOH + HOC2H5 CH3COCl + HOC2H5 CH3COOC2H5 + HCl
H2SO4
CH3COOC2H5 + H2O From ethers Ethers react with carbon monoxide in
Ethyl acetate presence of BF3 to give esters as follows:
18 18
H+
O
(II) C6H5–C–OH + R–O–H C6H5–C–OR + H2O ||
|| || BF3
R – O – R + CO R – C – OR
O O
Example,
Mechanism of Esterification O
||
Esterification occurs in following steps: BF3
CH3 – O – CH3 + CO CH3 – C – OCH3
(I) Protonation of Carbonyl Group: Methyl acetate
OH + O–H From silver salt of acids When silver salts of acids are
H+ R C
R C OH R C treated with alkyl iodide esters are formed as follows:
OH O–H
R – COOAg + I – R’ R–COOR’ + AgI
O I
Protonised Acid Example,
CH3 – COOAg + I – C2H5 CH3–COOC2H5 + AgI
Silver acetate
(II) Attack of Nucleophile (R–OH):
OH By Thischenko reaction It is the modified form of
: :
OH H−O−R cannizzaro reaction. Here aldehydes undergo condensation

R C R C O R
OH in presence of aluminium ethoxide to give esters.
OH H
Example,
II
Tetrahedral Indermediate Al(OC2H5)3
2CH3CHO CH3COOC2H5
Chapter 28
Al(OC2H5)3 O
2CH3–CH2–CHO CH3 CH2 COOCH2 CH2 CH3
n-Propyl propionate || CuO
R – C – OR’ + H2 R – CH2OH + R’OH
Physical Properties CuCr2O4
High ‘P’ 250oC
Example,
• Esters are colourless sweet smelling liquids. For
O
example, Ethyl acetate has a fruity smell. || CuO
• Ethyl acetate has a boiling point 350.5 K. CH3 – C– OCH3 + H2 C2H5OH + CH3OH
CuCr2O4
• Ethyl acetate is slightly soluble in water but more High ‘P’ 250oC
soluble in organic solvents like alcohol, ether etc. When Na/alcohol is used for reduction it is called
Bauveault Reduction.
Chemical Properties
Reaction with Grignard reagent (R–MgX) Grignard
Hydrolysis Esters undergo hydrolysis using boiling reagent reacts with esters to give ketones which again react
water or dilute acids or bases as follows: with grignard reagent to give tertiary alcohols as follows:
acid H+ O
RCOOR’ + H2O RCOOH + R’OH ||
Example, R – Mg – I + R – O – C – R
acid H+ O
CH3COOC2H5 + H2O CH3COOH + C2H5OH
||
RCOOR’ + NaOH RCOONa + R’OH R – C – R + R – OMgI
Example, Ketone
CH3COOC2H5 + NaOH CH3COONa + C2H5OH O R
|| |
Acidic hydrolysis is reversible while basic hydrolysis is R – C – R + R’MgX → R – C – OMgX
irreversible and called saponification. |
Reaction with bromine Esters react with bromine to give R’
α-bromo substituted ester. R
red P H2O
|
RCH2COOR’ + Br2 RCHBrCOOR’ + HBr R–C–OH + MgXOH
Example, |
red P R’
CH3COOC2H5 + Br2 CH2BrCOOC2H5 + HBr Tertiary alcohol
Splitting by ROH (Alcoholysis) In this reaction alkyl group
Claisen condensation When two moles of an ester having
of an ester is substituted by alkyl group of alcohol in presence
α-hydrogen atom are condensed in the presence of sodium
of sodium alkoxide. It is called trans esterification.
ethoxide (strong base) a β-keto ester is formed. For exam-
C2H5ONa ple, when two moles of ethyl acetate are condensed, ethyl
RCOOR’ + R”OH RCOOR” + R’OH acetoacetate or aceto acetic ester is formed as follows:
Example,
C2H5ONa
C2H5ONa 1. 2CH3COOC2H5
CH3COOC2H5 + CH3OH
CH3COOCH3 + C2H5OH CH3COCH2COOC2H5 + C2H5OH
Reduction When esters are reduced by LiAlH4 or Na/ Ethyl acetoacetate
C2H5OH alcohols are formed as follows: C2H5ONa
2. 2C2H5COOC2H5
LiAlH4
RCOOR’ + 4H RCH2OH + R’OH C2H5COCHCOOC2H5 + CH3CH2OH
Example, |
LiAlH4
CH3COOC2H5 + 4H 2CH3CH2OH CH3
Na /C2H5OH Ethyl 3-keto-2-methyl pentanoate
CH3CH2COOCH3 + 4H
CH3CH2CH2OH + CH3OH
TO Compounds
ALL APUL
Reaction with hydroxyl Amine Esters react with Example,

hydroxyl amine in presence of alcoholic KOH to give O
hydro-oxamic acid. ||
Example, CH3 – C – OC2H5 + NH2CH3
NH2OH
CH3COOC2H5 CH3CONH.OH + C2H5OH O
Hydroxamic acid ||
CH3 – C – NH – CH3 + C2H5 – OH
Reaction with hydrazine An ester reacts with hydrazine
to give acid hydrazide as follows: Reaction with PCl5 or SOCl2 Esters react with these to
O O give acid halides as follows:
|| || O O
R – C – OR’ + NH2NH2 R – C – NHH2 + R’OH || ||
R – C – OR’ + PCl5 R – C – Cl
Example, + RCl + POCl3
NH2NH2
CH3COOC2H5 CH3CONH.NH2 + C2H5OH For example
Acid hydrazine O O
Reaction with ammonia, amine Esters react with ammo- || ||
nia or amines to give amides or alkyl substituted amides as CH3 – C – OC2H5 + PCl5 CH3 – C – Cl
follows: C2H5Cl + POCl3
O O
|| ||
∆
R – C – OR’ + NH3 R – C – NH2 + R’ – OH
Example,
∆
CH3COOC2H5 + NH3 CH3CONH2 + C2H5OH
O O
|| ||
∆
R – C – OR’ + NH2R R – C – NH –R
+ R’ – OH
Chapter 28
CONCEPTS AT A GLANCE
Brady’s Reagent φ – C – Me (i) conc. H SO O
2 4
Aqueous solution of 2, 4-dinitrophenyl hydrazine (D.N.P.) || ||
(ii) H2O
is known as Brady’s reagent. It reacts with carbonyl com- N – OH CH3 – C – NHφ
Anti-phenyl Acetinilide
pounds (aldehyde and ketone) to give coloured precip- acetophenone oxime
itate. These precipitates have sharp melting point. The Blanc Rule
melting points of the precipitates confirm the carbonyl
It states that when dicarboxylic acids having two –COOH
compounds.
groups on the same carbon atom are heated monocar-
 Benzoic acid is used as an antiseptic in medicines meant
boxylic acids are formed. On the other hand, 1, 4 and 1, 5
for urinary disorders and in vapour form for disinfecting
dicarboxylic acids on heating with acetic anhydrides give
bronchial tubes.
cyclic ketones.
 Acetic anhydride reacts with N2O5 to give acetyl nitrate. R
In case of a α-β-unsaturated methyl ketone the C = O gp
(CH3CO)2O + N2O5 2CH3COONO2 R'
can be oxidised into –COOH gp by NaOCl.
Acetyl nitrate
e.g.,
 Reaction of acid chlorides with water decreases with the O
increase of C-atoms in alkyl groups. NaOCl
R CH = C C CH3
CH3COCl > CH3 – CH2 – COCl >
CH3 – CH2 – CH2COCl > ….. CH3
Curtius Rearrangement CHCl3 + R CH = C COOH

O O
CH3
|| NaN3 || . . +
R – C – Cl
–
R–C–N –N≡N R CH = CH CHO R CH2 = CH2 CH2OH
–NaCl (i) NaBH4
Acid azide (i) LiAlH4 (ii) H3O+ + 40%
(ii) H3O+
O R CH = CH CH2OH
|| 60%
∆ rearrangement R CH = CH CH2OH
R–C–N
–N2
Acylnitrene
CH2−SH
R’OH S−CH2 H /Ni
R–N=C=O R – NHCOOR’ CH2SH 2
C O C Ethanol
Alkyl isocyanate N-alkyl urethane dil. HCl S−CH2
H+ /H2O CH2SH
R – NH2 CH2 +
– CO2 – R’ – OH
p-amine CH2SH
Beckmann Rearrangement Intra molecular Aldol Condensation

Here oximes undergo rearrangement to form substituted
CHO dil.
amides on heating with conc. H2SO4 /PCl5 (Here Φ = C6H5) NaOH
CHO CHO
Me – C – φ O
(i) conc. H2SO4
|| ||
N – OH (ii) H2O φ – C – NHCH3
Syn-phenyl N-methyl
acetophenone oxime benzamide
TO Compounds
ALL APUL
;- - - - - - =
I
- -~
- -=-=-= - - ~=-:
---------- - - -- - -- - - -- - -- - - -- - -- - - -- ,
O Urotropine on Nitration gives famous explosive R.D.X I
(Research and development explosive)
NaOH
Intramolecular
CHO Aldol CH2
HNO3 NO2
Case (CH2)4N4 NO2
N N
O
C CH3 N R.D.X
or
1-Cyclopentenyl NO2 Cyclonite
Methyl Ketone
Acetophenone is used as an hypnotic under the name
In few cases both Cross Aldol Condensation and Cross
Hypnone.
Cannizaro reactions occur simultaneously. CH3 O
e.g., | ||
Al- tert-butoxides
CH2OH 2C6H5 COCH3 C6H5–C=CH–C–C6H5
Dypnone.
3HCHO/NaOH
CH3CHO HOCH2 C CHO
Aldol B.P in Decreasing order:
R–CONH2 > (R–CO)2O > R–COOH > R–COOR’ > R–COCl
CH2OH CH2OH
Stronger Stronger H-bonding NCH-bonding
HOCH2 C CH2OH H-bonding Vander Waal’s
HCHO forces
+ HCOONa Cannizaro Reaction
CH2OH
Penta erythritol
(Explosive)
, - -- -----------,
Chapter 28
EXERCISES
Single Option Correct Type

1. Aldehydes and ketones are distinguished by using 10. Which aldehyde will give Cannizzaro’s reaction?
(a) Tollen’s reagent (b) Lucas reagent (a) CH3CH2CH2CHO
(c) Borshe reagent (d) all of these (b) CH3CH2CHCHO
2. Carbonyl compounds undergo nucleophillic addition |
CHO
because of
(a) more stable anion with negative charge on oxygen (c) (CH3)3CCHO
and less stable carbocation (d) (CH3)2CHCH2CHO
(b) electromeric effect 11. Rearrangement of an oxime to an amide in presence
(c) electronegativity difference of carbon and oxygen of strong acid is called
atoms (a) Beckmann rearrangement
(d) none of these (b) Fries rearrangement
3. Clemmensen reduction is carried with (c) Sandmeyer reaction
(a) LiAlH4 in ether (d) Curtius rearrangement
(b) Zn-Hg and HCl 12. The reaction of benzoyl chloride with H2/Pd – BaSO4
(c) H2 in the presence of Pd produces
(d) NH2NH2 /glycol and KOH
(a) benzyaldehyde
4. The addition of HCN to carbonyl compounds is an (b) benzyl alcohol
example of (c) benzoic acid
(a) electrophillic addition (d) benzoyl cyanide
(b) nucleophillic addition 13. Reduction of >C = O to > CH2 can be carried out with
(c) nucleophillic substitution
(a) Na/C2H5OH
(d) electrophilic substitution
(b) LiAlH4
5. Cyanohydrin of which of the following will yield lac- (c) catalytic reduction
tic acid? (d) Wolff-Kishner reduction
(a) HCHO (b) CH3COCH3
14. Concentrated sodium hydroxide and benzaldehyde
(c) CH3CH2CHO (d) CH3CHO
react to produce
6. If formaldehyde and KOH are heated, then we get (a) cinnamic acid
(a) methyl alcohol (b) acetylene (b) hydrobenzamide
(c) methane (d) ethyl formate (c) benzyl alcohol
7. Which of the following will not give iodoform test? (d) benzophenone
(a) ethanol (b) ethanal 15. Aldol condensation will not be observed in
(c) pentan-3-one (d) pentan-2-one (a) hexanal (b) chloral
8. Oxidation of toluene to benzaldehyde by the use of (c) nitromethane (d) phenylacetaldehyde
chromyl chloride is called 16. Fomaldehyde when reacted with methyl magnesium
(a) Wurtz reaction bromide followed by hydrolysis gives
(b) Fittig reaction (a) HCHO (b) CH3COOH
(c) Etard’s reaction (c) C2H5OH (d) CH3CHO
(d) Rosenmund’s reaction 17. In which reaction aromatic aldehyde is treated with
9. In a reaction involving ring substitution of C6H5Y, the acid anhydride in presence of corresponding salt of
major product is meta isomer. The group Y can be the acid to give unsaturated acid?
(a) – NH2 (b) – Cl (a) Perkin’s reaction (b) Friedal-Craft reaction
(c) – CH3 (d) – COOH (c) Wurtz reaction (d) None of these
TO Compounds
ALL APUL
18. Formaldehyde + NH3 Y. The product Y is 27. When aliphatic aldehyde heat with Fehling solution
(a) hexamethylene tetramine product formed is
(b) formamide (a) CuO (b) Cu2O
(c) paraformaldehyde (c) CuSO4 (d) Cu
(d) methanol
28. Which of the following reagents is used to distinguish
19. Dimerisation is carboxylic acids is due to
acetone and acetophenone?
(a) intermolecular hydrogen bond
(a) NH4Cl (b) Na2SO4
(b) coordinate bond
(c) ionic bond (c) NaHSO3 (d) Grignard reagent.
(d) covalent bond 29. Conversion of benzaldehyde of 3-phenylprop-2-
20. Carboxylic acids are more acidic than phenol and energy-1-oic acid is
alcohol because of (a) aldol condensation
(a) formation of dimers (b) claisen condensation
(b) highly acidic hydrogen (c) oxidative reaction
(c) resonance stabilization of their conjugate base
(d) perkin condensation
(d) intermolecular hydrogen bonding
21. Which of the following gives aldol condensation 30. Which of the following reacts with both acetaldehyde
reaction? and acetone?
(a) CH3CH2 – CO – CH3 (a) Fehling’s solution
(b) (CH3)3C – CO – CH3 (b) CH3MgBr
(c) C6H5 – CO – C6H5 (c) Tollen’s reagent
(d) C6H5OH (d) Benedict solution
22. Acetaldehyde cannot exhibit 31. Schiff’s solution B is obtained when
(a) Iodoform test (a) sulphurous acid is passed through magenta dye
(b) Benedict’s test (b) chlorine is passed through magenta dye
(c) Lucas test (c) both (a) and (b)
(d) Tollen’s test (d) none of the above
23. Ketones (R1COR2); R1=R2= alkyl group, can be 32. Which of the following is oxidized to the correspond-
obtained in one step by ing carbonyl compound?
(a) hydrolysis of esters
(a) o-nitrophenol
(b) oxidation of primary alcohols
(b) 2-hydroxypropane
(c) oxidation of secondary alcohols
(c) reaction of acid halides and alcohlos (c) 2-methyl-2-hydroxypropane
(d) phenol
24. The product formed by the reaction of chlorine with
benzaldehyde in the absence of catalyst is 33. When ethanal is heated with Fehling’s solution it
(a) benzoyl chloride gives a precipitate of
(b) benzyl chloride (a) CuO
(c) chlorobenzene (b) Cu
(d) o-chlorobenzaldehyde (c) Cu + Cu2O + CuO
25. Which compound does not give cannizzaro’s reaction? (d) Cu2O
(a) trichloro acetaldehyde 34. Monomer of trioxane is
(b) benzaldehyde
(a) formaldehyde (b) acetone
(c) formaldehyde
(c) isoprene (d) acetaldehyde
(d) acetaldehyde
35. Which will not give formaldehyde on heating or upon
26. On reacting with grignard reagent acetone gives distillation?
(a) 1o alcohol (a) paraldehyde
(b) 2o alcohol (b) trioxane
(c) 3o alcohol (c) formalin
(d) none of these (d) paraformalehyde
Chapter 28
36. In the reaction, CH3CHO + HCN X, a chiral 46. Which of the following reagents converts
centre is introduced. The product X is C6H5COCHO to C6H5CH(OH)COOH?
(a) laevo rotatory (b) dextro rotatory (a) aq. NaOH (b) Acidic Na2SO3
(c) meso compound (d) racemic mixture (c) Na2CrO4 /H2SO4 (d) NaNO2 /HCl
37. Benzophenone can be converted into benzene using 47. The compound that will not give iodoform on treat-
ment with alkali and iodine is
(a) anhydrous AlCl3
(a) Acetone (b) Ethanol
(b) acidified dichromate
(c) Diethyl ketone (d) isopropyl alcohol
(c) sodium amalgam in water
(d) fused alkali 48. When benzene sulphonic acid and p-nitrophenol are
treated with NaHCO3, the gases released respectively
38. Which of the following react with NaOH to produce are:
an acid and an alcohol? (a) SO2, NO2 (b) SO2, NO
(a) CH3COOH (b) HCHO (c) SO2, CO2 (d) CO2, CO2
(c) C6H5COOH (d) CH3CH2COOH 49. Benzoyl chloride is prepared from benzoic acid by
39. Which of the following is incorrect? (a) Cl2, hv (b) SO2Cl2
(a) Fehling solution is used in detection of glucos (c) SOCl2 (d) Cl2, H2O
(b) NaHSO3 is used in detection of carbonyl 50. Schiff’s reagent gives pink colour with
compounds (a) acetone (b) acetaldehyde
(c) FeCl3 is used in detection of phenols (c) acetic acid (d) methyl acetate
(d) Tollen’s reagent is used in detection of
51. Hydrogenation of benzoyl chloride in the presence of
unsaturation.
Pd and BaSO4 gives
40. Formaldehyde on condensation in presence of (a) benzyl alcohol (b) benzaldehyde
Ca(OH)2 gives (c) benzoic acid (d) phenol
(a) formose (b) fructose 52. Oxalic acid when reduced with zinc and H2SO4
(c) maltose (d) xylose gives
41. In the following reaction, product ‘P’ is (a) glycol (b) glyoxal
O (c) glyoxalic acid (d) glycolic acid
|| H2 53. The reagent that can be used to distinguished between
R – C – Cl P methanoic acid and ethanoic acid is
Pd-BaSO4
(a) RCOOH (b) RCHO (a) sodium carbonate solution
(c) RCH3 (d) RCH2OH (b) ammonical silver nitrate solution
(c) phenolphthalein
42. Which one of the following responds to Tollen’s test? (d) neutral ferric chloride solution
(a) CH3COCH3 (b) CH3CHO 54. X + CH3COOH Ester + H2O, X is
(c) CH3COOH (d) C2H5OC2H5 (a) alcohol (b) pyridine
43. CH3CHCl2, on hydrolysis will give (c) alkane (d) acid
(a) CH3CHO (b) CH3COOH 55. Lactic acid on oxidation by alkaline potassium per-
(c) CHCl3 (d) CH3CH2OH manganate gives
44. The reagent used for the separation of acetaldehyde (a) propionic acid (b) cinnamic acid
(c) pyruvic acid (d) tartaric acid
from acetophenone is
(a) NH2OH (b) NaHSO3 56. Which of the following is the weakest acid?
(c) NaOH/I2 (d) C6H5NHNH2 (a) HCOOH (b) CH3COOH
45. Acetaldehyde gives orange coloured precipitate on OH COOH
treatment with
(a) 2, 4-DNP (b) NH2OH (c) (d)
(c) NaHSO3 (d) NaOH
TO Compounds
ALL APUL
57. The reaction 64. When a nucleophile attacks a carbonyl compound, the
RCH2CH2COOH Red P , Br2 one which is most reactive towards the nucleophile is
R – CH2 – CH – COOH (a) CH3COCOC2H5
| (b) CH3COCH2Cl
Br
is called as (c) H3CO CHO
(a) Sandmeyer reaction
(b) Reimer – Tiemann reaction (d) CH3COCH2CH2Cl
(c) Hell-Volhard Zelinshy reaction 65. The reaction,
(d) Cannizaro reaction
CH3
58. Which of the following orders of relative strengths of |
CO + HOCH3
acids is correct? CH3 – CH = CH2 H+ CH – CH3
(a) ClCH2COOH > FCH2COOH > BrCH2COOH |
(b) ClCH2COOH > BrCH2COOH > FCH2COOH COOH
(c) BrCH2COOH > ClCH2COOH > FCH2COOH is known as
(d) FCH2COOH > ClCH2COOH > BrCH2COOH (a) Koch reaction (b) Kolbe’s reaction
(c) Wurtz reaction (d) Clemmensen reduction
59. In the reaction product P is
Mg Br 66. Carboxylic acid undergoes ionization due to
(i) CO2 (a) hydrogen bonding
P (b) absence of α-hydrogen
(ii) H3 + O (c) high reactivity of α-hydrogen
(d) resonance stabilization of carboxylate ions
CHO OH
67. Benzoyl chloride is prepared from benzoic acid by
(a) (b) (a) Cl2, hv (b) SO2Cl2
(c) SOCl2 (d) Cl2, H2O
COOH 68. Which reagent will bring about the conversion of car-
boxylic acid into esters?
(c) (d) C6H5 – CO – C6H5 (a) Dry HCl + C2H5OH
(b) C2H5OH
60. Glacial acetic acid is obtained by (c) LiAlH4
(a) treating vinegar with dehydrating agents (d) Al(OC2H5)3
(b) crystallizing, separating and melting acetic acid 69. In an α-halogenation of aliphatic acids (HVZ reac-
(c) chemically separating acetic acid tion) the catalyst used is
(d) distilling vinegar (a) AlCl3 (b) P
61. What product is formed when acetic acid react with (c) Zn (d) FeCl3
P2O5? 70. The fatty acid which shows reducing property is
(a) acetyl chloride (b) trichloro acetic acid (a) ethanoic acid (b) oxalic acid
(c) acetic anhydride (d) dichloro acetic acid (c) formic acid (d) acetic acid
62. A and B react with Na gives H2 gas and by reaction of 71. A compound of molecular weight 180 is acetylated to
both A and B ethyl acetate is formed then A and B are give a compound of molecular weight 390. The num-
(a) CH3COOH, C2H5OH ber of amino groups in the compound is
(b) CH3COOH, CH3OH (a) 6 (b) 5
(c) C3H7COOH, C3H7OH (c) 4 (d) 3
(d) HCOOH, CH3COOH
72. The work of concentration. H2SO4 in esterification
63. Et. MgBr + CO2 Product is process is as
(a) C3H7COOH (b) C2H5COOH (a) dehydrating agent and catalyst
(c) C4H9COOH (d) HCOOH (b) dehydrating agent
Chapter 28
(c) hydrolyzing agent 82. Which compound gives CO2 with NaHCO3?
(d) catalyst (a) hexanol (b) phenol + acetic acid
73. Formic acid and acetic acid can be distinguished (c) n-butanol (d) acetic acid
chemically by 83. On strong heating, ammonium acetate gives
(a) reaction with HCl (a) urea (b) formamide
(b) iodoform test (c) acetamide (d) methyl cyanide
(c) reaction with NH3
(d) reaction with FeCl3 solution 84. Acetone when distilled with conc. H2SO4 gives
(a) (CH3)2C = CHCOCH3
74. CH3COCl reacts with
(a) C6H5NH2 (b) Salicylic acid (b) (CH3)2C = CHCOCH = C(CH3)2
(c) C6H5OH (d) all of these (c) (CH3)2C(OH)CH2COCH3
75. What will happen if LiAlH4 is added to an ester? CH3
(a) one unit of alcohol and one unit of acid is obtained (d) H C
3
(b) two units of alcohol are obtained
(c) two units of acids are obtained CH3
(d) none of these
85. Which one of the following statements is incorrect?
76. A fruity smell is produced by the reaction of C2H5OH Benzaldehyde can be produced by the
with
(a) reduction of benzoyl chloride
(a) PCl5 (b) CH3COOH
(b) oxidation of toluene
(c) CH3COCH3 (d) none of these
(c) hydrolysis of benzal chloride
77. Which of the following formula is more reactive for (d) reduction of benzyl chloride
hydrolysis?
86. What is the main reason for the fact that carboxylic
(a) – COOR (b) – CONH2 acids can undergo ionization?
(c) – COOH (d) – COCl
(a) Resonance stabilization of the carboxylate ion
78. In the mechanism of Hoffmann reaction, which inter- (b) Hydrogen bonding
mediate rearranges to alkyl isocyanate? (c) Absence of alpha hydrogen
(a) nitrene (b) amide (d) High reactivity of alpha hydrogen
(c) nitroso (d) bromamide
87. Which one of the following acids is thermally most
79. Ethyl acetate is obtained when methylmagnesium unstable?
iodide reacts with (a) CH3COCH2COOH
(a) ethyl formate (b) acetyl chloride (b) CH3COCH2CH2CH2COOH
(c) carbon dioxide (d) ethyl chloroformate (c) CH3COCOOH
80. Here the strongest acid is (d) CH3COCH2CH2COOH
(a) CH3 – COOH 88. When propanamide reacts with Br2 and NaOH then
(b) CH3CH2 – COOH which of the following compounds is formed?
(c) Cl – CH2 – COOH (a) propyl alcohol (b) ethyl alcohol
(d) Br – CH2 – COOH (c) ethylamine (d) propylamine
81. Identify the wrong statement from the following: 89. Conversion of acetaldehyde into ethyl acetate in pres-
(a) methyl salicylate is an ester ence of aluminium ethoxide is called
(b) salicylic acid is a monobasic acid (a) Tischenko reaction
(c) methyl salicylate does not occur in natural oils (b) aldol condensation
(d) salicylic acid gives violet colour with neutral fer- (c) Benzoin condensation
ric chloride as well as brisk effervescence with (d) Cope reaction
sodium bicarbonate.
TO Compounds
ALL APUL
90. Which reaction product is formed from benzaldehyde

and methyl amine? (a) (b)
COOH O O
(a) C6H5NH2 (b) C6H5CH = NCH3 OH
(c) C6H5CH2NH2 (d) C6H5CONH2
(c) (d)
O COOH O CHO
91. Treatment of propionaldehyde with dil. NaOH solu-
tion gives 97. The reaction of p-HOC6H4COOH with excess Br2
(a) CH3CH2COCH2CH2CHO forms
(b) CH3CH2CHOHCH2CH2CHO Br OH
(c) CH3CH2CHOHCH(CH3)CHO
COOH COOH
(d) CH3CH2COOCH2CH2CH3 (a) (b)
Br Br
92. Is treated with a strong base like NaOH solution, fol-
lowed by neutralization with aqueous acid to get OH
OH
CHO CH2ONa (c) Br (d) COOH
Br Br
(a) (b)
CH2OH COONa
Br
Br
CH2ONa CH2OH
(c) (d) 98. Formaldehyde gives an additive product with meth
COOH COOH ylmagnesium iodide which on aqueous hydrolysis
gives
93. Identify the final product in the following sequence of
reactions. (a) methyl alcohol
CH2−CH2 (b) isopropyl alcohol
O H3O+
CH3CH2MgBr (a) (b) (c) propyl alcohol
KMnO4
(d) ethyl alcohol
(c) 99. During reduction of carbonyl compounds by hydra-
(a) CH3CH(CH3)COOH zine and KOH, the first intermediate formed is
(b) CH3CH2CH2CH2OH (a) RCH = NH (b) RCONH2
(c) CH3CH2CH2COOH (c) RCH = NNH2 (d) RC ≡ N
(d) CH3CH2COOH
Cl Cl −
A
94. Identify (a) in the following sequence of reactions. t-BuO
100. A is
NH3 Br2 + NaOH t-BuOH
C4H7OCl (a) C4H9ON
CH3CH2CH2NH2 O
(a) CH3CH2CH2COCl Cl O-t-Bu
(b) CH3CH2CHClCHO (a) (b)
(c) CH3CH2CH(OH)CH2Cl
O
(d) CH3CH2COCH2Cl O
95. Carbonation of methylmagnesium bromide gives an t-BuO O −
organic compound. This compound is also obtained by

(c) (d)
(a) Hydrolysis of methyl formate with dilute mineral O
acid
(b) Oxidation of methyl alcohol
101. The reaction of benzaldehdye with alkali gives
(c) Hydrolysis of methyl formate with dilute mineral
acid (a) benzene + benzyl alcohol
(d) Hydrolysis of acetonitrile by a mineral acid (b) phenol + benzene
(1) OH– (c) benzene + benzyl alcohol
96. Br – (CH2)4 – COOH ?
(2) H+ (d) benzyl alcohol + sodium benzoate
Chapter 28
102. The cyanohydrin of a compound X on hydrolysis 109. Baeyer-Villiger oxidation of cyclohexanone with per-
gives lactic acid; the X is acetic acid
(a) (CH3)2CO (b) CH3CHO O
||
(c) HCHO (d) C6H5CH2CHO
(CH3 – C – O – O – H) gives
103. Which of the following products is formed when benz- O
aldehyde is treated with CH3MgBr and the addition CHO
product so obtained is subjected to acid hydrolysis? O
(a) (b)
(a) a primary alcohol
(b) phenol O
COOCH3 COOC2H5
(c) secondary alcohol
(d) tert-Butyl alcohol (c) (d)
104. From which of the following tertiary butyl alco- 110. If 3-hexanone is reacted with NaBH4 followed by
hol is obtained by the action of methyl magnesium hydrolysis with D2O, the product will be
iodide? (a) CH3CH2CD(OD)CH2CH2CH3
(a) CO2 (b) HCHO (b) CH3CH2CH(OD)CH2CH2CH3
(c) CH3CHO (d) CH3COCH3 (c) CH3CH2CD(OH)CH2CH2CH3
(d) CH3CH2CH(OH)CH2CH2CH3
105. A substance C4H10O yields on oxidation a compound,
C4H8O which gives an oxime and a positive iodoform 111. Which one of the following pairs is not correctly
test. The original substance on treatment with conc. matched?
H2SO4 gives C4H8. The structure of the compound is (a) > C = O > CH2
Clemmensen reduction
(a) (CH3)3COH
(b) CH3CHOHCH2CH3 (b) – COCl – CHO
Rosenmund reduction
(c) CH3CH2CH2CH2OH
(c) > C = O > CHOH
(d) CH3CH2 – O – CH2CH3 Wolff – Kishner reduction
106. In the reaction (d) – C ≡ N – CHO
∆, Pyridine Stephen reduction
CH3CHO + CH2(COOH)2 A
112. Which alkene is formed from the following yield car-
The compound A is
bonyl pair?
(a) CH3CH=CHCOOH CH3CH2CH2CH = PPh3 + 2-butanone
(b) COOHCH=CHCOOH (a) 1-methyl-5-methane
(c) CH3COOH (b) 3-methyl-3-heptene
(d) C2H5COOH (c) 4-methyl-3-heptene
NaCN H3O+ (d) 5-methyl-3-heptene
107. (CH3)2CO A B
(HCl) 113. Predict the product ‘B’ in the sequence of reaction
30 % H2SO4 NaOH
in the above sequence of reactions A and B are HC ≡ CH A B
HgSO4
(a) (CH3)2C(OH)CN, (CH3)2CHCOOH
(a) CH3CHO (b) CH3COOH
(b) (CH3)2C(OH)CN, (CH3)2C(OH)2
OH
(c) (CH3)2C(OH)CN, (CH3)2C(OH)COOH |
(d) (CH3)2C(OH)CN, (CH3)2C=O (c) CH3COONa (d) CH3 – CH – CH2CHO
108. The most reactive compound towards formation of 114. An organic compound ‘A’ has the molecular formula
cyanohydrin on treatment with KCN followed by C3H6O. It undergoes iodoform test. When saturated
acidification is with HCl it gives ‘B’ of molecular formula C9H14O.
‘A’ and ‘B’ respectively are
(a) p-nitrobenzaldehyde
(b) p-hydroxybenzaldehyde (a) Propanone and 2, 6-dimethyl-2, 5-heptadien-4-one
(c) benzaldehyde (b) propanone and mesitylene oxide
(d) phenylacetaldehyde (c) propanal and mesitylene
(d) propanol and mesityl oxide
TO Compounds
ALL APUL
115. The end product in the following sequence of reac- (a) two different oximes are formed
tions is (b) three different oximes are fomed
1% HgSO4 CH3MgX (c) two oximes are optically active
HC ≡ CH A B [O] (d) all oximes are optically active
20% H2SO4 H2O
(a) ethanol (b) acetone 123. m-Chlorobenzaldehyde on reaction with conc. KOH
(c) acetic acid (d) isopropyl alcohol at room temperature gives
116. A and B in the following reactions are (a) potassium m-chlorobenzoate and m-hydroxybe-
HCN B nzaldehyde
R – C – R’ A (b) m-hydroxybenzaldehyde and m-chlorobenzyl
KCN
|| alcohol
O (c) m-chlorobenzyl alcohol and m-hydroxybenzyl
R OH alcohol
C (d) potassium m-chlorobenzoate and m-chlorobenzyl
alcohol
R’ CH2NH2
124. A mixture of benzaldehyde and formaldehyde on
(a) A = RR’C(OH)(COOH), B = NH3 heating with aqueous NaOH solution gives
(b) A = RR’CH2CN, B = NaOH (a) benzyl alcohol and sodium formate
(c) A = RR’C(CN) (OH), B = LiAlH4 (b) sodium benzoate and methyl alcohol
(d) A = RR’C(CN)(OH), B = H3O+ (c) sodium benzoate and sodium formate
117. Cinnamic acid is formed when C6H5CHO condensa- (d) benzyl alcohol and methyl alcohol
tion with (CH3CO)2O in presence of 125. The appropriate reagent for the transformation
(a) sodium metal
(b) sodium acetate O
(c) anhydrous ZnCl2 CH2CH3
(d) conc. H2SO4 CH3
118. A compound gives a yellow ppt. on warming with the
aqueous solution of NaOH. Its vapour density is 29. HO HO
The compound is (a) Zn(Hg), HCl (b) NH2NH2, OH–
(a) CH3CH2CHO (b) CH3COCH3 (c) H2/Ni (d) NaBH4
(c) CH3CHOHCH3 (d) CH3CH2CH2OH
126. In a Cannizzaro reaction, the intermediate that will be
119. In the reaction best hydride donor is
H2SO4, HgSO4
CH3CH2C ≡ CH [A]
H
The compound [A] is
(a) O−
(a) CH3–CH2–CH2–COOH
OH
(b) CH3–CH2–CH2–CHO
(c) CH3–CH2–CO–CH3 H
(d) none of these (b) O−
120. The compound which reacts with hydroxyl amine but −
O
does not react with Tollen’s reagent is
(a) CH3CHO (b) HCHO H
(c) C2H5OH (d) CH3COCH3 O−
121. To convert 2-butanone into propionic acid O −
(a) NaOH + NaI/H+ (c) MeO

(b) Fehling’s test H
(c) I2/NaOH/H+
(d) Tollen’s reagent O−
122. The smallest ketone and its next homologue are O−
(d) O2N
reacted with NH2OH to form oxime then
Chapter 28
127. In the Cannizzaro reaction given below, 134. Identify (a) in the following reaction:
OH–
2Ph-CHO Ph – CH2OH + PhCO2–, OCH3 (i) H2O/H+ (A)
the slowest step is
(a) the attack of – OH at the carbonyl group OCH3 (ii) Δ
(b) the transfer of hydride ion to the carbonyl group COOH

(c) the abstraction of proton from the carboxylic acid OH
(d) the deprotonation of Ph – CH2OH. O
(a) CH3 (b)
CH3
128. The product obtained on the alkaline hydrolysis of
COOH
followed by acidification will be O
(a) H2NCH2CH2CH2CH2COCl + H2O
(b) HOOC.CH2CH2CH2CH2COOH + NH3
(c) O (d) O
(c) H2N – CH2CH2CH2CH2 – COONa
(d) H2NCH2CH2CH2CH2COOH COOH
129. Which of the following on oxidation followed by 135. Which is not true about acetophenone?
hydrolysis gives pyruvic acid? (1) Reacts with I2 /NaOH to form iodoform
(a) acetone cyanohydrin (2) Reacts with Tollen’s reagent to form silver mirror
(b) acetaldehyde cyanohydrin (3) On oxidation with alkaline KMnO4 followed by
(c) formaldehyde cyanohydrin hydrolysis gives benzoic acid
(d) none of these (4) Reacts to form 2, 4-dinitrophenyl-hydrazone
130. The refluxing of (CH3)2NCOCH3 with acid gives (a) 2 and 4 (b) 2 only
(c) 1 and 4 (d) 4 only
(a) 2CH3OH + CH3CONH2
(b) 2CH3NH2 + CH3COOH 136. Hydrolysis of an ester gives a carboxylic acid which
on Kolbe’s electrolysis yields ethane. The ester is
(c) (CH3)2NCOOH + CH4
(a) Methyl methanoate
(d) (CH3)2NH + CH3COOH (b) Methyl propanoate
131. The end product (b) in the following sequence of (c) Ethyl methanoate
reactions (d) Methyl ethanoate
KCN H+/ H2O 137. In the following sequence of reactions, what is D?
CH3Cl (a) (b) is
(a) HCOOH CH3
(b) CH3NH2 [O] SOCl 2 NaN 3
A B C
(c) CH3COOH
heat
(d) CH3COCH3 D
132. R–CH2–CH2OH can be converted into RCH2CH2 (a) an amide
COOH. The correct sequence of reagent is (b) phenyl isocyanate
(c) primary amine
(a) PBr3, KCN, H+ (b) HCN, PBr3, H+
(d) a chain lengthened hydrocarbon
(c) KCN, H+ (d) PBr3, KCN, H2
diethyl ether 138. In the reaction the final product C is
133. (CH3CO)2O A.
Anhyd. AlCl3 NH2
Product A is
(a) CH3COOC2H5 Br2 H2O
AC2O
A B C
(b) CH3COOCH3 CH3COOH H+
(c) CH3CH2COOC2H5
(d) CH3CH2COOH CH3
TO Compounds
ALL APUL
NHCOCH3 NH2
Br COCH3 (b)
(a) (b)
(c) N
CH3 CH3
+ –
(d) N OH
NH2 COCH3
Br Br
143. Which of the following carboxylic acids undergoes
(c) (d) decarboxylation easily?
OH
CH3 CH3
(a) COOH
139. CH3CO2C2H5 on reaction with sodium ethoxide in
ethanol gives A, which on heating in the presence of O
acid gives B. Compound B is
(a) CH3COCH2COOH (b) CH2COOH
(b) CH3OCH3
O NH2
(c) CH2 O (c)
COOH
OC2H5 O
(d) CH2= C
OC2H5 (d)
COOH
140. In the compound given below
The correct order of acidity of the positions (X), (Y)
144. The final product on acid hydrolysis and decarboxyl-
and (Z) is
ation of
+
NH3 H3CO COOC2H5
‘Y’ NH3
‘Z’ H3CO COOC2H5
COOH (a) O COOH

‘X’
COOH
(a) X > Y > Z (b) Y > X > Z (b) O
(c) Z > X > Y (d) X > Z > Y COOH
141. To convert 2-butanone into propionic acid (c) O

(a) NaOH + NaI/H+ (b) Fehling’s test
(c) I2 / NaOH / H+ (d) Tollen’s reagent H3CO
(d) COOH
142. The structure of the product (a) in the reaction is H3CO
given as product (a)
145. The end product (c) in this reaction,
N−H+O Product (A) CaCO3 Heat
CH3COOH A B
NH2OH
(a) N − CH C, is
(a) Acetaldehyde oxime
(b) Aceto oxime
Chapter 28
(c) Acetamide 151. Which of the following will be oxidized by HIO4?

(d) Ethane nitrile 1. R – C – C – R
|| ||
146. In the following sequence of reactions:
KMnO4 SOCl2 , NH3 O O
CH3CH2OH (a) 2. R – C – CH – R
(b) Br2 + NaOH (c) the end product (c) is || |
(a) Acetone (b) Ethylamine O OH
(c) Acetic acid (d) Methyl amine 3. R – CH – CH2 – CH – R
147. Which of the following will give yellow precipitate | |
with I2 /NaOH? OH OH
1. ICH2COCH2CH3 2. CH3COOCOCH3 4. R – CH – CH – R
3. CH3CONH2 4. CH3CH(OH)CH2CH3 | |
OH OH
(a) 1, 3 (b) 3, 4
Select the correct answer using the codes below:
(c) 1, 2 (d) 1, 4
(a) 1, 2 and 4 (b) 1, 2 and 3
148. Consider the following substances: (c) 2, 3 and 4 (d) 1, 3 and 4
1. HCHO
152. Place the following acid chlorides in the decreasing
2. CH3CHO order of reactivity to hydrolysis.
3. CH3CH2COCH3 (1) C6H5COCl
4. CH3CH2COCH2CH3 (2) p-O2NC6H4COCl
Correct order of reactivity towards nucleophillic (3) p-CH3OC6H4COCl
addition reaction is: (a) 2 > 1 > 3 (b) 3 > 1 > 2
(a) 1 > 4 > 2 > 3 (c) 1 > 2 > 3 (d) 1 > 3 > 2
(b) 1 > 2 > 4 > 3
(c) 1 > 3 > 2 > 4 153. Consider the following substances:
(d) 1 > 2 > 3 > 4 (1) C6H5COCH2COCH3
(2) (C2H5OCO)2CH2
149. Under Wolff-Kishner reduction conditions, the con- (3) CH3COCH2COOC2H5
versions which may be brought about are (4) CH3COCH2COCH3
1. Benzophenone into diphenylmethane Place these dicarbonyl compounds in decreasing
2. Benzaldehyde into benzyl alcohol order of their enol content.
3. Cyclohexanone into cyclohexane (a) 4 > 3 > 2 > 1 (b) 1 > 4 > 3 > 2
4. Cyclohexanone into cyclohexanol (c) 1 > 2 > 3 > 4 (d) 1 > 4 > 2 > 3
(a) 1, 2 (b) 1, 3
154. Consider the following acids:
(c) 1, 3, 4 (d) 2, 3, 4
(1) HCN (2) HCOOH
150. The correct decreasing order of alkaline hydrolysis is (3) CH3COOH (4) Cl – CH2 – COOH
COOCH3 COOCH3 The acid strengths of these acids are such that
(a) 4 > 3 > 1 > 2 (b) 1 > 3 > 2 > 4
(c) 2 > 3 > 4 > 1 (d) 4 > 2 > 3 > 1
(1) (2)
155. Consider the following acids:
NO2 (1) CH3COOH
(2) Cl2CHCOOH
COOCH3 COOCH3 (3) ClCH2COOH
(3) ClCH2CH2COOH
(3) (4) The correct sequence of acidity is:
(a) 3>1>2>4
OCH3 CH3 (b) 2>3>4>1
(a) 2 > 1 > 3 > 4 (b) 1 > 2 > 3 > 4 (c) 1>3>4>2
(c) 2 > 3 > 1 > 4 (d) 3 > 2 > 1 > 4 (d) 2>4>3>1
TO Compounds
ALL APUL
156. Which of the following are examples of aldol III. it does not undergo electrophillic substitution like
condensation? nitration at meta position.
dil. NaOH
1 2CH3CHO CH3CHOHCH2CHO IV. it does not undergo iodoform reaction with iodine
dil. NaOH and alkali.
2 2CH3COCH3
CH3COH(CH3)CH2COCH3 (a) I and II (b) II and IV
dil. NaOH (c) I and III (d) III and IV
3. 2HCHO CH3OH + HCOOH
dil. NaOH 160. Consider the following statements; Acetophenone
4. C6H5CHO + HCHO can be prepared by
C6H5CH2OH
I. oxidation of 1-phenylethanol
(a) 2 and 3 (b) 1 and 3 II. reaction of benzaldehyde with methyl magne-
(c) 1 and 2 (d) 1, 2 and 3 sium bromide
157. Consider the reaction sequence given below and iden- III. Friedal Crafts reaction of benzene with acetyl
tify the incorrect statement(s). chloride
IV. Distillation of calcium benzoate
CH3 – Which of the above statements are correct?
O3 ozonolysis dil. OH
P (a) I and III
(b) III and IV
oxidation NaOEt H3O +
Q R S (c) II and III

(d) I and IV
161. Which of the following reactants on reaction with
conc. NaOH followed by acidification gives the fol-
T
(1) S can be open chain structure while T a close ring lowing lactone as the only product?
structure O
(2) P is 2 keto-heptanol
C
COCH3
(3) Q is O
CH2
O
(4) R is COCH3 COOCH3 COOH
(a) (b)
COOH CHO
(a) 1 and 4 (b) 3 and 4
(c) 2 and 3 (d) 4 only CHO COOH
158. Consider the following acids: (c) (d)
(1) o-HOC6H4COOH CHO COOH
(2) o-CH3OC6H4COOH
(3) C6H5COOH 162. The correct order of reactivity of PhMgBr with
Arrange these acids in the decreasing order of their I O II O III O
acidities. || || ||
(a) 1 > 3 > 2 (b) 3 > 2 > 1 Ph – C – Ph CH3 – C – H CH3 – C – CH3 is
(c) 1 > 2 > 3 (d) 2 > 3 > 1 (a) I > II > III (b) III > II > I
159. Which of the following statements regarding chemi- (c) II > III > I (d) I > III > II
cal properties of acetophenone are wrong? 163. The product of acid hydrolysis of P and Q can be dis-
I. it is reduced to methylphenylcarbinol by sodium tinguished by
and ethanol
OCOCH3
II. it is oxidized to benzoic acid with acidified
KMnO4 P = H2 C
CH3
Chapter 28
Q = H3C 166. Which of the following undergoes aldol condensation?

1. Acetaldehyde
2. Propionaldehyde
3. Benzaldehyde
OCOCH3 4. Trideuteroacetaldehyde.
(a) 1, 2 (b) 1, 2, 3
(a) Lucas reagent (b) 2, 4-DNP
(c) 1, 2, 4 (d) 2, 4
(c) Felhing’s solution (d) NaHSO3
167. A new carbon-carbon bond formation is possible in
164. Compound ‘A’ (molecular formula C3H8O) is treated
with acidified potassium dichromate to form a prod- 1. Cannizzro reaction
uct ‘B’ (molecular formula C3H6O). ‘B’ forms a 2. Feirdel-Craft’s reaction
shining silver mirror on warming with ammoni- 3. Clemmensen reduction
cal silver nitrate. ‘B’ when treated with an aque- 4. Reimer – Teimann reaction
ous solution of H2NCONHNH2 HCl and sodium (a) 2, 4 (b) 1, 2
acetate gives a product ‘C’. Identify the structure (c) 2, 3 (d) 1, 2, 4
of ‘C’. 168. An aldehyde, C11H8O (X) which does not undergo
(a) CH3CH2CH = NNHCONH2 self aldol condensation gives benzaldehyde and two
(b) CH3 – C = NNHCONH2 moles of (Y) on ozonolysis. Compound (Y), on oxi-
| dation with silver ions gives oxalic acid. The structure
CH3 of (X) is given as:
(c) CH3 – C = NCONHNH2 CH =CH − CHO
|
(a)
CH3
(d) CH3CH2CH = NCONHNH2 CH = CH − C ≡ C − CHO
165. The enol form of acetone, after treatment with D2O, (b)
gives
OD O C C − CHO
| || (c)
(a) CH3 – C = CH2 (b) CD3 – C – CD3
OH OD CH = CH − CH = CH2
| |
(d)
(c) CH2 = C – CH2D (d) CD2 = C – CH2D
More than One Option Correct Type
169. Arrange the following compounds in decreasing 170. Which of the following compounds can be synthe-
order of reactivity towards RMgX sized by intramolecular aldol condensation in very
O O good yield (as a major product)?
O
(I) (II) CHO

F3C CF3 (a) (b)
CH3
O O
(III) (IV) O O
O
(c) (d)
(a) I > III > IV (b) II > I > III
(c) IV > III (d) II > IV
TO Compounds
ALL APUL
171. Which of the following will give characteristic colour (c) Condensation involves formation of new C – C
with FeCl3 ? bond.
(d) Molecular weight of the product is an integral
(a) O multiple of molecular weights of reactants.
CHO 175. Ph − CHO + NH2OH → (A)

(b) CH3 –CO – CH2 – COOC2H5 Which of the following is/are true about compound
(A)?
(c) OH (a) The syn- (A) on treatment with PCl5 in ether gives
N- phenyl formamide.
(b) The product (A) exists in 2 isomeric forms.
(d) O (c) The suitable pH for the reaction is between 4 to 6
(d) The anti- (A) on treatment with PCl5 in ether
followed by hydrolysis gives aniline and formic
172. Which of the following statement(s) is/are correct? acid.
(a) The nucleophilic addition of HCN to CH3 – CH =
CH – CHO results in major addition to C = O. 176. Which of the following reactions, yield a product
(b) The nucleophilic addition of HCN to CH3 – CH = with a three membered ring?
CH – CHO results in major addition to C = C. (a) CH3 – C(O) – CH2CH2CH2Cl KOH, H2O
(c) The nucleophilic addition of PhMgBr to PhCH =
(b) PhCHO + Br – CH2 – C(O) – OEt
CH – COCMe3 results in addition to C = C.
t-BuO−/ t-BuOH
(d) The nucleophilic addition of PhMgBr to PhCH
CH – CHO results in addition to C = O. mCPBA
(c) Ph – CH = CH – CH3
173. On warming with I2 and aqueous NaOH, iodoform −
OH/H2O
(d) 3- bromobutan -2- ol
and sodium succinate are formed. The formula of the
compound should be 177. Identify the products formed (X) and (Y) in the fol-
(a) CH3COCH2CH2CH3 lowing reaction
(b) CH3COC6H5
C6H5CHO + HCHO conc. OH (X) + (Y)
(c) CH3 – CO –CH2 – CH2 – COOH
(d) CH3COCH2CH2COCH3 (a) (X) is HCOO⊕
(b) (Y) is C6H5CH2OH
174. The true statements regarding aldol condensation are (c) (Y) is CH3OH
(a) It is an irreversible process. (d) (X) is C6 H5 COO⊕
(b) When aldehydes condense with ketones, it is
the α - hydrogen of the ketone involved in the
condensation.
Passage Based Questions
Passage-1 (B)
Compound (A), C6H12O2, optically active was oxidized HOCH2 – CH2 – C*H(CH3) – CH2 – CHO
by Ag(NH3)2+ to an optically active compound (B), CrO3 in pyridine
C6H12O3. (A) on oxidation with CrO3 in pyridine gives OHC – CH2 – CH(CH3) – CH2 – CHO
optically inactive compound (C) which on treating with (C)
Zn- Hg/ HCl gave 3-methylpentane. (A) on oxidation HOCH2 – CH2 – C*H(CH3) – CH2 – CHO
with H2CrO4 gave optically inactive compound (D). H2CrO4
Solution HOOC – CH2 – CH(CH3) – CH2COOH
HOCH2 – CH2 – C*H(CH3) – CH2 – CHO (D)
(A) Ag(NH3)2+ OHC – CH2 – CH(CH3) – CH2 – CHO Zn-Hg/HCl
HO – CH2 –CH2 – CH(CH3) – CH2 – COOH CH3 – CH2 – CH(CH3) – CH2 – CH3
3 – methylpentane
Chapter 28
178. Compound (B) on treating with dilute H2SO4 gives R1 OH R1

(a) CH3 – CH = C(CH3) – CH2CHO C H⊕ C = NZ
⊕
O R2 NHZ – H2O, –H R2
(b)
R1 and R2 may be –H, −R (alkyl) or –Ar(aryl)
O
Z = Alkyl, aryl, −OH, −NH2, PhNH−, −NHCONH2
O
(c) 181. If the medium of reaction is fairly alkaline in the
O beginning of the reaction and pH of the solution is
made to decrease gradually.
(d) None of these
(a) The rate of reaction increases throughout.
179. Compound (C) on treating with CH3O−/CH3OH will (b) The rate of reaction decreases throughout.
give (c) The rate of reaction reaches minimum at a partic-
OH OCH3 ular pH and then increases.
(d) The rate of reaction reaches maximum at a partic-
(a) O (b) O ular pH, and then decreases.
OCH3 OCH3 182. R1
OH C = O + H2N.NH2
R2
(c) (d) H+
O O Product (P)
OH Which of the following type of isomerism are possi-
ble in the product(P)?
180. Compound (D) on gently heating with P2O5 gives
(I) Optical
(a) O (b) O (II) Tautomerism
(III) Metamerism
O (IV) Geometrical
O
O (a) I and II (b) I and III
O (c) II and III (d) I, II, III and IV
(c) O (d) O 183. Rate of reaction is fastest when the ‘Z’ is
(a) –OH (b) −Me
O
O (c) –NH2 (d) O
O
O
– C – NH2
Passage-2
Nucleophiles such as ammonia and its derivatives H2N – Z Passage-3
add to the carbonyl group of aldehydes and ketones. The Aldehydes with at least one α- hydrogen undergo aldol
reaction is reversible and catalysed by acid. The equilibri- condensation. Two molecules of same or different alde-
um favours the product formation due to rapid dehydration hydes take part in such condensation. One of the two
of the intermediate to form aldehyde molecules must have an α- hydrogen. Ketones
under similar condition also give such condensation (ketol
C=N–Z condensation). These reactions take place in presence of
NaOH, KOH, Ba(OH)2. For ketol condensation (BaOH)2
R1 is the best reagent. Intermolecular aldol condensation is
C = O + NH2– Z + H+ given by dialdehyde or keto aldehydes. The diketones
R2 should be 2, 5; 2, 6; 2, 7; and 2, 8 diketones. Intramolecular
R1 aldol condensation is the best method for preparation of
OH
five or six membered rings.
C + H+
R2 NHZ CH3 – CO – H + CH3 – CO – H NaOH (dil)
CH3 – CH(OH) – CH2CHO
TO Compounds
ALL APUL
184. Which compound would you start with in an aldol 185. Cyclohexanone when treated with Ba(OH)2 gives
condensation cyclization to prepare the given com- (a) OH OH O
(b)
pound (A)?
O
CH3
(c) both (a) and (b) (d) does not give any reaction
(A)
OH 186. A hydrocarbon C7H12 on ozonolysis gives a com-
(a) CH3 – CO – CH2 – CH2 – CH2 – C(O) – CH3 pound which undergoes aldol condensation, giving
(b) CH3 – C(O) – CH2 – CH2 – C(O) – CH3 1- acetylcyclopentene. The hydrocarbon is
(c) CH3 – C(O) – CH2 – CH2 – CH2 – OH (a) (b)
(d) CH3CH2 – C(O) – CH2 – CH2 – CHO
(c) (d)
Match the Column Type
187. Match the following: (iii) A Schiff’s base

List I (Reactants) (iv) An acetal
The correct matching is:
Hg2+
1. HC ≡ CH + H2O 1 2 3 4
1. Cl2, ∆ (a) (iv) (iii) (ii) (i)
2. PhCH3 (b) (iv) (iii) (i) (ii)
2. H2O/OH-
(c) (iii) (iv) (ii) (i)
[Co(CO)4]2 (d) (i) (ii) (iii) (iv)
3. CH3 – CH = CH2 + CO + H2
PdCl2, CuCl2 189. Match the following:
4. H2C = CH2 + O2
List I (Compounds to be reduced)
H2O
1. BrCH2CH2CHO
List II (Products) 2. (CH3)2C(OH)CH2CH2COCH3
(i) CH3CHO 3. PhCH(OH)CH2COCH2CH3
(ii) PhCHO 4. PhCOCH3
(iii) CH3CH2CH2CHO List II (most suitable reduction)
The correct matching is: (i) Clemmensen reduction
1 2 3 4 (ii) Wolf-Kishner reduction
(iii) Both
(a) (iii) (ii) (i) (i)
(b) (i) (i) (ii) (iii)
1 2 3 4
(c) (ii) (iii) (i) (i)
(a) (iii) (ii) (ii) (i)
(d) (i) (ii) (iii) (i)
(b) (i) (ii) (ii) (iii)
188. Match the following: (c) (i) (iii) (iii) (ii)
List I (d) (ii) (iii) (ii) (i)
1. RCHO + 2R’OH dry HCl gas 190. Match list I (organic compounds oxidized by HIO4)
2. R2C = O + R’NH2 with list II (products of HIO4 oxidation) and select the
3. RCH = O (or R2C = O) + Phenyl hydrazine H+ correct answer:
4. PhCHO + NH2OH H+ List I
List II 1. CH3COCHO
(i) Benzaldehyde oxime 2. 1, 2-cyclohexanedione
(ii) A phenyl hydrazone 3. PhCH(OH)CHO
4. CH3CH2CH(OH)COCH3
Chapter 28
List II The correct matching is:

(i) PhCH = O + HCOOH 1 2 3 4
(ii) CH3CH2CHO + HOOCCH3 (a) (iv) (ii) (i) (iii)
(iii) HOOC(CH2)4COOH (b) (i) (iv) (iii) (ii)
(iv) CH3COOH + HCOOH (c) (i) (iv) (ii) (ii)
The correct matching is: (d) (iv) (i) (ii) (iii)
1 2 3 4 193. Match the following:
(a) (iii) (iv) (i) (iii) List I (Reaction)
(b) (iii) (ii) (i) (iv) 1. C6H5CHO + NaOH C6H5COOH
(c) (iv) (iii) (i) (ii) + C6H5CH2OH
(d) (iv) (iii) (ii) (i) Anhyd. AlCl3
2. C6H6 + CH3Cl C6H5CH3
191. Match list I (organic compounds oxidized by HIO4) Pd/BaSO4
with list II (products of HIO4 oxidation) and select the 3. RCOCl + H2 RCHO
correct answer. 1. heat, 2. H+
4. C6H5OH + NaOH + CO2
List I
HIO4 List II (Name of reactions)
1. CH3CH2CH – CH – CH2CH3
| | (i) Rosenmund reduction
OH OH HIO4 (ii) Kolbe’s reaction
2. PhCH2CH – CH – CH3 (iii) Claisen reaction
| |
(iv) Cannizzaro reaction
OH OH
3. CH2 – CH2 HIO4 (v) Friedal-Craft’s reaction
| | The correct matching is:
OH OH 1 2 3 4
HIO4
4. CH2 – CH – CH2 (a) (iv) (v) (i) (ii)
| | | (b) (v) (i) (ii) (iii)
OH OH OH (c) (v) (iii) (ii) (i)
List II (d) (iv) (ii) (iii) (i)
(i) 2 H2C = O + HCOOH
194. Match list I (products obtained on oxidative with
(ii) 2 CH3CH2CH = O HIO4) and list II (compounds that give products by
(iii) 2H2C = O HIO4 oxidation) and select the correct Answer.
(iv) PhCH2CH = O + CH3CH = O List I
The correct matching is: 1. PhCH = O + CH3COCH3
1 2 3 4
(a) (ii) (iv) (i) (iii) 2. O + H2C = O
(b) (iv) (ii) (iii) (i)
(c) (ii) (iii) (i) (iv) 3. 2H2C = O + HCOOH
(d) (ii) (iv) (iii) (i)
4. O = CH(CH2)3CH = O
192. Match the following: List II
List I (i) Cyclopentane-1, 2-diol
1. Formalin 2. Trioxane
3. Ketene 4. Metaldehyde OH
(ii)
List II CH2OH
(i) Trimer of HCHO
(ii) Compounds of the general formula, R2C = C = O (iii) Glycerol
(iii) A tetramer of acetaldehyde (iv) Ph – CH – C(CH3)2
| |
(iv) 40% aqueous solution of HCHO
OH OH
TO Compounds
ALL APUL
The correct matching is: (iii) P

1 2 3 4 (iv) LiAlH4
(a) (ii) (iv) (i) (iii) The correct matching is:
(b) (iv) (ii) (iii) (i) 1 2 3 4
(c) (iv) (ii) (i) (iii) (a) (ii) (iii) (iv) (i)
(d) (ii) (iv) (i) (iii) (b) (ii) (iii) (i) (iv)
195. Match the reactions given in list I with the reagents (c) (iii) (ii) (iv) (i)
given in list II and select the correct Answer. (d) (i) (iii) (iv) (ii)
List I 197. Match the following
1. C2H5 – CH = C(CH3)2
O O Column–I Column–II
|| || (a) CH3COCH3 (p) H2SO4 (conc.)
2. C2H5 – C – H + CH3 – C – CH3
O O (b) CH3CHO (q) I2 – OH–
|| || (c) CH3CHOH – CH3 (r) CH3MgI in ether
3. C6H5 – CH2 – O – C – NH – CH2 – C – OH (d) CCl3CHO (s) 2, 4- dinitrophenyl
4. C6H5 – CH3 + CO2 + H2N – CH2 – C – OH hydrazine
|| (t) NaOH (aq)
O
List II 198. Match the following
(i) KMnO4
Column–I Column–II
(ii) CHCl3 + aq. NaOH
(iii) O3 .Zn + H2O (a) Cl (p) Platinic chloride method
(iv) H2/Pd – C NO2 of estimation
1 2 3 4
(a) (iii) (i) (ii) (iv) (b) NH2 (q) Fehling’s test
(b) (iii) (i) (iv) (ii)
(c) (i) (iii) (iv) (ii)
(d) (i) (iii) (ii) (iv)
196. Match the following Br
List I (Reagents) (c) Urea (r) Beilstein test
1. C6H5– C – OC2H5 + CH3 – C – O-C2H5 (d) CHO (s) Lassaigne’s test
|| ||
O O
C6H5 – C – CH2– C – O – C2H5 + C2H5OH
|| || Cl
O O
(t) Sodalime test
2. CH3 – C – OH + Cl2 Cl – CH2 – C – OH
|| || 199. Match the following
O O
3. C6H6 + (CH3 – C = O)2O Column–I Column–II
C6H5 – C – CH3
||
(a) O (p) Alcohol
O ||
4. CH3 – C – CH2 – CH2 – CHO CH3–CH(OH) R1 – C – R2 + LiAlH4
|| CH1CH2CH2OH (b) R1 (q) Enantiomers
O C = O+ NH2OH
R2
List II H+/Δ
(i) Anhydrous ZnCl2
θ
(ii) C2H5O
Chapter 28
(c) O O (r) Racemic mixture (d) Claisen condensation (s) CH3 – CO – OC2H5
|| ||
R–C–C–R
LiAlH4 (t) CHO
O
(d) RCHO + HCN (s) Meso compound
HO– 201. Match the following
(t) Diastereomers Column–I Column–II

(A) (CH3)2CH – CHO (p) Aldol addition
200. Match the following
(B) C6H5CHO (q) Cannizaro reaction
Column–I Column–II (B) HCHO (r) Perkin condensation
(a) Cannizzaro reaction (p) PhCHO (D) CH3CHO (s) Haloform reaction
(b) Aldol condensation (q) CH3CHO (t) Positive test with Tollen’s
(c) Benzoin condensation (r) O reagent
Integer Type
202. The total number of β- hydroxycarbonyl compounds 207. An aldehyde (A) (C11H10O) which does not undergo
which can be got by the aldol condensation of self aldol condensation, gives benzaldehyde and 2
CH3CHO and CH3CH2 – CHO is _____. moles of (B) on ozonolysis. Compound (B) on oxi-
dation with Tollen’s reagent gives an oxalic acid.
203. The number of carbonyl groups in the given com- Calculate the number of π- bonds in the original
pound, which are reactive for nucleophilic addition is C5H12O.
______.
208. A diekmann condensation of diethyladipate was
1 carried out by heating with sodium ethoxide. One
CO
2 equivalent of benzyl bromide was then added and the
C=O resulting mixture was then refluxed in 5% HCl for
CO several hours and heated. How many chiral carbon (s)
3 is/are present in the final product?
204. Number of phenyl groups present in the product 209. 2, 6-octanedione is treated with alkali giving an aldol
formed when acetophenone is heated with conc. product. How many optically active isomer(s) is/are
H2SO4 is ________. present in the final product?
205. Formaldehyde is warmed with 50% NaOH. The order 210. How many molecules of acetone are needed in aldol
of reaction that takes place is ____. condensation to form phorone?
206. The total number of enolates that can be formed, 211. With how many molecules of ammonia does formal-
when 2- Butanone is treated with a base is _______. dehyde condense to form urotropine?
Previous Years' Questions

212. On vigorous oxidation by permanganate solution, (c) (CH3)2CHCO2H + CH3CH2COOH
(CH3)2C = CH – CH2 – CH3 gives [2002] OH OH
(a) (CH3)2CHOH + CH3CH2CH2OH | |
(b) (CH3)2C = O + CH3CH2COOH (d) CH3 – C – CH – CH2CH3
|
CH3
TO Compounds
ALL APUL
Cl2 alc. KOH 220. Which one of the following is reduced with zinc and
213. CH3CH2COOH A
red P hydrochloric acid to give the corresponding hydrocar-
B What is B? [2002] bon? [2004]
(a) CH3CH2CHO (a) ethyl acetate
(b) ClCH2CH2COOH (b) acetic acid
(c) CH3CH2COCl (c) acetamide
(d) CH2 = CHCOOH (d) butan-2-one
214. When CH2 = CH – COOH is reduced with LiAlH4 the 221. Among the following acids which has the lowest pKa
compound obtained will be [2003] value? [2005]
(a) CH3 – CH2 – COOH (a) CH3COOH
(b) CH2 = CH – CH2OH (b) HCOOH
(c) CH3 – CH2 – CH2OH (c) (CH3)2CH – COOH
(d) CH3 – CH2 – CHO (d) CH3CH2COH
215. In the anion HCOO– the two carbon-oxygen bonds are 222. The best reagent to convert pent-3-en-2-ol into pent-
found to be of equal length. What is the reason for it? 3-en – 2-one is [2005]
[2003] (a) acidic permanganate
(a) electronic orbits of carbon atom are hybridized (b) acidic dichromate
(b) The C = O bond is weaker than the C – O bond (c) chromic anhydride in glacial acetic acid
(c) The anion HCOO– has two resonating structures (d) pyridinium chloro-chromate
(d) the anion is obtained by removal of a proton from
the acid molecule 223. Reaction of cyclohexanone with dimethylamine in
the presence of catalytic amount of an acid forms a
216. The general formula CnH2n O2 could be for open chain compound if water during the reaction is continuously
[2003] removed. The compound formed is generally known as
(a) carboxylic acid (b) diols [2005]
(c) diketones (d) dialdehydes (a) a Schiff’s base (b) an enamine
217. The reaction (c) an imine (d) an amine
O O 224. Reaction of cyclohexanone with dimethylamine in
R−C + Nu R−C the presence of catalytic amount of an acid forms a
X Nu compound if water during the reaction is continuously
removed. The compound formed is generally known
+X+
is fastest when X is [2004] as [2005]
(a) Cl (b) NH2 (a) a Schiff’s base (b) an enamine
(c) OC2H5 (d) OCOR (c) an imine (d) an amine
218. On mixing ethyl acetate with aqueous sodium chlo- 225. Phenyl magnesium bromide reacts with methanol to
ride, the composition of the resultant solution is give [2006]
[2004] (a) a mixture of anisole and Mg(OH)Br
(a) CH3COOC2H5 + NaCl (b) a mixture of benzene and Mg(OMe)Br
(b) CH3COONa + C2H5OH (c) a mixture of toluene and Mg(OH)Br
(c) CH3COCl + C2H5OH + NaOH (d) a mixture of phenol and Mg(Me)Br
(d) CH3Cl + C2H5COONa
226. The increasing order of the rate of HCN addition to
219. Acetyl bromide reacts with excess of CH3MgI fol- compounds A – D is [2006]
lowed by treatment with a saturated solution of (a) HCHO (b) CH3COCH3
NH4Cl gives [2004] (c) PhCOCH3 (d) PhCOPh
(a) acetone (a) a < b < c < d
(b) acetamide (b) d < b < c < a
(c) 2-methyl-2-propanol (c) d < c < b < a
(d) acetyl iodide (d) c < d < b < a
Chapter 28
227. Among the following mixtures, dipole-dipole as the CH = CHCOCH3

major interaction, is present in [2006] Reagent
(a) benzene and ethanol HO
(b) acetonitrile and acetone
CH = CHCH2CH3
(c) KCl and water
(d) benzene and carbon tetrachloride
HO
228. The correct order of increasing acid strength of the
compound is [2006] (a) NaBH (b) NH2NH2, OH–
(c) Zn – Hg/HCl (d) Na, Liq. NH3
(a) CH3CO2H (b) MeOCH2CO2H
(c) CF3CO2H (d) (Me)2 CH CO2H 234. An organic compound A upon reacting with NH3
(a) b < d < a < c (b) d < a < c < b gives B. On heating B, it gives C. In the presence of
(c) d < a < b < c (d) a < d < c < b KOH reacts with Br2 to give CH3CH2NH2 A is
[2013]
229. In cannizaro reaction given below
(a) CH3 − CH − COOH
OH
Ph CHO Ph CH2OH + Ph CO2 the slowest CH3
step is: [2009] (b) CH3CH2COOH
(a) the transfer of hydride to the carbonyl group (c) CH3COOH
(b) the abstraction of proton from the carboxylic (d) CH3CH2CH2COOH
group
(c) the deprotonation of Ph CH2OH 235. In the reaction, [2014]
LiAIH 4 PCl5 AlC.KOH
(d) the attack of :OH at the carboxyl group CH3COOH 
→ A 
→ B → C,
230. A liquid was mixed with ethanol and a drop of con- the product C is:
centrated H2SO4 was added a compound with a fruity (a) Ethylene (b) Acetyl chloride
smell was formed. The liquid was: [2009] (c) Acetaldehyde (d) Acetylene
(a) HCHO (b) CH3COCH3 236. In the following sequence of reactions:
(c) CH3COOH (d) CH3OH KMnO
4 → A →
2 SOCl
2 H /Pd
Tolouene  B 
BaSO
→ C, the
4
231. Sodium ethoxide has reacted with ethanoyl chloride.
product C is [2015]
The compound that is produced in the above reaction is: (a) C6H5COOH (b) C6H5CH3
[2011] (c) C6H5CH2OH (d) C6H5CHO
(a) 2-Butanone (b) Ethyl chloride
(c) Ethyl ethanoate (d) Diethyl ether 237. In the Hoffmann bromamide degradation reaction, the
number of moles of NaOH and Br2 used per mole of
232. Trihloroacetaldehyde was subjected to cannizzaro’s Amine produced are [2016]
reaction by using NaOH. The mixture of the products (a) Four moles of NaOH and two moles of Br2
contains sodium trichloroacetate and another co mpound. (b) Two moles of NaOH and two moles of Br2
The other compound is: [2011] (c) Four moles of NaOH and one moles of Br2
(a) Trichloromethanol (d) One moles of NaOH and one moles of Br2
(b) 2, 2, 2-Trichloropropanol
(c) Chloroform
(d) 2, 2, 2-Trichloroethanol
233. In the given transformation, which of the following is
the most appropriate reagent? [2012]
TO Compounds
ALL APUL
ANSWER KEYS

1. (a) 2. (a) 3. (b) 4. (b) 5. (d) 6. (a) 7. (c) 8. (c) 9. (d) 10. (c)
11. (a) 12. (a) 13. (d) 14. (c) 15. (b) 16. (c) 17. (a) 18. (a) 19. (a) 20. (c)
21. (a) 22. (c) 23. (c) 24. (a) 25. (d) 26. (c) 27. (b) 28. (c) 29. (d) 30. (b)
31. (a) 32. (b) 33. (d) 34. (a) 35. (a) 36. (d) 37. (d) 38. (b) 39. (d) 40. (a)
41. (b) 42. (b) 43. (a) 44. (b) 45. (a) 46. (a) 47. (c) 48. (d) 49. (c) 50. (b)
51. (b) 52. (d) 53. (b) 54. (a) 55. (c) 56. (c) 57. (c) 58. (d) 59. (c) 60. (b)
61. (c) 62. (a) 63. (a) 64. (a) 65. (a) 66. (d) 67. (c) 68. (a) 69. (b) 70. (c)
71. (b) 72. (d) 73. (d) 74. (d) 75. (b) 76. (b) 77. (d) 78. (a) 79. (d) 80. (c)
81. (c) 82. (d) 83. (c) 84. (d) 85. (d) 86. (a) 87. (c) 88. (c) 89. (a) 90. (b)
91. (c) 92. (d) 93. (c) 94. (a) 95. (d) 96. (b) 97. (c) 98. (d) 99. (c) 100. (d)
101. (d) 102. (b) 103. (c) 104. (d) 105. (b) 106. (a) 107. (c) 108. (a) 109. (b) 110. (b)
111. (c) 112. (b) 113. (d) 114. (a) 115. (b) 116. (c) 117. (b) 118. (a) 119. (c) 120. (d)
121. (c) 122. (b) 123. (d) 124. (a) 125. (b) 126. (d) 127. (b) 128. (d) 129. (b) 130. (d)
131. (c) 132. (a) 133. (a) 134. (d) 135. (b) 136. (d) 137. (b) 138. (c) 139. (c) 140. (a)
141. (c) 142. (c) 143. (b) 144. (a) 145. (b) 146. (d) 147. (d) 148. (d) 149. (b) 150. (a)
151. (a) 152. (a) 153. (b) 154. (d) 155. (b) 156. (c) 157. (d) 158. (c) 159. (d) 160. (a)
161. (c) 162. (c) 163. (c) 164. (a) 165. (b) 166. (c) 167. (a) 168. (b)

169. (a, b, d) 170. (a, c) 171. (a, b, c) 172. (b, c, d)
173. (c, d) 174. (a, b, c) 175. (a, b, c) 176. (a, b, c, d)
177. (a, b)

178. (c) 179. (a) 180. (c) 181. (d) 182. (c) 183. (d) 184. (d) 185. (b) 186. (a)
Match the Column Type

187. (d) 188. (a) 189. (b) 190. (c) 191. (d)
192. (d) 193. (a) 194. (b) 195. (b) 196. (b)
197. a – (p, q, r, s, t); b – (p, q, r, s, t); c (p, q, r); d – (q, r, t) (aldehydes)
198. a – (r, s) b – (p, r, s, t); c – (r, t); d – (q, r, s) 199. a – (p, q, r); b – (t); c – (p, q, r, s, t); d – (p, q, r)
200. a – (p, t); B – (q, r); c – (p, t); d – (q, r, s) 201. a – (p, q); b – (q, r); c – (q); d – (p, s)
Integer Type
202. (4) 203. (2) 204. (3) 205. (3) 206. (3) 207. (6) 208. (1) 209. (4) 210. (3) 211. (4)
Previous Years' Questions

212. (b) 213. (d) 214. (b) 215. (c) 216. (a) 217. (a) 218. (a) 219. (c) 220. (d) 221. (b)
222. (d) 223. (b) 224. (b) 225. (b) 226. (c) 227. (b) 228. (c) 229. (a) 230. (c) 231. (c)
232. (d) 233. (b) 234. (b) 235. (a) 236. (d) 237. (c)
Chapter 28
HINTS AND SOLUTIONS

2. Carbocation with sexlet of electrons can easily take up a 50. Aldehydes, that is, acetaldehyde gives pink colour with
nucleophile. schiff’s reagent.
Pd-BaSO4
20. Resonance stabilization of their conjugate base, that is, 51. C6H5COCl + H – H
carboxylate ion. –KCl
22. Lucas test is given by alcohols and not aldehyde or ketones. C6H5CHO
23. Secondary alcohols on oxidation produce ketones. Benzaldehyde
24. C6H5CHO + Cl2 C6H5COCl + HCl 52. COOH CH2OH
| Zn/H2SO4 | + H2O
33. With Fehling’s solution, red precipitate of Cu2O are + 4 [H]
produced. COOH COOH
34. Three molecules of formaldehyde polymerize to give
Oxalic acid glycolic acid
trioxane.
35. Paraldehyde is a trimer of acetaldehyde and will not give 53. HCOOH reduced ammonical silver nitrate solution, that is,
formaldehyde. Tollen’s reagent but acetic acid does not.
36. During reaction of HCN and CH3CHO, a chiral car- 54. C2H5OH + CH3COOH CH3COOC2H5 + H2O
bon is synthesized. The attack of CN− on the flat Ethyl alcohol Acetic acid
aldehyde molecule can occur from either side, the product alk. KMnO4
formed is a racemic mixture. 55. CH3 – CHOH – COOH + [O]
fusion Lactic acid
37. C6H5COC6H5 + KOH C6H6 + C6H5CO2K CH3 – CO – COOH + H2O
Benzophenone Pot. benzoate Pyruvic acid
cannizzaro reaction 56. Its dissociation constant is less as compound to carboxylic
38. HCHO + KOH CH3OH + HCO2K
acids
39. Tollen’s reagent is not used in the detection of unsaturation
59. It is Kolbe’s reaction.
but is used for distinction of (i) aldehydes from ketones (ii)
terminal alkynes from non-terminal alkynes. 60. As acetic acid freezes at 16.6oC while water freezes at 0oC,
Ca(OH)2 therefore glacial acetic acid is obtained by crystallizing, sep-
40. 6HCHO C6H12O6 arating and melting acetic acid
H2 P2O5
41. RCOCl RCHO + HCl 61. CH3COOH (CH3CO)2O + H2O
Pd-BaSO4
(P) Acetic anhydride
42. R– CHO + 2[Ag(NH3)2]+ + 3OH– 63. Et.MgBr + CO2 C3H7COOH
RCOO– + 2Ag + 4NH3 + 2H2O 64. As the nucleophillic attack on a carbonyl carbon atom
Silver mirror depends on the electrophilicity of the carbon. atom.
2H.OH Here a strong electron withdrawing – CO group is
43. CH3CHCl2 CH3 – CH(OH)2 |
–3HCl
CH3CHO attached next to the carbonyl carbon atom so the electro-
–H2O
philicity of this carbon is considerably increased.
Acetaldehyde
66. Carboxylic acid undergoes ionization due to that tact the res-
44. NaHSO3 reacts with acetaldehyde to form addition com-
onance stabilizes the carboxylate ions.
pound which is precipitated. Acetaldehyde can be recovered
with dilute HCl. Acetophenone does not react. 67. C6H5COOH + SOCl2 C6H5COCl + SO2 + HCl
45. All carbonyl compounds produce orange precipitate with 2, 68. It is Fischer-Spierer reaction.
4-Dinitrophenyl. 70. HCOOH shows reducing properties.
46. This is an example of intramolecular cannizzaro 81. Methyl salicylate occurs in essential oils of winter green and
reaction. sweet birch.
47. As it does not have CH3CO– group. 82. CH3COOH + NaHCO3 CH3COONa
49. C6H5COOH + SOCl2 C6H5COCl + SO2 + HCl + H2O + CO2 ↑
TO Compounds
ALL APUL
∆ 95. Carbonation of CH3MgBr forms CH3COOH

83. CH3COONH4 CH3CONH2
∆ CH3MgBr + CO2 CH3CO2MgBr
Amm. acetate Acetamide
H2O
–H2O CH3COOH + MgBr(OH)
reduction
85. C6H5CH2Cl C6H5CH3. Hydrolysis of acetonitrile by a mineral acid also forms
CH3COOH.
86. O O
H3O+
|| || CH3CN CH3CONH2 H3O+
H2O
R – C – OH R – C – O– + H3O+ CH3COOH + NH4+
96. The OH– reacts first replacing the bromide ion at the end
chain to form HO – (CH2)4 – COOH which reacts further intra
molecularity in the presence of acid (H+) to form cyclic six
O– membered structure – a lactone.
|
R–C=O 98. CH2O + CH3MgI CH3CH2 OMgI
HOH CH3CH2OH + Mg.OH.I
Because of resonance stabilization of carboxylate ion, the
equilibrium shifts in the forward direction, thereby forming Ethyl alcohol
more and more of hydronium ions. NH2NH2 KOH
87. CH3COCOOH is a β-carboxylic acid, which undergo decar- 99. > C = O > C = NNH2 > CH2 + N2
boxylation simply on heating. –H2O ∆
hydrazone
Br2 /KOH NaOH
88. CH3CH2CONH2 CH3CH2NH2 101. C6H5CHO
H.P. reaction Cannizzaro reaction
Propionamide Ethylamine
C6H5CH2OH + C6H5CO2Na
Al(OC2H5)3
89. 2CH3CHO CH3COOCH2CH3 HCN H+/H2O
Ethyl acetate 102. CH3CHO CH3CH(OH)CN
This type of Cannizzaro reaction is called Tischenko reaction. Acetaldehyde CH3CHOHCOOH
Lactic acid
90. C6H5CHO + H2NCH3 C6H5CH=NCH3
(i) CH3MgBr
N-methylbenzaldimine 103. C6H5CHO C6H5CH(OH)CH3
(ii) H+ / H2O
91. This is aldol condensation. 2o alcohol
O (i) CH3MgI
|| 104. CH3COCH3 (CH3)3COH
dil (ii) H+ / H2O
CH3 – CH2 – C – H + H – CH – CHO tert-butyl alcohol
NaOH
|
CH3 106. CH3CH = O + H2C(COOH)2
–H2O
OH Heat
| CH3CH = C(COOH)2
–CO2
CH3CH2 – C – CH2 – CHO
CH3CH = CHCOOH
|
CH3 108. Due to electron withdrawing nature of NO2 group, the partial
(β-hydroxy aldehyde) positive charge on the carbon atom of the C=O group in p-
nitrobenzaldehyde increases and becomes more susceptible
92. This is an intramolecular Cannizzaro reaction. On acidifica-
to nucleophilic attack by the CN– ion.
tion, it gives a product containing an alcohol and a free acid
group. 109. Baeyer-Villiger oxidation of cyclohexanone gives a ring
93. In this reaction expanded product known as lactone.
110. O
[A] = CH3CH2CH2CH2O–MgBr+ ||
NaBH4
[B] = CH3CH2CH2CH2OH CH3CH2 – C – CH2CH2CH3
[C] = CH3CH2CH2COOH 3-hexanone
NH3 O–
94. CH3CH2CH2COCl |
D 2O
(a) CH3CH2 – CH – CH2CH2CH3
Br2 + NaOH
CH3CH2CH2CONH2 OD
|
CH3CH2CH2NH2 CH3CH2 – CH – CH2CH2CH3
Chapter 28
111. Wolff-Kishner reduction does not convert >CO to > CHOH 125. Both Zn(Hg), HCl (Clemmenson’s reduction) and NH2NH2,
but converts it to > CH2. OH– (Wollf-Kishner reduction)
112. CH3 O
| |
CH3CH2 – C = O + CH3CH2CH2CH = PPh3 can reduce – C – CH3
2-butanone
CH3 to group but as HCl may also bring about the dehydration of
| alcohol to give an alkene. So the most appropriate reagent
CH3CH2 – C = CHCH2CH2CH3 + Ph3PO will be NH2NH, OH.
3-methyl-3-heptene
126. The electron withdrawing nitro group facilitates the release
H2SO4 NaOH of hydride ion.
113. HC ≡ CH CH3CHO
HgSO4
OH 127. In cannizaro reaction the slowest step is transfer of hydride
ion to the carbonyl group
|
CH3 – CH – CH2CHO 128. The starting material is a cyclic amide or a lactam. When
the lactam undergoes hydrolysis, there is a cleavage of the –
HCl CO – NH bond resulting in an open chain structure. This on
114. 3CH3COCH3 propanone (a) acidification leads to the free δ-amino acid.
–2H2O
(CH3)2C = CHCOCH = C(CH3)2 129. OH O
| [O] ||
2, 6-dimethyl-2, 5-heptadien-4-one (b)
CH3 – CH – CN CH3 – C – CN
1% HgSO4 Acetaldehyde
CH3MgX
115. HC ≡ CH CH3CHO Cyanohydrin
20% H2SO4 H2O
(a)
[O] H+/H2O CH3COCOOH
CH3 – CHOH – CH3 CH3COCH3
Pyruvic acid
(b)
HCl
117. C6H5CHO + H2CHCO – O – COCH3 130. CH3CON(CH3)2 + H2O
Benzaldehyde acetic anhydride
(CH3)2NH + CH3COOH
CH3COONa H+/ H2O
KCN
C6H5CH = CHCO – O – COCH3 131. CH3Cl CH3CN CH3COOH
Perkin condensation
(b)
H3O+, boil PBr3 KCN
C6H5CH = CHCOOH + CH3COOH 132. RCH2CH2OH RCH2CH2Br
Cinnamic acid H+/H2O
118. Mol. Wt. = 2 × vapour density = 2 × 29 = 58 RCH2CH2CN RCH2CH2COOH
Two compounds CH3COCH3 and CH3CH2CHO show molec- diethyl ether
133. (CH3CO)2O CH3COOC2H5
ular weight 58. CH3COCH3 do not produce yellow ppt. on Anhyd. AlCl3
warming with aq. Solution of NaOH. Hence CH3CH2CHO is Ethyl acetate
the compound. 135. Acetophenone being a ketone does not react with Tollen’s
reagent to give silver mirror.
120. R2C = O + H2NOH R2C= NOH NaOH
–H2O 136. CH3COOCH3 CH3COONa
Oxime –CH3OH
Methyl ethanoate
NaOH + I2
121. CH3 – CO – CH2 – CH3
Kolbe’s electrolysis
2-butanone CH3–CH3
H+ –CO2, –NaOH, –H2 ethane
Cl3–CO–CH2CH3
CHI3 + CH3CH2COOH 139. It is an example of claisen condensation
Propanoic acid
140. Carboxylic acids are stronger acids than N+H3, therefore,
124. It is cross-cannizzaro reaction X is the strongest acid. since – COOH has – I effect which
NaOH decreases with distance, therefore, effect is more pronounced
C6H5CHO + HCHO
on Y than on Z. As a result, Y is more acidic than Z. therefore
C6H5CH2OH + HCOONa X > Y > Z.
TO Compounds
ALL APUL
141. CH3 – CO – CH2 – CH3 NaOH + I2 159. It undergoes electrophilic substitution at m-position and also
2-butanone give iodoform test.
[O]
H+ 160. C6H5 – CHOH – CH3 C6H5 – COCH3
Cl3 – CO – CH2CH3
CHI3 + CH3CH2COOH 1-Phenylethanol acetophenone
F.C.
Propanoic acid C6H6 + CH3COCl reaction C6H5COCH3
142. When a secondary amine reacts with a ketone as shown in + HCl
the reaction, it results in a stable product known as enamine. 164. Here B is an aldehyde as it gives silver mirror test with
KMnO4
146. CH3CH2OH CH3COOH ammonical AgNO3 solution. Tollen’s reagent B is formed
Oxidation
by oxidation of A, so A must be 1o alcohol (CH3CH2CH2 –
(a)
SOCl2 NH3
OH)
CH3COCl CH3CH2 – CH = O + H2NCONHNH2.HCl →
Br2 + NaOH
CH3CONH2 Hoffmann bromamide reaction CH3 – CH2 – CH = N.NHCONH2 + HCl, + H2O
(b)
CH3NH2 + Na2CO3 + NaBr + H2O 166. Here benzaldehyde has no α-hydrogen so it does not give
(c) aldol condensation.
149. In Wolff-Kishner reduction, carbonyl group (>C = O) is con- 167. Cannizzaro reaction involves transefer. Clemmensen reduc-
verted to >CH2 group. tion involves the formation of new C – H bond. Friedel craft
and Reimer-Tiemann reaction involves the formation of new
154. HCN is a very weak acid. CH3COOH is a weaker acid than C – C bonds.
HCOOH, because CH3– is electron donating, acid weaken-
ing group. Cl – CH2COOH is a stronger acid than CH3COOH 168. Compound (Y), on oxidation with Ag+ ions (a mild oxidizing
as Cl is electron withdrawing, acid strengthening group. agent) gives oxalic acid, therefore (Y) is HOOC – COOH.
Compound (X) gives two moles of (Y) and benzaldehyde,
156. Aldol condensation is given by those carbonyl compounds therefore (X) is
which have α-hydrogen atom.
CH = CH − C C ⎯ CHO
O O
|| ||
In CH3 – C – H and CH3 – C – CH3
α-hydrogen is present.
(X) ozonolysis
158. Both o-substituted acids are stronger than C6H5COOH, due
to ortho effect. Since –OCH3 is bulkier (ortho effect) than
–OH group, so it might be more acid strengthening. But CHO CHO
salicylate ion has the ability to undergo intramolecular
2
hydrogen bonding (chelation), which stabilizes conjugate +
base and therefore, enhances the acidity. COOH
171. β keto aldehydes and β- keto esters have sufficient O H O

enol content and develop colour with FeCl3. CH3 C C
CH O CH C2H5
O H But cyclohexanone has only negligible enolic form and it
O does not give characteristic colour with FeCl3. Phenol (100
CHO % enolic) develops colour with FeCl3.
O O
|| ||
CH3 – C – CH2 – C – OC2H5
Chapter 28
173. CH3COCH2CH2CH3 I2, NaOH CHI3 + Ph Ph OH

CH3 – CH2– CH2 – COONa C N C N
I2, NaOH H OH + H
CH3COC6H5 C6H5 – COONa + CHI3
Syn –(A) Anti –(A)
I2, NaOH
CH3COCH2CH2 – COOH CHI3 The reaction proceeds by nucleophilic attack of NH2OH on
CH2 – COONa PhCH = O followed by dehydration step, which is promoted
+ | by the presence of little amount of H+. So, pH of 4 −6 is
CH2 – COONa optimum for the good yield of oximes.
I2, NaOH Ph
CH3COCH2CH2COCH3 CHI3 H C NH Ph
C N
CH2 – COONa OH PCI5 in ether
H O
+ | + CHI3
CH2 – COONa N- phenyl
formamide
174. Molecular weight of the product may or may not be the inte-
gral multiple of molecular weights of the reactants. Ph OH
Ph C NH2
PH = 4 − 6 C N
175. Ph − CH = O + H2 N − OH PCI5 in ether
H O
−H2O
PhCO2H + NH3

178. CH3 CH2 COOH Dil.H2SO4 180. O Δ, P2O5
C
H CH2 CH2 OH −H2O
O CH2 – C
O–H
O CH3 – CH O–H
Cyclic
CH2 – C O
179. O
O CH2 – C
CH2 – C–H
OCH3 CH3 – CH O
CH3 – CH
CH2 – C
CH2 – C–H
O
O
+
OCH3 181. Increase in H promotes dehydration step. It proceeds most
effective at pH ≈ 3.5.
CH2 – CH When pH is decreased most of the reagent NH2 – Z
⊕
CH3 – CH O– gets converted into NH2 – Z and the first step slows down,
that becomes rate determining step.
CH2 – CH
182. Ph Ph NH3
C=N and C=N
O
Me NH3 Me
OCH3 OCH3 (Geometrical)
CH3OH Me Me
O −CH3O− O
| |
O– OH Ph – C = N – NH2 Ph – CH – N = NH
(Tautomerism)
TO Compounds
ALL APUL
Integer Type
202. α α 50% NaOH
205. 2HCHO CH3OH + HCOONa
CH3CHO + CH3CH2CHO HO– warm
Rate = k[CH2O]2 [OH−]
1. CH3CH(OH)CH2CHO
Order of the reaction is 3.
2. CH3CH2CH(OH)CH2CHO
207. As per given problem the structure of C11H10 is
3. CH3CH(OH)CH(CH3) – CHO CH = CH – CH = CH – CHO CHO
4. CH3CH2CH(OH) – CH(CH3) – CHO
203. Carbonyl groups numbered 1 and 3 are reactive towards nuc- O3
leophilic reagent H2O/Zn
(A)
O + 2(CHO)2 Ag(NO3)2+ (COOH)2

(B) Oxalic acid
No of π- bonds on (A) s 6
C1
C2 = O 208. O
C3
*
O
209. The product is
204. 3C6H5COCH3 conc. H2SO4 CH3
C6H5
* OH
* C – CH3
C6H5
C6H5 + 3H O
2 O
Optically active isomers 4
Previous Years' Question

KMnO4
212. (CH3)2C = CHCH2CH3 221. Since it is the strongest acid here so it will have lowest pKa
(CH3)2C = O + HOOCCH2CH3 value.
Cl2, red P 222. Pyridinium chlorochromate oxidizes an alcoholic group
213. CH3CH2COOH selectively in the presence of carbon-carbon double bond.
H.V.Z. reaction
alc. KOH 225. C6H5MgBr + HOCH3 C6H6 + Mg(Br)OCH3
CH3 – CH – COH
(dehydrochlorination)
| 227. Both these molecules are polar and possess dipole.
Cl 230. Here esterification reaction is involved as follows
H+
CH2 = CH – COOH CH3COOH(l) + C2H5OH CH3COOC2H5(l) + H2O
217. Cl– is the best leaving group.
218. Aqueous NaCl in neutral so there is no reaction between (–)
ethyl acetate and aqueous NaCl. 231. C2H5 O Na + CH3 – C – Cl
220. Carbonyl compounds are reduced to corresponding alkanes O
with (Zn + conc HCl). It is called Clemmensen reduction.
CH3 – C – O – C2H5 Ethyl Etnanoate
O
|| O
Zn(Hg) + HCl
CH3CH2.C – CH3 CH3CH2CH2CH3
Chapter 28
OH(–) 235. LiAIH4 PCl5

232. 2CCl3CHO CCl3COONa + CCl3CH2OH
CH3COOH CH3CH2OH CH3CH2Cl
Cannizaro reaction is a disproportionation reaction
heat
One aldtehyde molecule is oxidized to salt of the carboxylic
acid, other one is reduced to Alcohol. So the compound is
H3C=CH2
CCl3CH2OH (2, 2, 2- Trichloro ethanol)
(ethylene)
233. CH = CHCOCH3
NH2 − NH2/OH−
HO 236. CH3 COOH
CH = CHCH2CH3 KMnO4
HO
(A)
In order to product –OH group, reduction of > C = O takes SOCI2

place in alkaline media.
CHO COCI
234. CH3 − CH − C − OH
NH3 H2/Pd
O
CH3 − CH2 − C − ONH4 BaSO4
'
O (C) (B)
CH3 − CH2 − C − NH2
O
Hoffmann’s Bromide Br2 + KOH
CH3 − CH2 − NH2

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AIM : FREE EDUCATION TO ALL APUL

ALDEHYDES, KETONES, ACIDS AND ACID DERIVATIVES

• Ketones are named as alkanones as shown below: By Wacker method

isomerism. Hg, dil. H2SO4

By ozonolysis of alkenes Alkenes on ozonolysis and RCHO

By oxidation of alcohols • Tertiary alcohol: A Tertiary alcohol gives ketone

CH3 CH3 + HIO3 + H2O

R–CHO + NH3 + H2O

∆ Rosenmund’s reaction Aldehydes can be prepared by

Preparations for Aldehydes only Preparation for Ketones only

2. From Grignard reagent

C=C + CO + H2 under pressure

C C CHO 3. From Dialkyl cuprutes

By acylation of alkenes Chemical Properties

• It is an example of Markovnikov’s addition initiated E

• These have lower boiling points than alcohols

Example, • In case of hindered ketones like (CH3)3C–

Cl H O (a) Reaction with NH3 derivatives

H • On reaction with hydroxylamine (NH2OH )

In case of Semicarbozide the –NH2 and –NH groups

Thio Acetals or Ketals NH2—NH—C—NH2 NH2—NH—C=NH2

Substitution reactions In such reactions the oxygen NH2—NH=C—NH2

• On reaction with phenyl hydrazine (NH2.NH.C6 H5 ) R R OH

Reduction Reactions KOH, glycol

Name Reactions Crossed aldol condensation Aldol condensation between

For example Intramolecular Cannizzaro reaction Here, dispropor-

COOH COONa COONa 2CH3CHO [CH3COOH + CH3CH2OH]

(4) CH3 CH3

CHO CH2OH Wittig reaction The reaction between an aldehyde or a

Example, e.g., R–CH2–CHO

CH3 RCHO + 2[Ag(NH3)2]OH

RCH = C(COOC2H5 )2 CH2 = CH – CHO + Ag2O

• This test is not shown by benzaldehyde as aromatic Example,

H3C CH3 + H.NH2 + HCH2 COCH2

∆, conc. H2SO4 Beckmann’s rearrangement Here ketoximes are

Reduction of ketone into pinacol (diol) When Methods of Preparation

CH3 CH3 CHO

From benzyl chloride By Gattermann–Koch reaction

COCl + HCl • It is insoluble in water but soluble in organic solvents.

H2O 2. Reaction with Schiff’s reagent It gives pink colour

5. Reduction (a) Reaction with HCN

(c) Reaction with NaHSO3

The presence of electron withdrawing groups on OH

NO2 CX3 X CHO + H2N . OH

(c) Reaction with hydrazine 2. Nitration

CHO + H 2 N.NH CONH 2 H2SO4 + H2O

CHO + H2N.NH COCl +HCl

Phenyl Hydrazine Benzoyl chloride

5. Reaction with ammonia

CHO + H2N.NH NO2 −H2O CH N

Electrophillic substitution In benzaldehyde the –CHO CHO + HCHO + KOH

By oxidation of carbonyl compounds Carbonyl com- O

2C6H13 – COOH + 2H2O Physical Properties

NaIO O Chemical Properties

Example, R – COOH + N3H ∆

R – COOH + CH2.N2 Dil.

2. By the hydrolysis of benzamide [O]

COOH + HCl −+ 2 COOH

• From Grignard Reagent

COOH + HCl −+ 2 COOH