Aldehyde Ketone and Carboxylic Acid

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Chapter – 19
• AND CARBOXYLIC ACIDS

ALDEHYDES, KETONES
Aldehydes and ketones both possess a carbonyl group ( C=O)and therefore are called carbonyl
compounds. Formaldehyde is the simplest aldehyde, bonded to two hydrogens. In all other aldehydes, the
carbonyl group is bonded to a hydrogen and to an alkyl (or an aryl) group. The carbonyl group of a ketone
is bonded to two alkyl (or aryl) groups.
H R R
C=O C=O C=O
H H R
Formaldehyde An aldehyde A ketone
Aldehydes and ketones undergo two types of characteristic reactions.
(a) Nucleophilic addition reactions:
The carbonyl compounds can be readily attacked by nucleophiles due to the presence of
electrophilic carbon. In the overall reaction, nucleophilic addition takes place and not the
nucleophilic substitution as aldehydes and ketones possess very poor leaving groups,
R− and H− respectively.
(b) Reactions due to acidic nature of −hydrogen atoms:
Carbonyl compounds with −hydrogen atoms can loose H+ to a base to give carbanion, which is
resonance stabilized. This carbanion acts as nucleophile and can add to the electrophilic carbon of
same or different carbonyl compound to give final product.
1 IUPAC NOMENCLATURE OF ALDEHYDES AND KETONES

The IUPAC name of an aldehyde is obtained by removing ‘e’ from the alkane name and adding
‘al’. The position of the aldehyde group is not necessarily designated since it is always at the terminal and
is thus always at the number one position.
The common name of an aldehyde is same as the common name of the corresponding carboxylic
acid, except that ‘aldehyde’ is substituted for ‘ic acid’ (or ‘oic acid’). When common names are used, the
position of a substituent is designated by a lowercase Greek letter. The carbonyl carbon is not given a
designation, the carbon adjacent to the carbonyl carbon is the −carbon.
O O Br O
H C H CH3 C H CH3−CH C H
IUPAC name: Methanal Ethanal 2−Bromopropanal
Common name: Formaldehyde Acetaldehyde −bromopropionaldehyde
Cl O O O
CH3−CH−CH2−C−H H−C−CH2CH2CH2CH2−C−H
IUPAC name: 3−chlorobutanal Hexanedial
Common name: −chlorobutyraldehyde
If the aldehyde group is attached to a ring, the aldehyde is named by adding “carbaldehyde” to the
name of the cyclic compound.
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O
O
C−H
C−H
CH3
IUPAC name: trans−2−methylcyclohexane carbaldehyde Benzene carbaldehyde or phenylmethanal
Common name: Benzaldehyde
Ketones are named according to the IUPAC system by removing “e” from the alkane name and
adding “one”. The chain is numbered from that end, which gives smaller number to the carbonyl group. In
case of cyclic ketones, numbering is not necessary because the carbonyl group is assumed to be at number
1 position. For ketones, derived names are also used. In derived names, the substituents attached to the
carbonyl group are cited in alphabetical order followed by “ketone”.
O O CH3 O
CH3−C−CH3 CH3CH2−C−CH2CH2CH3 CH3CHCH2CH2CH2−C−CH3
IUPAC name: Propanone 3−hexanone 6−methyl−2−heptanone
Common name: Acetone
Derived name: Dimethyl ketone Ethyl propyl ketone Isohexyl methyl ketone.
O
O O O
CH3−C−CH2−C−CH3 CH3CH=CHCH2−C−CH3
IUPAC name: Cyclohexanone 2, 4−pentanedione 4−hexen−2−one
Common name: Acetylacetone
Common names are also used for some phenyl substituted ketones, the number of carbons (other
than those of the phenyl group) is indicated by the common name of the corresponding carboxylic acid
substituting “ophenone” for “ic acid”.
O O O
C−CH3 C−CH2CH2CH3 C
IUPAC name: Acetophenone Butyrophenone Benzophenone

Common name: Methyl phenyl ketone Phenyl propyl ketone Diphenyl ketone
1
2 METHODS OF PREPARATION OF ALDEHYDES AND KETONES
1. BY OXIDATION OF ALCOHOLS:
The oxidation of an alcohol involves the loss of one or more −hydrogen atoms from the carbon
bearing −OH group. The kind of product formed depends upon how many of these −hydrogen atoms the
alcohol contains, i.e. whether the alcohol is primary or secondary.
A primary alcohol (which has 2 −hydrogens) can lose one of the hydrogen to form an aldehyde
whereas secondary alcohol can lose its only −hydrogen to form a ketone.
RCH2OH Aqueous acidic RCHO + MnO2 or Cr3+
KMnO4 or Aqueous acidic K2Cr2O7
The reagents employed here are not highly selective since aldehyde can further be easily oxidised
to carboxylic acids, so isolation of aldehydes in this reaction is troublesome. Thus, for the convenient and
selective conversion of primary alcohol to aldehyde, pyridinium chlorochromate (PCC, C5H5NH+CrO3Cl−)
is used, which is formed by the reaction between chromic acid and pyridinium chloride.

C5H5NHCrO3Cl(PCC)
RCH2OH or CrO3 in glacial acetic acid
RCHO + Cr3+
or CrO3 in pyridine
R2CHOH ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯⎯→ R2CO + MnO2 or Cr3+
Aqueous acidic KMnO 4
or Aqueous acidic K 2Cr2O7
or CrO3 in glacial acetic acid or
CrO3 in pyridine
Secondary alcohols can also be oxidised by aluminium t−butoxide, [(CH3)3CO]3Al in acetone. The
reaction is called Oppenauer oxidation. In presence of p−benzoquinone solvent
1° alcohol can also be oxidised to aldehyde on distillation.
R2CHOH ⎯⎯ ⎯ ⎯⎯⎯→ R2CO + (CH3)2CHOH
3 3 [( CH ) CO ] Al
3
in acetone
For example,
CH3CH2CH2OH ⎯⎯ ⎯⎯→ CH3CH2CHO + Cr3+
PCC in
CH2Cl2
CH3 CH3
K2Cr2O7, H2SO4
H
OH O
(CH3)2CH (CH3)2CH
2. DEHYDROGENATION OF ALCOHOLS:
Dehydrogenation of alcohols can be affected by passing alcohol vapours over heated Cu, when
carbonyl compounds are produced. Dehydrogenation of 1° and 2° alcohols give aldehydes and
ketones respectively.
RCH2−OH ⎯⎯→
⎯
Cu
o
H2 + R–CH=O
350 C
R2CH−OH ⎯⎯→
⎯
Cu
o
H2 + R2C=O
350 C
[Note: 3° alcohol on similar reaction undergoes dehydration to give alkene]

3. BY HEATING CALCIUM OR BARIUM SALTS OF CARBOXYLIC ACIDS:
When calcium salt of formic acid is dry distilled, formaldehyde is obtained. If a mixture of calcium
salt of formic acid and any of its higher homologues is used, then aldehydes other
than formaldehyde are obtained while when only calcium salt of monocarboxylic acid
(other than formic acid) is dry distilled, the product obtained is a ketone.
(HCO2)2Ca ⎯⎯ ⎯ ⎯ ⎯
⎯→ HCHO + CaCO3
Dry distillati on
(HCO2)2Ca + (RCO2)2Ca ⎯⎯ ⎯ ⎯ ⎯
⎯→ 2RCHO + CaCO3 + RCOR + HCHO
Dry distillati on
(RCO2)2Ca ⎯⎯ ⎯ ⎯ ⎯ ⎯→ R2CO + CaCO3

Dry distillati on
If a mixture of calcium salts of acids is used, mixed ketones along with simple ketones are
obtained.
(RCO2)2Ca + (RCO2)2Ca ⎯⎯⎯→ RCOR + R 2 CO + R2CO + CaCO3
Dry
distillation
4. USING ACID CHLORIDE:

Acid chlorides can be reduced to aldehydes, only by the use of a bulky hydride reducing agent, tri−
t−butoxy lithium aluminium hydride. If LiAlH4 is used as a reducing agent, the product isolated is an
alcohol and not an aldehyde.
LiAlH( OBu− t )
R−COCl or Ar−COCl ⎯⎯⎯⎯⎯ ⎯3
→ R−CHO or Ar−CHO
Acid chlorides can also be reduced to aldehydes by H2 gas in the presence of Pd supported on
BaSO4 in xylene, poisoned with quinoline and sulphur. This reaction is called Rosenmund’s reduction,
which is applicable for the preparation of aliphatic as well as aromatic aldehydes.
H / Pd − BaSO
R−COCl or Ar−COCl ⎯⎯ ⎯ ⎯⎯→ R−CHO or Ar−CHO + HCl
2 4
Poisoned with
quinoline & S
Acid chlorides on reaction with lithium organocuprates, R2CuLi or Ar2CuLi yields ketones. Here,
the R part of organocopper compound acts as nucleophile and displaces Cl of acid chloride to undergo
nucleophilic substitution.
⎯→ RLi or ArLi ⎯⎯⎯→ R2 CuLi or Ar2CuLi
CuX
RX or ArX ⎯⎯
2 Li
− LiX − LiX
R 2 CuLi + 2RCOCl ⎯→ 2RCOR + CuCl + LiCl

(Note: R and R may be alkyl or aryl).
Grignard reagents can also react with acid chlorides, but the product is tertiary alcohols because
the ketone produced reacts with additional RMgX. This shows that organocopper reagents are less reactive
than Grignard reagents towards the carbonyl group of ketones and the reaction stops at the ketone
formation stage.
This low reactivity of organocopper compounds is useful in the light that it do not react with the
functional groups with which organomagnesium and organolithium reagents react. Thus, the presence of
some functional groups (like −NO2, −CN, −CO−, −CO2R etc.) does not interfere with the synthesis of
ketones.
For example,
2O2N C−Cl + (CH3)2CuLi 2O2N C−CH3 + CuCl + LiCl

O O
p−nitrobenzoyl chloride p−nitro acetophenone
CH3O−C−CH2CH2−C−Cl + (CH3)2CuLi CH3O−C−CH2CH2−C−CH3 + CuCl + LiCl

O O O O
methyl−4−oxopentanoate
Aromatic ketones can be synthesized using acid chlorides and benzene via Friedel−Crafts
acylation.
Anhydrous
Ar−H + R−C−Cl AlCl3
Ar−C−R + HCl
O  O
For example,
Anhydrous
+ C−Cl
AlCl3, 
O Route I
NO2
C
NO2
O
Anhydrous NO2
+ C−Cl AlCl3, 
m−nitro benzophenone
O Route II
There seems to be two possible routes to get m−nitro benzophenone using Friedel−Crafts
acylation. Route II is not feasible because nitrobenzene does not participate in Friedel−Crafts reaction, as −
NO2 is a strongly deactivating group. Thus, route I is the only feasible pathway to get m−nitro
benzophenone.
5. BY OXIDATION OF METHYL BENZENES (FOR AROMATIC ALDEHYDES ONLY):
Methyl benzene on treatment with either Cl2 in presence of ultraviolet light or CrO3 in acetic
anhydride gives Ar−CHCl2 or Ar−CH(OOCH3)2. Both these compounds on decomposition with water
gives benzaldehyde.
Cl2/h H2O
Ar−CH3 2. eqv.
Ar−CHCl2 ArCHO
CrO3 in acetic
anhydride
H2O
Ar−CH(OOCCH3)2 ArCHO
(Gem diacetate)
Overall reaction is the oxidation of methyl benzene to benzaldehyde. Oxidation of methyl benzene
to benzaldehyde by CrO3 in acetic anhydride is a better route than chlorination because the gem diacetate
formed is not further oxidisable while ArCHCl2 can further chlorinate to give ArCCl3, which on hydrolysis
finally gives ArCO2H.
For example,
CrO3 in H2O
O2N CH3 O2N CH(OAc)2 O2N CHO
acetic anhydride
p−nitro toluene p−nitro benzaldehyde
Cl2 / h H2O
Br CH3 Br CHCl2 Br CHO
2 eqv.
p−bromo toluene p−bromo benzaldehyde
6. REIMER−TIEMANN REACTION (FOR PHENOLIC ALDEHYDES ONLY):
When phenol is treated with chloroform and aqueous NaOH/KOH, an aldehyde group is
introduced in the aromatic ring, generally at the ortho position.
OH ONa ONa OH
CHCl2 1. 2OH−/–2Cl– CHO CHO
CHCl3, aq. NaOH HCl
2. −H2O −NaCl
Salicyldehyde
7. STEPHEN’S METHOD (ONLY FOR ALDEHYDES):
An alkyl or aryl cyanide dissolved in ether is reduced with stannous chloride and HCl to give
aliphatic or aromatic aldehydes. The reaction proceeds by the formation of aldimine hydrochloride (present
as stannichloride), which are not stable and hydrolyse to give aldehydes.
[RCNH]+Cl−
HCl
[RCH=NH2 ]2+ SnCl26 −
SnCl2 + HCl H2O
R−CN RCHO + NH3
8. SOMMELET REACTION (ONLY FOR ALDEHYDES):
When an aqueous solution of n−hexylamine hydrochloride is reacted with hexamethylene
tetramine in acetic acid and steam is passed into it, n−hexanal is produced. This reaction is called
Sommelet reaction.
CH3(CH2)4CH2NH2.HCl + (CH2)6N4 ⎯⎯ ⎯
⎯→ CH3(CH2)4CHO
Steam
n−hexanal
9. ACYLATION OF ALKENES (ONLY FOR KETONES):
−BF3Cl  
H2C=CH−R
R−C−Cl + BF3 R−C=O R−C−CH2−CH−R
Acylium ion
O O +BF3Cl−
−BF3 , −HCl
 
R−C−CH=CH−R
O
In this reaction, alkenes act as nucleophiles and cause nucleophilic substitution of Cl of RCOCl to
give , −unsaturated ketone.
10. RING KETONES FROM DICARBOXYLIC ACIDS:
When the calcium, barium or thorium salts of the carboxylic acids are distilled, cyclic ketones
(cycloalkanones) are produced.
CO2
(CH2)n Ca Distilled (CH2)n C=O + CaCO3 + H2O
CO2
When the ‘n’ value is 4, the product is cyclopentanone and when it is 5, the product is
cyclohexanone.
Also, when dicarboxylic acids are heated with acetic anhydride and then distilled at 300°C, cyclic anhydrides or
cyclic ketones are formed depending on the relative positions of two carboxyl groups.
O
CO2H C
Acetic anhydride,
(CH2)n (CH2)n O + H2O
distilled at 300°C
CO2H C
O
[n can be 2 or 3 i.e. the acid is 1, 4 or 1, 5−dicarboxylic acid].
CO2H
Acetic anhydride,
(CH2)n (CH2)n C=O + CO2 + H2O
distilled at 300°C
CO2H
[n can be 4 or 5 i.e. the acid is 1, 6 or 1, 7−dicarboxylic acid].
11. BY PASSING VAPOURS OF CARBOXYLIC ACIDS OVER MnO:
Aldehydes can be prepared by passing vapours of formic acid and any one of its homologue over
manganous oxide as catalyst at 300°C.
, MnO
RCO2H + HCO2H ⎯⎯⎯ ⎯→ RCHO + CO2 + H2O
Here, HCHO and R2CO are the by−products in this reaction.
When vapours of any monocarboxylic acid other than formic acid are passed over manganous
oxide at 300°C, ketones are formed.
, MnO
2RCO2H ⎯⎯⎯ ⎯→ R2CO + CO2 + H2O
A mixture of monocarboxylic acids when passed over MnO at 300°C gives mixed ketones.
, MnO
RCO2H + RCO2H ⎯⎯ ⎯ ⎯→ RCOR + CO2 + H2O
In this case, R2CO and R2 CO are obtained as by−products.
12. BY OZONOLYSIS:
Aldehydes can be prepared by the ozonolysis of alkenes of the type R−CH=CH−R in presence of
Zn (reductive ozonolysis).
O
O3
R−CH=CH−R ⎯⎯
⎯→ R−CH ⎯⎯2 ⎯ ⎯→ 2RCHO + ZnO + H2O
H O
/ Zn
CH−R
O O
Ketones can also be prepared by the ozonolysis of alkenes of the type R2C=CR2.
O
O3
R2C=CR2 ⎯⎯
⎯→ R2C ⎯⎯2⎯→ 2R2CO + H2O2
H O
CR2
O O
This oxidation of alkenes can also be achieved by Lemieux reagent, which is an aqueous solution
of sodium periodate and a trace of potassium permanganate.
13. FROM ALKYNES (FOR KETONES MOSTLY):
Acetylene gas when passed into hot dilute sulphuric acid in the presence of mercuric sulphate as
catalyst, is converted into acetaldehyde.
Tautomerize
HCCH + H2O ⎯⎯⎯ ⎯ → [CH2=CH−OH]
H SO
2 4
CH3−C−H
2+
Hg Vinyl alcohol
O
Homologues of acetylene form ketones when hydrated. For example, propyne gives acetone.
H SO
CH3−CCH + H2O ⎯⎯⎯ ⎯ → [CH3C(OH)=CH2] ⎯→ CH3COCH3
2 4
2+
Hg
H SO
R−CC−R + H2O ⎯⎯⎯ ⎯ → [R−C(OH)=CH−R] + [R−CH=C(OH)R]
2 4
2+
Hg
Tautomerize Tautomerize
R−C−CH2R RCH2−C−R
O O
14. ACETOACETIC ESTER SYNTHESIS (FOR KETONES ONLY):
This synthesis is used for preparing ketones only and is based on the fact that active methylene
group (which is sandwiched between two strongly electron−withdrawing groups) have more acidic
hydrogen than other −hydrogens.
+ R
NaOEt .. Na R−X
MeCOCH2CO2C2H5 Me−C−CH−C−OEt Me−C−CH−C−OEt
−EtOH −NaX
Ethyl acetoacetate
(Acetoacetic ester) AAE O O O O
Sodium salt of AAE H3O +
(−EtOH)
R

,
Me−C−CH2R Me−C−CH−C−OH
−CO2 
O O O
−keto acid
In the last step, −keto acid undergoes ready decarboxylation even on slightest warming to form
ketones.
1
3 GENERAL PHYSICAL PROPERTIES OF ALDEHYDES AND KETONES
The polar carbonyl group makes aldehydes and ketones polar in nature and thus they have higher
boiling points than non−polar compounds having comparable molecular weights. Their boiling points are
less than the comparable alcohols or carboxylic acid as they do not form intermolecular hydrogen bond.
The lower members of the aldehydes & ketones are appreciably soluble in water because of
hydrogen bonding between water and aldehydes or ketones. The solubility in water decreases as the
number of carbon atoms increases. The aldehydes and ketones are soluble in usual organic solvents.
Formaldehyde is a gas (boiling point −21°C) and is normally used either as an aqueous solution
(formalin, 40% aqueous solution of formaldehyde) or as its solid polymer, paraformaldehyde (CH2O)n or
trioxane, (CH2O)3. Formaldehyde is obtained by heating paraformaldehyde or trioxane.
O
CH2 CH2
−CH2OCH2OCH2O−
Paraformaldehyde O O
CH2 Trioxane
Acetaldehyde (boiling point 20°C) is generated from its high boiling trimer by heating it with acid.
O
H+
CH3−CH CH−CH3
3CH3CHO
O O
CH
CH3
Paraldehyde
(B. P. 125°C)
Carbonyl compounds exhibits some net dipole moment because of the polarization of C O
bond and the bond moments of R−C and C Obonds acting in the same direction.
R
C O
R
1
4 GENERAL CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES
(I) OXIDATION:
Aldehydes are easily oxidised to carboxylic acids but ketones are not. Aldehydes
are oxidised not only by the same reagents, which oxidizes primary and secondary alcohols
(like acidified KMnO4, K2Cr2O7) but also by mild oxidising agents like Tollen’s reagent, Fehling’s solution
and Benedict’s solution. Aldehydes are very easily oxidised and thus are very powerful reducing agents.
Tollen’s reagent contains diamminesilver(I) ion, which is obtained through ammoniacal AgNO3
solution. Tollen’s reagent oxidises aldehydes to acid salt and they reduces to free silver in the form of
silver mirror.
−
RCHO + 2Ag(NH3 ) 2+ + 3OH− ⎯→ RCO 2 + 2Ag + 4NH3 + 2H2O
Colourless Silver
solution mirror
Tollen’s reagent is useful in differentiating aldehydes from ketones because ketones do not react
with them. Tollen’s reagent is a mild and selective oxidising agent, attacking only aldehydic group,
keeping other groups untouched. Unsaturated aldehydes can be converted to unsaturated acid using
Tollen’s reagent.
   
Tollen’s
R−CH CH−CH O reagent R−CH CH− CO2− + Ag
, −unsaturated aldehyde , −unsaturated acid salt
Aldehydes are easily oxidised, thus they also reduce Fehling’s solution (an alkaline solution
containing a complex of copper tartarate) to red cuprous oxide. Aldehydes also reduce Benedict’s solution
(an alkaline solution containing a complex of copper citrate) to red precipitate of
cuprous oxide.
R−CHO + 2CuO ⎯→ RCOO− + Cu2O (Fehling’s and Benedict’s test)
(Red)
Ketones are not easily oxidised, thus they do not reduce Fehling’s solution or Tollen’s reagent. But
−hydroxy ketones (compounds containing the unit −CH(OH)−C−R) readily reduce The compounds
O
which respond to the test with Fehling’s solution and ammoniacal silver nitrate are given below in the
tabulated manner.
Name of the compounds Fehling’s test Tollen’s Test
Glucose, Fructose  
–hydroxy ketone  
–hydroxy aldehyde  
Glyoxal (OHC.CHO)  
Benzaldehyde & other aromatic aldehydes  
Formic acid  
Glyoxylic acid (OHC.CO2H)  
Succinaldehyde (OHCCH2CH2CHO)  
Pyruvaldehyde (CH3COCHO)  
Aldehydes restore the magenta colour of the Schiff’s reagent (rosaniline hydrochloride is dissolved
in H2O and SO2 is passed till the magenta colour is decolourised). Ketones do not restore the colour of
Schiff’s reagent except acetone, which restores the colour very slowly.
Oxidation of ketones requires breaking of carbon−carbon bonds, which requires vigorous
conditions. Cleavage involves the double bond of the enol form and wherever the structure permits, occurs
on both sides of carbonyl group. Thus, in general, ketones on oxidation give a mixture of carboxylic acids.
Acidified KMnO4
CH3CO2H + CH3CH2CH2CO2H

CH3CH2−C−CH2CH2CH3
Acidified KMnO4
O CH3CH2CO2H + CH3CH2CO2H

3−Hexanone gives a mixture of carboxylic acids because it can form two enols,
CH3CH=C(OH)CH2CH2CH3, which on cleavage gives CH3CO2H & CH3CH2CH2CO2H and
CH3CH2C(OH)=CHCH2CH3, which on oxidation gives 2 moles of CH3CH2CO2H.
Methyl ketones can be conveniently oxidised by hypohalite in the haloform reaction. Hypohalite is
a selective oxidising agent, used for detecting methyl ketones as well as it do not attack carbon−carbon
double bonds.
For example,
CH3−C−C2H5 + 3NaOI C2H5 CO 2− Na+ + CHI3 + 2NaOH
O Iodoform, yellow ppt.
(m.p. 119°C)
CH3 CH3
3KOCl
Ph−CH C−C−CH3 Ph−CH C−CO2K + CHCl3 + 2KOH
   
O Potassium −methyl cinnamate
, −unsaturated ketone
(II) REDUCTION:
Aldehydes can be reduced to primary alcohols and ketones to secondary alcohols, either by
catalytic hydrogenation or by LiAlH4.
For example,
O H OH
LiAlH4
or H2/Ni
Cyclopentanone Cyclopentanol
H2 /Ni
CH3CH CH−CH O or NaBH4
CH3CH2CH2CH2OH
Crotonaldehyde n−butanol
9−BBN HOCH2CH2NH2
Ph−CH CH−CH O Ph−CH CH−CH2OH
Cinnamaldehyde Cinnamyl alcohol
H2/Ni
or LiAlH4
PhCH2CH2CH2OH
or NaBH4
H2/ Wilkinson’s catalyst
PhCH2CH2−CH O
To reduce a carbonyl group that is conjugated with a carbon−carbon bond without reducing the
carbon−carbon double bond requires a regioselective reducing agent. One such reagent is 9−BBN, 9−
Borabicyclo[3.3.1]nonane. This reduction can also be achieved by LiAlH4 but not by NaBH4, which
reduces carbon−carbon double bond as well as the carbonyl group. While carbon−carbon double bond can
be selectively reduced without affecting carbonyl group by hydrogenation in presence of Wilkinson’s
catalyst. LiAlH4 reduces the carbon−carbon double bond, which is in conjugation with carbonyl group only
when the −carbon bears an aryl group.
Aldehydes & ketones can be reduced to hydrocarbons by the action of (a) amalgamated zinc and
concentrated hydrochloric acid (Clemmensen reduction) or (b) hydrazine (N2H4) and a strong base like
KOH or potassium tertiary butoxide (Wolff−Kishner reduction).
Zn−Hg/ H Clemmensen reduction for
C O C
Conc. HCl compounds sensitive to bases
H
N2H4, KOH
H Wolff−Kishner reduction for

C compounds sensitive to acids
H
For example,
Zn−Hg/
CH3CH2CH CHCHO CH3CH2CH CHCH3
conc. HCl
N2H4, OH−
Raney nickel desulfurization is also used for reducing carbonyl compounds to hydrocarbons.
Raney nickel has adsorbed hydrogen.
dry
S CH2 H
Raney Ni
C O + HSCH2CH2SH C C + HSCH2CH2SH
HCl
S CH2 H
Cyclic thioacetal
Ketones are reduced catalytically or by dissolving metals in alkaline solutions to alcohols but
reduction by dissolving metals in neutral or acid solution gives 1, 2−glycols. For example, acetone with
magnesium−amalgam gives pinacol. The reaction proceeds via a free radical and polar mechanism.
Me2C=O
Mg → Mg2+ + 2e− H3O+
+ [Me2C−O−]2Mg2+ Me2C CMe2 Mg2+ Me2C CMe2
− −
Me2C=O O O OH OH
Pinacol
(III) NUCLEOPHILIC ADDITION REACTIONS:
Due to the difference in electronegativity between carbon and oxygen, the −electrons shift
towards oxygen creating partial positive charge on carbon and making it electrophilic. So, this electrophilic
carbon can be attacked by different nucleophiles.
(a) Addition of Grignard reagents
Aldehydes and ketones add on a molecule of a Grignard reagent to give an adduct, which on
decomposition by aqueous acid gives an alcohol.
−+
OMgX + OH
H3O
C=O + RMgX C C + Mg2+ + X− + H2O
R R
The product is a primary alcohol, if carbonyl compound is formaldehyde. An aldehyde (other than
formaldehyde) gives secondary alcohol and a ketone leads to the formation of tertiary alcohol.
(b) Addition of water (Hydration)
Carbonyl compounds reacts with H2O to form a hydrate called gemdiol.

..
.. OH2 IMPE OH
C=O + H2O: C C
O OH
(gemdiol)
The rate of hydration is different for different carbonyl compounds. The value of equilibrium
constant for different carbonyl compounds at 20°C are given as:
HCHO: 2 × 103, CH3CHO: 2, CH3COCH3: 2 × 10−3 and Cl3CCHO: 2.7 × 104.
This implies that the rate of hydration decreases due to the presence of electron donating
substituents while electron withdrawing substituents increases the rate. The hydrate of chloral
(crystalline and isolable) is stable because repulsion between positively charged adjacent carbons
decreases on going from chloral to chloral hydrate as well as chloral hydrate is stabilized through
intramolecular H−bonding between OH and Cl.
H
Cl Cl O
+ +
O + +
Cl C−C + H2O Cl C C−H
H
Cl Cl O
H
There are some other stable hydrates like
O H−O O−H
Ph C Ph + H2O O C O
C C C
C
O O
Ph Ph
(Stabilized due to chelation)
OH
O + H2O
OH
The driving force of this reaction is the relief in angle strain on going from carbonyl compound
(C−C−C bond angle = 60°, compared with normal sp2 bond angle of 120°)
to hydrate (C−C−C bond angle = 60°, compared with normal sp3 bond angle of 109.5°).
(c) Addition of hydrogen cyanide
Aldehydes and ketones add on hydrogen cyanide to form addition product, cyanohydrin.
OH
C=O + HCN C
CN
Cyanohydrin
HCN is not the nucleophile in this reaction. Infact the nucleophile is CN−, which is more
nucleophilic than HCN. The rate law for the reaction is
−
Rate = k [ C=O] [CN ]
The addition of HCN to carbonyl compounds is base catalysed, which can lead to the generation of
more nucleophilic CN−.
Mechanism:
HCN H+ + CN−
OH−
H2O
Slow
O− OH
− H+
C O + CN C C
Fast
CN CN
−
The addition of CN is reversible and the equilibrium lies in the direction of carbonyl compound.
The presence of a proton donor shifts the equilibrium in the forward direction by converting into
cyanohydrin. The RDS of the reaction is attack by CN− while proton transfer is a rapid step. The
rate of reaction of HCN with aldehydes, simple aliphatic and cyclic ketones are fast but slow with
ArCOR and reaction does not take place at all with ArCOAr.
The CN− ion may attack from front side or back side as carbonyl group is planar to give
enantiomeric pair (provided the groups attached to carbonyl group are different).
CH3 CH3
H3C −
CN , H+
C O H OH + HO H
H
CN (Racemate) CN
Ph Ph
Ph CN , H− +
C O H OH + HO H
H
CN (Racemate) CN
The cyanohydrin obtained can be used to form amino alcohols, hydroxy amide or
hydroxy acid.
H2 / Ni
R−CH−CN
or
R−CH−CH2−NH2
OH LiAlH4 OH
Cyanohydrin Amino alcohol
H3O (Partial hydrolysis)

H3O+
R−CH−C−NH2 R−CH−C−OH
(Complete
OH O hydrolysis) OH O
Hydroxy amide Hydroxy acid
Illustration
Write structures for (A) through (D) in the given reaction sequence.
+ H SO 1. B H / THF
Me2C=O + HCN ⎯→ (A) ⎯⎯3 ⎯→ (B) ⎯⎯2 ⎯⎯ → (C) ⎯⎯ ⎯ ⎯ ⎯
⎯ → (D).
HO 4 2 6
−  2. H2O2 / OH
Product (D) is optically active.

Solution:
OH OH

(A): CH3−C−CN (B): CH3−C−CO2H (C): CH2=C−CO2H (D): HOCH2−CH−CO2H
CH3 CH3 CH3 CH3
(D) is optically active due to the absence of symmetry elements.
(d) Addition of sodium bisulphite
Aldehydes and ketones add on sodium hydrogen sulphite to form bisulphite compounds.
OH
C O + NaHSO3 C
SO3−Na +
This bisulphite formation is confined to aldehydes, methyl ketones and some cyclic ketones. Those
carbonyl compounds, which form bisulphite adduct can be separated from mixtures as they are crystalline
solids, insoluble in NaHSO3 solution and / or purified by isolation, purification and subsequent
decomposition of these adducts in dilute acids.
Mechanism:
The effective nucleophile of the reaction is SO 32− ion rather than HSO 3− and formation of SO 32−
is achieved in slightly basic solution.
NaHSO3 ⎯→ Na+ + HSO 3−
HSO3− H+ + SO 32−
OH−
H2O
+ s−
O
Slow
O− H+
OH
− O C
C O + :S O C
−
S O− fast
SO3−Na +
O
.. O
For example,
H
Ph
C O + NaHSO3 Ph C SO3Na
H
OH
Benzaldehyde bisulphite adduct
(CH3)2CH−C−CH(CH3)2 + NaHSO3 No reaction
O
Hindered ketones like di−isopropyl ketone, di−t−butyl ketone does not undergo any reaction with
NaHSO3.
(e) Addition of ammonia
Ammonia reacts with formaldehyde to form a condensation product, hexamethylene tetraamine
(HMTA), which is commercially called Urotropine. Urotropine has medicinal value and is used for
the treatment of urinary tract infections.
6HCHO + 4NH3 ⎯→ (CH2)6N4 + 6H2O
HMTA
The structure of Urotropine is
N
CH2 CH2
CH2
N
CH2 CH2
N N
CH2
Acetaldehyde or any other aldehyde reacts with ammonia to form acetaldehyde ammonia or
aldehyde ammonia addition product, which being unstable loses a water molecule to give aldimine.

R .. R NH3 IMPE R NH2 −H2O R
C=O + NH3 C −
C C=NH
H H O H OH H
(unstable) (Aldimine)
Acetone reacts with ammonia to form diacetone ammonia addition product, which is stable.
NH2 O
2CH3COCH3+NH3 → CH3–C–CH2–C–CH3
CH3
Benzaldehyde reacts with ammonia to form hydrobenzamide.
C6H5–CH=N
3C6H5CHO+2NH3 → CH–C6H5+3H2O
C6H5–CH=N
(Hydrobenzamide)
(f) Addition of ammonia derivatives
Aldehydes and ketones combine with a variety of ammonia derivatives of the type NH2−Z (where
Z = −OH, −NH2, −NHC6H5, −NHCONH2 etc). The general reaction is shown as
.. O− Intramolecular OH
−H2O
C O + NH2 Z C  proton
C C N Z
NH2 Z NH Z
exchange
(I) (II) (III)

The various ammonia derivatives and their products are indicated in the following table.
H2N−Z Product structure Name of the product

H2N−OH, Hydroxylamine C N−OH
Oxime (crystalline solid)
H2N−NH2, Hydrazine C N−NH2

Hydrazone (crystalline solid)
H2N−NHPh, Phenyl hydrazine C N−NHPh

Phenyl hydrazone (crystalline
solid)
H2N−NHCONH2, Semicarbazone (crystalline
C N−NHCONH2
Semicarbazide solid)
H2N−NH NO2
2, 4−Dinitro phenyl hydrazone
C N−NH NO2 (yellow crystalline solid −used
NO2
for identification of aldehydes
2, 4−Dinitro phenyl hydrazine NO2
& ketones)
(Brady’s reagent)
Brady’s regent with carbonyl compounds gives 2, 4−dinitro phenyl hydrazone, which is obtained
as a yellow crystalline solid. It is thus used for the identification of aldehydes and ketones.
Oximes are obtained with hydroxylamine.
OH
−H2O
C O + H2N−OH C C N−OH
NH−OH Oxime
With hydrazine, hydrazones and azines are formed.

OH
−H2O
C O + H2N−NH2 C C N−NH2
NH−NH2 Hydrazone
C O
(−H2O)
C N−N C
Azine
Phenyl hydrazine forms phenyl hydrazones.
OH
−H2O
C O + H2N−NHPh C C N−NHPh
NH−NHPh Phenyl hydrazone
Semicarbazide forms semicarbazones.
OH
−H2O
C O + H2N−NHCONH2 C C N−NHCONH2
NH−NHCONH2 Semicarbazone
The rate of such reaction is maximum at some particular pH. These reactions are catalysed by the
presence of slightly acidic conditions. In slightly acidic conditions, dehydration step is the RDS, whose rate
is increased by the protonation of OH, leading to overall increase in rate of the reaction. But, when the acid
strength increases, the rate of addition step decreases because concentration of NH2−Z reduces due to its
conversion to conjugate acid, NH3+− Z (which can not function as a nucleophile because of absence of lone
pair). Thus, at low pH, the addition step becomes the RDS.
For example,
H+
CH3−CH=O + H2N−OH ⎯⎯→⎯ CH3CH=N−OH + H2O
Acetaldoxime
(Capable of showing geometrical isomerism)
Ph−CH=O + H2N−NHPh ⎯→ Ph−CH=N−NHPh + H2O
Benzaldehyde phenyl hydrazone
(Capable of showing geometrical isomerism)
H3C H3C
C O + H2N−NHCONH2 C N−NHCONH2 + H2O
H3C H3C
Acetone semicarbazone
Illustration
There are two NH2 groups in semicarbazide that might react with a ketone or an aldehyde.
Explain why the reaction occurs with one of the terminal NH2.
Solution:
The NH2 group closer to the carbonyl group is deactivated due to resonance stabilization,
as compared to the other end NH2 group.
O O− O−
.. .. .. .. ..  ..  ..
NH2−NH−C NH2 NH2−NH C NH2 NH2−NH C−NH2
The electron pair availability is more on the terminal nitrogen, thus making it more
nucleophilic and semicarbazone is formed through its attack.
(IV) REACTION WITH PCl5:

Phosphorous pentachloride reacts with simple carbonyl compounds to give
1, 1−dichlorides (gem dichloride).
Cl
C=O + PCl5 ⎯→ C + POCl3
Cl
The possible mechanism of the reaction is
 Cl 
Cl− −OPCl4−
C=O + PCl +4 C−OPCl4 C C−Cl
OPCl4
Cl−
Cl
C
Cl
The reaction is initiated by the attack of PCl +4 (solid PCl5 is PCl +4 PCl 6− ) and the chloride ions are
obtained from PCl 6− .
(V) REACTION WITH SeO2:
Aldehydes and ketones with a methyl or methylene group adjacent to the carbonyl group are
oxidised by selenium dioxide in acetic acid at room temperature to dicarbonyl compounds. For
example, acetaldehyde forms glyoxal and acetone forms methyl glyoxal.
⎯⎯⎯
⎯→ OHC−CHO + Se + H2O
Acetic
CH3CHO + SeO2
acid
⎯⎯⎯
⎯→ CH3COCHO + Se + H2O
Acetic
CH3COCH3 + SeO2
acid
The actual reagent of the reaction is selenous acid (H2SeO3) and the probable mechanism is
C=O C−O−H C=O
−H2O
C=O
OH −H2O
CH2 CH C−O−Se + Se
O=Se C=O
Keto form Enol form OH H OH
(VI) REACTION WITH CHLOROFORM:
Ketones condense with chloroform in the presence of potassium hydroxide to give chloretone,
which is used as a hypnotic drug.
CH3COCH3 + CHCl3 ⎯⎯ ⎯→ (CH3)2C(OH)CCl3
KOH
Chloretone
The reaction proceeds as
..
H −CCl3 + OH− CCl3 + H2O
CH3 .. CH3 O− H2O CH3 OH
C=O + CCl3 C C
CH3 −OH− CH3 CCl3
CH3 CCl3
Chloretone
Chloral (trichloro acetaldehyde) on reaction with chlorobenzene in presence of H2SO4 gives
dichloro diphenyl trichloroethane (DDT). The product is used as an insecticide for killing insects
and mosquito. It is used in household under the name DDT.
Cl
O Cl Cl
H2SO4
Cl3C−C + 2 Cl−C C H + H2O
H
Cl
DDT Cl
(VIII) WITTIG REACTION:

It is a reaction used for converting carbonyl compounds to alkenes.
R1 R3 R1 R3
C=O + Ph3P=C Ph3P=O + C=C
R2 R4 R2 R4
The driving force of this reaction is the large amount of energy released during the formation of
very strong P=O bond (535 kJ mol−1).
The reaction is particularly useful for getting a double bond into positions that are difficult like
exocyclic methylene groups.
O + Ph3P=CH2 CH2
Ph3P=O +
(IX) CANNIZZARO REACTION:

Those aldehydes (aliphatic or aromatic), which do not have −hydrogen atom on treatment with
strong base undergoes a reaction involving its 2 moles, one getting oxidised to yield acid salt and the other
getting reduced to primary alcohol. The important condition is that there should not be a good leaving
group attached to the carbonyl group.
O
2 −C−H Conc. C + −CH2OH
OH−
O−
O
(Aldehyde with no Acid salt Alcohol
−H atom)
This reaction is an example of organic disproportionation.
Mechanism:
The first step of the mechanism involves reversible attack of OH− on an aldehyde molecule to give
hydroxy alkoxide. This hydroxy alkoxide in the subsequent step transfer hydride ion to second molecule of
either same aldehyde (simple Cannizzaro) or different aldehyde (crossed Cannizzaro). The hydroxy
alkoxide on transferring hydride becomes carboxylic acid molecule while second aldehyde molecule
becomes alkoxide. The carboxylic acid and alkoxide then undergoes proton exchange to form carboxylate
and alcohol respectively.
The reaction requires presence of strong bases and the rate law with PhCHO is of the type
Rate = k[PhCHO]2[OH−]
The slowest (rate−determining) step of the reaction is transfer of hydride ion.
O O−
OH−
Step (I): Ph−C Ph−C−OH
H
H
Hydroxy alkoxide
O− O O−
O
Slow
Step (II): Ph−C H + C−Ph Ph−C + Ph−C−H
OH H OH
H
Hydride donor Hydride acceptor Carboxylic acid Alkoxide
O O− O
Step (III): Ph−C + Ph−C−H Ph−C + Ph−CH2OH
OH O−
H Alcohol
Carboxylate
(More resonance
stabilized)
It is evident from the mechanism that the species acting as hydride donor finally forms acid salt
while the one, which accepts hydride will form primary alcohol.
When crossed Cannizzaro reaction is carried out between formaldehyde and benzaldehyde,
formaldehyde always forms formate salt while benzaldehyde yields benzyl alcohol.
50 % NaOH
HCHO + PhCHO ⎯⎯ ⎯ ⎯
⎯→ HCO 2−Na + + PhCH2OH
This is because carbonyl carbon of formaldehyde is more electrophilic than that of benzaldehyde.
−
So, OH initially attacks at formaldehyde (due to electronic, statistical and steric factors) to form hydroxy
alkoxide, which acts as hydride donor to finally form carboxylate while benzaldehyde accepts hydride to
form alcohol finally.
The presence of electron withdrawing substituent increases the rate of Cannizzaro reaction while
electron releasing substituent decreases the rate.
For example,
⎯→ CH3OH + HCO 2−Na +
50 % NaOH
2HCHO ⎯⎯⎯⎯

⎯→ PhCH2OH + PhCO 2−Na +

50 % NaOH
2PhCHO ⎯⎯⎯⎯

CHO CH2OH CO2−Na +
50 % NaOH
2 ⎯⎯ ⎯⎯→ +

Cl Cl Cl
CHO CH2OH CO2−K +
30 % KOH
2 ⎯⎯⎯⎯→ +

NO2 NO2 NO2

PhCHO + HCHO ⎯⎯⎯⎯→ PhCH2OH + HCO 2−K +
50 % KOH

50 % KOH
(CH3)2CHCHO ⎯⎯⎯⎯→ (CH3)2CHCOO−Na+ + (CH3)2CHCH2OH [Exception]

The above exception may be due to the fact that stability of −carbanion is less & attack of this
carbanion to the carbonyl carbon is difficult because of the steric crowding hence, aldol condensation is not
feasible.
⎯→ (CH3)3CCH2OH + HCO 2−Na +
50 % NaOH
(CH3)3CCHO + HCHO ⎯⎯⎯⎯

Intramolecular Cannizzaro:
Glyoxal on reaction with concentrated NaOH gives 2−hydroxy ethanoate by intramolecular
Cannizzaro reaction. The product is a −hydroxy acid.
H H H
OH− IMPE
H−C C−O−
Hydride
H−C C−H H−C C−OH H−C C−OH
transfer
O O O O− O− O OH O
IMPE: Intramolecular proton exchange
Phenyl glyoxal on similar reaction gives 2−hydroxy−2−phenyl ethanoate.
H H H
OH− IMPE
Ph−C C−O−
Hydride
Ph−C C−H Ph−C C−OH Ph−C C−OH
transfer
O O O O− O− O OH O
(X) ADDITION OF ALCOHOLS:
Carbonyl compounds add on one mole of alcohol to give hemi−acetals and hemi−ketals while
addition of two moles of alcohols give acetals and ketals.
R dry HCl R O− IMPE R OH ROH R OR

C O + ROH C  C C + H2O
dry HCl OR
H gas H O−R H OR gas
H
H Hemi−acetal Acetal
(gem diether)
Generally, hemi−acetals and hemi−ketals are not isolated while isolable products are acetals and
ketals.
Conversion of hemi−acetal to acetal is a specific acid catalysis reaction. Hemi−acetal is first
protonated, which then loses H2O molecule to give carbocation. Formation of this carbocation is the rate
limiting step. Carbocation is then attacked by neucleophile to give final product, acetal.
R OR H+ (Fast) R OR −H2O (Slow) R  ROH (Fast) R OR
C C  C−OR C 
H OH H OH2 H H O−R
H
−H+ (Fast)
R OR
C
H OR
This reaction is not so favourable with ketones under these conditions (with simple alcohols) but
reaction can be favoured if 1, 2 or 1, 3−diols are used. With diols, cyclic ketals
are formed. The reaction with simple alcohols was not favourable because entropy decreases
(S = −ve) as 3 molecules give 2 molecules on reaction while with diols, entropy change is zero, so
reaction becomes favourable.
R HO CH2 H+
R O CH2
C O + C + H2O
R HO CH2 R O CH2
Ketals are formed only by unhindered ketones.
Acetals or ketals are stable in neutral or basic conditions but in acidic medium, they undergo acid
catalysed cleavage similar to that of ethers to regenerate carbonyl compounds. Thus, this reaction is used to
protect carbonyl groups. For example, we want to convert 2−carbethoxy cyclopentanone to 2−hydroxy
methyl cyclopentanone. This can be achieved by protecting keto group and reducing −CO2Et group to −
CH2OH by LiAlH4.
O O O O O O
CH2−OH
CO2Et CO2Et CH2OH Aqueous
CH2−OH LiAlH4 acid
CH2OH
dry HCl −EtOH
gas
−H2O
For example,
dry HCl
CH3−CH=O + 2C2H5OH ⎯⎯ ⎯
⎯→ CH3CH(OC2H5)2 + H2O
gas
HO−CH2 O−CH2
dry HCl
CH3CH2CHO + CH2 ⎯⎯ ⎯
⎯→ CH3CH2CH CH2 + H2O
gas
HO−CH2 O−CH2
1, 3−diol
(XI) HALOGENATION OF KETONES:
Ketones can be halogenated (chlorinated, brominated or iodinated) to form −haloketone in the
presence of either base or an acid catalyst. So the reaction is referred as base−promoted halogenation and
acid−catalysed halogenation of ketones. For example,
base or
CH3COCH3 + Br2 CH3COCH2Br + HBr
acid
Rate of this reaction (in presence of acid or base both) depends upon the concentration of acetone
and of base/acid but is independent of bromine concentration.
Rate = k[Acetone] [Base] or Rate = k[Acetone] [Acid]
The mechanism of base−promoted halogenation is given as
RDS ..
Step I: CH3−C−CH3 + B− CH2−C−CH3 + B−H
(slow)
O O
.. fast
Step II: CH3−C−CH2 + Br−Br CH3−C−CH2Br + Br
O O
For a given [Acetone] and [Base], the bromination, chlorination and iodination proceed at identical
rates because value of rate constant (K) for the step I is same regardless of which halogen is involved.
The mechanism of acid−catalysed halogenation involves formation of enol in two step.
The first step is reversible protonation of the carbonyl oxygen while second step is slow loss of
an −hydrogen, which is the rate−limiting step. The enol in third step reacts rapidly with bromine to give
−haloketone in the last step.
Fast
Step I: CH3−C−CH3 + HX CH3−C−CH3 + X−
O :O−H

Step II: CH3−C−CH3 + X Slow

CH3−C CH2 + HX
:O−H OH

Step III: CH3−C=CH2 + Br2 Fast

CH3−C−CH2Br + Br
:OH :O−H

Fast
Step IV: CH3−C−CH2Br + X CH3−C−CH2Br + HX
:O−H O

(XII) ALDOL CONDENSATION:
Under the influence of dilute base, two molecules of an aldehyde or a ketone may combine to form
a −hydroxy aldehyde or −hydroxy ketone. This reaction is called the aldol reaction because product of
reaction of 2 moles of aldehyde is called aldol (“ald” for aldehyde and “ol” for alcohol). In every case, the
product results from addition of one molecule of aldehyde (or ketone) to a second molecule in such a
manner that the −carbon of the first becomes attached to the carbonyl carbon of the second. Because the
addition reaction is reversible, good yields of the addition product are obtained only if it is removed from
the solution as it is formed.
The aldol reaction in more favourable for aldehydes than for ketones because of more acidic −
hydrogen atoms and more electrophilic carbon.
Heating the aldol product in either acid or base leads to dehydration because the double bond
generated is in conjugation with the carbonyl group (making it more stable). If the product of an aldol
addition is dehydrated, the overall reaction is called an aldol condensation.
The dehydration product is  −unsaturated carbonyl compound. When the aldol product contains
an aryl (or phenyl) group at the −position, dehydration occurs under the conditions in which the aldol
addition is carried out, without additional heating. This is because the double bond formed is conjugated
not only with the carbonyl group but also with the aryl group. This makes the product a very stable
compound and is therefore easy to form. For example,
   
dil OH− NaHSO4, 
2CH3CHO CH3CH−CH2CHO CH3−CH CH−CH O
Acetaldehyde OH Crotonaldehyde
−hydroxybutyraldehyde (2−butenal)
   
dil OH− H+/ or OH−/
2CH3CH2CHO CH3CH2−CH−CH−CHO CH3CH2CH C−CH O
Propionaldehyde OH CH3 CH−CH O CH
3
3−hydroxy−2−methylpentanal 2−methyl pent−2−en−1−al
CH3 CH3
dil OH− NaHSO4, 
2CH3COCH3 CH3−C−CH2−C−CH3 CH3−C CH−C−CH3
Acetone OH O CH−CH O O
4−hydroxy−4−methyl−2−pentanone Mesityl oxide
O OH O O
OH− −H2O
2 C−CH3 C−CH2−C C CH−C
CH3 CH3
The carbonyl group plays two important roles in the aldol condensation. First, it makes −
hydrogens acidic enough for carbanion formation to take place and secondly, it provides the unsaturated
linkage at which nucleophilic addition takes place.
The mechanism of base catalysed aldol condensation can be outlined as:
O dil. OH− .. O− O−
Step I: CH2−C CH2−C CH 2=C
H −H2O H H
H H
Carbanion Enolate ion
−
O Slow O
.. O (Key step) O
Step II: CH3−C + CH2−C CH3−C−CH2−C
H H
H H
O− OH
O H2O O
Step III: CH2−C CH2−C −
CH3−CH−CH2−C
H −OH H
H
O O O−
dil. OH− ..
Step I: CH2−C−CH3 CH2−C−CH3 CH2=C−CH3
−H2O
H
O O− O
.. O
Step II: CH3−C + CH2−C CH3−C−CH2−C−CH3
CH3
CH3 CH3
− OH O
O O
H2O
Step III: CH3−C−CH2−C−CH3 CH3−C−CH2−C−CH3
−OH−
CH3 CH3
Aldol condensation can also be affected in presence of acidic medium but the mechanism is
different than base catalysed aldol. The mechanism of acid catalysed aldol condensation can be
outlined as:
H
H+X– X–
CH3–C–CH2CH3 CH3–C–CH CH3 CH3–C=CH–CH3
–X– –HX
:O
.. :O–H OH

(more stable enol)
CH3 CH3
CH3CH2–C + CH C–CH3 CH3CH2–C CH C–CH3
O CH3 :O−H
.. O CH3 :O–H

IMPE
CH3 CH3
  H+,   
CH3CH2–C C C–CH3 CH3CH2–C CH C–CH3
–H2O
CH3 O OH CH3 O
(, –unsaturated carbonyl compound)
Crossed aldol condensation:
When two different carbonyl compounds (with −H atoms) are used in an aldol condensation, four
products are formed because each carbonyl compound can react with itself (self aldol) as well as with the
other carbonyl compound (crossed aldol). For example, when two carbonyl compounds, A and B are
treated with dil OH−, both can lose a proton from the −carbon to form carbanion (acting as nucleophiles)
A− and B− respectively. A− can either react with A or B and B− can react with either B or A. The reaction of
A− with B or B− with A is called crossed aldol addition. All the four products have similar physical
properties, making them difficult to separate. Consequently, crossed aldol addition is not a useful synthetic
preparation.
O
 
O A/H2O CH3CH−CH2−C−H
..
CH2−C−H B/H2O OH O
 
A−
OH− CH3CH2−CH−CH2−C−H
  −H2O
CH3CHO + CH3CH2CHO OH
A B −
OH O
 
−H2O
O A/H2O CH3CH−CH−C−H
..
CH2CH−C−H B/H2O OH CH3
O
B−  
CH3CH2−CH−CH−C−H
OH CH3
All the four products are −hydroxy carbonyl compounds. Under certain conditions, a mixed aldol
reaction can lead primarily to one product. When one of the carbonyl compound does not have any −
hydrogen, it cannot form carbanion and number of possible products reduces to two. A greater amount of
one of the two products will be formed if the compound without −hydrogen is present in excess. The
carbanion will be more likely to attack the carbonyl compound without −hydrogen because there is more
of it in the solution.
O O O O
OH− −H2O  
Ph−C−H + CH3CH2−C−H Ph−CH−CH−C−H Ph−CH C−C−H
(Excess)
OH CH3 CH3
Another way to obtain a single aldol product is to convert one carbonyl compound completely into
carbanion. This cannot be done by using a weaker base (dil. OH−). To achieve this, we make use of a much
stronger base like LDA (lithium diisopropyl amide). Thus, this carbanion attacks over other carbonyl
compound to give only one product. For example,
O O O OH O 
 H .. O  CH−CH2CH3
 CH−CH2CH3
LDA/THF 1. CH3CH2−C−H
, −H2O
2. H2O
LDA = [(CH3)2CH]2NLi
Note that when mixture of an aldehyde and a ketone with −hydrogen atom are used, the
carbanion is exclusively formed by ketone and the carbanion generated attacks the carbonyl carbon of
aldehyde (as it is more electrophilic).
Intramolecular aldol condensation:
When a compound has two carbonyl groups, it can undergo intramolecular aldol condensation in
the presence of dilute base (if −H atoms are present in the compound).
An intramolecular reaction is readily favoured if the reaction leads to the formation of a 5 or 6−membered
ring. When one of carbonyl group is an aldehyde and other is a ketone, it’s the ketone, which forms
carbanion and this carbanion attack the carbonyl group of an aldehyde in such a manner that 5 or 6−
membered ring is formed.
For example, 2, 5−hexanedione in presence of dilute OH− undergoes intramolecular aldol
condensation to give 2 set of products as there are 2 different types of −hydrogens. One of the product
has a 5−membered ring and the other has a 3−membered ring. The major product of the reaction is a 5−
membered ring compound as 5−membered ring has greater stability than 3−membered ring.
O O CH3 CH3
+H2O −H2O
CH3
CH3−C−CH2CH2−C−CH −
OH 
.. 2 O −OH−
OH− 
O O O O O
−H2O
(major product)
CH3−C−CH2CH2−C−CH3
2, 5−hexanedione
(1, 4−diketone)
OH− H3C O− H3C OH H3C
−H2O O O 
+H2O
−H2O
CH3−C−CH2CH−C−CH
.. 3 −OH−

C−CH3 C−CH3 C−CH3
O O O
(minor product)
When 6−oxoheptanal is treated with dilute base, a mixture of three products is formed, of which
one of the product is major while other two are minor products.
O ..
CH2 O O O
C
O +H2O −H2O 
CH2 C CH3 OH− C H −OH−
−H2O
H 
CH2 O O− H OH (minor product)
CH2 O O O
C .. CH3 O
H OH−
CH2 C C−CH3+H2O C−CH3 −H2O 
O C−CH3
−H2O −
C H −OH
H H 
OH− −
−H2O O O OH (major product)
O O− CH3 OH CH3 CH3

CH3 
C 
C−H +H2O C−H −H2O C−H
C H −OH
.. O O O
O (minor product)
Illustration
The compound, pentaerythritol C(CH2OH)4, used in making explosives is obtained from the
reaction of acetaldehyde and excess of formaldehyde in the presence of calcium hydroxide.
Outline the probable steps in this synthesis.
Solution:
First a crossed aldol condensation takes place between CH3CHO and HCHO. This converts HCHO
into methylol group (−CH2OH).
O O O
OH− 
CH3−C−H + H−C−H H−C−CH2−CH2OH
Since the product has 2 more −hydrogens, so two more such conversions gives a tri−methylol
compound.
O O O CH2OH
HCHO
H−C−CH2−CH2OH H−C−CH−CH2OH
HCHO
H−C−C−CH2OH
OH− OH−
CH2OH CH2OH
Now crossed Cannizzaro reaction takes place, as no −hydrogens are now available.
In this reaction, HCHO gets oxidised to formate while the other compound gets reduced to
pentaerythritol.
O CH2OH CH2OH
OH− −
HCHO + H−C−C−CH2OH HCO + 2
CH2OH HOH2C−C−CH2OHCH2OH
Pentaerythritol
(XIII)CLAISEN CONDENSATION:
When ethyl acetate is treated with sodium ethoxide and the resulting mixture is acidified, then
ethyl −ketobutyrate (ethyl 3−oxobutanoate), generally known as ethyl acetoacetate or acetoacetic ester is
obtained.
O 
C2H5OH .. Na
2CH3CO2C2H5 + C2H5ONa CH3−C−CHCO2C2H5 + 2C2H5OH
Ethyl acetate Sodioacetoacetic ester
H+
O
CH3−C−CH2CO2C2H5
Ethylaceto acetate
(a −keto ester)
The reaction is similar to aldol condensation i.e involving nucleophilic attack by a carbanion on an
electron−deficient carbonyl carbon, but with two differences. First difference is that the −hydrogen of an
O
ester is less acidic than that of aldehydes or ketones, became of conjugation occur in −C group, so
OC2H5
dilute OH− is not the base employed here. We need a much stronger base than OH−, that’s why sodium
ethoxide is used as a base. The second difference is that in aldol condensation, nucleophilic attack leads to
addition but in Claisen condensation, nucleophilic attack leads to substitution (typical reaction of acyl
compounds).
Mechanism:
The generally accepted mechanism for the Claisen condensation is
 O .. O
Step I: CH2−C + −OC2H5 CH2−C + C2H5OH
OEt OEt
H Carbanion
O−
CH2=C
OEt
Enolate
O−
O ..
Step II: CH3−C + CH2CO2C2H5 CH3−C−CH2CO2C2H5
OEt
OC2H5
O
CH3−C−CH2CO2C2H5 + C2H5O−
O O
..
Step III: CH3−C−CH2CO2C2H5 + C2H5O− CH3−C−CHCO2C2H5 + C2H5OH
Stronger acid Weaker acid
Ethoxide ion in the first step abstracts a hydrogen ion from the −carbon of the ester to form
carbanion, which in the next step undergoes nucleophilic attack on the carbonyl carbon of second molecule
of ester to displace ethoxide ion and finally give −keto ester. But the product isolated is not a −keto
ester, it is sodium salt of −keto ester. This is because acetoacetic ester (having −hydrogens
between two carbonyl groups) is much stronger acid than ethyl alcohol. So, acetoacetic ester reacts with
ethoxide ion to form ethyl alcohol and the anion of sodio acetoacetic ester. The salt is readily stabilized by
resonance.
OEt OEt OEt
C O C O C−O−
HC HC .. HC
C−O− C O C O
CH3 CH3 CH3
Anion of sodioaceto
acetic ester
Claisen condensation can be driven to completion by removing a proton from the −keto ester.
This is easy to achieve as −carbon of the −keto ester is flanked by two electron withdrawing groups,
making its hydrogen more acidic than the −hydrogen of the reacting ester.
Successful Claisen condensation requires an ester with two −hydrogens and
an equivalent amount of base rather than a catalytic amount of base.
While drawing the product of Claisen condensation directly (without writing the mechanism), we
should remember to form carbanion (mentally) from −carbon of the ester and attach it to the carbonyl
carbon of other molecule of ester by ejecting ethoxide ion. The final product should be sodium salt of −
keto ester. For example,

−
.. Na
2CH3CH2COOC2H5 + OC2H5 CH3CH2−C−CHCO2C2H5 + 2C2H5OH
Ethyl propionate
O CH3
H+
CH3CH2−C−CH−CO2C2H5
O CH3
Ethyl−2−methyl−3−oxo pentanoate
(a −keto ester)
Mixed Claisen condensation:
Mixed Claisen condensation is a condensation reaction between two different esters. Like mixed
aldol condensation, a mixed Claisen condensation will be useful only when it is carried under conditions
that allows the formation of primarily one product, other wise, the result is a mixture of products that are
difficult to separate. Only one product will be formed when one of the ester has no −hydrogen and is
taken in excess while the other ester is added slowly to the reaction mixture.
O O O O
EtO− H+
Ph−C−OCH2CH3 + CH3CH2−C−OEt Ph−C−CH−C−OEt + 2EtOH
Ethyl benzoate Ethyl propionate
(excess) CH3
O O O
NaOEt H+
Ph−C + CH3−C Ph−C−CH2−C + C2H5OH
OEt OEt OEt
Ethyl benzoate O
Ethyl acetate
Ethyl benzoylacetate
O
NaOEt H+
HCOOC2H5 + CH3CO2Et H−C−CH2−C + C2H5OH
Ethyl formate Ethyl acetate OEt
O
Ethyl formylacetate
COOC2H5
CH3CO2Et NaOEt H+
+ H5C2OOC−C−CH2CO2C2H5 + C2H5OH
COOC2H5
O
Ethyl oxalate Ethyl oxaloacetate
A reaction similar to mixed Claisen condensation is the condensation of a ketone (but not
aldehydes) and an ester (taken in excess). As −hydrogens of ketones are more acidic than that of esters, so
carbanion is formed by ketones, which attacks the electrophilic carbon of ester to finally give a product, −
diketone (stabilized by intramolecular hydrogen bonding in the enol form).
O O O
O C−CH + EtOH 3
EtO− H+
CH3−C−OEt +
Ethyl acetate
(excess) −diketone (major product−
stabilized by tautomerism & intra
molecular H bonding)
EtO− H+
−H2O
CH−C−OEt
O
(minor product)
NaOC2H5 H+
CH3COCH3 + CH3CO2C2H5 CH3COCH2COCH3 + C2H5OH
2, 4−pentanedione
NaOEt H+
CH3COPh + Ph−CO2Et Ph−C−CH2−C−Ph + C2H5OH
O O
Dibenzoyl methane
(XIV) DIECKMANN CONDENSATION:
Intramolecular Claisen condensation of esters with −hydrogen atoms in the presence of sodium
ethoxide leading to cyclization is called Dieckmann condensation.
When ethyl adipate is treated with sodium ethoxide, followed by acidification gives 2−carbethoxy
cyclopentanone (a cyclic −keto ester).
OEt O OEt O O
C C ..
CH2CO2Et OEt− CHCO2Et CO2Et + EtO−
−EtOH
Ethyl adipate
O O
CO2Et H+ .. CO2Et + EtOH
Ethyl pimelate on treatment with sodium ethoxide gives 2−carbethoxy cyclohexanone.

OEt O OEt O O
C C ..
CH2CO2Et OEt CO2Et
CHCO2Et −OEt
−EtOH
(XV) PERKIN REACTION:

The reaction between aromatic aldehydes and alkanoic anhydrides in presence of alkanoate is
called Perkin reaction. The reaction is similar to aldol condensation.
In this reaction, the carbanion is obtained by the removal of an −hydrogen atom from acid
anhydride by carboxylate (anion of the corresponding acid of the acid anhydride).
The carbanion then attacks the aromatic aldehyde to yield alkoxide anion. The transfer of acetyl group then
takes place from the carboxyl oxygen to alkoxy oxygen via a cyclic intermediate to give a more stable
anion. Removal of an −hydrogen from this anion by carboxylate results in the loss of good leaving group
from the −position to give anion of the , −unsaturated acid. This on acidification gives , −
unsaturated acid. For example, PhCHO on reaction with excess acetic anhydride in presence of sodium
acetate followed by acidification gives cinnamic acid (3−phenyl propenoic acid).
O O
C − C CH3
CH3 MeCO2
Step I: O O ..
CH2−H −MeCO2H
C C CH2
O O
Step II:
O H3C O H3C O
O
C
−
C H3C O− C
H3C O O O
+ Slow O O O O−
Ph H .. C
CH2 O Ph O Ph O Ph O
H
H3C O O− OH
C −
Step III: O O− MeCO2

O H3O+ 
O
−MeCO2H
Ph Ph 
Ph O −
− MeCO2 Cinnamic acid
H
(XVI)REFORMATSKY REACTION:
It is an aldol type mechanism, in which an aldehyde or a ketone is treated with zinc and −halo
ester in ether as a solvent. The product obtained after hydrolysis is a −hydroxy ester. The aldehyde or
ketone used can be aliphatic, aromatic or heterocyclic. If the −position bears an aryl group, the product is
, − unsaturated ester because of dehydration. The reaction is said to proceed via an intermediate
EtOOC−C−ZnBr, that is analogous to RMgX.
H H H
 Zn H3O+ 
−C− + −C CO2Et −C CO2Et −C CO2Et
Ether

O Br −C− −C−
(−halo ester) OZnBr OH
(−hydroxy ester)
Mechanism:
H H
+ −
−C C−OEt + Zn Ether
BrZn−C C−OEt
Br O O
H H H
–   +
 
C−C−OEt + Zn2+ + Br− + H2O
H3O
C + −C C−OEt −C C C−OEt −C
+ O O
O ZnBr O BrZnO OH
(XVII) BENZOIN CONDENSATION:
2PhCHO ⎯⎯⎯⎯ ⎯→ PhCH(OH)COPh
Alcoholic
KCN
Benzoin
When aromatic aldehyde is treated with alcoholic KCN, the product is not a cyanohydrin but −
hydroxy aromatic ketone called benzoin. The product of aromatic aldehydes with KCN is different than
aliphatic aldehydes because after the attack of CN−, the intermediate (I) in aromatic aldehyde has sufficient
acidity (due to − I effect of Ph) so that intramolecular proton exchange takes place to form a carbanion,
which is resonance stabilized. This carbanion then attacks another molecule of aromatic aldehyde, which
undergoes intramolecular proton exchange and then ejection of CN− to give final product i.e. benzoin. The
rate−limiting step of the reaction is attack of carbanion on second molecule of aromatic aldehyde.
Mechanism:
O O− OH OH
IMPE .. ..
Ph−C + CN Ph−C−H Ph−C−CN
.. Ph−C=C=N
..

H CN
O Ph O− O−H OH O−
IMPE
Ph−C + :C−OH Ph−C C−Ph Ph−C C−Ph
H CN H CN H CN
−CN−
OH O
Ph−C C−Ph
H
IMPE = Intra molecular proton exchange Benzoin
(XVIII)BAEYER−VILLIGER OXIDATION:
The reaction of oxidation of ketones to esters by peroxy acids (CF3COOOH) or BF3/H2O2 or
H2O2/Base is called Baeyer−Villiger oxidation.
O O O
R−C−R RCO3H R−C−OR or R−C−OR + RCO2H
(I) (II)
Product (I) is formed when migratory aptitude of R is greater than that of R and if it is greater for
R, then product (II) is produced.
For example, acetophenone on treatment with peroxy trifluoro acetic acid gives phenyl acetate and
not methyl benzoate. This reflects phenyl group has a greater migrating tendency than methyl group.
Ph−C−CH3 + CF3CO3H CH3−C−OPh + CF3CO2H
O O
Phenyl acetate .
The overall reaction is an insertion of oxygen atom between the carbonyl group and the group that
has greater migrating tendency.
Mechanism:
The proposed mechanism involves transfer of acidic hydrogen from peroxy acid to carbonyl
oxygen and attack of CF3 CO 3− on carbonyl carbon of acetophenone. As O−O linkage is weak, it cleaves to
release CF3 CO 2− (which is a good leaving group) and oxygen becomes electron deficient. On electron
deficient oxygen, phenyl group migrates from the adjacent carbon to give a carbocation, which then loses
H+ to give phenyl acetate.
O H O..− H O−H O O−H
−
 IMPE CF3 CO2
Ph−C−CH3 +:O−O−C−CF
.. 3 Ph−C−O−O−C−CF3 Ph−C−O−O−C−CF3 Ph−C−O
O CH3 O CH3 CH3
~Ph
..
:OH
−H+
CH3−C−OPh CH3−C−O−Ph 
C−O−Ph
O O−H
.. CH3
Thus, the reaction establishes the migratory aptitude of various alkyl groups and
H as H > 3°R > 2°R > 1°R > CH3 and that of aryl groups as p−anisyl > p−tolyl > phenyl > p−chloro
phenyl > p−nitro phenyl. In case of alkyl aryl ketones, it is the aryl group which migrates (except in case of
(CH3)3C group. For example,
CF3CO3H
CH3−C−C(CH3)3 −CF3CO2H
CH3−C−OC(CH3)3
O O
t−butyl acetate
Cyclic ketones get converted to lactones with ring expansion on treatment with
peroxy acids.
O O
RCO3H O
Cyclopentanone −lactone
(XIX) BECKMANN REARRANGEMENT:
When oximes (especially ketoximes) are treated with acidic catalyst like H+, PCl5, SOCl2, SO3,
P2O5 etc., they are transformed into substituted amides. The structure of the substituted amide
depends on the structure of ketoxime as the migration of the groups does not depend on their
migratory aptitude but on the group that is at trans position to the hydroxyl group.
R OH R R Tautomerize
H+ R−C−NHR
C=N C=N
R .. HO ..
O
Syn (R) Substituted amide
R OH R R Tautomerize
H+ R−C−NHR
C=N C=N
R .. HO .. O
Anti (R) Substituted amide
Mechanism:
The given reaction adopts following mechanism, in which group that migrates is anti to
the −OH group.

R OH + R OH2 R
H H2O
C=N
.. C=N
.. C=N
R ~R  ..
R R
Anti (R) Removal of H2O and migration of alkyl H2O (−H+)
group takes place simultaneously
Tautomerize R
R−C−NHR C=N..
HO R
O
For example,
Ph OH
PCl5 in
C=N Ph−C−NHCH3
H3C . ether, 
O
Syn (Ph) N−methyl benzamide
H3C OH
PCl5 in
C=N H3C−C−NHPh
Ph .. ether, 
O
Anti (Ph) N−Phenyl acetamide
OH
N
H+, 
NH
O
Cyclohexanone Caprolactam
oxime
(XX) FAVORSKII REARRANGEMENT:
The reaction of −halo ketone with hydroxide ion to give carboxylic acid is called Favorskii
rearrangement. In place of hydroxide ion, alkoxide ion and amine can also be used and the
corresponding products are ester and amide respectively.
H
 OH−
−C C C− −C C C−OH
H2O
O Cl H O
For example, PhCH2COCH2Cl and PhCH(Cl)COCH3 both give same acid (PhCH2CH2CO2H) on
reaction with OH− in H2O. This is possible only if they form same intermediate. So, the mechanism
proposed for this reaction is
 ..
OH−
Ph–CH2–C–CH2–Cl –H2O
Ph–CH C CH2
O O Cl O
Cl Ph–CH C
OH−
.. CH2
Ph–CH–C–CH3 Ph–CH C CH2
 –H2O
O O OH−
Cl
O O
–H2O
..
PhCH2CH2–CO2H Ph–CH–CH2–C–OH Ph–CH C
–OH−
CH2 OH
Cyclic −halo ketones on Favorskii rearrangement undergo ring contraction.
Cl
 OR
C–OR
O O
(XXI) PINACOL − PINACOLONE REARRANGEMENT:
Pinacol (a vicinal diol) on treatment with hot and dilute sulphuric acid undergoes dehydration with
rearrangement to give aldehydes or ketones as the major product depending upon the structure of
diol. With pinacol, a major product is pinacolone.
CH3 CH3 CH3 CH3
CH3−C C−CH3 dil. H2SO4
CH3COC(CH3)3 + (CH3)2C C(CH3)2 + CH2 C C CH2

OH OH (major product) O
Pinacol
For a symmetrical 1, 2 –diol, any of the –OH group can be protonated but for an unsymmetrical 1,
2 –diol, that–OH group is protonated whose loss as H2O can form a stable carbocation. Although
the initially formed carbocation is 3° (or some other type of carbocation), it rearranges by alkyl or
aryl shift to give a secondary carbocation. This secondary carbocation formed as a result of
rearrangement is more stable than the initially formed carbocation because of lone pair
delocalization, it gives a resonating form in which octet of every atom is complete, except
hydrogen, which has a duplet only. The group that migrates is the one that has a higher migratory
aptitude. The rearranged carbocation then loses a proton to the base to give final product.
Some of the order of migratory aptitude of groups are
(i) Aryl > hydrogen > alkyl
(ii) p−anisyl > p−tolyl > m−tolyl > m–anisyl > phenyl > p−chlorophenyl > o−anisyl > o−tolyl
(iii) Me3C(3° alkyl) > Me2CH (2° alkyl) > MeCH2 (1° alkyl) > Me
Let us see some cases of pinacol−pinacolone rearrangement.
CH3 CH3 CH3 CH3 CH3

dil. H2SO4 −H2O 
CH3−C C−CH3 CH3−C C−CH3 CH3−C C−CH3
− HSO−4
OH :OH
.. OH OH
.. 2 OH CH3
Pinacol 3° carbocation (I)
~Me−
(1, 2−methyl shift)
CH3 CH3 CH3


−H +
CH3−C
CH3−C C−CH3 CH3−C C−CH3 C−CH3
O CH3 O−H
.. CH3 :O−H
.. CH3
Pinacolone (more stable) (2° carbocation)
The conjugated alkene product would be obtained when intermediate (I) loses another OH as H2O
to give a dication, which then loses 2 protons from −positions. The epoxide product would be
obtained when in intermediate (I), OH attacks C through its lone pair to form a three−membered
ring, which finally loses H+. But diene is a minor product as the dication formed is not stable due
to the presence of positive charges on adjacent carbanions. Epoxide is also not the stable product
as it gets cleaved in acidic medium to give back (I).
CH3 CH3 CH3 CH3 CH3 CH3

H+ ~Ph− 
Ph−C C−Ph Ph−C C−Ph Me−C C−Ph Me−C C−Ph
−H2O 
OH OH 
OH : OH
.. Ph O−H
.. Ph
3° Carbocation
2° Carbocation
−H+
CH3
Me−C C−Ph
O Ph
Ph CH3 Ph CH3 Ph Ph
H+ ~Me− 
Ph−C C−CH3 Ph−C C−CH3 Ph−C C−CH3 Ph−C C−CH3
−H2O

OH OH OH Me : O−H
.. Me O−H
..
3° Carbocation
2° Carbocation
−H+
Ph
Ph−C C−CH3
Me O
OMe Me OMe Me OMe
OMe
H+ ~ p−tolyl

Ph–C C–Ph –H2O Ph–C C–Ph Ph–C C–Ph
 Ph–C C–Ph
OH OH OH : O−H
..  O−H
(3° carbocation) ..
Me OMe −H+
(2° carbocation)
Me
Ph–C C–Ph
O
Me
Bicyclic 1,2−diols also undergo pinacol−pinacolone type mechanism with the ring expansion/ring
contraction depending on the ring sizes.
H+  ~ring
–H2O
alkyl 
OH OH OH
(3° carbocation)
: O–H
..
(2° carbocation)
−H+
O  O−H
..
Illustration
Ph
Give the product of the rearrangement of the cyclopentyl glycol, C−CH3 and show
OH OH
how it is formed.
Solution:
Ph Ph OH O
Ph Ph
~ring 
Ph
C−CH3 H +
C−CH3 C−CH3
−H2O CH3  CH3
 alkyl −H
OH OH OH OH2 OH

(XXII) MEERWEIN−PONNDORF−VERLEY REDUCTION:
When carbonyl compounds are heated with aluminium isopropoxide in isopropanol solution, they
are reduced to alcohols and isopropoxide is oxidised to acetone, which can be easily removed by
distillation. Aldehydes are reduced to primary alcohols and ketones to secondary alcohols. This method is
generally used for the reduction of ketones to secondary alcohols. The reducing agent employed in the
reaction is a specific reagent, used for reducing ketones or aldehydes in presence of reducible functional
groups like double bond, nitro group etc.
This reagent reduces only the carbonyl group, keeping other groups untouched.
R2CO + [Me2CHO]3Al R2CHOAl[OCHMe2]2 + MeCOMe
dil. H2SO4
R2CHOH
Mechanism:
O OCH(CH3)2
O OCH(CH3)2 R O−Al[OCH(CH3)2]2
R C Al R
C + Al R OCH(CH3)2 C CH3
R H O R H + C O
OCH(CH3)2
H O C CH3
C (CH3)2CHOH
CH3 CH3
CH3 CH3 Cyclic transition state
R2CHOH + [(CH3)2CHO]3Al
The reverse of this reaction is called Oppenauer oxidation, in which alcohols are oxidised to
carbonyl compounds. Primary alcohols are oxidised to aldehydes and ketones are obtained from secondary
alcohols.
(XXIII) PERIODIC ACID OXIDATION:
Compounds containing two or more C O or −OH groups attached to adjacent carbon atoms
undergo oxidation by HIO4 (periodic acid), resulting in the cleavage of carbon−carbon bonds. Oxidation
products can be drawn by cleaving carbon−carbon bond of any two adjacent carbons having −OH groups
or oxo groups and supplying each carbon with OH group and then deriving the final product from it.
For example,
R−C−C−R + HIO4 R−C−OH + R−C−OH + HIO3
O O O O
R−CH−CH−R + HIO4 RCHO + RCHO + HIO3
OH OH
R−CH−C−R + HIO4 RCHO + RCO2H + HIO3
OH O
R
R−C CH−R + HIO4 R2CO + RCHO + HIO3
OH OH
R−CH CH CH2 + 2HIO4 RCHO + HCO2H + HCHO + HIO3
OH OH OH
R−CH CH2 CH−R + HIO4 No reaction.
OH OH
The oxidation is particularly useful in determination of the structure of −hydroxy ketones or −
hydroxy aldehydes or 1, 2−dialdehydes or 1, 2−diketones or 1, 2−keto aldehydes. Qualitatively, oxidation
by HIO4 is indicated by the formation of white precipitate (AgIO3) upon addition of silver nitrate. The
nature and amounts of the products and the quantity of periodic acid consumed gives valuable information
regarding the structure of the compound.
(XXIV) DECARBOXYLATION OF −KETO CARBOXYLIC ACIDS:
−keto acids on slightest warming alone or in presence of a base undergoes ready removal of CO2.
The process of loss of CO2 is called decarboxylation. For example,
 

CH3−C−CH2−C−OH CH3−C−CH3 + CO2
O O O
The reaction occurs readily as the transition state involved is 6−membered. Decarboxylation is
catalysed by an intramolecular transfer of a proton from the carboxyl group to the carbonyl group with the
simultaneous ejection of CO2. The initial product of the reaction is an enol, which then tautomerizes to
keto form.
Mechanism:
CH2 CH2

CH3−C C=O CH3−C C=O CH3−C=CH2 + CO2
O O O O OH
H Enol form
H
Transition state
(6−membered) Tautomerizes
CH3−C−CH3
O
Keto form
In the presence of a base, −keto acid is converted into −keto carboxylate, which on heating loses
CO2 to give a carbanion that is stabilized by resonance.
, OH−  ..
CH3−C−CH2−C−OH CH3−C−CH2−C−O− CH3−C−CH2 CH3−C=CH2
−H2O −CO2
O O O O :O
.. :O:
..
−keto acid −keto carboxylate
H+ (from protic
solvent)
CH3−C−CH3
O
When a compound carrying two carboxyl groups on the same carbon is heated at about 150°C, it
also undergoes decarboxylation, in a manner similar to −keto acids. But higher temperature is required to
decarboxylates a −dicarboxylic acid than to decarboxylates a −keto acid as carbonyl oxygen is more
basic than carboxyl oxygen.
CH2 CH2

HO−C C=O HO−C C=O HO−C=CH2 + CO2
O O O O OH
H Enol form
H
Malonic acid Transition state Tautomerizes
(6−membered)
CH3−C−OH
O
Acetic acid
For example,

CH3CH2CH2−C−CH2−C−OH CH3CH2CH2−C−CH3 + CO2
−OH O O O
3−oxohexanoic acid 2−pentanone

HO−C−CH−C−OH CH3CH2−C−OH + CO2
O CH3 O O
−methylmalonic acid Propionic acid
O O
CO2H

+ CO2
2−oxocyclohexane Cyclohexanone
carboxylic acid
1
5 ANALYSIS OF ALDEHYDES AND KETONES
Aldehydes and ketones are characterized by the addition of nucleophilic reagents (especially
ammonia derivatives) to the carbonyl group.
For example, all aldehydes or ketones will react with 2, 4−dinitrophenylhydrazine to form an
insoluble yellow or red solid of 2, 4−dinitro phenyl hydrazone.
Aldehydes are characterized and in particular are differentiated from ketones through
their ease of oxidation: aldehydes give a positive test with Tollen’s reagent while most of the ketones do
not.
Aldehydes are also oxidized by many other oxidizing agents: cold, dilute, neutral KMnO4 and by
CrO3 in H2SO4.
A highly sensitive test for aldehydes is the Schiff’s test. An aldehyde reacts with the fuschin
aldehyde reagent to form a characteristic magenta colour.
Aldehydes and ketones are generally identified through the melting points of derivatives like 2, 4−
dinitrophenylhydrazones, oximes and semicarbazones.
Methyl ketone is characterized through the iodoform test.
Aldehydes can be oxidised by Fehling’s solution.
Fehling’s solution, an alkaline solution of cupric ion complexed with tartarate ion (or Benedict’s
solution, in which complexing is with citrate ion); the deep−blue colour of the solution is discharged, and
red cuprous oxide precipitates.
Fehling’s solution is made by mixing, Fehling A solution, which contains copper sulphate and
Fehling B solution, which contains sodium hydroxide and Rochelle salt (Sodium Potassium Tartarate).
During the oxidation of aldehydes to acids, the cupric ions are reduced to cuprous ions, which are
precipitated as red cuprous oxide.
RCHO + 2Cu2+ + 3OH− ⎯→ R CO 2− + 2Cu+ + 2H2O
2Cu+ + 2OH− ⎯→ Cu2O + H2O
Cuprous oxide (red)
Illustration
Give simple chemical tests to distinguish between the compounds in each of the following
pairs.
(a) PhCH=CHCH2OH and PhCH=CHCHO
(b) CH3CH2CH2CH2CHO and CH3CH2COCH2CH3
(c) PhCH2COCH2CH3 and PhCH(OH)CH2CH2CH3
(d) PhCH2CHO and PhCOCH3
Solution:
(a) and (b): The aldehydes give a positive Tollen’s test with Ag(NH3 ) 2+ . Also in (a), only the
aldehyde gives a precipitate with either H2NOH or PhNHNH2.
(c): Only the alcohol is oxidised by CrO3 (colour change from orange−red to green). Alternatively,
the ketone gives a solid oxime or phenyl hydrazone with H2NOH or PhNHNH2 respectively.
(d): Only the aldehyde gives a positive Tollen’s test and the given ketone gives a positive iodoform
test.
SOLVED OBJECTIVE EXAMPLES
Example 1:
dil. NaOH
In the reaction, HO−CH2−CHO
how many distinct products (saturated) are possible?
(a) 1 (b) 2 (c) 3 (d) 4
Solution:
Four possible products are
Aldol condensation
HO−CH2−CHO HO−CH2CH(OH)CH(OH)CHO
Tetrose
It can be D, L−erythrose and D, L−threose. The terms erythro and threo are used with
dissymmetric molecules whose ends are different. The erythro diastereomer is the one with similar
groups on the same side of the Fischer projection, while the threo diastereomer has similar groups
on opposite sides of the Fischer projection. The terms meso and () [or (d, l) are preferred with
symmetric molecules.
CHO CHO CHO CHO
H−C−OH HO−C−H HO−C−H H−C−OH
H−C−OH HO−C−H H−C−OH HO−C−H
CH2−OH CH2−OH CH2−OH CH2−OH
D−Erythro L−Erythro D−Threo L−Threo
 (d)
Example 2:
O
CH3 O C−OH
H+
C C (A)
CH3 H
The product (A) in the given reaction would be
O O O OH
C C C O
(a) H3C C OH (b) C C H
H CH3 H3C CH3
O O
CH3 H C OH C−H
(c) C H (d) C=C
CH3 CH3 CH3
Solution:
O H
H3C O C−OH + H3C O O
H
C C C C C O H
H3C H H3C H
unstable
−H −CO2
+
H3C H O H3C OH
C C C=C
H3C H H3C H
enol
 (c)
Example 3:
In which of the following substrate, rate of Benzoin condensation will be maximum?
(a) O2N CHO (b) H3C CHO
(c) HO CHO (d) H2N CHO
Solution:
O O O
O
N C + CN N C−H
O H
O CN
(I) (II)
O O−H
N C
O CN
(III)
Benzoin condensation is due to stability of intermediate (III) when negative charge on C is
extensively delocalised in benzene ring, Nitro and CN group. In all other cases, such dispersal is
not extensively possible. On the other hand, NO2− is also creating positive charge centre on
carbonyl carbon, making it more susceptible to nucleophilic attack of CN−.
 (a)
Example 4:
H
LDA
CH3−CH=CH−C=O (excess)

O
O
(a) H (b)
OH H
(c) (d)
Solution:
In the absence of −H on saturated carbon, −H becomes acidic. This acidic −H would be
abstracted by LDA to give carbanion, which condense with another molecule to give
cyclooctatetraene. The high temperature reaction condition helps in the dehydration of aldol
product.
O
O
LDA  H
H  H 
O
 (c)
Example 5:
O
1 
2 [(CH3]2CH]2N Li
+ CH3CHO
O OH O
(a) (b)
OH
O H
O
OH
H
(c) (d)
O
Solution:
LDA is a sterically hindered and strong base. It will abstract H+ from position (1) rather than
position (2). Carbanion formed will attack on CH3CHO to give intermolecular aldol reaction.
 (b)
Example 6:
The order of reactivity of the following compounds with PhMgBr is
(I) PhCOPh (II) CH3CHO (III) CH3COCH3
(a) (I) > (II) > (III) (b) (III) > (I) > (II)
(c) (II) > (I) > (III) (d) (II) > (III) > (I)
Solution:
Reactivity of carbonyl compounds with PhMgBr is based on electrophilicity of carbonyl group and
steric crowding around it. Based on electrophilicity and crowding, CH3CHO is the most reactive.
The least reactive would be PhCOPh due to excessive steric crowding.
 (d)
Example 7:
1. CH3COONa
CHO + (X) 2. H+
CH=CH−COOH
Identify the compound (X).
(a) CH3COOH (b) (CH3CO)2O
(c) BrCH2COOH (d) CHO−COOH
Solution:
CH3COONa
CHO + (CH3CO)2O CH=CH−COOH
(X)
Since, the given reaction is a Perkin reaction, it requires reaction between an aromatic aldehyde
and acid anhydride in the presence of corresponding acid carboxylate. As the acid carboxylate is
sodium acetate, so the acid anhydride would be acetic anhydride.
 (b)
Example 8:
Which structure is the most stable?
O O OH O
(a) (b)
OH O OH OH
(c) (d)
Solution:
The compound given in (a) is not stable because 1,3−dicarbonyl compound with −hydrogen atom
exists in enol form. Compounds in (b) and (c) are the mono enol forms of compound in (a), of
which enol in (c) is more stable because of conjugation of C=C double bond with carbonyl group.
Conjugation exists in (d) also, which is the dienol of compound in (a). Compound in (c) is more
stable than the compound in (d), as it involves greater delocalization of −electron density. Thus,
resonance energy of compound in (c) is more than that of compound in (d). Hence, compound in
(c) is the most stable.
 (c)
Example 9:
Which one of the following compound contains deuterium after reaction with NaOD in D2O?
(a) C6H5−C−H (b) C6H5−CH2−C−H
O O
(c) C6H5−C−C(CH3)3 (d) (CH3)3C−C−C(CH3)3
O O
Solution:
Reaction of the carbonyl compound (with an −hydrogen atom) with NaOD in D2O would replace
−hydrogen with deuterium. Carbonyl compound with −hydrogen atom is C6H5−CH2−C−H and
O
this compound on reaction with NaOD in D2O gives C6H5−CD2−C−H.
O
 (b)
Example 10:
What is the principal product of the following reaction?
CH2−CH=O
NaOH
H2O + ?
ethanol, water, heat
CH2−CH=O
CH=O CH=O
(a) (b)
CH=O
OH O
(c) (d)
OH O
Solution:
H .. CH=O CH=O
CH−CH=O −
CH−CH=O
 OH H2O
O OH
−H2O −OH−
CH2−CH=O CH2−CH=O
, −H2O
CH=O


(, −unsaturated aldehyde)
 (b)
SOLVED SUBJECTIVE EXAMPLES
Example 1:
Synthesize the following compounds, starting with cyclopentane (C5H10), alcohols of three
or fewer carbons, H2CO and inorganic reagents. (a) Cyclopentane carbaldehyde
(b) 1, 5−pentanedial and (c) 5−oxohexanal.
Solution:
Cl / h Mg / Dry ether H CO
⎯→ C5H9MgCl ⎯⎯2 ⎯
(a) C5H10 ⎯⎯2⎯⎯→ C5H9Cl ⎯⎯ ⎯ ⎯ ⎯ +
→ C5H9−CH2OH
H3 O
CrO3/Py
C5H9−CHO
KOH O3 / Zn
(b) C5H9Cl ⎯⎯⎯→ ⎯⎯⎯
⎯→ OHC(CH2)3CHO
EtOH
O Me
Me OH
1. DMSO 1. CH3Mg I H2SO 4 / 
(c) C5H9Cl ⎯⎯ ⎯⎯
−
→ ⎯⎯ ⎯ ⎯
+
⎯→ ⎯⎯⎯⎯
⎯→
2. HCO 3 2. H3O
O3/Zn
OHC(CH2)3COCH3
Example 2:
Write structures for (A) and (B) in the following reactions.
LBAH LiAlH
(A) ⎯⎯⎯ CH3CH(CH3)COCl ⎯⎯ ⎯
⎯4
→ (B)
0 C
where LBAH is lithium tri−t−butoxyaluminium hydride. Also account for the different
products.
Solution:
(A): CH3CH(CH3)CHO (B): CH3CH(CH3)CH2OH
LBAH is a less reactive reducing agent than LiAlH4 because of its bulky alkoxide groups, which
reduces its ability to donate hydride ion.
Example 3:
The reaction of RCOCl with R2CuLi gives a ketone, but with RMgX gives a 3° alcohol,
R2RCOH. Explain why the latter reaction does not give a ketone.
Solution:
With RMgX, initially a ketone is formed.
RCOCl + RMgX ⎯→ RCOR + MgX(Cl)
But since the ketone is more reactive than RCOCl, it reacts further with RMgX to form 3° alcohol.
R2CuLi reacts with the less reactive RCOCl but not with the more reactive RCOR. This is
because they do not react by typical nucleophilic addition of R− to C=O. Instead Cu complexes
+ −
with the Cl of RCOCl as R C Cl CuLiR2 producing an acylium like ion with greater
,
O
+ on the carbon. This strongly electrophilic carbon can form a bond with even less nucleophilic
R−
of R2CuLi.
Example 4:
Prepare (a) (CH3)2CHCH2CHO (b) PhCH2CHO (c) cyclopentyl carbaldehyde from
1, 3−dithiane.
Solution:
Aldehydes are prepared by alkylating 1, 3−dithiane at C2 and by hydrolyzing the resulting
thioacetal. The product RCHO has one more carbon from C2 of dithiane. The general equation of
preparation of aldehyde from dithiane is
n−BuLi RX HgCl2/MeOH
S S S S −X− RCHO
S S H2O
..
H H H H R
Carbanion Alkylated
product
To get (CH3)2CHCH2CHO, alkylate with (CH3)2CHCH2Cl. To prepare PhCH2CHO, alkylate with
PhCH2Br and in order to get cyclopentyl carbaldehyde, alkylate with cyclopentyl chloride.
Example 5:
Compare the acidity of hydroxylamine and oximes and explain the difference.
Solution:
Loss of a proton from H2N−OH gives a conjugate base, H2N−O−, in which the negative charge is
localized on oxygen. Loss of H+ from oxime, C=N−OH gives conjugate base C N O−  C−N=O .
The conjugate base of oxime is stabilized by lone pair−p delocalization. Thus, C=N−O− is a weaker
base than H2N−O− and consequently, oximes become more acidic than hydroxylamine.
Example 6:
Select the best way for reducing the C=O group in each of the following: (a) BrCH2CH2CHO
(b) (CH3)2C(OH)CH2CH2COCH3 (c) PhCH(OH)CH2COCH2CH3 (d) CH3CO−CH2−CH−CH2
O
Solution:
(a) Clemmensen reduction is used for reducing it. Strong base causes dehydrohalogenations.
HSCH2CH2CH2SH can displace Br−. (b) and (c) require Wolff−Kishner reduction or
desulfurization.
In (b), the 3° alcohol is dehydrated in acid. In (c), the 2° alcohol is easily dehydrated because the
C=C formed is conjugated with the benzene ring. (d) None. All methods lead to opening of the
epoxide ring.
Example 7:
How can we convert PhCH=CHCOCH3 to
(a) PhCH=CHCOOH (b) PhCH=CHCH(OH)CH3
(c) PhCH2CH2COCH3 (d) PhCH=CHCH2CH3
(e) Ph(CH2)3CH3?
Solution:
(a) Cl2 in NaOH (haloform reaction)
(b) [Me2CHO−]3Al3+ in Me2CHOH (Meerwein−Ponndorf reduction) or LiAlH4.
(c) To reduce only C=C of , −unsaturated carbonyls use dissolving metal conditions
(Birch reduction), Li in liq. NH3, ether.
(d) H2NNH2, OH− (Wolff−Kishner reduction)
(e) Reduce the compound in (d) with H2/Pt or reduce the compound in (c) by Clemmensen or
Wolff−Kishner method.
Example 8:
Two isomers are formed from the reaction of butanone with Mg/Hg. Write their structures.
Solution:
Two chiral carbons are formed in this reaction leading to a racemate and a meso structures.
Et Et Et
Me OH HO Me Me OH
and
HO Me Me OH Me OH
Et Et Et
Racemate meso
Example 9:
Give the product from the addition of HBr to methyl acrylate, CH2=CHCO2Me and the
mechanism for its formation.
Solution:
Initially H+ adds to the C=O and not to C=C , to give a resonance stabilised cation.
H+  
H2C=CH−C−OMe H2C=CH−C−OMe H2C=CH−C−OMe H2C−CH=C−OMe
O  O−H
.. O−H O−H
Br−
OH
H2C=CH−C−OMe + H2C−CH=C−OMe
Br Br OH
(1, 2−adduct) (1, 4−adduct)
tautomerize
H2C−CH2−C−OMe
Br O
(Major product)
Example 10:
Give the aldol products and the corresponding alkenes (aqueous NaOH or KOH used,
100°C) from
(a) 2, 5−hexanedione
(b) 2, 7−octanedione
(c) 2, 8−nonanedione and
(d) 2, 4−pentanedione
Solution:
O O
..
C C
dil. OH−
(a) CH3−C−CH2CH2−C−CH3 CH2 CH2 CH2 CH2
100°C
O O CH2 CH2
C
C
H3C O O− CH3
H2O (−OH−)
O O
C C
CH CH2 , −H2O CH2
CH2
CH2 CH2
C C
H3C HO CH3
..
CH2
dil. OH− CH3CO
(b) CH3−C−CH2CH2CH2CH2−C−CH3 CH3−C−CH CH2
O O O CH2
H3C C H3C O−
O H2O(−OH−)
O
CH3CO
CH3C , −H2O
H3C OH
H3C
..
CH2
dil. OH−
(c) CH3−C−CH2CH2CH2CH2CH2−C−CH3 CH3−C−CH CH2
O O O CH2
H3C C CH
2
O
O O O
CH3−C CH3−C CH3−C
, −H2O H2O(−OH−)
H3C H3C
H3C OH O−
O O
− .. CH3−C−CH2−C−CH3
(d) CH3−C−CH2−C−CH3 dil. OH CH3−C−CH−C−CH3
O O O O O− CH3
O
CH3C C
CH CH2
CH3−C C=O
O CH3
dil. OH−
O O O O− CH3
OH − CH3C C
CH3C CH3 CH3C O
CH3 CH2
CH −C CH −C
CH
CH3 2H2O, (−2OH ) −
CH3
C CH2 C CH2 CH3−C C=O
..
−
HO CH2−C O CH2−C O CH2
O O
 −2H2O
O O
CH3C CH3 CH3C CH3
C C C C
Tautomerize
CH3−C CH2 CH3−C CH
CH −C CH C
O OH
Multiple Choice Questions:

1. Nucleophilic attack on carbonyl carbon changes its hybridisation from
(a) sp to sp2
(b) sp2 to sp3
(c) sp3 to sp2
(d) sp to sp3 (JIPMER)
2. Benzaldehyde can be prepared from
(a) O
– C – Cl + H2 Pd / BaSO4
(b) O
– C – NH2 + Br2 + KOH
(c)
– C ≡ N + H2 Sn / HCl
(d)
– 𝑁2+ 𝐶𝑙 − + H2O
(AIIMS)
3. Consider the following reaction
COCl
H2 / Pd-BaSO4 A
The product ‘A’ is

(a) C6H5CHO
(b) C6H5OH
(c) C6H5COCH3
(d) C6H5Cl (AIPMT (Mains))
4. O
C CHO
Cl H2 / Pd-BaSO4
This reaction is called

(a) Etard’s reaction
(b) Stephen reaction
(c) Rosenmund’s reaction
(d) Gatterman-Koch reaction (AMU (Med.))
5. Which one of the following organic compound is a gas?
(a) CH3CHO
(b) CH2O
(c) CH3COCH3
(d) CHO
(AMU (Med.))
6. In one reaction, – Mg – Br is treated with CH3CN & then hydrolysed. In another reaction
– Mg – Br is treated with ethyl acetate & then hydrolysed.
– MgBr (i) CH3CN, (ii) H3O+ A

O
– MgBr (i) CH3 – C – OC2H5 , (ii) H3O+ B
A & B are
(a)
– CHO & J – CO – CH3
(b)
– CO – CH3 & J – CO – CH3
(c)
– CO – CH3 & J – CO – OC2H5
(d) O
– CO – CH3 & J – O – C – CH2 – CH3
(AIIMS)
7. The correct structure of the product ‘A’ formed in the reaction
O
H2 (gas, 1 Atmosphere) A is
Pd / Carbon, Ethanol
(a) OH
(b) O
(c) OH
(d) OH
+
(NEET Phase – I)
8. Which of the following reactions will not result in the formation of carbon-carbon bonds?
(a) Cannizzaro reaction
(b) Wurtz reaction
(c) Reimer – Tiemann reaction
(d) Friedel – Crafts acylation (WBJEE)
9. The following conversion

H H
CH3 – C = O + H – CH2CHO Dil. NaOH CH3 – C – CH2CHO
OH
Is known as
(b) Aldol condensation
(c) Polymerisation
(d) Benzoin condensation (AIIMS)
10. Which can be used to distinguish aldehydes & ketones?
(a) Fehling’s solution
(b) H2SO4 solution
(c) NaHSO3
(d) NH3 (JIPMER)
11. When aniline reacts with oil of bitter almonds (C6H5CHO) condensation takes place & benzal derivatives
is formed. This is known as
(a) Schiff’s base
(b) Benedict’s reagent
(c) Millon’s base
(d) Schiff’s reagent (JIPMER)
12. In which of the following reactions new carbon-carbon bond is not formed?
(b) Wurtz reaction
(c) Aldol condensation
(d) Friedel-Craft reaction
(e) Kolbe’s reaction (Kerala PMT)
13. Assertion: Mixture of benzaldehyde & acetaldehyde in hot alkaline medium gives cinnamaldehyde.
Reason: Benzaldehyde is strong electrophile than acetaldehyde.
(a) If both assertion & reason are true & reason is the correct explanation of assertion.
(b) If both assertion & reason are true but reason is not the correct explanation of assertion.
(c) If assertion is true but reason is false.
(d) If both assertion & reason are false. (AIIMS)
14. The reagent used to distinguish between acetaldehyde & benzaldehyde is
(a) Tollen’s reagent
(b) Fehling’s solution
(c) 2, 4-dinitrophenylhydrazine
(d) Semicarbazide (Kernataka CET)
15. Consider the reaction:
RCHO + NH2NH2 → RCH = N – NH2
What sort of reaction is it?
(a) Electrophilic addition-elimination reaction
(b) Free radical addition-elimination reaction
(c) Electrophilic substitution-elimination reaction
(d) Nucleophilic addition-elimination reaction (AIPMT (Mains))
16. Predict the products in the given reaction.

CHO
50% KOH
Cl
(a) CH2OH CH2COO–
+
Cl Cl
(b) CH2OH OH
+
OH OH
(c) CH2OH COO–
+
Cl Cl
(d) CH2OH COO–
+
OH OH (AIPMT)
17. An organic compound ‘A’ burns with a sooty flame. It is negative towards Tollen’s reagent test & positive
for Borsche’s reagent test. The compound ‘A’ is
(a) benzaldehyde
(b) acetophenone
(c) acetone
(d) salicylic acid (Karnataka CET)
18. Following compounds are given
(i) CH3CH2OH
(ii) CH3COCH3
(iii) CH3 – CHOH
CH3
(iv) CH3OH
Which of the above compound(s), on being warmed with iodine solution & NaOH, will give iodoform?
(a) (i), (iii) & (iv)
(b) only (ii)
(c) (i), (ii) & (iii)
(d) (i) & (ii) (AIPMT (Mains))
19. Compound A (molecular formula C3H8O) is treated with acidified potassium dichromate to form a
product B (molecular formula C3H6O). B forms a shining silver mirror on warming with ammoniacal
silver nitrate. B when treated with an aqueous solution of H2NCONHNH2, HCl & sodium acetate,
gives a product C. Identify the structure of C.
(a) CH3CH2CH = NNHCONH2
(b) CH3 – C(CH3) = NNHCONH2
(c) CH3 – C(CH3) = NCONHNH2
(d) CH3CH2CHNCONHNH2 (AIIMS)
20. What is true for acetophenone?

(a) It reacts with alkaline KMnO4 followed by acidic hydrolysis & forms benzoic acid.
(b) It reacts with iodine & NaOH to form triidomethane.
(c) It is prepared by the reaction of benzene with benzoyl chloride in presence of anhydrous
aluminium chloride.
(d) It does not react with freshly prepared ammoniacal silver nitrate solution. (J & K CET)
21. Identify Z in the reaction.
OH
CHCl3 + NaOH Conc. NaOH

X Z
(a) OH OH
CH
OH
(b) OH OH
CH2OH COONa
+
(c) OH OH
C
O
(d) OH OH
C – CH
O OH
(AIIMS)
22. Assertion: (CH3)3CCOC(CH3)3 & acetone can be distinguished by the reaction with NaHCO3.
Reason: HSO− 𝟑 is the nucleophile in bisulphite addition.
23. Which of the following undergoes disproportionation reaction on treatment with concentrated alkali?
(a) H3CCH2CHO
(b) (CH3)2CHCHO
(c) CH3 – CH – CHO
C6H5
(d) (CH3)3CCHO (AMU (Med.))
24. The enloic form of butanone contains
(a) 12 𝜎 bonds, 1 𝜋 bond & 2 lone pairs of electrons
(b) 11 𝜎 bonds, 1 𝜋 bond & 2 lone pairs of electrons
(c) 12 𝜎 bonds, 1 𝜋 bond & 1 lone pairs of electrons
(d) 10 𝜎 bonds, 2 𝜋 bonds & 2 lone pairs of electrons
(e) 13 𝜎 bonds, 1 𝜋 bond & 2 lone pairs of electrons. (Kerala PMT)
25. CHO
(i) Conc. NaOH,
(ii) 2H2O / H+
CHO
(a) COOH
COOH
(b) COOH
CH2OH
(c) COOH
OH
(d) CH2OH
COH (OJEE)
26. Reduction of aldehydes & ketones into hydrocarbons using zinc amalgam & conc. HCl is called
(a) Cope reduction
(b) Dow reduction
(c) Wolff-Kishner reduction
(d) Clemmensen reduction (AIPMT)
27. Which of the following compounds will be most reactive towards nucleophilic addition reaction?
(a) 3-Pentanone
(b) 2-Methylpentanal
(c) 2, 4-Dimethyl 1-3-pentanone
(d) 3, 4-Dimethyl 1-2-hexanone (AMU (Med.))
28. Which among the following compounds will give a secondary alcohol on reacting with Grignard
reagent followed by acid hydrolysis?
(I). HCHO
(II). C2H5CHO
(III). CH3COCH3
(IV) HCOOC2H5
Select the correct answer using the codes give below.
(a) II only
(b) III only
(c) I & IV
(d) II & III
(e) II & IV (Kerala PMT)
29. The acid which do not contain carboxylic acid group is
(a) glutaric acid
(b) picric acid
(c) stearic acid
(d) terephthalic acid (AMU (Med.))
30. Claisen condensation is not given by

(a)
– C – OO –
(b)
CH3CH2COO –
(c)
J – COOCH3
(d)
J – COOCH2CH2CH3
(UP CPMT)
31. Assertion: In sodium formate, both the C – O bonds have same value 1.27 Å.
Reason: Equal bond length is due to the phenomenon of resonance.
32. Glacial acetic acid is obtained by
(a) chemically separating acetic acid
(b) treating vinegar with dehydrating agents
(c) crystallising, separating & melting acetic acid
(d) distilling vinegar. (AFMC)
33. The best combination of reagents for carrying out the conversion RCH2CH2OH → RCH2CH2COOH is
(a) PBr3 , KCN, H3O+
(b) PBr3 , KCN, H2/Pt
(c) KCN, H3O+
(d) PBr3 , H3O+
(e) LiAlH4 , PBr3 (Kerala PMT, WB JEE 2008)
34. Which of the following compounds has maximum volatility?
(a) OH
COOH
(b) OH
COOH
(c) OH
COOH
(d) COOH
(WB JEE)
35. The oxidation of benzene by V2O5 in the presence of air produces

(a) maleic anhydride
(b) benzoic acid
(c) benzaldehyde
(d) benzoic anhydride (AIPMT)
36.The distinguishing test between methanoic acid & ethanoic acid is
(a) Tollen’s test
(b) Sodium bicarbonate test
(c) Litmus test
(d) Esterification test (Karnataka CET)
37. Match the reactant in column – I with the reaction in column – II.
Column – I Column – II
(i) Acetic acid (A) Stephen
(ii) Sodium phenate (B) Friedel-Crafts
(iii) Methyl cyanide (C) HVZ
(iv) Toluene (D) Kolbe’s
(a) i – C, ii – A, iii – D, iv – B
(b) i – D, ii – B, iii – C, iv – A
(c) i – B, ii – C, iii – A, iv – D
(d) i – C, ii – D, iii – A, iv – B (Karnataka CET)
38. Methyl benzoate can be prepared by
(a) C6H5COOH + CH3OH H+
(b) C6H5COCl + CH3OH Pyridine
(c) C6H5COOH + CH2N2
(d) All the above method. (AMU (Med.))
39. If phthalic acid is treated with NH3 & then it is first heated weakly then strongly, the final product
formed is
(a) CONH2
CONH2
(b) CONH2 Me
CO NH2
(c) COOH
CONH2
(d) O
C
NH
C
O (AIIMS)
40. In a set of reactions, acetic acid yielded a product S.

CH3COOH SOCl2 P Benzene/ anhy. AlCl3 Q HCN R HOH S
The structure of ‘S’ would be
(a) OH
C – COOH
CH3
(b) COOH
CH2 – C – CH3
OH
(c) OH
CH2 – C – CH3
CN
(d) CN
C – CH3
OH (AIIMS)
41. The relative acidic strengths of benzoic acid, o-toluic acid & p-toluic acid is of the decreasing order:
(a) p-toluic acid > o-toluic acid > benzoic acid
(b) o-toluic acid > p-toluic acid > benzoic acid
(c) p-toluic acid > benzoic acid > o-toluic acid
(d) o-toluic acid > benzoic acid > p-toluic (Karnataka CET)
42. Propionic acid with Br2 / P yields a dibromo product. Its structure would be
(a) Br
H – C – CH2COOH
Br
(b) CH2(Br) – CH2 – COBr
(c) Br
CH3 – C – COOH
Br
(d) CH2(Br) – CH(Br) – COOH (AIPMT)
43. Which of the following will not reduce Fehling solution?
(a) HCOOH
(b) CH3COOH
(c) HCHO
(d) CH3CHO (BHU)
44. Dichloroacetic acid is a stronger acid than acetic acid.
This is due to occurrence of
(a) mesomeric effect
(b) hyperconjugation
(c) inductive effect
(d) steric effect (J & K CET)
45. O O
CH2 – C – OCH3 NaBH4 X
In the given reaction select the correct option for the product ‘X’ is
(a) OH H
CH2 – C – OCH3
OH
(b) OH O
CH2 – C – OCH3
(c) O OH
CH2 – CH – OCH3
(d) None of these. (BHU)

46. Picric acid is a stronger acid than acetic acid & benzoic acid. It contains
(a) – SO3H group
(b) two – COOH groups
(c) phenolic group
(d) three – COOH groups. (J & K CET)
47. Benzoic acid is treated with lithium aluminium hydride. The compound obtained is
(a) benzaldehyde
(b) benzyl alcohol
(c) toluene
(d) benzene. (AIIMS)
48. The number of moles of hydrogen that can be added to 1mole of an oil is the highest in
(a) linseed oil
(b) groundnut oil
(c) sunflower seed oil
(d) mustard oil. (Karnataka CET)
49. Glycerol is present in
(a) lipid
(b) protein
(c) carbohydrates
(d) nucleic acid (UP CPMT)
50. Fries rearrangement is widely used in the synthesis of
(a) allyl phenol
(b) aryl acetates
(c) phenolic ketones
(d) biphenols (AMU (Med.))
51. When calcium acetate & calcium formate are dry distilled, the product obtained is
(a) Acetaldehyde
(b) Propanaldehyde
(c) Acetone
(d) Methylate
52. Cyclohexene on ozonolysis followed by reaction with zinc dust & water gives compound E.
Compound E on further treatment with aqueous KOH yields compound F. Compound F is
(a)
CHO
(b)
CHO
(c)
COOH
(d)
CO2H
CO2H
(AIIMS)
53. Assertion: Aldol condensation can be catalysed both by acids & bases.
Reason: 𝛽-Hydroxy aldehydes or ktones readily undergo acid catalysed dehydration.
54. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition reactions.
Ethanal (I) , Propanal (II) , Propanone (III) , Butanone (IV)
(a) III < II < I < IV
(b) II < I < III < IV
(c) IV < III < II < I
(d) I < II < III < IV (J & K CET)
55. The appropriate reagent for the following transformation,
O
CH3 CH2CH3
HO HO
(a) Zn (Hg), HCl
(b) NH2NH2 , OH −
(c) H2 / Ni
(d) NaBH4 (BHU)
ANSWERS OF MCQ QUESTIONS

𝑠𝑝3
𝛿+ 𝛿−
1. (b) C = O Nu– C – O– H+ C – OH
𝑠𝑝2 Nu Nu
2. (a)
O Pd / BaSO4
– C – Cl + H2 h – CHO + HCl
O
– C – NH2 + Br2 + KOH j – NH2 + K2CO3 + 2KBr + 2H2O
Sn / HCl
– C ≡ N + H2 – CH2NH2
– 𝑁2+ 𝐶𝑙 − + H2O – OH + N2 + HCl
3. (a) O = C – Cl H–C=O
H2 / Pd / BaSO4
It is Rosenmund’s reaction.
4. (c)
5. (b) CH2O or formaldehyde is a colourless, strong smelling gas.
6. (c)
– Mg – Br + CH3 – C ≡ N
CH3 – C = N – MgBr CH3 – C = O
H3O+
(A)
O
– Mg – Br + CH3 – C – OC2H5
O – MgBr OH
CH3 – C – OC2H5 CH3 – C – OH CH3 – C = O
H3O+ – H2O
(B)
Thus, in both cases, the same product, cyclohexyl methyl etone is formed.
7. (b) O O
H2(g), 1 atm
Pd/C, C2H5OH
C = C bond is reduced faster than C = O bond with H2 (Pd – C).
8. (a) Cannizzaro reaction:
2C6H5CHO 50% NaOH C6H5CH2OH + C6H5COO–Na+
Wurtz reaction:
R – Cl + 2Na + R – Cl dry ether R – R + 2NaCl
(carbon-carbon bond)
Riemer-Tiemann reaction:
OH O–Na+
CHO
+ CHCl3 + NaOH Δ
(Carbon-carbon bond)
Friedel-Crafts acylation:
C–R
+ R – C – Cl Anhy. AlCl3 O
9. (b)
10. (a) All aldehydes gives red ppt. with Fehling’s solution but ketones do not reduce Fehling’s solution.
11. (a) Benzaldehyde reacts with primary aromatic amines to form Schiff’s base.
C6H5CH = O + C6H5NH2 → C6H5CH = NC6H5 + H2O
Benzaldehyde Aniline Schiff’s base
12. (a) 2HCHO + NaOH → HCOONa + CH3OH
Formaldehyde Sodium formate Methyl alcohol
No new C – C bond is formed.
13. (a) This is a Claisen-Schmidt reaction.
O HO H
C6H5 – C – H + CH2CHO Hot alkali C6H5 – CH – CH – CHO Δ, H+, – H2O C6H5CH = CHCHO
Benzaldehyde Acetaldehyde Aldol (unstable) Cinnamaldehyde
(Electrophile (Nucleophile
as it does not as it contain
contain α-H) α-Hydrogen)
14. (b) R – CHO + 2Cu2+ + 5OH– Δ, – 3H2O RCOO– + Cu2O ↓
Aliphatic Cuprous oxide
Aldehyde Fehling’s solution (Red ppt.)
Banzaldehyde does not respond to Fehling’s solution due to alkaline nature of this reagent.
15. (d)
16. (c) Aldehydes having no α-hydrogen atoms on heating with concentrated alkaline solution (50%) undergo
Cannizzaro’s reaction.
CHO CH2OH COO–
50% KOH +
Cl Cl Cl
17. (b) Ignition test – burning with a sooty flame indicates presence of aromatic compound.
Negative test towards Tollen’s reagent indicates absence of aldehydes.
Positive test for Borsche’s reagent test indicates ketones (possibility of aldehydes being nullified).
So, ‘A’ is an aromatic ketone.
18. (c) Methyl alcohol does not respond to the iodoform test. The iodoform test is exhibited by ethyl alcohol,
acetaldehyde, acetone, methyl ketones, those alcohols which possess CH3CH(OH) – group,
acetophenone, α-hydroxypropionic acid, keto acid etc.
19. (a) C3H8O K2Cr2O7 / H+ C3H6O amm. AgNO3 Silver mirror
A B
H2NCONHNH2 . HCl C
Reaction of B indicates that B is an aldehyde thus B should be C2H5CHO or CH3CH2CHO &
therefore C should be CH3CH2CH = NNHCONH2.
CH3CH2CH2OH [O] CH3CH2CHO CH3CH2COOH + 2Ag ↓
[A] [B]
CH3CH2CHO + H2NNHCONH2 CH3CH2CH = NNHCONH2
Semicarbazide Semicarbazone
[C]
20. (b) Acetophenone reacts with iodine & NaOH to form iodoform.
COCH3 COONa
3I2 / NaOH + CHI3 + HI
Iodoform
21. (b) OH
X is CHO ; which undergoes Cannizzaro’s reaction to give Z.
22. (b) HSO−3 is a bulky nucleophile, hence, cannot attack on sterically hindered ketones.
23. (d) Aldehydes having no α-H undergo Cannizzaro reaction (disproportionation reaction).
24. (a) O OH
CH3 – CH2 – C – CH3 ⇌ CH3 – CH2 – C = CH2
Keto form Enol form
Enol form of butanone contain 12 𝜎 bond, 1𝜋 bond & 2 loan pairs of electron.
25. (b) This is an example of Intramolecular Cannizzaro reaction.
CHO COONa COOH
(i) Conc. NaOH, H2O
(ii) 2H2O / H+ H+
CHO CH2OH CH2OH
26. (d) Aldehydes & ketones are converted to alkane when treated with zinc amalgam & conc. HCl. This is
known as Clemmensen reduction.
Here C = O group is reduced to CH2 group.
O
R – C – H + 4[H] Zn – Hg / conc.HCl R – CH3 + H2O
27. (b) More the electron donating methyl group attached to carbonyl carbon, lesser will b reactivity towards
nucleophilic addition reaction.
28. (c) Only II & IV will give secondary alcohol while; I & III give primary & tertiary alcohol respectively.
29. (b) Picric acid is 2,4,6-trinitrophenol.
OH
O2N NO2
(– COOH group is absent)

NO2
30. (a) In In Claisen condensation aromatic aldehydes having no α-hydrogen atom react with aldehydes,
ketones or esters having α-hydrogen atoms in presence of dilute alkali to form 𝛼, 𝛽-unsaturated
carbonyl compound. It is not given by:
CH3Cl KCN (A) H+/H2O (B)
as it does not have α-hydrogen atom.
31. (a) Formate ion shows resonance & gives rise to identical bond lengths.
1.23Å 1.27Å
O O
H–C H–C– Na+
O–H O
1.36Å 1.27Å
Sodium formate
32. (d) Acetic acid is a colourless liquid a pungent smell. Below 17o C, it solidifies to an ice mass, known as
glacial acetic acid. It is obtained by distilling vinegar with conc. H2SO4.
33. (a) RCH2CH2OH PBr2 RCH2CH2Br KCN RCH2CH2CN H3O+ RCH2CH2COOH + NH3
34. (c) Para derivatives undergo association due to intermolecular hydrogen bond, hence para derivatives
have high boiling point whereas in case of ortho derivatives due to intramolecular hydrogen bond
no such association is possible. Consequently, the ortho derivatives are more volatile than para
derivatives. So option (c) has maximum volatility.
H
O O
C
O–H
35. (a) O
V2O5 , 773K CHCOOH Δ CHC
9
+ O2 – 2CO2 , – H2O CHCOOH – H2O O
2
Maleic acid CHC
O
Maleic anhydride
36. (a) Formic acid contains a hydrogen atom & behaves like an aldehyde as well as a carboxylic acid.
Like aldehydes it reduces Tollen’s reagent.
37. (d) HVZ reactions:
H. CH2COOH + Cl2 Red P,– HCl H. CHClCOOH Red P/Cl2 / – HCl H. CCl2COOH Red P/Cl2 / – HCl
Acetic acid α-Monochloroacetic acid α,α-Dichloroacetic acid
Cl3CCOOH
α,α,α-Trichloroacetic acid
38. (d) C6H5COOH + CH3OH H+ C6H5COOCH3 + H2O
C6H5COCl + CH3OH Pyridine C6H5COOCH3 + HCl
C6H5COOH + CH2N2 C6H5COOCH3 + N2
39. (d)
O
C – OH C – ONH4 C – NH2
NH3 Weakly heated 573K/Δ Strongly
C – OH C – ONH4 C – NH2
O
Phthalic acid O
C
NH
C
O
40. (a) CH3COOH SOCl2 CH3COCl Benzene/Anhy. AlCl3 – COCH3 HCN
(P) (Q)
OH OH
– C – COOH HOH J – – C – CN
CH3 CH3
(S) (R)
41. (d) o-substituted benzoic acids are stronger acids than benzoic acid due to ortho effect. Since, CH3 group
is e– donating due to hyper conjugation effect whereas hyper conjugation cannot operate on p-toluic
acid. Therefore, electron donating (– CH3) group decreases the acidity of p-toluic acid.
42. (c) This is Hell-Volhard Zelinsky reaction. in this reaction, acids containing α-hydrogen react with
X2 / red P giving product in which the α-hydrogens are substituted by X.
Br
CH3CH2COOH Br2 / P CH3 – C – COOH
Br
43. (b) Aldehyde reduces Fehling solution & among the acids only HCOOH reduces.
HCOOH + 2CuO Cu2O + CO2 + H2O.
44. (c) Chlorine is electron withdrawing group. The acidity of acid increases as the number of chlorine atoms
increases at α-position.
CCl3COOH > CCl2HCOOH > ClCH2COOH > CH3COOH
𝑝𝐾𝑎 0.7 1.48 2.85 4.71
45. (b) Sodium borohydride is a mild reducing agent which reacts rapidly with aldehydes & ketones but
only slowly with esters.
OH O
CH2 – C – OCH3
46. (c) OH COOH

O2N NO2
> > CH3COOH
NO2
Acidity in decreasing order
Due to the presence of three electronegative nitro groups, it is a stronger acid than phenol & its
properties are comparable to carboxylic acid.
47. (b) COOH CH2OH
LiAlH4
Reduction
Benzyl alcohol
48. (a) Linseed oil has highest percentage of unsaturation & hence highest number of moles of hydrogen
can be added to it.
49. (a) Glycerol is a component of lipids.
50. (c) The rearrangement of phenolic esters to form o – or p-hydroxyketone or a mixture of both in
presence of Lewis acid is called Fries rearrangement.
O O
O–C–R AlCl−
3 C
O+ R O – AlCl−
3
AlCl3−
𝑅 − 𝐶 ≡ 𝑂+
OH OAlCl2
H2O – HCl
R–C=O R–C=O
51. (a)
52. (a) H OH
(1) O3 CHO OH– C=O
(2) Zn, H2O CHO aldol condensation CHO
CHO
(E) Δ
CHO
(F)
53. (b) Both carbanions (formed in presence of base) & enol form (formed in presence of an acid) act as
nucleophiles & hence add on the carbonyl group of aldehydes & ketones to give aldols.
54. (c) Reactivity of aldehydes & ketones are mainly governed by two factors:
(i) Inductive effect:
The reactivity of the carbonyl group towards the addition reactions depends upon the magnitude of
the positive charge on the carbonyl carbon atom. Hence, any substituent that increases the positive
charge on the carbonyl carbon must increase its reactivity towards addition reactions.
The introduction of negative group (– I effect) increases the reactivity while introduction of alkyl
group (+I effect) decreases the reactivity, therefore, greater the number of alkyl groups attached to
the carbonyl group hence, lower is its reactivity towards nucleophilic addition reactions.
Thus, the following decreasing order of reactivity is observed:
H H3C H3C H5C2 H5C2
C=O > C=O > C=O > C=O C=O
H H H3C H3C H5C2
Formaldehyde Acetaldehyde Acetone Ethyl methyl ketone Diethyl ketone
(ii) Steric effect:
In formaldehyde, there is no alkyl group while in all other aldehydes there is one alkyl group, so
here the nucleophilic attack is relatively more easy, but in ketones there are two alkyl group attached
to carbonyl group & these cause hindrance to the attacking group. This factor is also called steric
hindrance (crowding). In other words, as the hindrance increases, the reactivity decreases
accordingly. Thus, the order of reactivity is : I > II > III > IV.
55. (b) Both Wolff-Kishner & Clemmensen reduction are used to convert > CO to > CH2.
The later is not suitable as it will also attack –OH group of ring.
IMPORTANT PRACTICE QUESTION SERIES FOR IIT-JEE EXAM – 1

1. On heating with aqueous alkali, chloroform yields:
a) HCHO b) HCOOH c) CH3 OH d) CO2 and H2 O
2. A keto ester (𝐴) with molecular formula C6 H10 O3 on treatment with NaOH + I2 does not give
iodoform but on boiling with dilute KOH gives a compound (𝐵) with molecular formulaC4 H5 O3 K
which upon acidification followed by heating undergoes decarboxylation to give acetone. The
keto ester (𝐴) is
a) CH3 COCH2 CH2 COOCH3 b) CH3 COCH2 COOC2 H5
c) CH3 CH2 OCH2 COOCH3 d) CH3 − COCH(CH3 )COOCH3
3. In the reaction, HCHO + NH3 → 𝑋, 𝑋 is
a) meta-formaldehyde b) para-formaldehyde c) urotropine d) None of these
4. CH3 CH2 − CHO →
Dil.
product
alkali
The product in the above reaction is
a) CH3 CH2 COOH b) CH3 CH2 − CH2 OH
c) d)
5. One mole of an organic compound requires 0.5 mole of oxygen to produce an acid. The
compound may be:
a) Alcohol b) Ether c) Ketone d) Aldehyde
6. Acetic acid reacts with PCl5 to form
a) CH2 ClCOOH b) CHCl2 COOH c) CH3 COCl d) CH3 COOCl
7. The calcium salt of the final oxidation product of ethanol on dry distillation gives:
a) Formaldehyde b) Acetaldehyde c) Acetone d) Formic acid
8. Coal-tar is obtained as by product during :
a) Destructive distillation of wood
b) Destructive distillation of coal
c) Destructive distillation of bones
d) None of the above
9. CH3 COOH and C6 H5 COOH can be distinguished by:
a) Flame test b) Solubility in water c) Physical state d) All of these
10.
a) b) c) d)
11. Methylene chloride on hydrolysis yields:

a) HCHO b) CH3 CHO c) CH3 COCl d) None of these
12.
Product is
a) b) c) d)
13. Which of the following compounds does not have a carboxyl group?
a) Methanoic acid b) Ethanoic acid c) Picric acid d) Benzoic acid
14. 2,4-dichlorophenoxy acetic acid is used as a:
a) Fungicide b) Insecticide c) Herbicide d) Moth repellent
15. Which one of the following is reduced with zinc and hydrochloric acid to give the corresponding
hydrocarbon?
a) Ethyl acetate b) Acetic acid c) Acetamide d) Butan-2-one
16. 3-pentanol on reaction with aluminium tertiary butoxide in the presence of acetone gives
a) 3-pentanal b) 2-pentanal c) 3-pentanone d) 2-pentanone
17. Bakelite is obtained from phenol by reacting with:
a) HCHO b) (CH2 OH)2 c) CH3 CHO d) CH3 COCH3
18. The silver salt of a fatty acid on refluxing with an alkyl halide gives an
a) Acid b) Ester c) Ether d) Amine
19. In the reaction, 𝑃 is:
a) CH3 COCHO b) CH3 COOCH3 c) CH3 COCH2 OH d) None of these

20.
Product is
a) b)
c) d)
21. Which will give Hofmann bromamide reaction?

d) All of these
a) b) CH3 CONH2 c) H2 NCONH2
22. Distillation involves all the following processes except:

a) Change of state b) Boiling c) Condensation d) Evaporation
23.
[𝐴]and [𝐵] are
a) b)
c) d)
24. The reaction,

CH3 CHO+ H2 N—NH2 ⟶CH3 CH=N∙NH2 is:
a) Elimination b) Addition c) Addition-elimination d) None of these
25. Which of the following would undergo aldol condensation?

d) HCHO
a) CCl3 CHO b) c) CH3 CH2 CHO
26. Acetalsehyde reacts with:

a) Only nucleophiles
b) Both electrophiles and nucleophiles
c) Only electrophiles
d) Only free radicals
27.
This reaction is called

a) The Stevens reaction b) The carbonylation reactionc
c) The Koch reaction d) Oxidation
28. Which of the following statement is correct?
a) Acidity increases with increase in carbon atoms in carboxylic acids.
b) Solubility of carboxylic acid increases with increase in carbon atoms.
c) Boiling points of acids are higher than corresponding alcohols.
d) None of the above.
29. The best reagent to convert pent-3-en-2-ol into pent-3-en-2-one is
a) Pyridinium chloro-chromate b) Chromic anhydride in glacial acetic acid
c) Acidic dichromate d) Acidic permanganate
30. The catalyst used in Rosenmund reaction is
a) Zn/Hg b) Pd/BaSO4 c) Raney Ni d) Na in ethanol
31. Claisen condensation is not given by
a) b)
c) d)
32. Which of the following is a flavouring agent called ‘oil of winter green’?
a) Olive oil b) Vinegar c) Methyl acetate d) Methyl salicylate
33. The following reaction is known by the name of:
a) Stephen’s reduction
b) Rosenmund’s reaction
c) Cannizzaro’s reaction
d) None of these
34. The enol form of acetone, after treatment with D2 O gives
a) b) c) d)
35. CH COOH NH 3∆
→ →?
3
The product of the reaction is isomeric with
d) All of these
a) b) CH3 CH = NHO c) HCONH − CH3
36. The acid formed when propyl magnesium bromide is treated with CO2 is:
a) C3 H7 COOH b) C2 H5 COOH c) Both (a) and (b) d) None of these
37. Tamarind contains
a) (+) tartaric acid b) (−) tartaric acid c) ± tartaric acid d) None of the above
38. The splitting of an ester by an alcohol is known as:
a) Acidolysis b) Alcoholysis c) Ammonolysis d) Hydrolysis
39. The product formed when hydroxylamine condenses with a carbonyl compound is called
a) Hydrazide b) Oxime c) Hydrazine d) Hydrazone
40. ΦCHO undergoes Claisen condensation with another aldehyde to give cinnamaldehyde. The
aldehyde is
a) Formaldehyde b) Acetaldehyde
c) Crotonaldehyde d) Propanaldehyde
41. Two mole of acetic acid are heated with P2 O5. The product formed is:
a) 2 mole of ethyl alcohol
b) Formic anhydride
c) Acetic anhydride
d) 2 mole of methyl cyanide
42. The nitrogen content in the proteins can be quantitatively estimated by:
a) Carius method
b) Kjeldahl’s method
c) Victor Meyer’s method
d) Rast method
43. Correct order of reducing power of the following carbonyl compounds
a) HCHO > 𝐶H3 COCH3 > 𝜙𝐶𝐻𝑂 b) CH3 COCH3 > 𝜙𝐶𝐻𝑂 > 𝐻𝐶𝐻𝑂
c) HCHO > ϕCHO > 𝐶H3 COCH3 d) CH3 COCH3 > 𝐻𝐶𝐻𝑂 > ϕCHO
44. Cyanohydrin of which of the following forms lactic acid?
a) HCHO b) CH3 COCH3 c) CH3 CHO d) CH3 CH2 CHO
45. Ethyl acetate on reaction with a Grignard reagent gives,
a) Alcohol b) Aldehyde c) Acid d) Ketone
46. Acetaldehyde reacts with HCN followed by hydrolysis forms a compound which shows:
a) Optical isomerism
b) Geometrical isomerism
c) Metamerism
d) Tautomerism
47. Carboxylic acids dissolve in 𝑎𝑞. NaOH because the acids undergo:
a) Protonation b) Deprotonation c) Carboxylation d) Decarboxylation
48. Which of the acids cannot be prepared by Grignard reagent?
a) Acetic acid b) Succinic acid c) Formic acid d) All of these
49. Compound 𝐴 when treated with ethyl magnesim iodide in dry ether forms an addition
compound which on hydrolysis form compound 𝐵. The compound 𝐵 on oxidation form 3-
pentanone. Hence, the compound 𝐴 and 𝐵 are
a) Propanol, 3-pentanol b) Pentanol, 3-pentanol c) Ethanal, pentanal d) Acetone, 3-pentanol
50. Suggest appropriate structures for the missing final compound. (The number of carbon atom
remains the same throughout the reaction.)
a) b) c) d)
51. Lactic acid on heating with conc. H2 SO4 gives

a) Acetic acid b) Formic acid c) Acrylic acid d) Propionic acid
52. Urea can be detected by
a) Benedict test b) Molisch test c) Ninhydrine test d) Biurate test
53. Which of the following does not give brick red precipitate with Fehling’s solution?
a) Acetaldehyde b) Formalin c) D-glucose d) Acetone
54. Which of the following statements is wrong?
a) Formic acid is stronger than acetic acid
b) 𝑜-bromobenzoic acid is weaker than 𝑜-chlorobenzoic acid
c) Lactic acid does not answer the silver mirror test
d) Benzaldehyde does not reduce Fehling’s solution
55. Pick out the reaction in which formic and acetic acid differs from each other:
a) Sodium replaces hydrogen from the compound
b) Forms esters with alcohols
c) Reduces solution of ammoniacal silver nitrate or Fehling’s solution of dil. acid KMnO4
d) Turns red litmus blue
56. An organic substance from its aqueous solution can be separated by:
a) Solvent extraction b) Steam distillation c) Distillation d) Fractional distillation
57. The strongest acid amongst the following compounds is
a) CH3 COOH b) HCOOH c) CH3 CH2 CH(Cl)CO2 H d) ClCH2 CH2 CH2 COOH
58. What is obtained what acetyl chloride is heated with benzene in presence of anhydrous AlCl3
a) Acetyl benzoic acid b) Anisol c) Acetonephenone d) Chlolorobenzene
59. Reaction of formaldehyde and ammonia gives
a) Hexamethylene tetramine b) Bakelite
c) Urea d) Triethylene tetramine
60. 4-methyl benzene sulphonic acid reacts with sodium acetate to give
a) b) c) d)
61. An acyl halide is formed when PCl5 reacts with an:

a) Acid b) Alcohol c) Amine d) Ester
62. Generally it is more difficult to purify organic compounds than inorganic compounds because:
a) They are very unstable
b) Their m. p. and b. p. are low
c) Organic compounds have low solubility
d) Physical constants of organic compounds and the impurities associated with them are very
close to each other
63. The acetophenone can be converted to ethylbenzene by reaction with
a) LiAlH4 b) H2 NOH c) Pd⁄BaSO4 − H2 d) Zn − Hg/HCl
64. When propionic acid is treated with aqueous sodium bicarbonate, CO2 is liberated. The C from
CO2 comes from
a) Methyl group b) Carboxylic acid group
c) Methylene group d) Bicarbonate
65. Boiling points of carboxylic acid are:
a) Lower than corresponding alcohols
b) Higher than corresponding alcohols
c) Equal to that of corresponding alcohols
d) None of the above
66. The —COOH group in a carboxylic acid can be replaced by ‘H’ by heating the acid with:
a) Zn with HCl
b) H2 in presence of nickel
c) Sodalime
d) Bromine and concentrated aqueous alkali
67. The product obtained in the reaction
a) b)
d) There is no reaction
c)
68. Which of the following would produce secondary alcohol?
a)
b)
c)
d)
69. Which factor/s will increase the reactivity of >C=O group?

I. Presence of a group with positive inductive effect.
II. Presence of a group with negative inductive effect.
III. Presence of large alkyl group.
a) Only (i) b) Only (ii) c) (i)and(iii) d) (ii)and (iii)
70.
This reaction is called the

a) Cannizaro reaction b) Schrodinger reaction
c) Hell-Volhard-Zelinsky reaction d) Reimer-Tiemann reaction
71. (CH3 )2 C=CHCOCH3 can be oxidised to (CH3 )2 C=CHCOOH by:
a) Cu at 300℃ b) KMnO4 c) Chromic acid d) NaOI
72. The correct order of decreasing boiling points of CH3 CONH2(𝐴), CH3 COCl (𝐵), CH3 COOH (𝐶) and
(CH3 CO)2 O (D) is:
a) 𝐴 > 𝐷 > 𝐶 > 𝐵 b) 𝐴 > 𝐵 > 𝐶 > 𝐷 c) 𝐷 > 𝐶 > 𝐵 > 𝐴 d) None of these
73. Rate of reaction,
is fastest when Z is
a) Cl b) NH2 c) OC2 H5 d) OCOCH3
74. Which is useful for separating benzoic acid from a mixture of benzoic acid and methyl benzoate?
a) NaHCO3 (𝑎𝑞. ) b) Dil. HCl c) Dil. H2 SO4 d) Dil. HNO3
75. The compound X, in the reaction is
CH3 CHO Hydrolysis
𝑋→ 𝑌→ Mg(OH)I + CH3 COOH
a) CH3 CHO b) CO2 c) (CH3 )2 CO d) HCHO
76. Which of the following does not undergo polymerization?
a) CH3 CHO b) HCHO c) CH3 COCH3 d) None of these
77. The reaction ,
CCl4
𝑅COOAg + Br2 → 𝑅Br + AgBr + CO2 is called:
a) HVZ reaction b) Hunsdiecker reaction c) Hofmann’s reaction d) Carbylamine reaction
78. Methyl ketones are characterised through:
a) The Tollen’s reagent
b) The iodoform test
c) The Schiff’s test
d) The Benedict’s reagent
79. An organic compound X contains Y and Z impurities. Their solubility differs slightly. They may
be separated by:
a) Simple crystallization
b) Fractional crystallization
c) Sublimation
d) Fractional distillation
80. Which of the following reactants on reaction with conc. NaOH followed by acidification gives
following lactone as the product
a) b) c) d)
81. An ester (A) with molecular formula C9 H10 O2 was treated with excess of CH3 MgBr and the
complex so formed was treated with 𝐻2 𝑆𝑂4 to give an olefin (B). Ozonolysis of (B) gave a ketone
with molecular formulC8 H8 O which shows positive iodoform test. The structure of (A) is
a) C6 H5 COOC2 H5 b) C6 H5 COOC6 H5
c) C6 H5 COOCH3 d) p-H3 CO − C6 H4 − COCH3
82. Acetone reacts with Grignard reagent to form
a) 3° alcohol b) 2°alcohol c) Ether d) No reaction
83. When petroleum is heated gradually, first batch of vapours evolved will be rich in:
a) Kerosene b) Petroleum ether c) Diesel d) Lubrication oil
84. Decarboxylation of malonic acid gives
a) CH4 b) CH3 COOH c) Both (a) and (b) d) None of these
85. What is the product in the reaction
NaOH2 /HCl
CH3 CONH2 → 𝑋?
+
a) CH3 COOH b) c) CH3 NH2 d) CH3 CHO
CH3 CONH3 Cl−
86. Which of the following substances cannot be used for the replacement of —OH group in organic
compounds by Cl?
a) S2 Cl2 b) SOCl2 c) PCl3 d) PCl5
87. Acetyl nitrate is formed when acetic anhydride reacts with
a) Nitrogen pentoxide b) Nitric acid c) Nitrous acid d) Potassium nitrate
88. Which one is not prepared from tartaric acid?
a) Tartar emetic b) Fenton’s reagent c) Fehling’s solution d) Rochelle salt
89. The reagent used in Clemmensen’s reduction is
a) Conc. H2 SO4 b) Zn−Hg /conc.HCl c) aq. KOH d) alc.KOH
90. ∗ H +
In the reaction, C6 H5 COOH + CH3 H → Ester + water
O
Isotopically labeled oxygen (O18 ) is present
a) b) O18 is present with ester
in water
c) O18 shifts from acid to alcohol d) No reaction takes place
91. The technique of gas chromatography is suitable for compounds which are:
a) Liquids
b) Highly volatile
c) Soluble in water
d) Vaporise without decomposition
92. There are several criteria of purity of organic compounds. Which is considered to be the best?
a) Melting point
b) Mixed melting point
c) Colour
d) Microscopic examination
93. ϕCHO + NH3 →? Product is
a) b) ϕ CH = NH c) d)
94. The ease of hydrolysis with an alkali in the compounds

CH3 COClCH3 CO − O − COCH3
I II
CH3 COOC2 H5 CH3 CONH2
III IV
Is of the order
a) I>II>III>IV b) IV>III>II>I c) I>II>IV>III d) II>I>IV>III
95. What is the formula of adipic acid?
a) COOH(CH2 )4 COOH b) CH2 (COOH)CH2 COOHc) COOH(CH2 )3 COOH d) None of the above
96. CH3 CHO and C6 H5 CH2 CHO can be distinguished chemically by:
a) Tollen’s reagent test b) Fehling solution test c) Benedict test d) Iodoform test
97. Acrolein on complete reduction gives:
a) Allyl alcohol b) Propanol c) Propanal d) None of these
98. Identify the starting material of the following reaction
a) b) c) d)
99. Which one of the following is not a fatty acid?

a) Stearic acid b) Palmitic acid c) Oleic acid d) Phenyl acetic acid
100.CH CN → 𝐴 →
H 2 O diazomethane
𝐵
3
𝐴 and 𝐵 are
a) Acetamide, N-methyl acetamide b) Acetic acid, ethyl ethanoate
c) Acetic acid, methyl acetate d) Acetamide, acetone
IMPORTANT PRACTICE QUESTION SERIES FOR IIT-JEE EXAM – 1 (ANSWERS)
1) b 2) b 3) c 4) d
5) d 6) c 7) c 8) b
9) d 10) b 11) a 12) b
13) c 14) c 15) d 16) c
17) a 18) b 19) a 20) c
21) d 22) d 23) b 24) c
25) c 26) b 27) c 28) c
29) b 30) b 31) a 32) d
33) b 34) a 35) d 36) a
37) a 38) b 39) b 40) b
41) c 42) b 43) c 44) c
45) d 46) a 47) b 48) c
49) a 50) a 51) c 52) d
53) d 54) c 55) c 56) a
57) c 58) c 59) a 60) a
61) a 62) d 63) d 64) d
65) b 66) c 67) b 68) b
69) b 70) c 71) d 72) a
73) a 74) a 75) b 76) c
77) b 78) b 79) b 80) c
81) a 82) b 83) b 84) b
85) a 86) a 87) a 88) b
89) b 90) b 91) d 92) b
93) c 94) a 95) a 96) d
97) b 98) c 99) d 100) c
1 (b)
HOH
CHCl3 → CH(OH)3 ⟶ HCOOH
2 (b)
The keto-ester (𝐴) does not give haloform reaction inspite of the presence of CH3 CO −
group in it. The reason is the presence of active methylene group (𝑖𝑒, −CH2 −), which
prevents the conversion of CH3 CO − to C𝑋3 CO −
3 (c)
Formaldehyde reacts with NH3 to form urotropine which is used as medicine to cure
urinary infections.
6HCHO + 4NH3 → (CH2 )6 N4
Formaldehyde ammonia hexamethylene
tetramine urotropine
4 (d)
Aldehydes and ketones having α-hydorgen atom undergo aldol condensation in presence of
dilute base
5 (d)
[O]
CH3 CHO → CH3 COOH
6 (c)
Acetic acid reacts with PCl5 to form acetyl chloride.
CH3 COOH + PCl5 ⟶ CH3 COCl + POCl3 + HCl
acetic acid acetyl chloride
9 (d)
C6 H5 COOH is solid, less soluble in water and burn with smoky flame.
11 (a)
HOH
CH2 Cl2 → HCHO
12 (b)
When aromatic carboxylic acids are subjected to Birch reduction (𝑖𝑒, Na or K in NH3 and an
alcohol), 1, 4-additional of hydrogen takes place and 1, 4-cyclohexadiene carboxylic acids
are produced
13 (c)
Picric acid is 2,4,6-trinitrophenol.
14 (c)
Herbicides are the substances that kills plants or inhibit their growth. Selective herbicides
affect only particular plant types, making it possible to attack weeds growing among
cultivated plants.
18 (b)
The silver salt of fatty acid on refluxing with an alkyl halide, give an ester.
∆
𝑅COOAg + 𝑅 ′ Cl → 𝑅COO𝑅′ + AgCl
ester
19 (a)
SeO2
CH3 COCH3 → CH3 CO ∙ CHO + Se + H2 O
20 (c)
1, 2 diketone undergoes rearrangement to α-hydroxy carboxylic acid in presence of base.
This reaction is known as benzilic acid rearrangement
23 (b)
In the given compound, carbonyl group is reduced to – OH group by NaBH4 and it does not
affect double bond. The another is hydroboration-oxidation reaction, in which one water
molecule is added to double bond
26 (b)
Na/C2 H5 OH
CH3 CHO → CH3 CH2 OH
28 (c)
1. Acidity decreases with increase in number of carbon atoms in carboxylic acid.
2. Solubility of carboxylic acid decrease with increase in number of carbon atoms.

Higher acids are insoluble in H2 O.
3. Boiling points of acids are higher than corresponding alcohols due to greater extent
of hydrogen bonding.
∴ (c) is correct answer.
29 (b)
Only suitable reagent is chromic anhydride in glacial acetic acid. Other will also effect (C=C)
bond.
30 (b)
In the Rosenmund’s reaction the acid chlorides are converted to corresponding aldehydes
by catalytic reaction. This reaction is carried in the presence of palladium deposited over
barium, sulphate.
O
||
Pd,BaSO4
CH3 − C − Cl + H2 → CH3 CHO + HCl
Acetyl chloride acetaldehyde
31 (a)
In Claisen condensation aromatic aldehydes having no 𝛼 −hydrogen atom react with
aldehyde, ketones or esters having 𝛼 −hydrogen atom in presence of dilute alkali to form
𝛼, 𝛽 −unsaturated carbonyl compound. 𝑒. 𝑔. ,
As it does not contain𝛼 −hydrogen atom.

32 (d)
Methyl salicylate an ester has smell of oil of winter green and used as medicine in iodex; the
pain reliever of strains in muscles.
33 (b)
Rosenmund’s reaction involves reduction of acid chlorides to aldehydes by the action of H2
in presence of Pd/BaSO4. BaSO4 acts as poison for Pd and prevents further reduction of
aldehydes to alcohol.
34 (a)
After treatment with D2 O, the H + ion of − OH group is replaced by D+ ion, because of being
more reactive than deuterium
D2 O
CH3 − C = CH2 → CH3 − C = CH2
||
OHOD
35 (d)
NH3 ∆
CH3 COOH → CH3 COONH4 → CH3 CONH2
−H2 O
acetic acid ammonium acetate acetamide

The isomers of CH3 CONH2 is
NH2 CH2 CHO
CH3 − CH = NOH
H − CONH − CH3
38 (b)
CH3 COOCH3 + C2 H5 OH ⟶ CH3 COOC2 H5 + CH3 OH
40 (b)
Cinnamaldehyde is prepared by the Claisen reaction between benzaldehyde and
acetaldehyde
NaOH
C6 H5 CHO + CH3 CHO → C6 H5 OH = CHCHO + H2 O
cinnamaldehyde
41 (c)
P 2 O5
2CH3 COOH → (CH3 CO)2 O + H2 O
P2 O5 acts as dehydrating agent.
44 (c)
𝐻2 𝑂/𝐻 +
Carbonyl compound + HCN →cyanohydrin→ hydroxy acid
Latic acid is
∴ Cyanohydrin of acetaldehyde forms lactic acid.

46 (a)
Carbon is asymmetric.
48 (c)
Carboxylic acids are prepared by reaction of Grignard reagent with CO2 .
∵ Formic acid (HCOOH)has only one carbon atom
∴ Formic acid cannot be prepared from Grignard reagent.
O
||
HOH
𝑅Mg𝑋 + CO2 → 𝑅 − C − OMg𝑋 → 𝑅COOH
Grignard reagent acid
51 (c)
Lactic acid on heatng with conc. H2 SO4 to give acrylic acid
52 (d)
When urea is heated it gives the biurate which give violet colour with CuSO4 and NaOH.
56 (a)
An immiscible solvent is added to the solution. Some of the solute passes in this solvent
𝐶1
maintaining Nernst distribution law 𝐾 = 𝐶2
, where 𝐶1 and 𝐶2 are concentration of solute in
two phases.
57 (c)
Electron withdrawing group (-I effect) stabilizes the anion, and thus increases acidic nature.
Thus (c), (d)> (a), (b) acidic
Farther the electron withdrawing group from the –COOH group, its effect in increasing acid
strength decreases thus (c) with Cl at 𝛼 −position is stronger than (d) with Cl at
𝛾 −position.
58 (c)
When, benzene is heated with acetyl chloride, in presence of anhydrous AlCl3 , electrophilic
substitution takes place and acetophenone is obtained. The reaction is known as Friedel-
Craft acylation.
59 (a)
: 6HCHO + 4NH3 → (CH2 )6 N4 + 6H2 O
hexamethylene
tetramine
60 (a)
4-methyl benzene sulphonic acid is stronger than acetic acid thus, it will release acetic acid
from sodium acetate.
61 (a)
PCl5
𝑅COOH → 𝑅COCl.
63 (d)
Clemmensen reduction can be used to convert acetophenone into ethyl benzene as it
reduce>C=O group into > 𝐶H2
64 (d)
Carboxylic acids reacts with weaker bases such as bicarbonates producingCO2 . The CO2
evolved comes from NaHCO3 , not from carboxylic group as shown below :
67 (b)
𝐼𝑠𝑜-propyl magnesium bromide reduces di-𝑖𝑠𝑜-propyl ketone to secondary alcohol.
However, only – H + ion adds to ketone in spite of bulky alkyl group due to steric hinderance
68 (b)
In (a) 𝑡-alcohol, in (c) initially 𝑠-alcohol converting to ether. In (d) 𝑝-alcohol.
69 (b)
Carbonyl carbon becomes more reactive towards nucleophilic addition depending upon the
magnitude of the positive charge on the carbonyl carbon atom. The introduction of negative
inductive effect showing group (-I effect) increases the reactivity while introduction of alkyl
group (+I effect) decreases the reactivity. So, large alkyl group decreases the reactivity of >
C=O.
71 (d)
Unsaturated ketones may be converted to unsaturated acids by sodium hypohalite, 𝑖. 𝑒.,
NaOCl, NaOI, etc.
72 (a)
The b.p. are CH3 CONH2>(CH3 CO)2 O>CH3 COOH>CH3 COCl
222℃ 139℃ 116℃52℃
74 (a)
Former reacts with 𝑎𝑞. NaHCO3 .
75 (b)
CO2 adds to Grignard’s reagent to yield acids.
CH3 MgI H.OH
CO2 → CH3 COOMgI → CH3 COOH + Mg(OH)I
78 (b)
All methyl ketones give iodoform test.
80 (c)
This is an example of Cannizaro reaction
82 (b)
Grignard reagent =CH3 MgX
Clemmensen reduction=Zn − Hg⁄Conc HCl
Rosenmund reduction=H2 ⁄Pd − BaSO4
Wolff-Kishner reduction=N2 H4⁄KOH /CH2 OH
|
CH2 OH
84 (b)
Decarboxylation of malonic acid give acetic acid and CO2
85 (a)
Amides, on treating with HNO2 , give acids.
NaNO2 /HCl
CH3 CONH2 → CH3 COOH + N2 + H2 O
(HNO2 )
acetic acid
87 (a)
Acetyl nitrate is formed, when acetic anhydride reacts with nitrogen pentoxide.
88 (b)
Fenton’s reagent is FeSO4 + H2 O2 .
89 (b)
In Clemmensen’s reduction
Zn − Hg⁄conc . HCl is used
This method is used to convert carbonyl compound into alkane.

93 (c)
Bezaldehyde does not yield a simple addition product with ammonia, but forms a complex
product, hydrobenzamide (90%)
94 (a)
The order of the acidic characters of acid derivative or their ease of hydrolysis with alkali is
given below :
CH3 COCl > CH3 CO − O − COCH3 > 𝐶H3 COOC2 H5 > 𝐶H3 CONH2
95 (a)
It is adipic acid.
97 (b)
Reduction
CH2 =CHCHO→ CH3 CH2 CH2 OH
99 (d)
Stearic acid (C17 H35 COOH), palmitic acid (C15 H31 COOH) and oleic acid (C17 H33 COOH; an
unsaturated acid) are fatty acids.

Aldehyde Ketone and Carboxylic Acid

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Aldehyde Ketone and Carboxylic Acid

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• AND CARBOXYLIC ACIDS

1 IUPAC NOMENCLATURE OF ALDEHYDES AND KETONES

IUPAC name: Acetophenone Butyrophenone Benzophenone

[Note: 3° alcohol on similar reaction undergoes dehydration to give alkene]

(RCO2)2Ca ⎯⎯ ⎯ ⎯ ⎯ ⎯→ R2CO + CaCO3

4. USING ACID CHLORIDE:

R 2 CuLi + 2RCOCl ⎯→ 2RCOR + CuCl + LiCl

2O2N C−Cl + (CH3)2CuLi 2O2N C−CH3 + CuCl + LiCl

CH3O−C−CH2CH2−C−Cl + (CH3)2CuLi CH3O−C−CH2CH2−C−CH3 + CuCl + LiCl

p−nitro toluene p−nitro benzaldehyde

H Wolff−Kishner reduction for

H3O (Partial hydrolysis)

Product (D) is optically active.

(I) (II) (III)

H2N−Z Product structure Name of the product

H2N−NH2, Hydrazine C N−NH2

H2N−NHPh, Phenyl hydrazine C N−NHPh

With hydrazine, hydrazones and azines are formed.

(IV) REACTION WITH PCl5:

(VIII) WITTIG REACTION:

(IX) CANNIZZARO REACTION:

⎯→ PhCH2OH + PhCO 2−Na +

NO2 NO2 NO2

R dry HCl R O− IMPE R OH ROH R OR

Step II: CH3−C−CH3 + X Slow

Step III: CH3−C=CH2 + Br2 Fast

O O− CH3 OH CH3 CH3

Ethyl pimelate on treatment with sodium ethoxide gives 2−carbethoxy cyclohexanone.

(XV) PERKIN REACTION:

Step III: O O− MeCO2

CH3 CH3 CH3 CH3 CH3

CH3 CH3 CH3

CH3 CH3 CH3 CH3 CH3 CH3

(a) O2N CHO (b) H3C CHO

(c) HO CHO (d) H2N CHO

(, −unsaturated aldehyde)

Multiple Choice Questions:

The product ‘A’ is

This reaction is called

– Mg – Br is treated with ethyl acetate & then hydrolysed.

– MgBr (i) CH3CN, (ii) H3O+ A

9. The following conversion

16. Predict the products in the given reaction.

20. What is true for acetophenone?

CHCl3 + NaOH Conc. NaOH

30. Claisen condensation is not given by

35. The oxidation of benzene by V2O5 in the presence of air produces

40. In a set of reactions, acetic acid yielded a product S.

(d) None of these. (BHU)

ANSWERS OF MCQ QUESTIONS

– 𝑁2+ 𝐶𝑙 − + H2O – OH + N2 + HCl

CH3 – C = N – MgBr CH3 – C = O

3I2 / NaOH + CHI3 + HI

(– COOH group is absent)

46. (c) OH COOH

IMPORTANT PRACTICE QUESTION SERIES FOR IIT-JEE EXAM – 1

11. Methylene chloride on hydrolysis yields:

a) CH3 COCHO b) CH3 COOCH3 c) CH3 COCH2 OH d) None of these

21. Which will give Hofmann bromamide reaction?

22. Distillation involves all the following processes except:

[𝐴]and [𝐵] are

24. The reaction,