ALDEHYDES AND

KETONES
This Chapter Aldehydes and Ketones is taken from our:

ISBN : 9789384089108
14 .1 Nomenclature and Isomerism 14 .6 Special Reactions Given by Aromatic Aldehydes and
14 .2 Structure of the Carbonyl Group (Cf. carbon-carbon double Ketones
bond) 14 .7 Analysis of Aldehydes and Ketones
14 .3 Preparation of Aldehydes and Ketones 14 .8 Illustrative Examples
14 .4 Physical Properties EXERCISE
14 .5 Chemical Properties SOLUTIONS

14.1 Nomenclature and Isomerism

Aldehydes and ketones are the compounds containing a carbonyl group, > C=O. They have the same general
formula, CnH2nO. The general structure of aldehydes is RCHO, except for formaldehyde where R=H ; and that of ketones
is RRCO ; the groups R and R may be aliphatic, aromatic or alicyclic.
The common names of aldehydes are derived from the names of the corresponding carboxylic acids by replacing -
ic acid by -aldehyde. In IUPAC system, aliphatic aldehydes are named as alkanals.
O O O O
|| || || ||
H C H CH 3CH 2CH 2C H ClCH 2 CH 2 C H C 6 H 5 CH 2 C H
Methanal Butanal 3 -Chloropropanal Phenylethanal
(Formaldehyde) ( n -Butyraldehyde) (b -Chloropropionaldehyde) (Phenylacetaldehyde)
Aldehydes in which the CHO group is attached to a ring system are named as substitutively by adding the
suffix carbaldehyde.

CHO CHO
CHO

Benzenecarbaldehyde Cyclohexane- 2-Naphthalenecarbaldehyde

(Common name : Benzaldehyde) carbaldehyde

Common name for ketones are obtained simply by adding the word ketone to the name of the two alkyl groups.
In IUPAC system, these are named as alkanones.
 672

O
||
CH 3 CH2 CCH 3 CH 3 COCH 2 CH=CH 2 C6 H 5 CH 2 COCH 3
Butanone 4-Penten-2-one 1-Phenyl-2-propanone
(Ethyl methyl ketone) (Allyl methyl ketone) (Benzyl methyl ketone)
A ketone in which the carboxyl group is attached to a benzene ring is named as a - phenone.
O

C
COCH3 COCH2CH2CH3 COC6H5
NO2

CH3
Acetophenone n-Butyrophenone Benzophenone 3-Nitro-4 -methylbenzophenone

When it is necessary to name the CHO and COR groups as prefix, these are named as methanoyl (or formyl)
and alkanoyl (or acyl) groups respectively.
COCH3

CHO
COOH

SO3H
2-Methanoylbenzoic acid 4-Ethanoylbenzenesulphonic acid
(o -Formylbenzoic acid) (p-Acetylbenzenesulphonic acid)

Aldehydes show chain and functional isomerism.

Chain isomers. CH 3 CH2 CH 2 CHO (CH 3 )2 CHCHO
n -Butanal 2-Methylpropanal (iso-Butanal)
Functional isomers.
CH3CH2CHO CH3COCH3 CH2 = CHCH2OH CH 3CHCH2 CH2 = CH.O.CH3

O
Propanal Acetone Allyl alcohol a, b-Propylene oxide Methyl vinyl ether
Ketones show chain, functional and metamerism. Examples of functional isomerism is given above in aldehydes.
O O
|| ||
Chain isomers. CH 3 CH2 CH 2 C CH 3 (CH 3 ) 2 CH C CH 3
Methyl propyl ketone Methyl isopropyl ketone

O O
|| ||
Metamers. CH 3 CH2 CH 2 C CH 3 CH 3CH 2 C CH 2CH 3
Methyl propyl ketone Diethyl ketone

1. Give IUPAC names of the following compounds :

CH3O
CHO
(a) OHC CHO (b) (c) HO CHO (d) CH2COCH2
C6H5

(e) CH.CHO (f) CHO (g) C6H5CH=CHCOC 6H5

CHO
2. Write down the structural formulas for (a) the seven carbonyl compounds of formula C5H10O, (b) the five carbonyl compounds of
formula C8H8O having a benzene ring.
 673

14.2 Structure of the Carbonyl Group (Cf. carbon-carbon double bond)

Like the carbon-carbon double bond of alkenes, the carbon-oxygen double bond of the carbonyl group is composed
of one s and one p bond.
In the carbonyl group, carbon atom is in a state of sp2 hybridisation. The CO s bond is
R 120
produced by overlap of an sp2 orbital of carbon with a p orbital of oxygen. On the other hand, the C
O p bond is formed by the sideways overlap of p orbitals of carbon and oxygen. The remaining two sp3 C=O
120
orbitals of carbon form s bonds with the s orbital of hydrogen or sp2 orbital of carbon of the alkyl group.
Now since the three s bonds of the carbonyl carbon utilize sp2 orbitals, they lie in one plane and are R 120
120 apart (similarity with C = C).
However, it is important to note that the carbon-oxygen double bond is different from carbon-carbon double
bond. Due to greater electronegativity of oxygen atom, the p electron cloud is attracted towards oxygen. Consequently,
oxygen attains a partial negative charge and carbon a partial positive charge. This polar nature of the carbonyl group
causes intermolecular attraction in aldehydes or ketones and hence accounts for their higher boiling points than that of
hydrocarbons and ethers of comparable molecular weight. Moreover, polar nature of the carbonyl group also explains the
dipole moment in aldehyde and ketones. However, the high values of dipole moments (2.3 2.8 D) of aldehydes and
ketones cant be accounted for only by inductive effect ; this can be accounted for if carbonyl group is a resonance hybrid
of the two structures.
+
d d +
C = O: CO :

: :
C=O

:
Polarity due to inductive effect Polarity due to resonance

Other important difference in carbon-oxygen and carbon-carbon double bonds lies in the fact that the carbonyl
group undergoes nucleophilic addition reactions, while olefinic bond undergoes electrophilic addition reactions.

14.3 Preparation of Aldehydes and Ketones

1. By oxidation of primary and secondary alcohols. Discussed in the chapter on Monohydric Alcohols.
pyridinium chlorochromate, CH 2 Cl 2
RCH2OH RCHO
OH PCC, CH2Cl2 H

1-Heptanol
Heptanal
O

OH CrO3 in glacial acetic acid

O

or K2Cr2 O7 + H2SO4

Cyclohexanol Cyclohexanone

Since ketones are oxidised with difficulty, so these can be easily prepared by oxidizing 2 alcohols with acidic
dichromate (difference from aldehyde preparation).
Recall that solution of chromic anhydride in pyridine is known as Saretts reagent, while solution of chromic
anhydride in water, acetone and sulphuric acid is known as Jones reagent.
Primary and secondary alcohols may also be oxidised to aldehyde and ketones respectivley by heating with
copper at about 250300C (dehydrogenation of alcohol).
Ketones can also be prepared by oxidizing 2 alcohols with aluminium tert-butoxide (Oppenauer oxidation).
R R
(tert-BuO)3Al
CHOH CO
R R

OH O
674

1. Can an aldehyde be prepared by oxidation of a 1 alcohol with acid dichromate ? If, yes mention the condition.

2. By reduction of acid chlorides, esters, and nitriles (only for aldehydes). Theoretically, we may think that
aldehydes can be prepared by reducing carboxylic acids with lithiumaluminium hydride (LiAlH4 or LAH).
However, LAH is a very powerful reducing agent and hence aldehydes formed as intermediate are very readily
further reduced to primary alcohols.
LiAlH 4 LiAlH 4
RCOOH [RCHO] RCH2OH
However, a modified version of the reaction is used for preparing aldehydes. For this,
(i) a derivative of a carboxylic acid, which is more easily reduced than the carboxylic acid itself is taken as a starting
material. Three such acid derivatives are acid chlorides, esters and nitriles ; which in turn are easily prepared
from carboxylic acids.
(ii) a less reactive aluminium hydride derivative than LiAlH4 is used. Two such derivatives are lithium tri-tert-
butoxyaluminium hydride (LBAH) and diisobutylaluminium hydride (DBAH).

OC(CH3)3
CH2CH(CH3)2
+
Li HAlOC(CH3)3
Al
OC(CH3)3 H CH2CH(CH3)2
Lithium tri-tert -butoxyaluminium hydride Diisobutylaluminium hydride

These two hydrides are less reactive than LiAlH4 as they are much more sterically hindered and, therefore, face
difficulty in transferring hydride ions. Reduction by these reagents is brought about by the transfer of a hydride
ion from the aluminium atom to the carbonyl carbon (in case of acid chlorides and esters) or the nitrile carbon (in
case of nitriles). Subsequent hydrolysis of the intermediate liberates the aldehyde.

O O Al (OCMe3)3 O
LiAlH (OCMe3)3 + H2O
(a) R C RCH Li RCH + LiCl + Al(OCMe3)3
ether, 78C
Cl Cl

(i) LiAlH (OBu-t )3

O2N COCl O2N CHO
(ii) H2O

Acid chlorides may also be reduced to aldehydes by catalytic hydrogenation (H2/Pd)

Pd/BaSO 4
RCOCl + H2 RCHO + HCl
over deactivated (by sulphur or quinoline) palladized barium sulphate or carbonate. (Rosenmund reduction).

Pd/BaSO 4
RCOCl + H2 RCHO
S or quinoline

Partial deactivation of the catalyst is necessary to check further reduction of the product aldehyde.

O OAl(iso-Bu)2
(iso-Bu)2AlH H2O
(b) CH3(CH2)10 C CH3(CH2)10 CH CH3(CH2)10CHO
hexane, 78C
OC2H5 OC2H5

NAl(iso-Bu)2
( iso - Bu)2 AlH |
| H2 O
(c) CH3CH=CHCH2CH2CN CH3CH=CHCH2CH2 CH CH3CH=CHCH2CH2CHO
hexane

Ketones cant be prepared by this method.

 675
3. By hydration of alkynes (Discussed in alkynes).

H 2SO 4 , Hg 2+
HC CH CH2 = CHOH CH3CHO

H 2SO 4 , Hg 2+
CH3CH2C CH CH3CH2COCH3
4. Hydroboration of alkynes (Discussed in alkynes). Hydroboration of terminal alkynes followed by oxidation of
the intermediate (vinylboranes) with alkaline hydrogen peroxide gives aldehydes.

BH3.THF H2O2/OH
CH3C CH [CH3CH = CH ]3 B CH3CH = CHOH CH3CH2CHO
Propyne Vinylborane Propanal

Similar reaction with non-terminal alkynes gives ketones

BH3.THF H2O2
CH3C CCH3 [CH3CH=C ]3 B
CH3CH = COH CH3CH2COCH3
OH
Butyne-2 Butanone-2
CH3 CH3

To get good yield of vinylboranes and hence aldehydes, sterically hindered alkylboranes should be used instead
of borane itself.
R 2 BH.THF 2 2 H O /OH -
CH 3C CH (CH3CH = CH)BR2 CH3CH = CHOH CH 3CH 2CHO

1. Write structures for A and B in the following reactions :

LBAH LAH
B CH3CH(CH3) COCl A
0 C

2. Prepare CH3CH2CH2CHO from (a) an ester, (b) a nitrile, and (c) an acid chloride.
3. Give an outline of the scheme for preparing 3-phenylpropanal from benzene and oxirane.
4. Use hydroboration method for preparing following aldehydes or ketones.
(a) Pentanal (b) Cyclohexanone (c) n-Butyl cyclopentyl ketone (d) Dicyclohexyl ketone.

5. From organometallic compounds.

(a) Aldehydes are obtained by the reaction of (i) Grignard reagent with hydrogen cyanide, or (ii) Grignard reagent
with alkyl formate in equimolar amounts. For details, consult chapter on Grignard reagents.

MgBr HC = NMgBr CHO

ether H2O
(i) HC N + + MgBrNH2

O O O
+
H3O
(ii) HCOC2 H5 + CH3MgBr HCOC2H5 CH3CH + C2H5O

CH3

(b) Ketones from Grignard reagents (Details discussed earlier).

R R
ether H2O
(i) RC N + R MgX RC = NMgX RC = O
A nitrile
676

O
(i) ether
CH3C N + MgBr CCH3
(ii ) H2O

Cyclohexyl methyl ketone

(i) ether
(ii) RCOCl + CH3MgBr + RCOCH3 + MgBrCl
(ii) H3O
An acid chloride

70C
(iii) (RCO)2O + CH 3MgBr RCOCH3 + RCOOMgBr
An acid anhydride

(i) ether
(iv) CH3COOC2H5 + C2H5MgBr
+ CH3COC2H5
(ii ) H3O
Ethyl ethanoate

(c) Ketones from organolithium compounds

(i) ether
CH3C N + CH3CH2CH2Li
+ CH3COCH2CH2CH3
(ii) H3O

Even though a nitrile has a triple bond, addition of the Grignard or lithium reagent takes place only once
because addition of second molecule of the reagent would place a double negative charge on the nitrogen.

R
RLi +
R Li 2 +
RC N RC = N Li RCN 2Li

R R

Alternatively, organolithium reagents react with carboxylic acids in the following way to form ketones.

O O O -Li+ OH O
|| || | - H2 O ||
LiOH R'Li
| H 3O +
R - C - OH R - C - O - Li +
R - C - O - Li +
R - C - OH R - C- R '
| |

R' R'

O-Li+
OH O
| | ||
- H O H 3O +
R - C - O - Li +
Or RCOOH + 2R 'Li R - C - OH 2
R - C- R '
| |

R' R'

(d) Ketones from lithium dialkylcuprates, also known as Gilman reagent (Organocopper compounds).

ether
R 2 CuLi + R COCl RCOR + RCu + LiCl
Lithium 78 C
dialkylcuprate

ether
(CH3)2CuLi + COCl COCH3 + CH3Cu + LiCl
78C

Cyclohexyl methyl ketone

Li CuI 2(CH3 )2 CHCOCl

n-C4H9Br n-C4H9Li (n-C4 H 9 )2 CuLi 2 n-C 4 H9 COCH(CH 3 )2
Lithium di-n-butylcuprate 2 - Methyl-3-heptanone
 677
Organocopper reagents (lithium dialkylcuprate) are less reactive than Grignard reagents and organolithium
compounds toward the carbonyl group of ketones, hence the reaction stops at the ketonic stage whereas in other
reagents, tert-alcohols are usually formed because ketones are more reactive than acid chlorides. Although
organocopper compounds are more reactive than Grignard reagents toward alkyl halides, however, these do not
react with many of the functional groups (e.g. NO2, CN, CO, COOR, etc.) with which Grignard reagents
and organolithiums do react. In short, organocopper compounds are highly selective toward different functional
groups.
CH 3OOC.CH2CH 2COCl + [(CH 3)2CHCH 2CH 2]2CuLi CH 3OOC.CH 2CH 2COCH 2CH 2CH(CH 3)2
Lithium diisopentylcuprate Methyl-4-oxo-7-methyloctanoate
(e) Ketones from organocadmium compounds
RCOCl + RCdR RCOR + RCdCl
Dialkyl cadmium
Like organocopper compounds, organocadmium compounds are also less reactive than Grignard reagents and
organolithiums.

1. Account for the difference in behaviour of RMgX and R2CuLi.

2. (a) Identify the compounds A and B.

(i) Br O + (CH 2=CH)2CuLi A (ii) O N

2
COCl + B O2N COCH2CH 3 .

(b) Would it be feasible to prepare p-nitroacetophenone in the following way ?

O2N CuLi + CH3COCl O2N COCH3

2

Lithium di (-p-nitrophenyl) cuprate p-Nitroacetophenone

6. Ozonolysis of alkenes. Alkenes and ozone react readily at low temperatures to yield ozonides which on
decomposition with a reducing agent yield aldehydes or ketone depending upon the structure of the alkene.

O
O3 H2O, Zn
RCH = CH2 RCH CH2 RCHO + CH2O

O O

(i) O 3 CHO
CH 2 = CH CH=CH 2 | + 2HCHO
(ii) H 2 O/Zn
1, 3-Butadiene CHO
Glyoxal

(i) O 3
(CH3)2C = CHCH3 (CH3)2CO + CH3CHO
(ii) H 2 O/Zn

7. By the hydrolysis of gem-dihalides.

OH -
CH3CH2CHCl2 CH3CH2CH(OH)2 CH3CH2CHO + H2O

OH -
CH3CCl2CH3 CH3C(OH)2CH3 CH3COCH3 + H2O
8. By the reduction of nitriles. This method is used only for aldehydes.
678

SnCl2 H 2O
(a) CH3C N CH3CH = NH CH3CHO (Stephen reduction)
HCl

( i ) (iso - Bu)2 AlH 2 , 40 C

(b) CH3C N CH3CHO
( ii ) H3 O+

9. By dry distillation of calcium salts of fatty acids. Calcium formate, on pyrolysis, gives formaldehyde ; calcium
formate mixed with calcium salt of any other fatty acid gives aldehydes; calcium salts of fatty acids other than
calcium formate yield ketones.

H COO O OCH
Ca + Ca 2HCHO + 2CaCO3
H COO O OCH

Calcium formate (2 moles) Formaldehyde (2 moles)

CH3CHO
CH3COO OOCH
Ca + Ca + + 2CaCO3
CH3COO OOCH CH3CHO
Cal. acetate Cal. formate Acetaldehyde

CH3.CO.CH3
CH3COO OOCCH3
Ca + Ca + + 2CaCO3
CH3COO OOCCH3 CH3.CO.CH3
Calcium acetate (2 moles) Acetone (2 moles)

When calcium salts of dicarboxylic acids are heated, cyclic ketones are formed.

O

O 2+ heat
Ca O + CaCO3
O

O
Calcium succinate Cyclopropanone

COO heat
2+
Ca O + CaCO3
COO
Calcium adipate Cyclopentanone

Instead of using calcium salts of an acid, vapours of acid or mixture of acids can be passed over heated MnO at
300C.
MnO
CH3COOH + HCOOH CH3CHO + CO2 + H2O
300 C
2CH3COOH CH3COCH3 + CO2 + H2O
CH3COOH + CH3CH2COOH CH3COCH2CH3 + CO2 + H2O

PREPARATION OF AROMATIC ALDEHYDES

1. Gattermann aldehyde synthesis.

CHO

3 AlCl
+ HCN + HCl
 679
Mechanism

AlCl +
H - C N + HCl
ClCH NH
3
C H = NH + AlCl -4
Electrophile

H CH = NH CH = NH CHO
+ + +
CH = NH H HO
2

2. Gattermann Koch aldehyde synthesis.

CHO

3 AlCl
+ CO + HCl

3. Oxidation of toluene.

CH3 CHO
CrO Cl
2 2



Etard reaction
CH2CH3 CH2CHO
CrO Cl
2 2

Industrial methods.
(a) Formaldehyde, a starting material for a number of plastics, is prepared by oxidation of methanol over a silver or
iron oxide-molybdenum oxide catalyst at elevated temperature.

1 Catalyst
CH3OH + O HCHO + H2O
2 2 500 C

(b) Acetaldehyde can be prepared by (i) hydration of acetylene, or (ii) more economically by aerial oxidation of
ethylene in presence of palladium chloride and copper (II) chloride as catalysts (Wacker process).

1 PdCl 2 , CuCl 2
CH2 = CH2 + O CH3CHO
2 2 H 2O

PdCl , CuCl
Similarly, CH 3 CH = CH2
2 2
CH 3 CH 2 CHO
H2O

O
P
CH 3 CH = CHCH3
CH3 - C - CH 2 CH 3

(c) Aldehydes can also be prepared by hydroformylation, a reaction in which alkenes are converted to aldehydes
containing an additional carbon atom by reaction with carbon monoxide and hydrogen in presence of a suitable
cobalt or rhodium-based catalyst.

Co 2 (CO)8
RCH = CH2 + CO + H2 RCH 2 CH 2 CHO + R CH. CHO
(Major) |
CH 3
(Major)
 680

14.4 Physical Properties

(i) The carbonyl group is a polar group, therefore, the dipole-dipole attractive forces between molecules are stronger
and hence aldehydes and ketones have higher boiling points than hydrocarbons (non-polar) of comparable
molecular weight. However, aldehydes and ketones cannot have strong hydrogen bonds between their molecules,
hence they have lower boiling points than the corresponding alcohols.
(ii) The carbonyl oxygen atom of aldehydes and ketones form hydrogen bonds to water molecules, hence lower
aldehydes and ketones show appreciable solubility in water.
(iii) Formaldehyde is a gas (b.p. 21C), and is handled either as an aqueous solution (formalin), or as one of its solid
polymers : paraformaldehyde, (CH2O)n, or trioxane, (CH2O)3. When dry formaldehyde is desired (as in reaction
with a Grignard reagent), it is obtained by heating paraformaldehyde or trioxane. Similarly, acetaldehyde is
usually generated by heating its higher-boiling trimer with acid.

O O +
H2C CH2 CH3CH CHCH3 H
CH2 OCH2OCH2O 3CH3CHO
O O O O
Paraformaldehyde CH2 CH
Trioxane CH3
Paraldehyde

1. Identify A to C in the following reactions :

CO, H 2 O 2 , PdCl 2 CO, H 2

(a) [B] CH3CH = CH2 A (b) (CH3)2C = C(CH3)2 C
CuCl2 , H 2 O

2. Which of the components of each of the following pair has higher boiling point ?
(a) Hexane or hexanal (b) Hexanal or 1-hexanol (c) 2-Pentanol or 2-pentanone
(d) Benzaldehyde or benzyl alcohol (e) 2-Phenylethanol or acetophenone.
3. n-Butanol boils at 118C and n-butanal boils at 76C, although their molecular weights are nearly similar. Explain.

14.5 Chemical Properties

The carbonyl group, C = O governs the chemistry of aldehydes and ketones in two ways : (a) by providing a site for
nucleophilic addition, and (b) by increasing the acidity of the hydrogen atoms attached to the alpha carbon. Both of these
effects is due to the ability of oxygen to accommodate a negative charge.

(A) Carbonyl group as a site for nucleophilic addition

The mobile p electrons of the carbon-oxygen double bond are pulled strongly towards
oxygen, which makes carbonyl oxygen electron-rich and carbonyl carbon electron-deficient. R d+ d
: :

C==O
Further, since carbonyl group is flat, it is relatively open to attack from above or below. R
The positive charge on the carbonyl carbon atom means that it is especially susceptible to attack by a nucleophile. On the
other hand, the negative charge on the carbonyl oxygen atom means that nucleophilic addition is susceptible to acid
catalysis.
Thus nucleophilic addition to the carbon-oxygen double bond occurs in either of two general ways.
 681
1. When the reagent is a strong nucleophile, addition usually takes place in the following way, in which trigonal
planar aldehyde or ketone is converted into a tetrahedral product.
:Z Z Z Z
R H2O
C=O R C R C R C
R R Od R O or nucleophile R OH
Reactant Transition state * Product
(Trigonal) (Becoming tetrahedral) (Tetrahedral)

Note that as the nucleophile is forming a bond through its electron pair with the carbonyl carbon atom, the
electron pair of the carbon-oxygen p bond shifts out to the carbonyl oxygen (as indicated by full negative charge
on oxygen) and thus oxygen gets a negative charge which it can accommodate easily. Thus the ability of oxygen
to carry a negative charge is the real cause of reactivity of carbonyl group toward nucleophiles. (The polarity
of the carbonyl group is not the cause of the reactivity, it is simply another manifestation of the electronegativity
of oxygen).
2. When the reaction is acid-catalysed, nucleophilic addition on carbonyl group takes place in the following way.
:Z Z Z
R H
+
R +
C=O C=O H R C d+ R C
R
R R R OH
OH
An oxonium cation

(i) The oxonium cation is highly reactive toward nucleophilic attack at the carbonyl carbon atom because the
carbonyl carbon atom carries more positive charge than it does in the unprotonated compound.
(ii) Prior protonation of the carbonyl group lowers the Eact for nucleophilic attack, because it permits oxygen to
acquire the p electrons without having a negative charge.
(iii) This mechanism operates when carbonyl compounds are treated with strong acids (sometimes Lewis acids)
in presence weak nucleophiles.

Relative reactivity of aldehydes and ketones toward nucleophilic addition. The reactivity of the carbonyl
group toward the nucleophilic addition reactions depends upon the magnitude of the positive charge on the carbonyl
carbon atom (electronic factor) and also on the crowding around the carbonyl carbon atom in the transition state (steric
factor). Both these factors predict the following order
O O O
H CH > R CH > R CR
(i) Formaldehyde has no alkyl group, whereas other aldehydes and ketones contain one and two alkyl groups
respectively. Since an alkyl group is larger than the hydrogen atom, greater the number of alkyl or aryl group
more will be crowding in the transition state which has four groups on C (sp3) and lesser will be its stability.
(ii) Aldehydes have only one electron-releasing group to partially neutralize, and thereby stabilize, the positive
charge at their carbonyl carbon atom. Ketones have two electron-releasing groups and are thus stabilized more.
Greater stabilization of the ketone (the reactant) relative to the product means lesser reactivity.
d d d
O O O
d+ d+ d+
C C C

H H R H R R

Carbonyl carbon atom becomes lesser positive,
successively increasing stability of the compound

In short, any substituent in the carbonyl compound that decreases the positive charge on the carbonyl carbon
will increase the stability (or decrease the reactivity) of the molecule toward nucleophilic addition and vice versa.
Thus, the decreasing order of reactivity of certain carbonyl compounds is
(a) NO2CH2CHO > ClCH2CHO > CH3CHO > CH3CH2CHO
O O O
|| || ||
(b) CH 3COCH3 > CH 3 C C 2H 5 > CH3 C CH(CH 3 ) 2 > CH3 C C(CH 3 ) 3

* Note that this transition state is relatively roomy as compared to the transition state for an SN2 reaction in which carbon is pentavalent.
 682
(iii) An alkyl group releases electrons, and thus destabilizes the transition state by intensifying the negative charge
developing on oxygen.
(iv) An aryl group has an electron-withdrawing inductive effect, and thus it is expected to destabilize the reactant or
stabilize the transition state and thus should speed up the reaction. However, it seems to stabilize the reactant
even more, by resonance and thus causes net deactivation.

: :

: :

: :

: :
RC = O : RCO : RCO: RCO : RCO:

+ +
+

Addition of water, alcohols, hydrogen cyanide, sodium bisulphite, ammonia derivatives, hydride ion (in the
form of LiAlH4 and NaBH4), organometallic compounds, etc. are examples of nucleophilic addition on carbonyl group.
1. Addition of water (gem-diol formation). Aldehydes and ketones react with water in presence of acid or base in
a rapidly reversible equilibrium.

O OH
fast
RCR + H 2O RCR
OH
Like the general nucleophilic additions, hydrate formation follows the following order :
HCHO > CH3CHO > (CH3)3CCHO > CH3COCH3
% of hydrate formed 99.96 50 19 0.14

1. Arrange the following compounds in decreasing order of reactivity toward nucleophilic addition.
(a) RCHO, CH2O, R2CO and RCOY : (b) R2CO, Ar2CO, ArCOR and ArCH2COR.
2. In contrast to negligible hydration of acetone, hexafluoroacetone is completely hydrated. Explain.
3. Account for the isolation of CH3CO 18CH3 from a solution of CH3CO 16CH3 in excess of H2O18.
4. Ninhydrin has three ketonic groups, which one of them is likely to be hydrated easily ?

O
a
b
O
c

O
5. Arrange the following in decreasing ease of hydration to form gem-diol.

O O O O
(a) MeO C NO2 C O2N C NO2 MeO C OMe

A B C D
(b) CH3CH2CHO CH3CHFCHO CH3CHClCHO CH2ClCH2CHO
A B C D

2. Addition of alcohols (Acetal formation). Anhydrous alcohols add to the carbonyl group of aldehydes in the
presence of anhydrous hydrogen chloride to form acetals via hemiacetals.
+
R dry HCl R OH R OH, H R OR
C = O + R OH C C
H H OR H OR
Hemiacetal Acetal (an ether)
(an alcohol, as well as an ether) (stable to alkalies)
 683
(i) With a few exceptions, open-chain hemiacetals are too unstable to be isolated. However, cyclic hemiacetals
with five- or six-membered rings are usually much more stable.
(ii) All steps in the formation of an acetal from an aldehyde are reversible.
(iii) Acetal formation is not favoured when ketones are treated with simple alcohols and gaseous HCl (remember
that the usuage of hemiketals and ketals have been replaced by hemiacetals and acetals respectively).
However, cyclic acetal formation is favoured when a ketone is treated with an excess of a 1, 2-diol and a
trace of acid.
R HOCH2 H
+
R OCH2 H2O/H
+
R CH2OH
C=O + C C=O+
R HOCH2 R OCH2 R CH2OH
(excess) Cyclic acetal

(iv) Like ethers, acetals are cleaved by acids and are stable toward bases. However, acetals differ from ethers, in
the extreme ease with which they undergo acidic cleavage, actually acetals are rapidly converted into
aldehydes and alcohols by dilute mineral acids even at room temperature. Thus acetal formation may be
used to protect the aldehydic and ketonic group against undesired reactions in basic solutions.
Thus we can reduce only ester group in the following group by protecting ketonic group.
O O
O
O HA (i) LiAlH4, ether
OC2H5 O OC2H5
HOCH2CH2OH (ii) H2O

Ketonic group protected

O +
CH2OH H3 O O CH2OH

O H2O

Several other examples have been discussed in ethylene glycol in the chapter on Polyhydric Alcohols.

OH O
+ CH2I2 CH2
1.
OH O
Answer the following with reference to above reaction.
(a) The above reaction is an example of which familiar synthesis ?
(b) To what family of compounds does the product belong ?
(c) Give the reaction of the product with acid, and base.
2. Account for the fact that anhydrous acids bring about formation of acetals while aqueous acids bring about hydrolysis of acetals.
3. Give the structure of the acetal formed in each of the following reactions.
CH2OH
(a) O+ (b) Butanal + 1, 3-propanediol (c) BrCH2CH2COCH3 + CH2OH.CH2OH.
CH2OH
4. Give steps involved in the conversion of each of the following.
O O

(a) CH2=CHCHO CH2(OH)CH(OH)CHO (b)

H3C CH3 H3C CH3
O OH

(c) HOCH2CH2CH2CH2CHO
O OCH3
684
3. Addition of hydrogen cyanide. Hydrogen cyanide adds to the carbonyl groups of aldehydes and most ketones to
form cyanohydrins. Ketones in which carbonyl group is highly hindered do not undergo this reaction.
OH
C = O + HCN C
CN
(i) Addition of hydrogen cyanide itself takes place very slowly because HCN is a poor source of the nucleophile,
CN. However, addition of potassium cyanide, or any base that can generate cyanide ions from the weak acid
HCN, causes a dramatic increase in the rate of reaction. The cyanide ion, being a stronger nucleophile, is able
to attack the carbonyl carbon atom much more rapidly than HCN itself, and this is the source of its catalytic
effect. Bases stronger than cyanide ion catalyze reaction by converting HCN (pKa = 9) to cyanide ion.
(ii) Liquid hydrogen cyanide can be used for this reaction (HCN is a gas at room temperature), but since HCN
is a very toxic and volatile, it is generally produced in the reaction mixture for which an acid (generally
H2SO4) is added to a solution of the aldehyde or ketone and aqueous sodium or potassium cyanide.
Cl Cl
NaCN, ether, water,
Cl CHO Cl CHC N
then HCl
OH
2, 4-Dichlorobenzaldehyde 2, 4-Dichlorobenzaldehyde cyanohydrin

O OH
NaCN, H2O,
CH3CCH3 CH3CCH3
then H2SO4
CN
Acetone Acetone cyanohydrin

Cyanohydrins are useful intermediates in organic synthesis. A cyano group may be hydrolysed to an a-
hydroxy carboxylic acid or to an a, b-unsaturated acid (depending upon the condition used) or may be
reduced to a primary amine.

CH3 CH3 CH3

+
CN , H HCl, H2O
CH3CH2C = O CH3CH2CCN CH3CH2CCOOH
heat
2-Butanone
OH OH
Conc. H2SO4, 2-Hydroxy-2-methylbutanoic acid
heat

CH3 CH3
CH3CH2CCOOH CH3CH=CCOOH
2-Methyl-2-butenoic acid
OH

O OH OH
HCN (i) LiAlH4
CN CH2NH2
(ii ) H2O

A b-amino alcohol

1. Arrange the following compounds in decreasing ease of formation of cyanohydrin.

COCH3 CH2CHO COCH3 COCH3

NO2 OCH3
I II III IV
 685
2. Can you draw a scheme for converting acetone to methacrylonitrile, CH2=C(CH3)CN, an industrial chemical used in the production
of plastics and fibres ?
3. Following compounds are converted into their corresponding cyanohydrins. Predict the number of fraction and their optical
activity status in each case.
(a) CH3CHO (b) (CH3)2CO (c) R (+) CH2OHCHOHCHO (d) () CH2OHCHOHCHO.
4. (a) In cyanohydrin formation, an optimum pH of 910 is recommended. Explain.
(b) Which is the more favourable equilibrium situation for cyanohydrin formation ?
RCHO + NaCN or RCHO + HCN (both in water).

4. Addition of sodium bisulphite. Aldehydes, methyl ketones and cyclic ketones (not aromatic) react with sodium
bisulphite in presence of ethanol to give solid adduct.
+
R +
R + 2 +
R SO3 Na
C = O + Na HSO3 COH + : SO3 + Na C
H H H OH
Sodium bisulphite (adduct)
(solid)
NOTE.

(i) A CS bond is formed rather than CO because S has more nucleophilic site than O.
(ii) Sulphite ion, SO32 is a large ion and hence reacts only if C = O is not sterically hindered ; as in the case for
RCHO, RCOCH3, and cyclic ketones.

The solid adduct is filtered from the ethanolic solution and then decomposed by acid or base to regenerate the
carbonyl compound. Hence this reaction is used for the purification and separation of carbonyl compounds.
+
R SO3 Na +
H (or OH )
R 2
C C = O + SO2 (or SO3 )
H OH H
(Extracted with ether)

Separation of RCHO from unreacted RCH2OH.

NaHSO 3 H+
RCH2OH RCHO RCH(OH) SO 3 Na RCHO
C2 H 5 OH Separated from
unreacted RCH 2OH

5. Addition of derivatives of ammonia. Certain compounds related to ammonia (such as hydroxylamine, NH2OH;
phenylhydrazine, H2NNHC6H5 ; and semicarbazide H2NNHCONH2, etc.) react with carbonyl compounds to
form compounds, having carbon-nitrogen double bond, known as imines. The reaction is acid catalyzed and
involves two stages : addition of the ammonia derivative to form carbinolamine followed by dehydration to yield
imine which is a mixture of E- and Z-isomers
+
H H O
C = O + H2NG CNHG 2 C = NG
(addition) (elimination)
OH Imine

Like ammonia, these derivatives of ammonia are basic and hence form salts with acids, viz. hydroxylamine
hydrochloride N +H 3OHCl , phenylhydrazine hydrochloride, C 6H 5NHNH 3 +Cl ; and semicarbazide
hydrochloride, NH2CONHNH3+Cl. These salts are less easily oxidized by air than the free bases, and hence
these ammonia derivatives are best used in the form of their salts. When used, the parent reagents are liberated
from their salts in the presence of the carbonyl compound by adding a base, generally sodium acetate.

GNH 3 + Cl + CH 3 COONa GNH 2 + CH3 COOH + NaCl

Stronger acid Stronger base Weaker base Weaker acid

Imine formation requires a moderate pH (between 45), because very low as well as very high pH retards the
reaction. To know why it is so, we must know the steps involved during the reaction
:NH2G (free base) +
+
H + OH OH2 +
C=O C = O H C +
C C = NG + H3O
N H 2G NG

H
686
From the above steps, it is obvious that an acid is essential to protonate the carbonyl oxygen which makes
carbonyl carbon more susceptible to nucleophilic attack. Hence protonation of the carbonyl group is favoured by
..
high acidity. However, in presence of strong acid, the ammonia derivative (H2 N G) can also undergo protonation
to form the ion, H3N+G lacking the unshared electrons which thus will no longer be nucleophilic. Hence the
addition of reagent (H2NG) will be favoured by low acidity. Thus optimum acidity is the compromise between the
two steps to carry out the reaction successfully, i.e. the solution must be acidic enough for an appreciable fraction
of the carbonyl compound to be protonated, but not so acidic that the concentration of the free nitrogen compound
is too low. The exact conditions used depend upon the basicity of the reagent, and upon the reactivity of the
carbonyl compound.
Reaction of aldehydes and ketones with derivatives of ammonia, (H2NG)

C = O + H2NG C = NG

Reagent H2NG and its name Name of product with specific example

C 2H 5 C2H5
H2NC2H5
H2NR, 1 Amine C=O C=NC2H5
CH3 CH3
An Imine
(A Schiff s base)

CH3 CH3
H2NOH, Hydroxylamine C=O H2NOH C = NOH
H
H
Acetaldoxime oxime

CH 3 CH 3
C=O H2 NNH2
H2NNH2, Hydrazine C = NNH2
CH 3 CH 3
Acetone hydrazone

C 6H 5 H2NNHC6 H5
C6H5
H2NNHC6H5, Phenylhydrazine C=O
+ C=NNHC6H5
CH 3 H3O , CH3COOH CH3
Acetophenone
phenylhydrazone

CH 3 2, 4-Dinitro- CH3
H2NHN NO2 , C=O C = NNH NO2
phenylhydrazine
H H

NO2 NO2
Acetaldehyde
2, 4-dinitrophenylhydrazone

O H2NNHCONH2
H2NNHCONH2, Semicarbazide NNHCONH2

Cyclohexanone semicarbazone

The products of the reaction of aldehydes and ketone with hydroxylamine, phenylhydrazine, 2, 4-
dinitrophenylhydrazine and semicarbazide are usually insoluble solids with sharp characteristic melting points.
Moreover, oximes and hydrazones when refluxed with dil HCl, they regenerate the parent aldehyde or ketone.
Hence, formation of oximes and hydrazones is used for the detection and purification of aldehydes and ketones
HCl
C = O + H2NOH C = NOH C = O + NH2OH.HCl
reflux

HCl
C = O + H2NNHPh C = NNHPh C = O + H2NNHPhHCl
reflux
 687
Unlike, 2, 4-dinitrophenylhydrazones, simple hydrazones have low melting points and are hence occasionally
used to identify carbonyl compounds. However, they form the basis for a useful method to reduce carbonyl
group to methylene group (Wolf-Kishner reduction).
base
C = O + H 2NNH 2 C = NNH2 CH2 + N2
heat
Hydrazone

Ammonia reacts with formaldehyde, other aldehydes and ketones in different ways.
6HCHO + 4NH3 (CH2)6N4 + 6H2O
Hexamethylene tetramine
(Urotropine)

CH3 CH3 OH
C = O + NH3 C
H H NH2
Acetaldehyde ammonia

CH3 HNH2 CH3 NH2

C=O + C
CH3 HCH2COCH3 CH3 CH2COCH3
Diacetoneamine

Secondary amines, R2NH add to aldehydes and ketones to form carbinolamines which are dehydrated easily to
form enamines

OH
C = O + R2NH C C = NR2
NR2
Enamine

O + HN N + H2O

Cyclopentanone Pyrrolidine N-(1-Cyclopentenyl)-pyrrolidine

6. Addition of organometallic compounds. Organometallic compounds, such as Grignard reagents, alkyllithiums

and organozinc compounds provide nucleophile which add on carbonyl group to form alcohols.

d d+ R +
R
R:M + H3O
C = O CO: M
: :

COH

Such reactions with Grignard reagents and alkyllithiums have already been discussed at length, so here we will
confine only to addition of organozinc compounds.
In short, it can be summarised that Grignard reagents (M = MgX) or alkyllithium (M = Li) react with formaldehyde,
other aldehydes and ketones to form 1, 2 and 3 alcohols respectively.
Addition of organozinc compounds (The Reformatsky reaction). Reformatsky reaction involves the reaction of
an aldehyde or ketone with an a-bromoester in presence of zinc metal to form b-hydroxy ester.

OZnBr +
OH
Zn H3O b a
C = O + BrCH2COOR CCH2COOR CCH2COOR
benzene
a-Bromoester b-Hydroxy ester

Actually an organozinc compound is first formed as an intermediate which then adds to the carbonyl group in
a manner analogous to that of a Grignard reagent.

benzene d+ d
BrCH2COOC2H5 + Zn BrZ n CH 2 COOC 2 H 5
Organozinc compound
688
Since organozinc reagent is less reactive than a Grignard reagent, it does not add to the ester group.

OH
(i) Zn |
CH3CH2CH2CHO + BrCH2COOC2H5 CH 3 CH 2 CH 2 CHCH 2 COOC2 H 5
(ii) H 3 O + b -Hydroxy ester

The b -hydroxy esters produced in the reaction are easily dehydrated to a, b-unsaturated esters because the
resulting product contains a more stable conjugated system.

OH
| O
H 3 O+ ||
CH 3 CH 2 CH 2 CHCH 2 COOC2 H 5 CH3CH2CH2CH = CH C OC2H5 + H2O
heat

1. What are Schiff bases. Give the structure of the product of the following reactions :
(a) Cyclohexanone + tert-Butyl amine (b) CH3COCH3 + H2NCONHNH2
(c) 2-Butanone + [H3N+OH]Cl, CH3COONa (d) Acetophenone + Cyclohexyl amine

(e) CH3COCH2C6H5 and HN (f) CH3CH2COCH2CH3 + HN

O O NH2 CHO
(g) + (h) +
N NH2 CHO
H
2. Explain the following :
(i) Reaction of hydroxylamine with acetone gives a single oxime, while similar reaction with an aldehyde or a methyl ethyl ketone
forms two isomeric oximes.
(ii) Oximes are more acidic than hydroxylamine.
(iii) Although semicarbazide has two NH2 groups, only one of them reacts with an aldehyde or ketone.
3. (a) How would you prepare following compounds using Reformatsky reaction ?
OH OH
|
(i) (CH3)2 CCH 2 COOCH2CH3 (ii)
CHCOOCH2CH3
CH3
(b) Why is Mg or Cd not used in place of Zn in the Reformatsky reaction ?

7. Cannizzaro reaction. Aldehydes containing no a-hydrogen atom, when treated with concentrated alkali, (aqueous or
alcoholic), undergo self oxidation-reduction (also known as disproportionation) to yield a mixture of an alcohol and a
salt of a carboxylic acid. This reaction, known as Cannizzaro reaction, is carried out at room temperature ; remember
that under these conditions, aldehydes having a-hydrogen atom undergo aldol condensation.
50% NaOH
2HCHO CH 3 OH + HCOONa
Methanol Sodium formate

50% NaOH
2(CH3)3CCHO (CH3)3CCH2OH + (CH3)3CCOONa
In general, a mixture of two aldehydes (each having no a-hydrogen atom) undergo Cannizzaro reaction to form
a mixture of all possible products. However, if one of the aldehydes is formaldehyde, reaction always yields
sodium formate as one of the products and the alcohol (second product) corresponding to the other aldehyde.
Cannizzaro reaction between different aldehyde molecules is known as crossed Cannizzaro reaction.
conc. NaOH
C6H5CHO + HCHO C6H5CH2OH + HCOONa
Benzaldehyde Formaldehyde Benzyl alcohol Sod. formate
 689
Mechanism.
The reaction involves two successive nucleophilic addition, of course at different carbonyl groups.
H H

Step 1. ArC = O + OH ArCO
OH
I

H H H

Step 2. ArC = O + ArCO ArCO + ArC = O
OH H OH
(Second molecule) +
I

H H

ArCH2OH ArCOO

Intramolecular or Internal Cannizzaro reaction

O OH
CHO conc. NaOH CH2OH conc. NaOH
; CCHO CHCOONa
CHO COONa
Remember that keto group can only be reduced, not oxidised, in internal Cannizzaro reaction.
Although aldehydes having a-hydrogen atom do not undego Cannizzaro reaction, they along with all their
aldehydes can be made to undergo such reactions in presence of aluminium ethoxide. The reaction is now
known as Tischenko reaction and here esters are isolated instead of alcohol and carboxylic acids.
Al(OC2H5 )3
2RCHO [RCH2OH + RCOOH] RCOOCH2R
Ester

8. Addition of ylides (The Wittig reaction). An ylide is a neutral molecule having a negative carbon adjacent to a
positive hetero atom (e.g. P or S), each atom has an octet of electrons and directly bonded to each other. Aldehydes
and ketones react with phosphorus ylides to yield alkenes and triphenylphosphine oxide. The reaction, known
as Wittig reaction, has proved to be a valuable method for synthesizing alkenes.

R + R R
C = O + (C6H5)3P = C or (C6H6)3PC C=C + O = P(C6H5) 3
R R R
Phosphorus ylide Alkene Triphenylphosphine oxide

Thus the net result of the reaction is the replacement of carbonyl oxygen, = O, by the group = CRR . The reaction
is carried out under mild conditions and in presence of solvents like tetrahydrofuran (THF) and dimethyl
sulfoxide (DMSO).
+ DMSO +
O + (C6H5)3P CH 2 CH2 + (C6H5) 3P O

Wittig reaction has a great advantage over most other alkene syntheses in that no ambiguity exists as to the location
of the double bond in the product.
Mechanism. The ylide acting as a nucleophile attacks the carbonyl carbon of the aldehyde or ketone to form an
unstable intermediate betaine followed by oxaphosphetane which then spontaneously loses triphenylphosphine
oxide to form an alkene. The driving force for the Wittig reaction is the formation of the very strong PO bond
(DH = 540 kJ mol1).

R R
R R
R
C :C CCR CCR C=C + :O = P(C6H5)3
+ R
:

+ +
O: P (C6H5)3 :O: P(C6H5)3 : O P(C6H5)3
:

Betaine Oxaphosphetane Alkene Triphenylphosphine oxide

 690

1. Give the structure of the product(s) obtained in each of the following reactions.

conc. NaOH conc. NaOH

(a) (b) conc. NaOH
C6H5COCHCl2 (c) ArCDO

O CHO

D D
OH
OH
(d) D C = O (e) D C = O
2. In the crossed Cannizzaro reaction, formaldehyde is always oxidised. Explain.
3. Which of the following intermediate (I or II) is considered as a better hydride donor to an aldehyde ?

H H

RCO RCO

OH O
I II

4. Identify the alkene produced in each of the following Wittig reactions :

-
..
+
(a) Benzaldehyde + Ph3P+
(b) Butanal + Ph 3 P C HCH = CH 2

-
..
(c) Cyclohexyl methyl ketone + Ph 3 P+ = C H 2

5. Give the structure of an ylide and a carbonyl compound from which each of the following could be prepared.

(a) CH3CH2CH2CH = C(CH3)CH2CH3 (b) C6H5CH = CHC6H5 (c) CHCH3

(B) Acidity of a-hydrogens of carbonyl compounds

In addition to nucleophilic addition reactions, carbonyl compounds exhibit the unusual acidity of a-hydrogen
atoms. Actually, in the first type of properties carbonyl group acts as a functional group, while in the second type carbonyl
group acts as a substituent and exerts its effect on the adjacent (alpha) carbon atoms.

O
RCCC
H H
a-Hydrogen, acidic b-Hydrogen, not acidic
(pKa = 19 20) (pKa = 40 50)

The unusual acidity of the a-hydrogens of carbonyl compounds is due to its strong electron-withdrawing nature
which in turn makes a-carbon also electron-withdrawing. Hence in presence of base, it easily loses hydrogen as proton
and itself converted into carbanion. Once the anion (carbanion) is formed, it is stabilized by resonance.

B: H
BH d d
CC = O: C = CO:
:

: :

CC = O CCO
Carbanion Enolate anion
(larger contribution)

Resonance stabilized anion

 691
Thus the carbonyl group affects the acidity of a-hydrogens in just the same way it affects the acidity of carboxylic
acids, i.e. by helping to accommodate the negative charge of the anion.

O O O O +
+
C C C +H or C +H
OH O O O
Resonance stabilized carboxylate anion
(Equivalent contributing structures)

O O O O
+ +
C C C +H or C +H
CH C C C
Resonance stabilized enolate anion
(Non-equivalent contributing structures)

Although a-hydrogen atoms of an aldehyde or ketone are very weakly acidic than the hydrogen atom of a
COOH group, they are considerably more acidic than hydrogen atoms anywhere else in the molecule and they are acidic
enough for producing carbanions in significant concentration. It is interesting to note that the two important properties of
a carbonyl group : (a) susceptibility to nucleophilic attack, and (b) acidity of a-hydrogens, is due to the ability of oxygen to
accommodate the negative charge.

1. Account for the following facts.

(a) (+) C6H5CH(CH3)CHO undergoes reacemization, when treated with base.
(b) The diketone 2, 4-pentanedione is almost as acidic as phenol, and much more acidic than acetone.
(c) g-Hydrogens of a, b-unsaturated carbonyl compounds are acidic.
2. Write down the structure of the product in the following reactions.
CH3 O
KOD
(a) O + 4 D2O (b) CH3C = CHCCH3 + NaCN (aqueous)

Reactions of carbonyl compounds due to acidic hydrogen atom, i.e. due to enols and enolate anions.
9. Aldol condensation. Two molecules of an aldehyde or a ketone, containing at least one a-hydrogen atom, when
treated with dilute base (like NaOH, Ba(OH)2, K2CO3, etc.) at room temperature (or below) combine to form a b-
hydroxyaldehydes or b-hydroxyketones. This reaction is called aldol condensation. In every case, it is the a-
carbon and a-hydrogen atoms of one molecule that add to the carbonyl carbon and oxygen atoms respectively of
the second molecule.
H
H
OH
(i) CH3C = O + CH3.CHO CH3CCH2CHO

OH
3-Hydroxybutanal

H
H
b a OH
(ii) CH3CH2C = O + H3CCH2CHO CH3CH2CCHCHO
Propionaldehyde (2 moles)
OH CH3
3-Hydroxy-2-methylpentanal

CH3 CH3 O

(iii) CH3C = O + CH3.CO.CH3 OH
CH3CCH2CCH3

OH
4-Hydroxy-4-methyl-2-pentanone
 692
Mechanism.

Step 1. CH3CHO + OH [CH2CHO] + H2O
Carbanion, I

H H

Step 2. CH3C = O + [CH2CHO] CH3CCH2CHO
I (Nucleophile)
O
Alkoxide ion, II

H H

Step 3. CH3CCH2CHO + H2O CH3CCH2CHO + OH
O OH
Remember that presence of a-hydrogen in aldehyde or ketone is the essential condition for aldol condensation,
since only such carbonyl compounds can form carbanions, the actual nucleophile, which then attacks the
carbonyl carbon to form the product. Hence, aldehydes or ketones, not having a-hydrogen atom, do not undergo
aldol condensation.

dilute
ArCHO, HCHO, (CH3)3CCHO, ArCOAr, or ArCOCR3
- No reaction
OH

However, in presence of concentrated base, above compounds undergo Cannizzaro reaction.

Dehydration of aldol products. The b-hydroxy aldehydes and b-hydroxy ketones obtained from aldol condensation
are very easily dehydrated, on heating, to form a, b-unsaturated carbonyl compound (conjugated system).

H H H H
+
H or OH
CH3CCHC = O heat
CH3C = CHC = O + H2O
2-Butenal
OH H
Aldol

Dehydration under acidic conditions follows a mechanism similar to those of other acid-catalyzed alcohol
dehydration. The steps involved in base-catalyzed dehydration of aldol are summarised below.
O O O
OH, (H2 O) ..
CH3 CH CH CH CH3 CH CH CH CH3 CH = CH CH + OH
OH H OH
Enolate ion Conjugated system

Note that in the second step, hydroxide ion which is not a good leaving group in an E2 elimination is removed.
However, here OH can serve as a leaving group in a strongly exothermic step leading to a highly stable
(conjugated) compound.
In some cases, especially when the double bond produced is conjugated with an aromatic ring, dehydration of
the aldol product occurs so readily that we cannot isolate the product in the aldol form.

CH3
C2H5ONa
CCH3 + CH3C CCHC
O O OH H O
Acetophenone (Hypnone)
CH3
H2O
C = CHC
O
1, 3-Diphenyl-2-buten-1-one (Dypnone)
(a fully conjugated system)
 693
Synthetic applications. (i) Aldol reaction is a general reaction given by aldehydes and ketones having an a-
hydrogen atom.
(ii) Further, aldol reaction gives us a product by introducing a new carbon-carbon bond between two molecules.
(iii) Aldol products contain two functional groups, OH and CHO, each of which can be used to carry out
a number of subsequent reactions.

OH OH
OH NaBH4
2RCH2CHO RCH2CHCHCHO RCH2CHCHCH2OH

R R
Aldehyde An aldol A 1, 3-diol

+
H , (H2O)

H2 /Ni LiAlH4
RCH2CH2CHCH2OH RCH2CH = CCHO RCH2CH = CCH2OH
high P
R R R
A saturated alcohol An a, b -unsaturated aldehyde An allylic alcohol

H2, PdC

RCH2CH2CHCHO

R
A saturated aldehyde

Acid-catalyzed aldol condensations. Aldol condensation can also be brought about with acid catalysts. The
enol serves as a weak nucleophile to attack an activated (protonated) carbonyl group. Steps involved in the acid-
catalyzed aldol condensation of acetaldehyde are given below.

+ .. +
OH : OH OH OH OH OH
+
CH3 CH + CH2 = CH CH3CH CH 2 CH CH3CH CH 2 CH
protonated enol form of
acetaldehyde acetaldeyde

OH O +
O
ROH H
+
CH3CH CH2CH CH3CH = CHCH + H2O
RO H2
Aldol

Similarly acetone, when treated with hydrogen chloride gives 4-methyl-3-penten-2-one. Here, the aldol formed
undergoes dehydration to form 4-methyl-3-penten-2-one.

O OH O O
|| | || ||
HCl
2CH 3 - C CH 3
CH 3 CCH 2 C CH 3
CH 3 C = CH C CH 3
| ( - H 2 O) |
CH3 CH3
Acetone (2 mole) Diacetone alcohol 4 - Methyl - 3 - penten - 2 - one
(Mesityl oxide)

Mesityl oxide may further undergo crossed aldol condensation to form phorone as final product.

O O OH O CH3 O CH3
H2O
CH3C = CHCCH3 + CH3CCH3 CH3CCH2CCH = CCH3 CH3C = CHCCH = CCH3
Crossed aldol
(3rd mole)
CH3 condensation
CH3 CH3
2, 6-Dimethyl-2, 5-heptadien-4-one (Phorone)
Crossed aldol condensation. An aldol condensation between two different carbonyl compounds each having at
least one a-hydrogen atom (crossed aldol condensation) gives a mixture of the four possible products, hence it
is not always feasible in the laboratory. For example, reaction of acetaldehyde and propanal in presence of dilute
NaOH gives a mixture of four products.
694

OH OH CH3
OH
CH3CHO + CH3CH2CHO CH3CHCH2CHO + CH3CH2CH CHCHO
Ethanal Propanal 3-Hydroxybutanal 3-Hydroxy-2-methylpentanal

(from 2 molecules of ethanal) (from 2 molecules of propanal)
OH

OH CH3 OH
CH3CH CHCHO + CH3CH2CHCH2CHO
3-Hydroxy-2-methylbutanal 3-Hydroxypentanal
(from 1 molecule of ethanal and 1 molecule of propanal)
(Ethanal as a carbonyl group (Propanal as a carbonyl group
and propanal as a nucleophile) and ethanal as a nucleophile)

Intramolecular aldol condensation (Cyclization via aldol condensation). A dialdehyde, a keto aldehyde, or a diketone
undergoes aldol condensation to form five and six-membered (sometimes even longer) cyclic compounds, e.g.
O O

OH
OHC

1-Cyclopentenyl methyl ketone

In the above keto aldehyde, three different enolates are possible, however it is the enolate from the ketone side of
the molecule that adds to the aldehyde group leading to the product. The reason being greater reactivity of
aldehydes toward nucleophilic addition than the ketones due to electronic as well as steric factors.

1. Write structural formulas for the products obtained by the aldol condensation of following compounds:
CHO
(a) O (b) COCH3 (c) CHO +

O
O
(d) (e) C6H5CHO + CCH3

Other reactions related to aldol condensation

There are large number of condensations that are closely related to the aldol condensation, each of these reactions
has its own name, viz. Claisen-Schmidt, Knovenagel, Perkin (given only by aromatic aldehydes), etc. At first
glance each may seem to quite different from the others, closer examination shows that each of these involves
attack by a carbanion on a carbonyl group. In each case carbanion is generated like that in aldol condenstion, i.e.,
hydrogen a-to the carbonyl group is abstracted by base.
(a) Claisen-Schmidt reaction. A crossed aldol condensation in which an aromatic aldehyde reacts with an
enolizable aldehyde, ketone or ester, eg CH3COOC2H5 to form a, b-unsaturated carbonyl compound is
known as Claisen-Schmidt reaction.

RO
OH
C6H5CHO + RCH2COR C6H5CH = C CR + H2O
(R = H or alkyl) a , b-Unsaturated carbonyl compound
O
O
OH
C6H5CHO + (CH3)3CCCH3 C6H5CH = CHCC(CH3)3
4, 4-Dimethyl-1-phenyl-1-penten-3-one
 695
(b) Knoevenagel reaction. Condensation between an aldehyde or ketone with compound containing active
methylene group* in the presence of ammonia, amines, pyridine, piperidine etc. to form a, b-unsaturated
compound is known as Knoevenagel reaction.

heat
(i) CH3CHO + H2C(COOH)2 CH3CH = C(COOH)2 CH3CH = CHCOOH
CO 2

Malonic acid Crotonic acid

(i) heat
(ii) C6H5CHO + H2C(COOH)2 C6H5CH = CHCOOH
(ii) CO 2

Cinnamic acid
Note that in Knoevenagel reaction, enol (or enolate ion) is provided by molonic acid and not by aldehyde.

1. Give the structure of the mixed aldol condensation product of the following.

O
CHO
(a) C6H5CHO + C6H5COCH3 (b) CHO + O = (c) +

2. Give the final product in each case.

KOH C2 H 5ONa
(a) CH3CHO + CH3NO 2 (b) C6H5CHO + C6H5CH2CN
NH 3
(c) C6H5CHO + CH3COCH2COOC2H5

10. a-Halogenation of aldehydes and ketones. Aldehydes and ketones having a-hydrogen atom react with halogens
to form a-haloaldehyde or ketone.
H O X O
acid or
C C + X2 C C + HX
base

The reaction is regiospecific for substitution of an a-hydrogen.

O O
Cl
H2O
+ Cl2 + HCl

Cyclohexanone 2-Chlorocyclohexanone

CHO CHO
CHCl3
+ Br2 Br + HBr

Cyclohexanecarbaldehyde 1-Bromocyclohexanecarbaldehyde

C6H5COCH3 + Cl2 C6H5COCH2Cl

Acetophenone Phenacyl chloride
Phenacyl chloride is a relatively harmless but powerful lachrymator or tear gas and is used by police to disperse
mobs.
* A methylene group flanked on both sides by negative groups is known as active methylene group, e.g.,
COOH COCH3 CN
CH2 CH2 CH2
COOH COOC2H5 COOC2H5
Malonic acid Ethyl acetoacetate Ethyl cyanoacetate
696
(i) a-Halogenation of aldehydes and ketones can be carried out in a variety of solvents like water, chloroform,
acetic acid and diethyl ether.
(ii) The reaction is quite different from the free-radical halogenation of alkanes and involves the formation of
resonance stabilized enols.
(iii) Unlike ketones, aldehydes are easily oxidized, and since halogens are strong oxidizing agents, halogenation
of aldehydes usually results in oxidation to carboxylic acids.

O O
|| ||
R C H + X 2 + H2 O
R - C - OH + 2HX

(iv) Since one of the reaction products is hydrogen halide, the process when catalyzed by acids is said to be
auto-catalytic. However, halogenation promoted by base is more important and discussed here.
Mechanism. The rate of reaction depends upon the concentration of acetone and of base, but is independent of
bromine concentration.

slow
Step 1. CH3CCH3 + : B CH3CCH2 CH3C = CH2 + H : B
O O O

.. fast
Step 2. CH 3 C C H 2 + Br Br CH 3 C CH 2 B r Br
|| ||
O O

Since base is not regenerated during the reaction, halogen of ketones in presence of base is called base-promoted,
rather than base-catalyzed reaction. As we will discuss below in haloform reaction, multiple halogenation of
aldehydes and ketones having more than one a H occurs.
Mechanism of acid catalyzed a-halogenation of ketones. The ketone is dissolved in acetic acid, which serves
as both the solvent and the acid catalyst. In contrast with basic halogenation, acidic halogenation can selectively
replace just one hydrogen or more than one if appropriate amounts of the halogen are used.
In the first step, the carbonyl oxygen is protonated to form enol which reacts with the halogen (electrophile).

+ OH
||
H+ Base
CH 3 - C - CH 3
CH 3 - C - CH 3 CH 3 - C = CH 2
|| (say H 2 O) |
O OH
enol

Br - Br + Br -

CH 3 - C - CH 2 Br CH 3 - C - CH 2 Br
CH 3 - C - CH2 Br + HBr
( - Br - ) | || ||
:OH
.. + O- H O

11. Haloform reaction. When methyl ketones (or acetaldehyde) react with halogen in the presence of base, multiple
halogenation of the a -methyl group takes place because introduction of the first halogen (due to its
electronegativity) makes the remaining a hydrogens on the methyl carbon more acidic. Actually, introduction of
the first halogen is slowest, while that of last (i.e. third) is fastest.

O
O
O
X2 , OH X2, OH
CH3CCH2X CH3CCHX2 CH3CCX3

In short,

O O
base
CH3CCH3 + 3X2 + 3OH CH3CCX3 + 3X + 3H2O
 697
When methyl ketones react with halogens in aqueous sodium hydroxide (i.e. hypohalite solutions), an additional
reaction takes place. Hydroxide ion attacks the carbonyl carbon atom of the trihaloketone (nucleophilic addition) and
causes a cleavage of the carbon-carbon bond between the carbonyl group and the trihalomethyl group (:CX3), the latter,
being a good leaving group*, departs easily forming a carboxylic acid and the trihalomethyl anion.

:
O: :O :

:

O
OH
CH3CCX3 CH3CCX3 CH3C + : CX3
OH OH

OH H2O

O

CH3CO HCX3
Carboxylate anion Trihalomethane

Since haloform (CHCl3, CHBr3 or CHI3) is produced in the reaction, it is known as haloform reaction (reaction of
methyl ketones with alkaline halogen to form haloform, CHX3).
Importance of haloform reaction.
1. Haloform reaction is used as a means of preparing carboxylic acids from methyl ketones. For this, chlorine
and bromine are most commonly used as the halogen component because resulting haloform (chloroform
and bromoform) are water immiscible liquids and hence are easily separated from the aqueous solution
containing the carboxylate anion.
O

(CH3)3CCCH3 + Br2 + OH (CH3)3CCOOH + CHBr3
3, 3-Dimethyl-2-butanone 2, 2-Dimethylpropanoic acid

2. Haloform reaction, particularly iodoform reaction is used as a laboratory test for identifying methyl ketones,
acetaldehyde and methyl secondary alcohols which are first oxidized to methyl ketones under the reaction
conditions.

H
I2 3I2 + 3OH
CCH3 CCH3 CCI3 + 3I + 3H2O
OH O O
Methyl sec. alcohol Methyl ketone Triiodoketone
or acetaldehyde

CCI3 + OH CO + CHI3
O O Yellow precipitate

1. Give the product of the reaction of 1 equivalent of Br 2 in H3O+ with

(a) propanal (b) acetophenone (c) cyclopentanone.
2. Arrange the following in decreasing ease of bromination.
CH3COCH3, CH3COCH2Br, CH3COCH2Cl, CH3COCHBr2.
3. Explain the following.
(a) Ketone I undergoes racemization in basic solution, but ketone II does not.
CH 3

C6H5 C CH C 6 H5 C6H5 C C C 6H5

O CH3 O C2 H 5
I II
(b) ArCHO, HCHO and RCH2CHO (R H) do not undergo haloform reaction.
 698

(C) Other reactions of aldehydes and ketones.

12. Oxidation. Aldehydes are much more easily oxidized, than ketones, to carboxylic acids. Aldehydes are oxidized
not only by the same reagents that oxidize primary and secondary alcohols, viz. permanganate and dichromate,
but also by the very mild oxidizing agent as silver ion. Oxidation by silver ion requires an alkaline medium
under which conditions it forms insoluble silver oxide, hence to dissolve this oxide a complexing agent ammonia
is added, which brings silver ion as diamminosilver (I) ion, Ag(NH3)2+. This alkaline solution of silver nitrate in
presence of ammonia is commonly known as Tollens reagent.

O O + O
KMnO4, OH
H3O
RCH RCO R COH
or K2Cr2O7 + H2 SO4

O O + O
Ag2O, OH
H3O
RCH RCO RCOH
Note that in the above reactions, aldehydes lose the hydrogen that is attached to the carbonyl carbon atom, and
since ketones do not have such hydrogen, they are resistant to oxidation.
Oxidation by Tollens reagent is accompanied by colour change (due to reduction of Ag+ ion to metallic silver),
hence the reagent is commonly used for detecting the presence of an aldehyde in laboratory.
RCHO + Ag(NH3)2+ RCOO + Ag
Colourless solution Silver mirror
Since Tollens reagent is a mild oxidising agent, it does not attack carbon-carbon double bond, hence it is used
for the synthesis of unsaturated acids from unsaturated aldehydes which are easily obtained from aldol condensation.
- Ag(NH 3 )2 +
OH heat
CH 3 CHO CH 3 CHOHCH 2 CHO CH 3 CH = CHCHO CH 3 CH = CHCOOH
Acetaldehyde Aldol Crotonaldehyde Crotonic acid

Aldehydes (except benzaldehyde) also reduce Fehlings solution (an alkaline solution of cupric ion complexed
with tartarate ion) and Benedicts solution, in which complexing agent is citrate ion.

O O
2+ +
RCH + 2Cu + 3OH RCO + 2Cu + H2O
(deep blue colour) (red ppt.)

Oxidation of ketones requires breaking of carbon-carbon bonds, and hence (except for haloform reaction) takes
place only under vigorous conditions. It is the double bond of the enol form that is cleaved during oxidation of ketones,
thus where structure permits oxidation may occur on either end of the carbonyl group to form a mixture of carboxylic
acids.

H OH O OH H

CC = C CCC C = C C

H H H H
Enol Keto Enol

O
oxidation
oxidaton
RCH2COOH + RCOOH
(b route) (a route)
b a

Methyl ketones are oxidized smoothly by means of hypohalite (NaOH or KOH + halogen) to form carboxylate
ion and haloform, and hence the reaction is commonly known as haloform reaction. (Details discussed earlier).
O O
|| ||
R C CH3 + 3X2 + 4OH R C O + CHX3 + 3X + 3H2O

H CH3 O H CH3
| | || | |
Oxidation
C6 H 5 C = C C CH 3 C6H5 C = C COO + CHX3
 699
Aldehydes and ketones having a methyl or methylene group adjacent to the carbonyl group are oxidised by
selenium dioxide.
SeO 2 2 SeO
CH 3 CHO CHO.CHO ; CH 3 COCH 3 CH 3 COCHO
Ethanal Glyoxal Propanone Methylglyoxal

Baeyer-Villiger oxidation. Both aldehydes and ketones are oxidised by peroxy acids. This reaction, called
Baeyer-Villiger oxidation, is however especially useful with ketones, because it converts them to carboxylic esters.
O O O O
RCR + R COOH ROCR + R COH
Ketone Peroxy acid Ester Carboxylic acid

Note that an oxygen from the peroxy acid is inserted between the carbonyl carbon and carbon atom of one the
alkyl groups of the ketone. In case of mixed ketones, oxygen insertion occurs between the carbonyl carbon and
the larger of the two alkyl groups of the ketone
O O
C6H5CO3H
CCH3 OCCH3

Cyclohexyl acetate

C6H5CO3H

O
O O
Mechanism, taking the example of cyclopentanone.
H O O
O HO OOCR HO OOCR
H O +
+
H
+ OOCR

+
OH
+
HO OOCR HO O
+ O O
+ H
H RCOOH

The tendency of a group to migrate (migratory aptitude) in all reactions where the group migrates with its
electron pairs (i.e. as anions) follows the order :
H > phenyl > 3 alkyl > 2 alkyl > 1 alkyl > methyl

1. Give the products of reaction for

(a) Benzaldehyde + Tollens reagent (b) CH3CHO + dil. KMnO4
(c) 3-Hexanone + Strong oxidant (d) Cyclohexanone + HNO3, heat
(e) Propanol + Ag(NH3)2+ (f) Methyl ethyl ketone + HNO 3, heat
2. Give the products of the reaction of I2 in KOH
(i) CH3CH2CHO (ii) CH3CH2OH (iii) C6H5CHO (iv) C6H5CH2COCH3
(v) Me 3C.COCH3 (vi) CH3CH2COCH2CH2COCH3 (vii) C6H5CH2OH.
3. What is the product of the reaction of each of the following ketones with peroxybenzoic acid ?

O NO2

(a) C6H5COC6H5 (b) (c) CHO (d) O

700
13. Reduction.
(a) Aldehydes and ketones can be reduced to primary and secondary alcohols respectively by a variety of reagents.
Catalytic hydrogenation over a metal catalyst and reduction with lithium aluminium hydride or sodium
borohydride are common methods and have been discussed in detail in the chapter on Monohydric Alcohols.
Sodium in ethanol is useful for reduction of ketones.
H2/Ni or
C = O CHOH
LiAlH4 or NaBH4

Benzaldehyde undergoes coupling reaction with Na/C2H5OH, so it can be reduced into alcohol by Na/C2H5OH.

(i) LiAlH , or NaBH H /Ni

4 4
CH 3 CH = CHCH 2 OH CH 3 CH = CHCHO
2 CH 3 CH 2 CH 2 CH 2 OH
(ii) H +

LiAlH4
O
+ OH
H
Cyclopentanone Cyclopentanol

Remember that reduction of carbonyl compounds to alcohols by LiAlH4 or NaBH4 is an example of nucleophilic
addition reactions in which hydride ion, H : (from LiAlH4 or NaBH4) is transferred from the metal to the
carbonyl carbon.

H H
3 C=O
C = O + H AlH3 COAlH3 CO Al
4
Tetraalkyloxyaluminate

H
4H2O
4 COH + Al (OH)4

(b) Aldehydes and ketones can be reduced to hydrocarbons by the action (i) of amalgamated zinc and
concentrated hydrochloric acid (Clemmensen reduction), or (b) of hydrazine (NH2NH2) and a strong base
like NaOH, KOH or potassium tert-butoxide in a high-boiling alcohol like ethylene glycol or triethylene
glycol (Wolf-Kishner reduction).
Zn(Hg), HCl
C = O CH2
or NH2 NH2, KOH, glycol

Both these methods reduce neither carboxylic acid nor the carbon-carbon double or triple bonds (however,
remember that Zn and HCl reduces NO2 to NH2 group).

2 NH NH
2
O
base

Cyclopentanone Cyclopentane

OH OH OH

CH3(CH2)4COOH Zn(Hg)

ZnCl2 HCl
OH OH OH
Resorcinol
CO(CH2)4 CH3 CH2(CH2)4CH3
4-n-Hexylresorcinol
(a constituent of dettol )
 701
(c) Aldehydes and ketones can be reduced to hydrocarbons through thioacetal formation too.

R HA R SCH2CH3
C = O + 2CH3CH2SH C + H2O
R R SCH2CH3
Aldehyde Ethanethiol Thioacetal
or ketone

R HSCH2 BF3 R SCH2

C=O+ C + H2O
R HSCH2 R SCH2

Aldehyde Ethane-1, 2-dithiol Cyclic thioacetal

or ketone

R SCH2 Raney Ni R
C CH2 + CH3CH3 + 2NiS
H2
R SCH2 R

(d) Many aldehydes and ketones are converted into amines by reductive amination (reduction in presence of
ammonia). Reduction can be done catalytically or by sodium cyanohydridoborate, NaBH 3CN. Reaction
involves reduction of an intermediate imine.

R R H2, Ni or R
C = O + NH3 C = NH CHNH2
R R NaBH3CN R
An aldehyde or ketone An imine 1 Amine

(e) Reduction of ketones to pinacols in presence of magnesium has already been discussed in the chapter on
Polyhydric Alcohols

CH3 CH3
Mg/benzene
2CH3COCH3 CH3CCCH3
Acetone
OH OH
Pinacol

14. Formation of dihalides. Aldehydes and ketones react with PCl5 and sulphur tetrafluoride to form corresponding
dihalide.

PCl5 Cl
O + POCl3
Cl

O F
SF4
F + SOF2

1. Write down the structure and IUPAC name of the products in each of the following reactions.
(a) 4, 4-Dimethylcyclohexanone + NH2NH2, OH (b) Pent-3-enal + NH2NH2, OH
(c) Acetylacetic acid + Zn(Hg) and HCl (d) Pent-2-enal + Zn(Hg) and HCl.
702
2. Give structures of the compounds A to D.

dry HCl Raney

(a) C6H5CHO + HSCH2CH2SH [A] [B]
Ni

(i) BH 3/THF NaBH 4

(b) [D]
-
O CH2 [C].
(ii) H 2 O2 , OH

3. (a) Write structures for the products of the reaction of PCl5 with
(i) propanal (ii) propanone (iii) benzophenone
(b) Give the products in the following reactions :

heat
(i) C6H5CHO + SF4 (ii) O + MoF6

15. Polymerisation. Lower aldehydes undergo polymerisation to form different products under different conditions.
evaporate to dryness
nHCHO (CH2O)n
(n = 6 to 50) Paraformaldehyde
room temp.
3HCHO (CH2O)3
Metaformaldehyde
(6-membered cyclic compound)
conc. H2SO 4
3CH 3CHO (CH3CHO)3
Paraldehyde
(6-membered cyclic compound)
conc. H2SO4, 0C
4CH 3CHO (CH3CHO)4
Metaldehyde
(8-membered cyclic compound)
CH3

conc. H2SO4
3CH 3COCH3
heat
H3C CH3
Mesitylene

14.6 Special Reactions Given by Aromatic Aldehydes and Ketones

1. Reaction with ammonia. Benzaldehyde reacts with ammonia to form hydrobenzamide, recall that aldehydes
other than formaldehyde give aldehyde ammonia, while formaldehyde forms hexamethylenetetramine, commonly
known as urotropine, an important urinary antiseptic.

C6H5CH = O H2NH C6H5CH = N

+ + O = CHC6H5 CHC6H5
C6H5CH = O H2NH C6H5CH = N
Hydrobenzamide

2. Benzoin condensation. Aromatic aldehydes, when heated with aqueous ethanolic NaCN or KCN, undergoes
self condensation to form benzoins. For example,
OH
KCN, heat

oxi. benzil-benzilic acid
2C6H5CHO C6H5CHOHCOC6H5 C6H5COCOC6H5 C6H5 C COOH
C2H 5 OH rearrangement

C 6 H5
Benzoin Benzil Benzilic acid
(An a-hydroxyketone)
 703
3. Perkin reaction. Condensation of an aromatic aldehyde with an acid anhydride in presence of sodium salt of the
same acid to form a, b-unsaturated acid is known as Perkin reaction.

(i ) CH 3 COONa
(i) C6H5CHO + (CH3CO)2O C6H5CH = CHCOOH
(ii ) H+

Benzaldehyde Acetic anhydride Cimmanic acid

CH 3
(i ) CH3 CH 2 COONa
(ii) C6H5CHO + (CH3CH2CO)2O C6H5CH = CCOOH
(ii ) H+
Benzaldehyde Propanoic anhydride a-Methylcinnamic acid
Remember that it is the a-carbon atom of the anhydride that reacts with the aldehydic group, observe (ii) example.
4. Reaction with benzene nucleus. Aromatic aldehydes and ketones undergo electrophilic substitutions in the
meta position. However, these reactions are slow because of deactivating influence of the carbonyl group. Moreover,
certain side reactions like oxidation make the yield poor.

14.7 Analysis of Aldehydes and Ketones

1. Aldehydes and ketones can be differentiated from non-carbonyl compounds through their reactions with
semicarbazide, 2, 4-dinitro-phenylhydrazine, and hydroxylamine with which they form precipitates.
Semicarbazones and oximes are colourless, while 2, 4-dinitrophenylhydrazones are usually orange. The melting
points of these derivatives can also be used in indentifying specific aldehydes and ketones.
2. Aldehydes are differentiated from ketones through their ease of oxidation. They give a positive test with Tollens
reagent, while ketones do not. However, a positive Tollens test is also given by few other easily oxidisable
compounds, e.g. a-hydroxy ketones, certain phenols and hydroxylamines.
3. Schiffs test is a highly sensitive test for aldehydes. An aldehyde reacts with the fuchsin-aldehyde reagent to
form a characteristic megenta colour.
4. Aldehydes are easily oxidised by cold, dilute, neutral KMnO4 and by CrO3 in sulphuric acid.
5. Aliphatic aldehydes and ketones having a-hydrogen react with bromine in CCl4 (caution this is also a test for
unsaturation).
6. Methyl ketones, acetaldehyde, ethyl alcohol and methyl secondary alcohols give positive iodoform test. In
general, iodoform test is given by following groupings.

O O
|| ||
(a) C CH3 present in ethanal, H C CH3 and all methyl ketones

OH

(b) C CH3 present in ethanol and all secondary methyl ketones.

H

O
P
(c) R - C - CH2 X since these products are formed during holoform reaction.

X
|
(d) R - CH - CH3 since these on hydrolysis with aq. NaOH give 2 alcohols having methyl group.
704

1. What happens when an aldehyde or a ketone is treated with the following reagents ?
Conc. H2SO 4, cold dil., neutral KMnO4, CrO3 in H2SO 4, and Br2 in CCl4.
2. By rapid test tube reactions distinguish between
(a) 2-Pentanol and 2-pentanone (b) Pentanal and diethyl ketone
(c) C6H5COCH2CH3 and C6H5CH(OH)CH2CH2CH3 (d) C6H5CH = CHCH2OH and C6H5CH = CHCHO.

14.8 Illustrative Examples

Example 1 :
Give various steps involved in the following conversions :
C6H5CH = CHCHO to C6H5CHBrCHBrCH2Cl.
Solution :
Conversion involves two main reactions, viz. addition of Br2 on C = C and conversion of CHO to CH2Cl. Since
bromine oxidizes CHO to COOH, so CHO first be converted to CH2Cl before adding bromine.

(i) NaBH 4 PCl5 Br2

C6H5CH = CHCHO C6H5CH = CHCH2OH C6H5CH = CHCH2Cl C6H5CHBrCHBrCH2Cl.
(ii) H 2 O

Example 2 :
Write structures of the compounds from A to I.

HF (i) BH3 /HF CrO 3 (i) CN -

(a) C6H6 + CH2 = CHCH2OH [A] [B] [C] [D]
(ii) H 2O 2 /OH - Pyridine (ii) H3 O +

Zn CrO 3 3
HOCH 2 CH2 OH LiAlH 4 H O+
(b) CHO + BrCH2COOC2H5 [E] [F] [G] [H] [I].
Pyridine

Solution :
(a) [A] is C6H5CH2CH = CH2, [B] is C6H5CH2CH2CH2OH,
(obtained by Friedel-craft alkylation) (obtained by anti-Markovnikov hydration)
[C] is C6H5CH2CH2CHO ; [D] is C6H5CH2CH2CHOHCOOH

OH O
O O
(b) COOC2H5 COOC2H5 COOC2H5

[E] (Perkin reaction) [F] [G] (Protection of keto group)

O
O O CH2OH
CH2OH

[I] (Regeneration of keto group)

[H] (Reduction of ester)
 705

Example 3 :
Write structures for A to D in the following.

CN - H 3O+ H2SO 4 (i) BH 3 /THF

(CH3)2CO [A] [B] [C] [D].
heat (ii) H2 O 2 , OH -

Solution :

OH OH
CH3CCN CH3CCOOH CH2 = CCOOH HOCH2CHCOOH
CH3 CH3 CH3 CH3
[A] [B] [C] [D]

Example 4 :
Identify A to C in the following :

2NBS H 3O+ NaOCl

C6H5CH2CH3 [A] [B] [C] + [D]
Solution :
C6H5CBr2CH3, C6H5COCH3, C6H5COONa+ + CHCl3
[A] [B] [C] and [D]

Example 5 :
Identify A to C in the following reactions.

CH2 OHCH 2 OH NaBH 4 H 3O+

O [A] [B] [C]
OHC H+ CH3 OH

Solution :
Aldehydes are more reactive than ketones, hence acetal formation at first step will be with the CHO group ; this
is done to protect the aldehydic group.

H
O OH
O O H
OH
O O
OHC
[A] [B] [C]

Example 6 :
Complete the following reactions.

C2 H5 MgBr (i) CO 2 H2 SO4 , Hg 2

(a) CH CH [A] B C
CrO
[D]
3

(ii) H H2 SO 4

NBS NaCN (i) C6H11MgBr

(b) C6H5CH3 E F G
(ii) H3 O
706
Solution :
C 2H5 MgBr (i) CO 2 H SO , Hg 2+
(a) CH CH HC CMgBr HC C COOH
2 4
(C2 H6 ) +
[A] (ii) H [B]

tautomerises CrO 3
HOCH = CHCOOH OHCCH 2 COOH HOOCCH 2 COOH
anti -Markownikov hydration [C] [D]
due to I effect of COOH

CH3 CH2Br CH2CN CH2COC6H11

NBS NaCN C6 H11MgBr

(b)

[E] [F] [G]

Cyclohexyl benzyl
ketone

Example 7 :
Give steps involved in the following conversions.
(a) Acetaldehyde to 2, 3-dibromopentanoic acid (b) Acetaldehyde to a-hydroxypropanoic acid (lactic acid)
(c) Benzene to p-chlorobenzaldehyde (d) Cyclopentane to cyclopentanecarbaldehyde.
Solution :
OH, heat
(a) 2H3CHO CH3CHOHCH2CHO CH3CH = CHCHO

[Ag(NH 3 )2 ] Br2
CH3CH = CHCOOH CH3 CH CH COOH

Br Br

NaCN H+
(b) CH3 CHO CH3 CHOHCN CH 3 CHOHCOOH
Lactic acid

(i) Br2 , Fe (i) CH2O Cl 2 , Fe

(c) C6 H6 C6 H5 MgBr C6 H5 CH2 OH p-Cl.C6H4CH2OH
(ii) Mg, ether (ii) H3 O+

CrO 3 , Pyridine
p-ClC6H4CHO

Cl MgCl CH2OH CHO

Cl2 Mg, ether (i) CH2 O CrO3

(d) +
hv (ii) H3O Pyridine

Example 8 :
Perform each of the following transformations :

O CHO CHO

(a) (b)

COOH CHO
 707

H
O
H
(c)
O
O
Solution :
O Cl Cl

PCl 5 2NaNH2
(a)

O
CHO CH O O
CHO
O O O +
HOCH2CH 2OH SOCl2 H2 and Pd H3O
(b)
protection of CHO BaSO4

COOH COOH COCl CHO CHO

O OH
NaBH4 conc. H2SO4 (i) O3
(c) CHO
heat (ii) Zn CHO

Example 9 :
Illustrate the following series of reactions by providing structure to each of the intermediate.

AlCl 3 Zn /Hg HF Zn /Hg Pd/C

C6H6 + [A] [B] [C] [D] [E]
O O O HCl HCl

Solution :
O O

AlCl3 Zn/Hg
+ O
HCl
HOOC
O [A]

HF Zn/Hg Pd/C

(H2O) HCl
HOOC [D] [E]
[B] [C] O

Example 10 :
Give steps involved in the following conversions.
(a) 14CH OH to CH 14CH OH (b) 14CH OH to 14CH CH OH
3 3 2 3 3 2
(c) 14CH CH OH to 14CD CHO (d) 14CH CHO to 14CH CHDOH.
3 2 3 3 3
Solution :

Cu (i) CH3 MgBr

(a) 14CH OH
3
H214C = O CH314CH2OH
300C (ii) H 3O +
708

HBr Mg (i) CH2 O

(b) 14CH OH 14 CH Br
14 CH MgBr
14 CH CH OH
3 3 3 3 2
ether (ii) H 3 O+

Cu D 2 O, OD, (trace)
(c) 14CH CH OH
3 2 14CH
3CHO 14CD
3CHO
D 2 /Pt or H2 O
(d) 14CH CHO
3 14 CH CHDOD
3 14CH CHDOH.
3
LiAlD 4

Example 11 :
How will you carry out following transformations ?

O O
(a) to (b) CHO to
O O O Ph Ph

+
H
(c)
H2O
CHO OH
OH

Solution :
The sterically unhindered keto group in (a) and the more reactive aldehyde group in (b) are more easily effected.

HSCH2CH2SH Raney + HS SH
(a)
Ni
O O OS S O

O O O
S
(b) CHO HSCH2CH2SH
S
Ph Ph Ph

+
H 2HO
(c) H H H +
(H )
O OH OH OH
+ + OH

Example 12 :
Write down the steps involved in the following reactions, each involves aldol condensation.
O
O
COOH
(a) (b) H OH
H

OH OH
O OH O

(c) (d)
H OH H

OH OH
 709
Solution :
O

(i) OH CHO (i) CH3CHO
(a) 2 H (
ii ) (H O)

(ii) H2O
2

CHO mild oxidation COOH

+
[Ag(NH3 )2]
Sorbic acid ( food preservative)

O OH

OH CHO heat
(b) 2 H
(H2O)

CHO H2/Pt

OH

2-Ethyl-1-hexanol

OH
OH
H2/Pt
CHO OH CHO
(c) 2 OH

2-Ethyl-1, 3-hexanediol
(an insect repellant )

H CH2OH CH2OH
Ca(OH) 2 CH2O
(d) HCCH = O + 3CH2 = O HOCH2CCHO
HOCH2CCH2OH + HCOO
(aldol condensation) OH

H CH2OH CH2OH
Acetaldehyde Pentaerythritol (a humectant )

Example 13 :
Give steps involved in the following conversion.

O
OH CH3
OH
H2SO4
CCH3 C6H5

C6H5

Solution :

OH OH O
OH
OH + OH +
CH3 H+ CH3 CH3
H + ring : CH2
CCH3 CCH3 C6H5 C6H5 C6H5
(H2O) shift
C6H5 C6H5 (Enol) (Keto)
3 Carbocation
(conjugated with Ar)
710

Example 14 :
Identify the final product formed in each case and explain its formation.

(i) NaNH 2 OH H
+
(a) CH3COCH3 + CH CH (b) (CH 3) 2C
(ii) H + CH2OH

Me 3 COK CN -
(c) O + CH2ClCOOCH2CH3 (d) + NH3
O

Solution :

HC CH

NaNH2

CH3 : C CH CH3 O H
+ CH3 OH
(a) C=O C C
CH3 CH3 C CH CH3 C CH

+ +
OH H O H2
(b) (CH3)2 C (CH3)2 C
CH2OH CH2OH (H2O)

3 alcohol is more basic than 1

+ H + tautomerization
(CH3)2 CCH 2 OH [CH3)2C = CHOH] (CH3)2CHCHO

Me3 CO -
(c) CH2ClCOOCH2CH3 C HClCOOCH 2 CH 3

Cl

O O CHCOOC2H5 OCHCOOC2H5

CHClCOOC2H5

(Cl )

CN CN

CN H2O
+ NH3
(d)
O NH NH NH2

Example 15 :
Predict the product and explain its formation in each of the following reactions.

O O

OH OH
(a) + CH2 = CHCN (b) + CH3CH2NO2
 711
Solution :
O O O O

:
CH2CHCN
OH : CH2 = CHCN CH2CH2CN
H2O
(a)
(CN is I group) + OH

CH3 CH3
O OH CH C
H NO2
NO2
OH
(b) + HCNO2
CH3

Example 16 :
Can you suggest a proper mechanism for the following reaction ?

H+
2C6H6 + (CH3)2CO (C6H5)2C(CH3)2.
Solution :

CH3
OH
+
O OH CCH3 + CCH3 CC6H5
+ H C6H6
H C6H6
CH3CCH3 CH3CCH3 CH3 CH3
+ CH3 (H2O)
An electrophile Another electrophile

Example 17 :
Semicarbazide (1 mol) is added to a mixture of cyclohexanone (1 mol) and benzaldehyde (1 mol). If the product
is isolated immediately, it consists almost entirely of the semicarbazone of cyclohexanone, if the product is
isolated after several hours, it consists almost entirely of the semicarbazone of benzaldehyde. Explain.
Solution :
Semicarbazone formation is reversible. Cyclohexanone reacts more rapidly because its C = O group is not sterically
hindered (its R groups are tied back into a ring), but benzaldehyde gives the more stable product,
C6H5CH = NNHCONH2, because of conjugation. Hence, initially the rate controlled product (cyclohexanone
semicarbazone) is formed ; later, after equilibrium is established the equilibrium controlled product (i.e. the more
stable benzaldehyde semicarbazone) is formed.

Example 18 :
An organic compound of the formula C 5H8O2 reduces Tollens reagent and also responds iodoform test. It reacts
with hydroxylamine hydrochloride to form a dioxime and can be reduced to n-pentane. Deduce the structure of
the compound.
Solution :
Positive test with Tollens reagent indicates the presence of CHO group, while positive iodoform test indicates the
presence of COCH3 grouping. Two carbonyl groups is also indicated by the formation of dioxime. Reduction of
the compound to n-pentane indicates the presence of 5 carbon atoms in a continuous chain. Hence the compound
should be CH3 C CH2CH2CHO.
||
O
712

Example 19 :
Compound X, C9H10O, is inert to Br2 in CCl4. Vigorous oxidation with hot alkaline permanganate yields benzoic
acid. X gives a precipitate with semicarbazide hydrochloride and with 2, 4-dinitrophenylhydrazine (DNPH). Write
all possible structures for X. How can these isomers be distinguished by using simple chemical tests ?
Solution :
Formation of benzoic acid, on oxidation of the compound X, indicates that X is having only one side chain. The
formula reveals five degree of unsaturation, four for the benzene ring indicated by the formation of benzoic acid and
hence fifth must be present in the side chain. The side unsaturation must be due to C = O group, indicated by
reaction with DNPH. Thus the possible structures for the compound X are

CH 3

C6 H 5 COCH 2 CH 3 C6 H 5 CH 2 COCH 3 C6 H 5 CH 2 CH 2 CHO C 6 H 5 CHCHO
I II III IV
Difference between I, II, III and IV. Aldehydes III and IV undergo oxidation by cold KMnO4 and CrO3 in H2SO4;
while compound II undergoes iodoform reaction.

Example 20 :
The Grignard reagent of an alkyl halide (I) reacts with propanal to give a secondary alcohol (II). II is converted into
another alkyl halide (III), Grignard reagent of (III) is hydrolyzed to form an alkane (IV). Compound IV can be
produced by coupling alkyl halide (I). Establish the structure of I and explain the reactions involved.
Solution :
Let us translate the given description into chemical equations.
R
Mg (i) CH 3CH 2 CHO HBr
RBr RMgBr CH 3 CH 2 CH(OH)R CH3CH2CH Br
I ether (ii) H 3 O+ II
III

R
Mg, ether H 2O
CH3CH2 CH MgBr CH3CH2CH2R
IV
Since IV is formed by coupling of I, it must be symmetrical, i.e. R should be CH3CH2CH2. Hence compound
I is CH3CH2CH2Br and thus the various reactions can be written as below.
CH 2 CH3
Mg, ether (i) CH 3CH2 CHO
CH 3 CH 2 CH 2 Br CH 3 CH 2 CH 2 MgBr CH3CH2CH2 CHOH
+
I II (ii) H 3O

CH 2 CH3 CH 2 CH 3 CH2 CH3

HBr
Mg, ether Na
CH3CH2CH2CHBr CH3CH2CH2 CHMgBr HOH
CH3CH2CH2 CH 2 2BrCH 2 CH2 CH3
(coupling) I
III

Example 21 :
Glycerol and ethanal are treated in equivalent amounts. Predict the number of isomeric acetals formed.

CH 2 OHCHOHCH 2 OH + CH 3 CHO

Solution :
Cyclic acetal may be formed by the reaction of CH3CHO (a) with the 1- and 2- OH groups, and (b) with 1- and 3- OH
groups. The former possibility creates two chiral centers, hence two pairs of enantiomers will be formed, one pair is the
cis- and the other is trans.
 713

O H O
OH CH3
CH2 C CH2
CH2 H H H C
+
+ O=C C CH3 C H
CH OH CH3 O O
HOH2C HOH2C
CH2OH cis trans

Reaction of CH3CHO with 1- and 3- OH groups will give cis- and trans- isomers, none of which is chiral. These
isomers are diastereomers.

OH
CH2
H O H O CH3
H H
CHOH + O = C +
OH CH3 OH H
CH3 O O
CH2
cis trans
OH

Thus, on the whole six isomers will be formed.

Example 22 :
The three isomeric dioxanes; 1,2-dioxane, 1,3-dioxane and 1,4-dioxane; behave differently. One of these acts
like an ether and is used as an excellent solvent for Grignard reactions, the other isomer when heated explodes,
and the third quickly hydrolyzes in dil. acid. Predict which one is which, and explain the difference.
Solution :
O O O
O
O
O
1,2-Dioxane, 1,3-Dioxane, 1,4-Dioxane,
I II III

The isomer I has an peroxide linkage (OO) which decomposes on heating to give radicals. In the presence of
organic compounds, radical reactions can be explosive. The isomer II behaves like an acetal which hydrolyzes in
dil. acid to alcohol and HCHO, while the III isomer behaves like a simple ether, the two oxygens are far enough apart
to act independently.

Example 23 :
Acetone, when dissolved in water having labelled oxygen (O18) gives CH3CO18CH3, and this conversion is catalyzed
by traces of strong acids and strong bases. Devise a mechanism for this.
Solution :
Acid catalyzed reaction :
+
O +
OH 18
OH +
OH
|| H || H2 O | H |
CH 3 - C - CH 3 CH 3 - C - CH 3 CH 3 - C - CH 3 CH 3 - C - CH 3
+ 18 +
H H2O |+ H |
18 OH 18 OH
2

+ OH
2 +
+
H | H2O + H
CH 3 - C - CH 3 CH 3 - C - CH 3 CH 3 - C - CH 3 CH 3 - C - CH 3
| +
+ | || H ||
H +H2O
.. - H
18 OH :O 18 OH 18 O
+
714
Base-catalyzed reaction :
18 18
OH + H2O H2O + OH

O O- OH
|| | H2O |
CH 3 - C - CH 3 + 18
OH - CH 3 - C - CH3 CH 3 - C - CH 3
| |
18 OH OH 18 OH

OH
OH | OH
CH 3 - C - CH 3 CH 3 - C - CH3
| ||
H2O OH
18 O
- 18 O

Example 24 :
Bisphenol A, an important constituent of many polymers like polyurethanes, polycarbamates, and epoxy resins, is
synthesized from phenol and acetone in presence of HCl. Propose a mechanism for this reaction.

CH3
HCl
2HO + (CH3)2C = O 2HO C OH

CH3
Bisphenol A

Solution :

CH3
.. HO
HCl + + ..
(CH 3 )2 C = O : (CH3 )2 C = O H (CH ) C - OH HO C OH
.. 3 2 ..
+ H CH3

CH3 CH3

Cl HCl +
HO C OH HO C
(Cl )
CH3 CH3

OH CH3 CH3

Cl
HO C OH HO C OH
H
CH3 + CH3
Bisphenol A

Example 25 :
H
O + OH
N(CH3)2 H3O +
O + (CH ) NH
3 2 2
H
(a) Propose a mechanism for the above hydrolysis of aminoacetals.
(b) Although aminoacetals are easily and quickly hydrolyzed by dilute acids, the nucleosides (having an
aminoacetal functional group) which are building blocks of DNA are not easily hydrolysed. Explain.
 715
Solution :
H ..
O .. O O
NMe2 + NMe2 ..
H3O + +
(a)
Resonance stabilized
carbocation

H
.. H .. +
O
.. + O
.. + O
H2 O OH H OH H OH
+

H H
H
O .. O H +. . OH
O H2O
+ .. H OH O HO CHO

(b) In the nucleosides the lone pair of electrons on nitrogen (forming a part of aminoacetal functional group) is
involved in aromatic sextet, hence not easily available for protonation with dilute acids. Protonation may
occur with extremely strong acids.

Example 26 :
Complete the following by supplying structures to compounds A and B

cold dil. HNO (i) OH - OH

C6 H 5 CH = CHC6 H5 [A] 3
[B] (C6 H 5 )2 C
KMnO 4 (ii) H+ COOH

Propose mechanism for the conversion of compound (B) to the final product.
Solution :
OH OH O O
| | || ||
C6 H 5 CH - CHC6 H 5 C6 H 5 - C - C - C6 H5
(A) (B)

O O O O O- O
|| ||
OH - ||
benzilic
| | ||
H+ OH
C6 H 5 - C - C - C6 H 5 C6 H5 - C - C - OH C6 H 5 - C - C - OH
(C6 H 5 )2 C
(B), Benzil | acid | COOH
C6 H5 rearrangement C6H5
Benzilic acid

Example 27 :
Identify compounds A, B, C and D through the structure of the compound Z.

(i) BuLi
S S [ ] [B]
(ii) A
Hg

3
O

2S

CH3
3)
2+
H3

(i)

H
O
,

(C
+

OH OH
)
(ii

CH3 (i) C
Z
(i) D
+ +
(ii) H3O (ii) H3O CH3

[E] [F] O
716
Solution :
The structure of compound Z can be established with the help of the known structure of the compounds E and F with
the help of following facts.
(a) Both are 3 alcohols and formed by identical reaction which seems to be Grignard reagent. Further both E and F
have CH3CH2CH2CH2 group as common, so the compound Z can be a Grignard reagent or a ketone with
n-butyl group as one alkyl group.
(b) Further the formation of Z from A and B suggests that Z is a ketone rather than the Grignard reagent.
Thus the compound Z is hexa-2-one which explains all reactions.

MgBr
OH
MgBr
CH3 CH3
(i) C (i) O
D
O
+ +
(i) H3O (i) H3 O
O O
E Z F
Formation of Z from A and B separately :
2+ R
BuLi nC4H9Br Hg (i) O3
S S S S (A) S S H3O
+ (ii) (CH3)2S R
CH3

CH3 O
H n-C4H9 Z (B)
CH3

Example 28 :
Give steps involved in each of the following conversions.
CH=CHCH3 CH2CH2NH2 O OH

(a) (b) +

OCH3 OCH3 O OH
Anethole Tyramine

Solution :

CH=CHCH3 CHO CH=CHNO2 CH2 CH2NH2 CH2CH2NH2

(i) O3, Zn CH3NO2 H2 / Ni (i) HI, heat

(a) (ii) CH3COOH (ii) neutralize
OH

OCH3 OCH3 OCH3 OCH3 OH

O O O OH

Diels-Alder NaBH4
(b) + reaction (Diels-Alder
reaction)
O O O OH
 717

EXERCISE 14.1 (MCQ - ONE option correct)

7. An organic compound A of the molecular formula C5H10Cl2 is
1. has its IUPAC name as hydrolyzed to compund B, C5H10O which gives an oxime with
hydroxylamine and yellow precipitate with a mixture of iodine
and sodium hydroxide. The compound A should be
(a) divinyl ketone (b) 1, 4-pentdien-3-one (a) CH3CH2CCl2CH2CH3
(c) 1, 3-penten-2-one (d) 1, 4-pentandione-3. (b) CH3CH2CH2CCl2CH3
2. In the following reaction, the compound A is (c) CH3CH2CH2CH2CHCl2
H 2SO 4 , HgSO 4 (d) CH3CH2CH2CHClCH2Cl.
[A] CH3CH2COCH3 8. Identify the nature of the reagent in the following reaction.
(a) HC CCH2CH3 (b) CH3C CCH3 ?
(c) Either of the two (d) CH3CH2CH = CH2 C6H5CH = C(CH3)COCH3 C 6H5CH = C(CH3)COOH
Hg 2+ / H + (a) alk. KMnO4 (b) conc. HNO3
3. C6H5C CCH3 A. Here A is (c) NaOI, H+ (d) any of the three.
O 9. Identify the compound X in the following reaction.
C6H5 C6H5
(a) (b) OH
O C6H5COCHO X
(a) C6H5COCH2OH (b) C6H5CHOHCH2OH
OH (c) C6H5CHOHCOO (d) C6H5COO + CH3OH.
(c) C6H5 (d) OH HCl
10. CH3CHO + H2O18 Acetaldehyde. The structure of the
product acetaldehyde is
4. Carbonyl compounds show two types of important properties : (a) CH3CHO (b) CH3CHO18
nucleophilic addition and acidity of a-hydrogen atoms. Which (c) A mixture of (a) & (b) (d) Reaction is not possible.
factor is most useful in explaining these two ? 11. Observe the following two reactions, here the products (A) and
(a) Presence of carbon-oxygen double bond (B) are
(b) Resonance in carbonyl group (i) CH3CHO + LiAlD4 [A]
(c) Ability of oxygen to accommodate negative charge Pt
(d) All are equally important. (ii) CH3CHO + D2 [B]
5. Identify the end product in the following series of reactions (a) CH3CD2OD (b) CH3CHDOD
AlCl 3 Mg (c) CH3CH2OD (d) CH3CHDOH.
C6H6 + CH3CH2COCl [B] End product
ether
(a) C6H5COCH2CH2Mg H 2O, H +
12. Identify P in the reaction, P
OH

(b) C6H5 C CH2 CH3 (a) HOCH2CH2CH2CH2CH2CH2OH + C2H5OH

(b) OHC.CH2CH2CH2CH2CHO
CH 2CH 3 (c) HOCH2CH2CH2CH2CHO + C2H5OH
(d) No reaction.
C6 H 5 C6 H5 13. Identify the product, if any, in the following chemical equation
KOD
(c) CH3CH2 C C CH2 CH3
+ 4D2O
reflux

OH OH
OC 2 H5
(a) (b)
(d) C6H5 C CH2 CH3

OC 2 H5
6. Identify the nature of the compound (Z).
CrO3/Pyridino
CH 3 CH 2 CH 2 CH 2 OH [X] (c) (d) No reaction takes place.
n-Butyl alcohol

(CH 3 )2 CHCH 2 MgBr CrO 3

[Y] [Z]
Pyridine 14. The most likely acid-catalysed aldol condensation products of
(a) 2CH3CH2CH2COOH each of the two aldehydes I and II will respectively be
(b) CH3CH2CH2COOH + (CH3)2CHCOOH
(c) CH3CH2CH2COCH2CH(CH3)2 CHO (I) and (II)
(d) CH3CH2CH2CHOHCH2CH(CH3)2.
 718

(i) NaOH / 100 C

(a) and 17. Major product is
+
(ii) H /H 2O

(b) and

(a)

(c) and

(b)
(d) and

C 2 H 5 MgCl
15. Identify A : A

(c)

(a)

(b)
(d)

(c)
18. Which of the following will undergo hydration most readily ?
(a) CH3COCH3 (b) CH3COCCl3
(c) CCl3COCCl3 (d) CF3COCF3.
(d) 19. In the following reactions [A] and [B] respectively are

16. is formed by intramolecular aldol condensation

of

(a) and
(a) (b)

(c) (d)
(b) and
 719
27. Among the following compounds, which will react with acetone
to give product containing >C = N .
(a) C6H5NHCOCH3 (b) (CH3)3N
(c) C6H5NHC 6H5 (d) C6H5NHNH2.
(c) and
H+
28. C6H5CH(OH)CH(OH)CH3 [A]. Here [A] is
(a) C6H5CH = CHCH3 (b) C6H5CH = C(OH)CH3
(c) C6H5COCH2CH3 (d) C6H5CH2COCH3.
(i) Mg, ether CH 3 CH 2 COCl
29. C6H11Cl [A] [B].
(d) and (ii) Li, (iii) CuLi
The compund B is
20. Acetic acid on heating gives OH
(a) methane (b) ethane
(a) C6H11 C CH2 CH3 (b) C6H11COCH2CH3
(c) methyl radical (d) ketene.
21. Which one is the best method for reducing 3-bromopropanal to
1-bromopropane ? CH 2 CH3
BrCH2CH2CHO BrCH2CH2CH3 (c) C6H11CH2COCH3 (d) C6H11CH2CH2CHO.
(a) Wolf-Kishner reduction 30. Which of the following compunds is oxidised to prepare methyl
ethyl ketone ?
(b) Clemmensen reduction
(a) 2-Propanol (b) 1-Butanol
(c) Either of the two
(c) 2-Butanol (d) tert-Butyl alcohol.
(d) None of the two. 31. The product formed by the reaction of chlorine with C 6H5CHO
22. The appropriate reagent for the following transformation in the absence of catalyst is
(a) chlorobenzene (b) benzyl chloride
(c) benzoyl chloride (d) o-chlorobenzaldehyde.
32. Which alkene is formed from the following ylide carbonyl pair ?
is CH3CH2CH2CH = PPh3 + 2-Butanone
(a) 3-Methyl-3-heptene (b) 4-Methyl-3-heptene
(c) 5-Methyl-3-heptene (d) 1-Methyl-5-heptene.
33. An organic compound A has the molecular formula C3H6O. It
(a) Zn (Hg), HCl (b) NH2NH2,OH undergoes iodoform test. When saturated with HCl it gives B of
(c) H2/Ni (d) NaBH4. molecular formula C9H14O ; A and B respectively are
23. Aldehydes when treated with alcohols form first hemiacetals (a) propanal and mesitylene
and then acetals in the following way (b) propanone and mesityl oxide
(c) propanone and 2, 6-dimethyl-2, 5-heptadien-4-one
H H (d) propane and mesitylene oxide.
H+ H+ 34. Compound A (molecular formula C3H8O) is treated with acidified
R C = O + ROH R C OR
(- H 2O) dichromate to form a product B (molecular formulae C3H6O). B

OH forms a shining silver mirror on warming with ammonical silver
nitrate.B when treated with an aqueous solution of
A hemiacetal H2NCONHNH2HCl and sodium acetate gives a product C.
Identify the structure of C
H H H
+ +
(a) CH3CH2CH = NNHCONH2
(i) ROH
R C OR R C = OR R C OR (b) (CH3)2C = NNHCONH2
(ii) H + (c) (CH3)2C = NCONHNH2
I II
OR (d) CH3CH2CH = NCONHNH2.
In the above reaction, which of the two cations is more stable? 35. Identify the final product (D).
(a) I (b) II AlCl 3 Zn / Hg
(c) Both are equally stable (d) None is stable. C6H5CH3 + (CH2CO)2 O [A]
HCl
24. The enol form of acetone, after treatment with D2O gives
HF (i) CH 3 MgI
OD O [B] [C] [D]
| || (ii) H 3O +
(a) CH3 C = CH 2 (b) CD3 C CD3
CH3
OH OD

(c) CH2 = C CH2D (d) CD2 = C CD3
(a) (b)
25. How many a hydrogens are present in benzyl methyl ketone,
OH
(a) 3 (b) 4 (c) 5 (d) No
26. In the Cannizzaro reaction, given below, CH3
OH -
2C 6H5CHO C 6H5CH2OH + C6H5COO
the slowest step is
(a) the attack of OH at the carbonyl group (c) (d)
(b) the transfer of hydride to the carbonyl group
H3C
(c) the abstraction of proton from the carboxylic acid CH3 OH
(d) the deprotonation of C6H5CH2OH.
 720
36. Identify the final product [E] 41. Which of the following will give yellow precipitate with I2/NaOH?
(a) ICH2COCH2CH3 (b) CH3COOCOCH3
Br2 / Fe (CH 3CO) 2 O,AlCl 3
C6H6 [A] [B] (c) CH3CONH2 (d) CH3CH(OH)CH2CH3
42. Which of the following reactants on reaction with conc. NaOH
CH 3 OH / HCl (i) Mg H3O + followed by acidification gives adjacent lactone as the product?
[C] [D] [E] O
(ii) D 2O
C
O
CH2
(a) (b) COOCH3 COOH
(a) (b)
COOH CHO
COOH CHO
(c) (d)
COOH CHO
43. The smallest ketone and its next homologue are reacted with NH2OH
to form oxime
(a) Two different oximes are formed
(c) (d) (b) Three different oximes are formed
(c) Two oximes formed are optically active
(d) All oximes formed are optically active
44. Cyclohexene on ozonolysis followed by reaction with zinc dust
and water gives compound E. Compound E on further treatment
with aqueous KOH yields compound F. Compound F is
37. Identify the final product D in the following reaction.
(a) CHO (b) CHO
C 6 H 6 , HF H 2 / Pt NBS alc. KOH
[A] [B] [C] [D]. CO 2 H
(c) COOH (d)
CO 2 H
45. In the following reaction sequence, the correct structures of E, F
and G are
O O
(a) (b) Heat I

[E]
2
NaOH
[F] + [G]
Ph OH
*
(c) Both (d) None. [* implies 13C labelled carbon)
O O
38. Which compound(s) does(do) not undergo Cannizzaro
condensation? E= * F= * G = CHI3
(a)
(a) Methanal (b) Trichloroacetaldehyde +
Ph CH3 Ph O Na
(c) Benzaldehyde (d) Ethanal
O O
39. Treatment of propionaldehyde with dil. NaOH solution gives
E= F= * G = CHI3
(a) CH 3 CH 2 COOCH 2 CH 2 CH 3 (b) +
*
Ph CH3 Ph O Na
(b) CH 3 CH 2 CH(OH).CH(CH 3 ).CHO
O O
(c) CH 3 CH 2 CHOHCH 2 CH 2 CHO *
E= F= G = CHI3
(c)
(d) CH 3 CH 2 COCH 2 CH 2 CHO * +
Ph CH3 Ph O Na
40. Which of the following forces explain the boiling point of aldehydes
O O
and ketones?
*
(a) Hydrogen bonding (b) Vander waal E= F= G = CH3 I
(d)
* +
(c) Dipole-dipole attraction (d) Any other Ph CH3 Ph O Na

EXERCISE 14.2
(b) The product is a mixture of two compounds which can be
DIRECTIONS for Q. 1 to Q. 44 : Multiple choice questions with separated by fractional distillation.
one or more than one correct option(s). (c) The product is a mixture of two compounds which cant
be separated by fractional distillation.
(d) The product on hydrolysis gives a single compound.
1. Which of the following statement is true regarding the following 2. One mole of C6H5COCH2CH3 is treated with one mole of Br2 in
chemical reaction ? basic solution, the product(s) formed is (are)
HCN (a) 1 mole of C6H5COCBr2CH3
CH3CHO CH3CHOHCN (b) 1 mole of C6H5COCHBrCH2Br
(a) The product on hydrolysis gives a mixture of two (c) 0.5 mole of C6H5COCBr2CH3
compounds : (d) 0.5 mole of unreacted C6H5COCH2CH3.
 721
3. Pentaerythritol, an important industrial chemical, is prepared 8. Which of the following can be used for the preparation of
by the following reaction chloroform?
(a) C6H5CHCl2 (b) CH3CHO
CH2 OH
(c) CD3COCH3 (d) CCl3CHO
Ca[OH] 2
9. The product of acid hydrolysis of P and Q can't be distinguished
4CH2O + CH3CHO CH2OH C CH2OH
by

CH2 OH
Pentaerythritol
(P) (Q)
This reaction involves
(a) Cannizzaro reaction (b) aldol condensation
(c) Crossed Cannizzaro (d) crossed aldol condensation (a) Lucas reagent (b) 2, 4-DNP
4. A mixture of cinnamaldehyde and crotonaldehyde is treated (c) Fehling solution (d) NaHSO3.
with concentrated alkali, 10. Acetaldehyde is obtained in the reactions
b a g b a OH 1. O
C6H5 CH = CHCHO + CH 3CH = CHCHO (a) CH 2 = CH - CH 2 - CH = CH 2 3
2. Zn , H 2O
which statement is not true about the above reaction ?
(a) Aldol condensation takes place and a-carbon atom of 1. O3
crotonaldehyde provides the carbanion, (b) CH3CH 2. Zn, H2O
(b) Aldol condensation takes place and b-carbon atom of
HgSO
crotonaldehyde provides the carbanion. (c) HC CH + H 2O
4
H 2SO4
(c) Aldol condensation takes place and g-carbon atom of
crotonaldehyde provides the carbanion. Pd - BaSO
(d) CH 3COCl + H 2 O
4
(d) Aldol condensation takes place and a-carbon atom of
cinnamic aldehyde provides the carbanion. 11. Which of the following statements are correct about a carbonyl
group?
5. Which of the following undergoes Cannizzaro reaction ?
(a) Thecarbonyl carbon issp2hybridized
(a) (CH3)3C.CHO (b) (CH3)3CCDO
(b) The carbonyl carbon is sp3hybridized
(c) C6H5CH2Cl (d) CH3CHO
(c) The three groups attached to the carbonyl carbon lie in
6. Each of the following two ketones is treated with a base (KOH)
different planes
O CH3 (d) The three groups attached to the carbonyl carbon lie in the
|| | OH -
(+) C6H5 C CH C6 H5 PI ; same plane
12. Phosphorus pentachloride reacts with
I
(a) alcohols (b) ketones
O CH 3 (c) ethers (d) amines
|| | OH -
13. Which of the following aldehydes undergo aldol condensation?
(+) C6H5 C C C6 H5 PII
(a) CH3CHO (b) C6H5CHO
C2 H5 (c) C6H5CH2CHO (d) pClC6H4CHO
14. Which of the following do not undergo base catalysed aldol
II
condensation?
Which of the following statement is false regarding above reactions?
(a) Benzaldehyde
(a) Both PI as well as PII are racemic mixtures
(b) 2,2, dimethyl propionaldehyde
(b) Both PI as well as PII are optically pure enantiomers
(c) 2-methyl propionaldehyde
(c) PI is optically pure while PII is a racemic mixture
(d) p-methylbenzaldehyde
(d) PI is a racemic mixture while PII is optically pure.
15. Which of the following statements are correct about the
7. Predict the nature of products C = O bond?
(a) It is made up of one p-bond and one s-bond
(b) It is used the sp2-hybrid orbital of carbon for its formation
(c) It is planar in nature
(d) It undergoes addition reactions
16. Which compound(s) undergoes (undergo) aldol condensation?
(a) Acetaldehyde (b) Benzaldehyde
COO K COO K
+ +
(c) Phenylacetaldehyde (d) Ethylmethyl ketone
17. Dry distillation of a mixture of calcium acetate and calcium
formate can form
(a) (b) (a) acetone (b) formaldehyde
(c) acetaldehyde (d) propanone
OH Cl
18. Which of the following are generally used for preparing derivatives
CH 2OH CH 2OH of aldehydes and ketones?
(a) Hydroxylamine hydrochloride
(b) 2,4-Dinitrophenylhydrazine
(c) (d) (c) Phenylhydrazine hydrochloride
(d) Hydrogen cyanide
H Cl
 722
19. Base catalysed aldol condensation occurs with : 30. Which of the following compounds will give haloform test?
(a) propionaldehyde
O
(b) benzaldehyde ||
(c) 2-Methyl propionaldehyde (a) CH 3 - C - CH 2 I (b) CH 3 - CH - CH 3
|
(d) 2, 2-Dimethyl propionaldehyde Cl
20. Which of the following compounds will give a yellow precipitate (c) C CH3 (d) CH3CH2Br
with iodine and alkali?
(a) 2-Hydroxy propane (b) Acetophenone O
(c) Methyl acetate (d) Acetamide
reaction R
21. Which of the following compounds will react with ethanolic KCN? 31. O or reagent R ; R can be :
(a) Ethyl chloride (b) Acetyl chloride
(c) Chlorobenzene (d) Benzaldehyde (a) Wolf Kischner reduction(b) Clemmensen reduction
22. Keto-enol tautomerism is observed in (c) (P + HI) mixture (d) Rosen mund reduction
32. Cannizzaro reaction will be given by :
O O
|| ||
(a) H 5C 6 -C - H (b) H 5 C6 - C -CH3
(a) CHO (b) CHO
O O
|| ||
(c) H 5C 6 -C -C6H5 (d) H 5 C6- C -CH 2 -CH 2 - CH 3
(c) CHO (d) CCl3CHO
23. Which of the following are the examples of aldol condensation?
dil. NaOH
(a) 2CH3CHO
CH3CHOHCH2CHO O
dil. NaOH ||
(b) 2CH3COCH3
(CH3)2COHCH2COCH3 SeO 2
33. CH 3 - C - CH 3 A; A will :
dil. NaOH
(c) 2HCHO
CH3OH (a) reduce Tollens reagent (b) give iodoform test
dil. NaOH (c) form dioxime (d) give Cannizzaro reaction
(d) C6H5CHO + HCHO C6H5CH2OH
24. A new carbon-carbon bond formation is possible in O
(a) Cannizzaro reaction (b) FriedelCrafts alkylation || conc. H 2 SO 4
34. 3CH 3 - C - CH 3 A; which is/are correct
(c) Clemmensen reduction(d) ReimerTiemann reaction
25. Which of the following will undergo aldol condensation? statement(s) about A :
(a) Acetaldehyde (b) Propanaldehyde (a) A is an aromatic compound
(c) Benzaldehyde (d) Trideuteroacetaldehyde (b) A can be oxidised to carboxylic acid
26. Among the following compounds, which will react with acetone (c) A can undergo free radical as well as electrophilic
to give a product containing > C = N bond ? substitution reaction
(a) C6H5NH2 (b) (CH3)3N (d) A contains two carbonyl group
(c) C6H5NHC6H5 (d) C6H5NHNH2. 35. Identify the set from the following which contains the two
27. Select correct statements : compounds each of which can form acetone in a single-step reaction:
(a) CH3CH(OH)CH3, (CH3)2C = CH2
(a) OH and OH both give colour with (b) (CH3COO)2Ca, (CH3)2C = CH2
(c) (CH3COO)2Ca, CH3C CH
neutral FeCl3 solution (d) CH3C CH, CH3C(Cl)2CH3
(b) 2-Pentanone and 3-pentanone are position isomers as well
HgSO 4 /H 2 SO 4 reaction R
as metamers 36. CH CH B A. A, B and
(c) When benzaldehyde reacts with hydroxylamine product reaction R are :
formed shows geometrical isomerism
(d) 1, 2-Dibromocyclohexane shows geometrical and optical O
||
isomerism (a) CH 3 - C - Cl, CH 3 CHO, Rosenmund (Pd/BaSO4, H2)
(b) CH3COOH, LiAlH4, hydroboration oxidation
28. O ; This change can be carried out using:
(c) CH3CN, CH3CHO, Stephen (SnCl2 / HCl)
(a) NH2NH2, glycol/OH (b) Sn(Hg)/conc. HCl (d) CH CH, CH3CHO, hydroboration oxidation
(c) P/HI (d) NH3/LiAlH4 37. Which is/are correct statement(s)?
29. In which cases products formed are not according to reaction? (a) In presence of conc. H2SO4, CH3CHO changes to cyclic
trimer-paraldehyde which is a hypnotic
H2SO 4 (b) At room temperature, HCHO forms cyclic trimer-trioxan
(a) OH + HNO3 NO2
(c) In presence of Ba(OH)2, HCHO forms hexose
(d) Bakelite is the polymer of HCHO and urea
H2SO 4
(b) OH+ HNO3 ONO 2 NaOH
38. 3HCHO + CH 3 CHO A ; A formed can :
(a) reduce Tollens reagent
(c) CH 2 = CH - CHO + LiAlH 4
CH 3 CH 2 CH 2 OH
(b) give Cannizzaro reaction
Cl + CH3 ONa O CH 3 (c) react with Na
(d)
(d) give green colour with Cr2O72 / H+
 723
39. A formed in previous question further reacts with NaOH to give: 45. The reaction is an example of
(a) aldol condensation
CH2 OH (b) crossed aldol condensation
|
(a) HOH 2 C - C - CH 2 OH by reduction (c) intramolecular aldol condensation
| (d) none of the three
CH 2OH
46. How many carbanions are possible in this case ?
I
(a) 1 (b) 2
(c) 3 (d) 4
CH 2OH
| 47. Which of the functional group is acting as nucleophile ?
(b) HOH 2 C - C - COONa by oxidation (a) Aldehyde (b) Ketone
| (c) Either of the two (d) None of the two
CH 2OH
II
PASSAGE 2
(c) only I (d) only II The carbonyl group C = O governs the chemistry of aldehydes
40. Which are correct statements : and ketones in two ways (a) : by providing a site for nucleophilic
(a) Cannizzaro reaction is proton-hydride transfer reaction addition, and (b) by increasing the acidity of the hydrogen atoms at-
(b) Hofmann-degradation of acid amide involves tached to the alpha carbon.
intramolecular migration of alkyl/aryl group from C to N The mobile p electrons of the carbon-oxygen double bond are
(c) Fries migration is intramolecular pulled strongly towards oxygen, which makes carbonyl oxygen elec-
(d) Cannizzaro reaction is disproportionation tron-rich and carbonyl carbon electron-deficient. Further, since carbo-
nyl group is flat, it is relatively open to attack from above or below. The
41. m-Chlorobenzaldehyde on reaction with conc. KOH at room
positive charge on the carbonyl carbon atom means that it is especially
temperature gives
susceptible to attack by a nucleophile. On the other hand, the negative
(a) potassium m-chlorobenzoate charge on the carbonyl oxygen atom means that nucleophilic addition
(b) m-hydroxy benzaldehyde is susceptible to acid catalysis.
(c) m-chlorobenzyl alcohol In addition to nucleophilic addition reactions, carbonyl com-
(d) m-hydroxybenzyl alcohol pounds exhibit the unusual acidity of alpha-hydrogen atoms. The
42. A mixture of benzaldehyde and formaldehyde on heating with unusual acidity of the alpha-hydrogen of carbonyl compounds is due
aqueous NaOH solution gives to its strong electron-withdrawing nature which in turn makes alpha-
(a) benzyl alcohol (b) sodium benzoate carbon also electron-withdrawing. Hence in presence of base it easily
loses hydrogen as proton and itself converted into carbanion.
(c) sodium formate (d) methyl alcohol
48. The carbonyl carbon is more reactive toward the nucleophile
43. Which of the following reactants on reaction with conc. NaOH
(a) in presence of acids
followed by acidification gives following lactone as the product?
(b) in absence of acids
O (c) equally reactive in both cases
C (d) in presence of base
O 49. The yield of hydrate is maximum in
(a) CH3CHO (b) HCHO
CH2
(c) O2NCH2CHO (d) CH3COCH3
COOCH3 COOH 50. Which of the following reactions of aldehydes is due to nucle-
ophilic addition on carbonyl group as well as due to acidic nature
(a) (b) of the a-carbon atom?
COOH CHO
(a) Reformatsky reaction (b) Aldol condensation
COOH CHO (c) Cannizzaro reaction (d) Wittig reaction
(c) (d) 51. The final product obtained during aldol condensation of propanal
COOH CHO is reduced in two ways.
44. The smallest ketone and its next homologue are reacted with CH 3
NH2OH to form oxime |
H 2 , Pd / C LiAlH
[B]
CH 3CH 2 CH = C CHO
4 [A]
(a) Two different oximes are formed
(b) Three different oximes are formed Which of the above reactions is a nucleophilic addition?
(a) Reaction leading to [A] (b) Reaction leading to [B]
(c) Two oximes formed are optically active
(c) Both (d) None
(d) All oximes formed are optically active
52. The compounds A and B in the above question are
CH3 CH 3
| |
INSTRUCTION for Q. 45 to 61 : Read the passages given below and (a) CH 3CH 2 CH = C CH 2 OH, CH 3CH 2 CH 2 C HCH 2 OH
answer the questions that follow.
CH3 CH 3
| |
(b) CH 3CH 2 CH = C CH 2 OH, CH 3CH 2 CH 2 C HCH O
PASSAGE 1
CH3 CH3
O O | |
(c) CH3CH 2 CH = CCH 2 OH, CH 3CH 2 CH = C OH

OH
CHO CH3 CH3
| |
(d) CH 3CH 2 CH 2 C HCH 2OH, CH 3CH 2 CH 2 C HCH 2 OH
 724

PASSAGE 3 O
In the following reaction sequence, product I, J and L are formed.
K represents a reagent. (c) + PhCH2MgBr
1.Mg / ether Ph H
1.NaBH 2.CO K
Hex - 3 - ynal
2.PBr
4
I
2
+ J O O
3 3.H3O
(d) +
Cl Ph H Ph MgBr
H
Me 2
Pd/ BaSO quioline
L 57. The structure of compound I is
4
Ph CH 3 H 3C Ph
O (a) (b)
53. The structure of the product I is H Ph H Ph
Ph C H3 H 3C CH3
(a) Me Br (c) (d)
(b) Me H CH 2Ph Ph H
Br 58. The structure of compounds J, K and L respecitvely, are
(a) PhCOCH3, PhCH2COCH3 and PhCH2COOK+
(c) Me Br (b) PhCHO, PhCH2CHO and PhCOOK+
(d) Me Br (c) PhCOCH3, PhCH2CHO and CH3COOK+
(d) PhCHO, PhCOCH3 and PhCOOK+
54. The structures of compound J and K, respectively, are
(a) Me COOH and SOCl2 PASSAGE 5
A carbonyl compound P, which gives positive iodoform test,
undergoes reaction with MeMgBr followed by dehydration to give an
OH olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which
(b) and SOCl2 undergoes intramolecular aldol reaction to give predominantly S.
Me
O 1. MeMg Br 1. O 1. OH

(c) Me P
+ Q
3
R S
2.H , H O 2. Zn,H O 2. D
2 2
COOH 3.H 2SO4 ,
(d) Me COOH and CH3SO2Cl 59. The structure of the carbonyl compound P is
Me
55. The structure of product L is
Me CHO (a) (b)
(a) O Me O Me
O
(b) Me CHO
CHO (c) (d)
(c) Me
O Et Me
(d) Me CHO 60. The structures of the products Q and R, respectively, are
O
PASSAGE 4
A tertiary alcohol H upon acid catalysed dehydration gives a Me , H
(a)
product I. Ozonolysis of I leads to compounds J and K. Compound J
COMe
upon reaction with KOH gives benzyl alcohol and compound L, whereas Me Me Me Me
K on reaction with KOH gives only M.
O O

H3 C (b) , H
Ph CHO
Me
M= Me
Me Me

H O
Ph
56. Compound H is formed by the reaction of H
(c) ,
O CHO
Me Et
Me Et
(a) + PhMgBr
Ph CH3 Me O
O CH3
(d) ,
(b) + PhCH2MgBr CHO
CH3 Me Me Et
Ph
 725
61. The structure of the product S is 64. Column I Column II
O (A) Schiffs reagent (a) Elimination reaction
(B) Alcoholic KOH (b) colourless solution
(a) (b) due to SO2
O (C) Ammonical AgNO3 (c) Aldehydes
Me Me
Me (D) Benedict solution (d) Chloroform
O O
Me
(c) (d) Instructions for Q. 65 to 70 : Following questions are Assertion and
Reasoning Type Questions :
Me Me
Note : Each question contains STATEMENT-1 (Assertion) and
STATEMENT-2 (Reason). Each question has 5 choices (a), (b), (c),
Instructions for Q. 62 to Q. 64 : Following questions are Multiple (d) and (e) out of which ONLY ONE is correct.
Matching type Questions : (a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
62. CHO > C = O (b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
Column I Column II correct explanation for Statement-1.
O (c) Statement -1 is True, Statement-2 is False.
+ OH (d) Statement -1 is False, Statement-2 is True.
(A) OHC (a) Cyclization
(e) Statement -1 is False, Statement-2 is False.
(B) + C6H 5CO 3H (b) Aldol condensation

O
65. Statement 1 : Acetaldehyde on treatment with alkali gives aldol.
(C) (c) Ring expansion
Statement 2 : Acetaldehyde molecule contains hydrogen atom.
+
+H 66. Statement 1 : Acetylene on treatment with alkaline KMnO4
CHO produce acetaldehyde.
Statement 2 : Alkaline KMnO4 is a reducing agent.
(D) HOCH 2 CH 2 CH 2 CH 2 Cl + OH - (d) Williamson synthesis 67. Statement 1 : Hydroxyketones are not directly used in Grignard
63. Column I Column II reaction.
OH Statement 2 : Grignard reagents react with hydroxyl group.
68. Statement 1 : Isobutanal does not give iodoform test.
(A) (a) aldol condensation
O Statement 2 : It does not have a-hydrogen
CHO 69. Statement 1 : Cyclohexanone forms cyanohydrin in good yield
but 2, 4, 6-trimethyl cyclohexanone does not.
(B) (b) Cannizzaro reaction
Statement 2 : The formation of cyanohydrin involves the
OHC CHO nucleophilic attack by CN ion on the carbonyl carbon.
70. Statement 1 : There are two NH2 groups in semicarbazide.
(C) (c) haloform reaction
Statement 2 : One group is involved in the formation of
O semicarbazones.
(D) (d) reaction with chlorine

EXERCISE 14.3 (Subjective Problems)

1. Give IUPAC names for the following : 4. Compare the polarities of the C = O and C = C bonds. How
does this difference influence the reactivity of each bond as a
nucleophilic site for reaction ?
(a) C6H5CH = CHCHO (b) 5. Account for the following :
(a) The boiling points of 2-propanol, propanone, and 2-
methylpropene differ very much, although they have ap-
proximately same molecular weight.
(c) (d) (b) Carbonyl compounds are more soluble in water than the
corresponding alkanes but less than the corresponding
alcohols.
2. Give the structural formula of (c) 2-Butanone has a lower DH of combustion than butanol.
(a) Trimethylacetaldehyde 6. What is a ketene ? Give the structural formula and atomic
(b) a, g-Dimethylcaproaldehyde orbital representation of ketene.
(c) p, p-Dimethylbenzophenone. 7. (a) How will you prepare an aldehyde by the reduction of a
3. What are the expected HCO and HCH bond angles in carboxylic acid ester ?
CH2O ?
 726
(b) Give the product of the reaction of cis-1, 2-cyclohexanediol 18. (a) Write down the structure of the product(s) obtained by treat-
with periodic acid. Why is the trans-glycol almost inert to ing each of the following aldehyde with conc. OH
this reagent ? (i) Benzaldehyde (ii) Trimethylacetaldehyde
8. Give reagent(s) used for preparing (CH3)2CHCH2COCH3 from
(a) an alkyne (b) an alcohol (iii) (iv) Benzal chloride
(c) an acid chloride + organocopper compound
(d) a carboxylic acid (v) tert-Butyldichloromethane
(e) an acid chloride + organocadmium compound (b) Write down the structure of the product(s) obtained by
(f) a nitrile. treating each of the following with conc. NaOH.
9. Write the organometallic compound and other chemical com- (i) C6H5CH2CHO (ii) CH3CH = CHCHO
pound (a carbonyl compound) used for preparing following (iii) C6H5CH = CHCHO + CH3CH = CHCHO
alcohols. (iv) CH3CHO + 4 HCHO.
(a) 1-Phenyl-1-propanol (b) 2-Phenyl-2-propanol 19. Identify A to D in the following series of reactions :
(c) 1-Phenyl-2-propanol (d) 3-Phenyl-1-propanol
(e) 1-Methylcyclohexanol (f) Cyclohexylmethanol
(g) 1-Cyclohexylethanol (h) 1-Pentyn-3-ol (i) CH 3 MgI H 2SO4 (i) O 3/H 2 O/Zn OH -
[B] [C] [D]
[A]
(i) 3-Pentyn-2-ol (j) 1-(p-tolyl) ethanol. (ii) H 2 O heat
10. Write down the structure of the compound obtained when phe-
nyl acetaldehyde or cyclohexanone is treated with each of the 20. Complete the following reactions :
following reagents ? (a) C6H5COCH2CH3 + SO2Cl2
(a) Tollens reagent (b) CrO3/H2SO4
(c) Cold dil. KMnO4 (d) Acidic KMnO4, heat (b) Me 2 + NBS
(e) H2, Ni, pressure (f) NaBH4 21. Describe a simple chemical test that can be applied for
(g) C6H5MgBr, H2O (h) Me 2CHMgCl, H2O distinguishing between
(i) HC CLi, H2O (j) Semicarbazide (a) phenylacetaldehyde and benzyl alcohol
(k) ethyl alcohol, dry HCl (gas) (l) tert-Butyl amine (b) 2-pentanone and 3-pentanone
(m) C2H5SH, H+. (c) cyclohexanone and cyclohexyl methyl ether
11. Convert propanal into following (d) diethyl acetal and n-valeraldehyde
(a) n-Propanol (b) a-Hydroxybutanoic acid (e) diethyl acetal and di-n-propyl ether
(c) sec-Butyl alcohol (d) 1-Phenyl-1-propanol (f) methyl m-tolyl ketone and propiophenone
(e) 2-Methyl-3-pentanol. (g) 2-pentanone and 2-pentanol
12. Name the reagent used to convert 2-methyl-2-pentenal to (h) paraldehyde and diisobutyl ether
(a) 2-methyl-2-pentenol (b) 2-methylpentanol (i) dioxane and trioxane.
(c) 2-methylpentane (d) 2-methylpentanal. 22. Identify compounds [A] to [D] and explain their formation.
13. A carbonyl group can be reduced to methylene group by three
methods : Clemmensen, Wolf -Kishner and Raney Ni PCl 3 AlCl 3
desulphurization. How would you decide which method should [A] [B]
C 11H 13OCl C 11H 12 O
be applied for a particular carbonyl compound?
14. Select the best way for reducing the carbonyl group to methyl-
ene in each of the following : NH 2 NH 2 , OH - AlCl 3
(a) BrCH2CH2CHO (b) (CH3)2C (OH) CH2CH2COCH3 [C] [D]
heat C11H 14 or Conc. C10 H 13CH 2OH
(c) C6H5CHOHCH2COC2H5 (d) H2 SO 4
23. Identify the compounds [A] to [E] in the following reactions.
LiNH 2 CH 2ClCH 2CH 2 Br (i) Mg
15. Identify the reduced product.
n-C 5H11C CH [A] [B]
(ii) R CHO

H 2 , Lindlar CrO 3
Pt, 1 eq. H 2
(a) [C] [D] [E]
[A] catalyst
24. Identify [A] in the following reaction.
H+ C6 H 5Cl
Cl + CCl3CH(OH)2 [Intermediate] [A]
H+
1 eq. NaBH 4
(b) [B] 25. Give the possible product(s) obtained in each of the following
CH 3OH reactions.
Et
+
16. How will you convert C6H5CH = CHCOCH3 to CHO base N CH2COC6H5 base
(a) C6H5CH = CHCOOH (b) C6H5CH = CHCHOHCH3 (a) (b)
CHO N CH COC H
(c) C6H5CH2CH2COCH3 (d) C6H5CH = CHCH2CH3 2 6 5
(e) C6H5CH2CH2CH2CH3. 26. Complete the following explaining each step
17. Arrange the following in decreasing ease of hydration : O
(a) CH3CHO, (CH3)2CO, HCHO, CH2ClCOCH3, CH2ClCHO
+
(a) CH3OCH=PPh3 H , H2O
CHO [A] [B]
Br
(i) O 3 base
(b) [C] [D]
(b) (ii) Zn, CH3COOH
 727

1. (a) 1, 5-Pentandial or Pentanedial (b) 3-Phenyl-2-propenal

(c) 4-Hydroxy-3-methoxybenzaldehyde (d) 1, 3-Diphenyl-2-propanone
(e) 2-Phenylpropanedial (f) Cyclopentanecarbaldehyde
(g) 1, 3-Diphenyl-2-propen-1-one.
2. (a) CH3CH2CH2CH2CHO CH3CH2CH(CH3)CHO (CH3)2CHCH2CHO (CH3)3CCHO
Pentanal 2-Methylbutanal 3-Methylbutanal 2, 2-Dimethylpropanal
CH3CH2CH2COCH3 CH3CH2COCH2CH3 (CH3)2CHCOCH3
2-Pentanone 3-Pentanone 3-Methyl-2-butanone
(b) C6H5CH2CHO CH3 . C6H4 . CHO C6H5COCH3
Phenylethanal o-m-and p-Tolualdehyde Acetophenone

1. Primary alcohols can be quantitatively oxidised to aldehydes by acid dichromate only when the aldehyde product is more volatile than
the reactant alcohol and water, and it is removed from the reaction mixture as soon as it is formed by distillation otherwise it will
undergo oxidation to form carboxylic acid as the final product. Thus acetaldehyde (b.p. 20C) and propionaldehyde (b.p. 49C) can
be obtained from their respective 1 alcohols.
Na 2 Cr2 O 7
CH 3CH 2OH CH 3CHO
b.p. 78C H 2 SO 4 b.p. 20 C

Na 2 Cr2 O 7
CH 3CH 2CH 2OH CH 3CH 2CHO
b.p. 97C H 2 SO 4 b.p. 49 C

K 2 Cr2 O 7
CH 3CH 2CH 2CH 2OH CH 3CH 2CH 2CHO
b.p. 118C H 2 SO 4 b.p. 75

1. A = CH3CH(CH3)CH2OH, B = CH3CH(CH3)CHO
2. (a) CH3CH2CH2COOC2H5 + DBAH, (b) CH3CH2CH2CN + DBAH,
(c) CH3CH2CH2COCl + LBAH.
AlCl 3 SOCl 2 CN (i) DBAH
3. C6H6 + CH2 CH2 C 6H5CH2CH2OH C6H5CH2CH2Cl C6H5CH2CH2CN C 6H5CH2CH2CHO
(ii) H 2 O

O
(i) BH 3 .THF
4. (a) CH3CH2CH2C CH
- CH3CH2CH2CH2CHO
(ii) H 2 O 2 /OH

(b) 2

(c) 2
 728
O
(i) CO, H 2O ||
BCH2CH2CH2CH3 C CH 2CH 2CH 2CH3
-
(ii) H 2 O 2 /OH

2
n-Butyl cyclopentyl ketone

O
BH
BH3.THF (i) CO, H2O
(d) 2

(ii) H2O2 , OH
2
Dicyclohexyl ketone

1. Organocopper, R2CuLi and organocadmium compounds are less reactive than organomagnesium and organolithium compounds
because CCu and CCd bonds are less ionic than CMg and CLi bonds, hence the alkyl group of organocopper and organocadmium
are less nucleophilic and consequently less reactive than the R groups from R Mg X and RLi. In general, the more electropositive a metal,
more will be ionic character of the bond through which it is attached to carbon, and hence more will be nucleophilic character of the R
group attached to it.

2. (a) (i) CH2 CH O (The cuprate does not add to C = O, but only couples).

(ii) (CH3CH2)2Cd or (CH3CH2)2CuLi.

(b) No, because the required organocopper compound would have to be prepared from the organo-lithium reagent and the nitro group
would interfere with any attempt to form that reagent.

1. (a) CH3CH2CHO, CH3CH2CH2CHO (b) (CH3)2CHC(CH3)2CHO

[A] [B] [C]

2. (a) Hexanal (b) 1-Hexanol (c) 2-Pentanol (d) Benzyl alcohol (e) 2-Phenylethanol.
3. n-Butanol can associate through hydrogen bonding between their molecules.

1. (a) A change from a trigonal sp 2 to a tetrahedral sp 3 carbon in the transition state is accompanied by crowding of the four groups on
carbon. Crowding and hence destabilization of the transition state increases in the order : CH 2O, RCHO and R2CO. Hence the order
of reactivity should be CH2O >RCHO >R2CO.
This can also be explained on the basis of destability produced by electron releasing character of the alkyl group(s) which intensifies
the negative charge developed on oxygen in the transition state.
In RCOY, reactivity toward nucleophilic addition is minimum because positive charge on carbon is not developed due to possibility
of resonance.

d
O: :O: O
:
:

+ d+
R C Y R C Y
:

RCY

Hence acid derivatives (RCOX) are less reactive than aldehydes and ketones toward nucleophilic addition.
 729
(b) Due to presence of ArC = O grouping, resonance is possible and hence presence of Ar on the C = O group deactivates the carbonyl
group toward nucleophilic addition. Two Ars are more deactivating than one Ar. However, in case of ArCH2COR, extended p
bonding between C = O and Ar is absent, and hence only the electron-withdrawing inductive effect of Ar prevails, which increases
the reactivity of CH2COR toward nucleophilic addition. Thus the decreasing order of reactivity is
O O O O
|| || || ||
Ar CH 2 C R > R C R > Ar C R > Ar C Ar
Most reactive due to I Least reactive
effect of Ar and absence of due to extended
extended p bonding p bonding between
C = O and 2 Ar-groups.
2. In acetone, the two methyl groups stabilize the carbonyl group by electron donation and hence acetone undergoes nucleophilic
additions very slowly. On the other hand, the two trifluoromethyl groups destabilize the carbonyl group by withdrawing electrons,
making hexafluoroacetone very reactive.

Od
||d +
H 3C C CH 3

Acetone (C = O group stabilized Hexafluoroacetone (Repulsion from adjacent

due to dispersal of d+ on C) d+ charges destabilizes the molecule)

3. Although the equilibrium between acetone and its hydrate mostly favours the ketone, some hydrates exist.

O16 O16 H
|| |
CH3 C CH 3 + H2O18 CH3 C CH 3 CH3 C CH3 + H2O16
||
O18 H O18

When the hydrate loses water, there is a little more chance for O18 to be retained in the ketone because the 18OC bond is slightly
stronger when the 16OC bond.
4. The central C = O group is hydrated easily because these will give the product in which d+ on the other two carbon atoms will be
separated.

d d
O O
d+ d+
d+ d OH
O + H2O
OH
d+ d+
Od Od

Repulsion between both pairs of the C = O Repulsion between adjacent d+ charges removed
5. (a) C > A > B > D (b) B > C > D > A

1. (a) Williamson synthesis (b) Acetals (cyclic)

(c) Treatment with acid gives catechol and formaldehyde, while there will be no reaction with base.
2. High alcohol, low water concentrations shift the hemiacetal-acetal and aldehyde-hemiacetal equilibria in the direction of the acetal.
Low alcohol, high water concentrations shift the equilibria in the direction of the aldehyde.

3. (a) (b) (c)

4. (a) For this we will have to protect CH2OH group via acetal formation.
C2H 5OH alk. KMnO4 H 2 O, H +
CH2 = CHCHO CH2 = CHCH(OC2H5)2 CH 2 CH CH(OC 2H 5 ) 2 CH 2 CH CHO
Acrolein H+
OH OH OH OH
Glyceraldehyde
 730

(b)

CH3OH

(c) hemiacaetal CHOCH3
formation
CHO O OH O OCH3
O
H H

1. II > III > I > IV.

CH3 CH3 CN +
HCN H
2. CO C CH3 C CN
(H2O)
CH3 CH3 OH CH2

3. (a)

(b)

(c)

(d)
 731
4. (a) A small amount of baseis necessary to convert someHCN to CN, after which the CN is regenerated. However, too much base
decomposes cyanohydrin, reversing the equilibrium.

R OH R O R
NaOH
C C C = O + CN
H CN H CN H

(b) CN adds to RCHO to give RCH(CN)O which is a more basic (alkoxide) anion than the CN ; in this situation the side with the
weaker base is favoured. Thus in this reaction, the equilibrium lies more towards RCHO than in the HCN reaction ; in other words
Keq(for HCN) > K - .
eq (for CN )

1. Schiff base is the product obtained by the condensation of an aldehyde or a ketone with a primary amine.
RCHO (or R2CO) + RNH2 RCH = NR (or R2C = NR)
A Schiff base (An N-substituted amine)

(a) (b) (CH3)2C = NNHCONH2

(c) Sodium acetate frees H2NOH, from its salt H3N+OHCl, which then reacts with 2-butanone to form oxime, CH3 CCH2CH3 .
||
NOH

(d) (e) (f)

(g) (h)

2. (a) Rotation about the p bond in >C = N is not free and therefore geometrical isomerism is possible when the two substituents on the
carbon are different.

(b) Loss of H+ from H2NOH gives the conjugate base, H2NO in which negative charge is localized on oxygen. On the other hand, loss
of H+ from oximes gives the conjugate base which stabilizes due to extended p bonding.

Due to delocalization of electrons in the conjugate base of oximes, these are weaker bases and hence their conjugate acids, the
oximes are more acidic.
(c) The NH2 group closer to the carbonyl group is deactivated (resonance-stabilized) compared with the other end NH 2 group.
.. Deactivated
..
O O
..
..
..

.. .. +
H2N NH C NH2 H2N NH C = N H2
 732
OH

(i) Zn / benzene
3. (a) (i) (CH3)2 C = O + BrCH2COOC2H5
+
(CH3)2 CCH2COOC2H5
(ii) H 3O

(i) Zn / benzene
(ii) + Br CHCOOC 2H 5
(ii) H 3O +

CH 3

(b) The order of electropositivity is Mg > Zn > Cd. The order of ionic character is MgC > ZnC > CdC. Thus the order of
nucleophilicity of R in Md+Rd is MgR > ZnR > CdR. Therefore, BrMgCH2COOC2H5 reacts with the C = O part of the second
molecule of the ester. BrZnCH2COOC2H5 can only react with the carbonyl group of aldehydes and ketones because these are more
reactive than esters towards nucleophilic addition. CdR2 does not react with ketones and aldehyde because its alkyl groups are not
nucleophilic enough to add to carbonyl group.

1. (a)

OH
OH -
H 2O OH -
(b) C6H5COCHCl2 C 6H5COCH(OH)2 C 6H5COCHO C 6H5 CHCOONa
D O D O
|| ||
(c) ArCD2OH + ArCOO (d) H C OH + D C ONa (e) D C OH + D C O

H D
(Remember that B.E. of CD >> CH)

2. Since formaldehyde is the most reactive aldehyde, it exists in aqueous OH solution mainly as the conjugate base of its hydrate,
H2C(OH)O. Moreover, formaldehyde has two hydrogens available for transfer as hydride ion as compared to other aldehyde hydrate
anion which has one such hydrogen.
3. Loss of hydride ion from II yields the resonance-stabilized species III directly, hence II is a better hydride donor.

4. In a Wittig reaction, replace the carbonyl oxygen of the aldehyde or ketone by the negatively charged substituent attached to
phosphorus.

(a) (b) n-C 3H7CH = CHCH = CH2 (c)

5. (a) CH3CH2CH2CHO + Ph3P+ (CH3)CH2CH3 or CH3CH2CH2 HP+Ph3 + CH3COCH2CH3

(b) C6H5CHO + Ph3P+ HC 6H5 (c)

1. (a) Racemization takes place in the presence of acids or bases because the aldehyde or ketone slowly but reversibly changes to its enol
and the enol is achiral. When the enol reverts to the keto form, it produces equal amounts of the two enantiomers.
H O OH

OH , H2 O
C6H5 C C H C6H5 C C H C6H5CH(CH3)CHO

CH 3 CH 3
(+)- Enol form (achiral) ()-
 733
(b) Hydrogen on the carbon lying between the two carbonyl groups is the most acidic. Removal of a proton yields an anion that is highly
stabilized by accommodation of the negative charge by two oxygens (rather than by only one).

(c) g-Hydrogens of a, b-unsaturated carbonyl compunds, e.g., 2-butenal, CH3CH = CHCHO is acidic because the negative charge of
the anion in accommodated by the electronegative oxygen through the conjugated system.

2. (a)

(b) CN adds to the conjugated system in the way that the more stable anion, the one in which the charge is partly accommodated by
oxygen which is best able to accommodate it, is formed.
CN CN CH3
CN
CH3 C = CH C CH3 CH3 C = CH C CH3 CH3 C CHCO


CH 3 O CH3 O CH 3

(Unstable, since resonance not possible) Stable (resonance possible)

CN CH3 CN CH 3 CN CH3
H+
CH3 C CH = C OH CH3 C CH C O CH3 C CH 2 C = O


CH3 CH 3 CH 3
enol form keto form (more stable)

1. (a) 2

O OH O
OH - | - H2 O
(b) 2 C6H5COCH3 C 6H5 C CH 2 CC6 H5 C6 H 5 C = CH CC6 H5

CH 3 CH 3
 734

(c) C6H5CHO + C6H5

Note that here it is the g-hydrogen atom which is taking part in aldol condensation. It is because of the fact that it is quite acidic in
nature due to extended p bonding which leads to negative charge on oxygen.

(d)

It can said to be an example of intramolecular aldol condensation.

(e)

1. (a) C6H5CH = CHCOC6H5 (b) (c)

2. These are aldol condensation related reactions.

O- OH
OH -
CH 3CHO H+
(a) CH3NO 2 CH 2 NO2 CH3 CHCH 2 NO2 CH3 CHCH2 NO2 CH3CH = CHNO2

CN

C 2 H 5 ONa
(b) C6H5CHO + C6H5CH2CN C 6H5CH = CC6H5

hydrolysis CO 2
(c) C6H5CHO + CH3COCH2COOC2H5 C6H5CH = C COCH 3 C6H5CH = CCOOH C6H5CH = CHCOOH

COOC2 H 5 COOH

1. (a) CH3CHBrCHO (b) C6H5COCH2Br (c)

2. CH3COCHBr2 > CH3COCH2Cl > CH3COCH2Br > CH3COCH3

Presence of electron-withdrawing group increases the acidity of the hydrogen atom present on such carbon atom.
3. (a) I can give a carbanion which being planar becomes chiral, hence proton on it may attach to either face of the carbanion producing
racemic mixture. On the other hand, II does not have a-hydrgoen and hence cannot form a carbanion.
(b) In case of ArCHO, HCHO and RCH2CHO (R H), the basic anions that must be displaced by the nucleophile OH are : Ar, : H and
: R respectively ; all of which are more basic than : OH, hence their displacement by the weaker base : OH is impossible.
 735

1. (a) C6H5COONH4+, Ag (b) CH3COOH

a
(c) CH3COOH + HOOCCH2CH2CH3
cleavage

CH3CH2COOH +HOOCCH2CH3

(d) (e) No reaction (alcohols are inert to Tollens reagent)

(f) CO2 + HOOCCH2CH3 CH3COOH + CH3COOH

2. (i) No reaction (ii) HCOO + CHI3 (iii) No reaction

(iv) C6H5CH2COO + CHI3 (v) Me 3CCOO + CHI3
(vi) CH3CH2COCH2CH2COO + CHI3 (vii) No reaction.

3. (a) C6H5OCOC6H5 (b) (c) (d)

1. (a) (b) CH3CH = CHCH 2CH3

Pentene-3

(c) CH3CH 2CH 2COOH (d) CH3CH 2CH = CHCH3

Butanoic acid Pentene-2

2. (a) [A] ; C6H5CH3 [B]

(b) [C] ; O [D]

3. (a) (i) CH3CH2CHCl2 (ii) CH3CCl2CH3 (iii) C6H5CCl2CH3

(b) (i) C6H5CHF2 (ii)

1. Reagent Conc. H2SO 4 cold, dil neutral KMnO4 CrO3 Br 2 in CCl4

Aldehydes Dissolves Colour changes Colour changes Colour changes
Ketones Dissolves No reaction No reaction Colour changes
Colour change with bromine takes place only in aldehydes and ketones having a-hydrogen atom. Colour change is slow and accompained
by evolution of HBr.
2. (a) Although both give iodoform test, only 2-pentanol is oxidised by CrO3 (indicated by colour change from orangered to green);
while only 2-pentanone gives a solid oxime with NH2OH.
(b) Pentanal, an aldehyde, gives a positive Tollens test (silver mirror).
(c) Only the alcohol is oxidized by CrO 3, while the ketone gives a solid oxime (with NH2OH) and phenyl- hydrazone (with
phenylhydrazine).
(d) Only aldehyde gives positive test with Tollens reagent, and precipitate with NH2OH and C6H5NHNH2.
 736

EXERCISE 14.1
1 (b) 6 (c) 11 (b) 16 (b) 21 (b) 26 (b) 31 (c) 36 (c) 41 (d)
2 (c) 7 (b) 12 (c) 17 (c) 22 (b) 27 (d) 32 (a) 37 (b). 42 (d)
3 (a) 8 (c) 13 (c) 18 (d) 23 (b) 28 (c) 33 (c) 38 (d) 43 (b)
4 (c) 9 (c) 14 (d) 19 (b) 24 (b) 29 (b) 34 (a) 39 (b) 44 (a)
5 (c) 10 (b) 15 (c) 20 (d) 25 (c) 30 (c) 35 (c) 40 (c) 45 (c)

1. Theoretical
H 2 SO 4
2. HC CCH2CH3 or CH3C CCH3
2+ CH3CH2COCH3
Hg

H+ +
3. C6H5C CCH3 C H C = CHCH
6 5 3
Benzylic type carbocation
(more stable)

+
OH2 OH
H+ tautomerises
C6H5 C = CHCH 3 C6H5 C = CHCH3 C6H5COCH2CH3
( a)
4. Theoretical

C6H 5C6H5
AlCl 3 Mg, ether
5. C6H6 + C2H5COCl C6H5COC2H5 C2H5C C C2H5
(bimolecular reduction)

OH OH

CrO3 Me 2CHCH 2 MgBr CrO3 / Pyridine

6. n-C 3H7CH2OH n-C 3H7CHO n-C 3H7CH(OH)CH2CHMe2 n-C3H7COCH2CHMe2
Pyridine

I 2 / OH -
7. CH3CH2CH2CCl2CH3 [CH 3 CH 2 CH 2 C(OH)2 CH 3 ] CH3CH2CH2COCH3 CHI3
unstable
8. Alk. KMnO4 and conc. HNO3 cant be used because they oxidize the C = C bond too. Since the compound has COCH 3 grouping, it
can easily be oxidised by alkaline halogen (NaOX) ; haloform reaction.
9. It is an example of internal crossedCannizzaro reaction.
OH -
C6H5COCHO C 6H5CH(OH)COO Na+

10. CH3CHO + H2O18 LMCH CHO

3
18
H OP CH3CHO18 + H2O
MM OH PP
N Q
Hydrate

The unstable half-labelled hydrate loses H2O but not H2O18 because CO18 bond is strong as compared to CO16, hence relatively
difficult to cleave.
11. >C = O + D2/Pt (or LiAlD4) >CDOD

OH
OC2 H5 OC2H5
+
CHO
H , H2O
12. O OH + C2H5OH
OH

13.
 737
Reaction is repeated till all other a-hydrogen atoms are replaced.

OH
+ OH
H H2O
CHO CHO CHO
14. or CHO

I Conjugated system (stable)

2 . It does not lose water because

the double bond so formed will be isolated.

It does not lose water because the double bond so formed will be isolated.

15.

3 alcohol
16. Since the product is having an aldehydic group, the reactant should be a dialdehyde because CHO are more reactive than ketones
so in a ketoaldehyde the final product should have a ketonic group.
17. It is an example of intramolecular Cannizzaro reaction followed by cyclization.
18. Presence of electron-withdrawing group on the carbonyl carbon atom increases nucleophilic addition.
19. Halogenation of carbonyl compounds takes place in a-position ; since aldehydes are easily oxidisable so here CHCl3 is used and not
water.
heat
20. CH3COOH CH2 = C = O + H2O. This is an industrial method for the preparation of ketene, another method is
700
CH3COCH3 CH2 = C = O + CH4.
Zn (Hg)
21. BrCH2CH2CHO BrCH2CH2CH3
HCl
Wolf-Kishner reduction will cause dehydrobromination (HBr) because it involves alkaline conditions.
22. Zn(Hg), HCl is not used here, because the acidic medium of the reagent may cause dehydration.
23. II cation (oxonium ion) is more stable because here every atom has an octet of electrons
H H
+ .. +
R C OR
.. R C = OR
..
I II
(+vely charged C has six electrons) (each atom, except H, has eight electrons)
24. Recall that a Hs of carbonyl compounds are easily replaced by D of D2O.

25.

26. Consult mechanism of Cannizzaro reaction.

27. Only C6H5NHNH2 has NH2 group.
H+ H +
+
28. C6H5 CH CHCH3 C 6H5CH2 C CH3 C6H5CH2COCH3
H 2 O

OH OH OH
Benzylic 2 carbocation 3 carbocation
(i) Mg, ether CH 3 CH 2 COCl
29. C6H11Cl [C6H11]2 LiCu C 6H11COCH2CH3
(ii) Li, (iii) CuCl
[A] [B]
30. Methyl ethyl ketone (a C4 compound) cant be prepared from 2-propanol (a C3 compound) ; tert-butyl alcohol, being 3 alcohol, is not
oxidised easily, 1-butanol, a 1 alcohol will form aldehyde. Thus 2-butanol should be the answer.
OH
Oxidation
CH3 CHCH 2CH3 CH3COCH2CH3
 738
Cl 2 , hv
31. C6H5CHO C 6H5COCl
CH3

Wittig
32. CH3CH2CH2CH = PPh3 + CH3COCH2CH3 CH3CH2CH2CH = CCH2 CH 3
reaction
3-Methyl-3-heptene
33. Since the compound A has the molecular formula C3H6O and undergoes iodoform test, it should be CH3COCH3. Further reaction of
A with HCl gives C9H14O having three times the number of carbon atoms in A, hence B should be trimer of acetone, i.e., it should be
phorone.
(CH3)2C = O + H3CCOCH3 + O = C(CH3)2 (CH3)2C = CHCOCH = C(CH3)2
Acetone (3 moles) 2, 6-Dimethyl-2, 5-heptadien-4-one (phorone)

K Cr O 2 2 H NCONHNH HCl
C3 H8 O
2 2 7 C H O
3 6 C
34. H 2 SO 4 CH3 COONa
(A) (B)

Ammonical AgNO3
B
Silver mirror
Since B reduces ammonical silver nitrate, it should be an aldehyde and hence A is primary alcohol, which should be C 2H5CH2OH.
Hence
K Cr O , H SO H 2 NCONHNH 2
2 2 7 2 4
CH3CH2CH2OH CH3CH2CHO CH3CH2CH = NNHCONH2
(A) (B) (C)

O

(CH3CO)2O Zn/Hg HF
35.
AlCl3 H Cl
H 3C H 3C HOC H 3C HOC H 3C

O
O O
[C]
[A] [B]

(i) CH3MgI

+
( ii) H3O
H 3C
OH CH3
[D]

36.

37.
 739

EXERCISE 14.2
1 (a,c) 2 (c,d) 3 (a,b) 4 (a,b,d) 5 (a,b,c) 6 (a,b,c) 7 (b,d) 8 (b,c,d)
9 (a,b,d) 10 (b, c, d) 11 (a, d) 12 (a, b, c) 13 (a, c) 14 (a, b, d) 15 (a,b,c,d) 16 (a, c, d)
>1 CORRECT 17 (a, b, c) 18 (a, b, c) 19 (a,c) 20 (a, b) 21 (a, b, d) 22 (b, d) 23 (a, b) 24 (b, d)
OPTION 25 (a, b, d) 26 (a, d) 27 (a,b,c,d) 28 (a, b, c) 29 (a, c, d) 30 (a,b,c,d) 31 (a, b, c) 32 (b, c, d)
33 (a,b,c,d) 34 (a, b, c) 35 (a,b,c,d) 36 (a, c, d) 37 (a, b, c) 38 (a,b,c,d) 39 (a, b) 40 (a,b,c,d)
41 (a, c) 42 (a, c) 43 (d) 44 (b)
PASSAGE 1 45 (c) 46 (c) 47 (b)
PASSAGE 2 48 (a) 49 (b) 50 (b) 51 (a) 52 (b)
PASSAGE 3 53 (d) 54 (a) 55 (c)
PASSAGE 4 56 (b) 57 (a) 58 (d)
PASSAGE 5 59 (b) 60 (a) 61 (b)
62 (A)- a, b ; (B) c ; (C) - a ; (D) - a, d
MATCH THE
63 (A)-a, c, d ; (B)-b ; (C)- a, b, d ; (D)- a, c, d
FOLLOWING
64 (A) b, c; (B) a; (C) c, d; (D) c
A/R 65 (a) 66 (e) 67 (e) 68 (c) 69 (a) 70 (b)
1. Since the product, CH3CHOHCN has a chiral carbon and is a mixture of two enantiomers (racemic mixture) which cant be separated
by fractional distillation. By fractional crystallisation from a suitable solvent they can be separated.
2. Substitution by one mole of Br gives C6H5COCHBrCH3 ; the electron-withdrawing Br increases the acidity of the remaining a hydrogen
which reacts more rapidly than the hydrogens on the unsubstituted ketones.
Less acidic More acidic
B
C H COCH CH
0.5 mole Br2 B
[C6H 5COCHBrCH3 ] C6H 5COCBr2CH 3
0.5 mole Br2
6 5 2 3 -
0.5 mole OH (0.5 mole, but not isolated) OH - 0.5 mole
3. Acetaldehyde having three a-hydrogen atoms undergo aldol condensation with three moles of CH2O. The product formed now
undergoes intermolecular Cannizzaro reaction with the fourth mole of CH2O to form pentaerythritol.

CH 2OH CH 2OH
H
Ca(OH) 2 CH 2 O, OH -
H C CHO + 3CH2O CH2OH C CHO CH2OH C CH 2OH + HCOO
(aldol condensation) Cannizzaro
reaction
H CH 2OH CH OH 2
4. Removal of g-hydrogen of crotonaldehyde provides more stable allylic carbanion, hence here g-carbon (not a) provides the carbanion
(nucleophile) for carbonyl carbon of cinnamaldehyde.
LM H H OP

OH -
MMH CH = CH C = O
H 2C = CH CH = C O
PP
N 2C Q
5. Only the first three compounds give Cannizzaro reaction ; C 6H5CHCl2 is converted into C6H5CHO, under the Cannizzaro conditions,
hence it also responds the reaction.
6. Carbonyl compounds having aH form carbanion on treatment with a base, carbanion being flat can be attacked by proton on either side
of the face forming racemic mixture. Only ketone I has a H, so it will form carbanion while ketone II does not form such carbanion.
7. It is an example of Cannizzaro reaction.
8. Only b, c and d will undergo haloform reaction, but not a because on hydrolysis by alkali it gives C 6H5CHO, having no aH.

9.
Acetone and propanal can be distinguished by Fehling solution, and not by others.

EXERCISE 14.3
1. (i) 3-Phenylpropenal (ii) 4-Methyl-3-penten-2-one (iii) 4-Methyl-3-hexanone
(iv) 4-Ketopentanoic acid (COOH group has a higher priority over CO group).
 740

CH 3 CH 3

2. (a) (CH3)3CCHO (b) CH3CH2 CHCH 2 CHCHO (c)

3. H2C = O is a planar molecule, i.e., its C is sp 2 hybridised (theoretically, its bond angle should be 120). However, the HCO bond
angle is slightly greater (121.8) than the expected 120, while the HCH angles are 116.5, slightly less than 120.
d+ d-
4. The C = O bond is polarised ( C = O ) due to more electronegative nature of oxygen, while the C = C bond is nearly non-polar. The p bond
of C = C is an electron source, and is a nucleophilic site, while in C = O, the nucleophilic site is O.
5. (a) 2-Propanol has highest boiling point due to intermolecular Hbonding, since propanone and 2-methylpropene have no hydrogen
on oxygen, they cant undergo association. However, the dipole-dipole attractive forces of carbonyl compounds are responsible for
their higher boiling point than those of alkenes.
(b) Oxygen of C = O forms Hbond with the H of water making the former to dissolve in the latter (water) ; such hydrogen bond
formation is not possible in an alkene as it has no oxygen. However, carbonyl group has no H atom which can form Hbond with
the O of H2O, hence these are less water soluble than alcohols.
(c) Alkyl substituents stabilize C = O as they do C = C by releasing electrons towards the sp 2 hybridized C. The enthalpy of the ketone
is lower because it has two R groups, while the aldehydes have only one.
6. Ketenes have the general formula, R2C = C = O. Structural formula for the ketene is H2C = C = O,

7. (a) Reduction of RCOOR with LiAlH4 gives RCH2OH, since the intermediate aldehyde RCHO is generally susceptible to further
reduction. Hence one equivalent of the less reactive diisobutyllithium aluminium hydride (DBAH) is used at 70C followed by
hydrolysis ; when aldehyde is obtained in good yield.

(b)

cis-1, 2-Cyclohexanediol Hexan-1, 6-dial

The corresponding trans-form does not form transition state easily, hence it is not oxidised by periodic acid.
8. (a) (CH3)2CHCH2C CH + H2O in HgSO4, H2SO 4
(b) (CH3)2CHCH2CHOHCH3 + KMnO4 or a Cr(VI) reagent
(c) (CH3)2CHCH2COCl + (CH3)2CuLi (from CH3MgI + Li, then Cu)
(d) (CH3)2CHCH2COOH + 2CH3Li
(e) (CH3)2CHCH2COCl + (CH3)2Cd (from CH3MgI + CdCl2)
(f) (CH3)2CHCH2C N + CH3MgI or CH3Li.
9. In such cases, proceed backward i.e., first write down the structure of the required compound and then apply your memory for getting
the two required components for its preparation.
OH

(a) C6H5 CHCH 2CH3 C6H5MgBr + CH3CH2CHO or C6H5CHO + CH3CH2MgBr
A 2 alcohol

OH

(b) C6H5 C CH 3 C6H5MgBr + (CH3)2CO or C6H5COCH3 + CH3MgBr

CH 3

A 3 alcohol
(c) C6H5CH2CHOHCH3 C6H5CH2CHO + CH3MgBr (d) C6H5CH2CH2CH2OH C6H5CH2CH2MgBr + HCHO
1-Phenyl-2-propanol, a 2alcohol 3-Phenylpropanol, a 1 alcohol

(e) + CH3MgBr (f) + CH2O

 741

(g) + CH3CHO or

(h) CH3CH2CHOHC CH CH3CH2CHO + HC CLi

A 2 alcohol
(i) CH3CHOHC CCH3 CH3CHO + CH3C CLi
A 2 alcohol
(j) p-CH3C6H4CHOHCH3 p-CH3C6H4MgBr + CH3CHO or p-CH3C6H4CHO + CH3MgBr

10. Reagent Product from C6H5CH2CHO Product from

(a) Tollens reagent C6H5CH2COOAg+ No reaction

(b) CrO3/H2SO 4 C6H5CH2COOH No reaction
(c) Cold dil KMnO4 C6H5CH2COOH No reaction
(d) KMnO4, H+, heat C6H5COOH HOOC(CH2)4COOH
(e) H2, Ni, Pressure C6H5CH2OH C6H11CHOH
(f) NaBH4 C6H5CH2OH C6H11CHOH

(g) C6H5MgBr, H2O C6H5CH2CHOHC6H5

(h) Me2CHMgCl, H2O C6H5CH2CHOHCHMe2

(i) HC CLi, H2O C6H5CH2CHOHC CH

(j) NH2CONHNH2 C6H5CH2CH = NNHCONH2 C6H10 = NNHCONH2

(k) C2H5OH, HCl C6H5CH2CH(OC2H5)2

(l) Me3CNH2 C6H5CH = NMe3 C6H10 = NCMe3

(m) C2H5SH, H+

Where C6H11 is , C 6H10 is ; C6H10 = is

11. Write down the structure of the compound to be prepared.

LiAlH 4 H 2O, H + CN
(a) CH3CH2CH2OH CH3CH2CHO (b) CH3CH2 CHCOOH CH3CH2 CHCN CH3CH2CHO
or H , Ni 2 H+
OH OH
(c) CH3CH2 CHCH3 CH3CH2CHO + CH3MgBr (d) CH3CH2 CHC6 H 5 CH3CH2CHO + C6H5MgBr

OH OH
(e) CH3CH2 CHCH(CH 3 ) 2 CH3CH2CHO + (CH3)2CHMgBr

OH
12. 2-Methyl-2-pentenal, CH3CH2CH = C(CH3)CHO to
CH3 CH3

(a) CH3CH2CH = C CH2OH (b) CH3CH2CH2 CHCH 2OH
(reduction of only CHO to CH2OH, (reduction of CHO to CH2OH as well as
hence NaBH4 is used) C = C, hence H2/Pt is used)
 742

CH 3 CH 3

*(c) CH3CH2CH2 CHCH3 **(d) CH3CH2CH2 CHCHO
(reduction of CHO to (reduction of only C = C, hence
>CH2 and also of C = C) CHO must be first protected)

CH 3 CH3 CH 3
NH 2 NH 2 , OH - , heat H 2 / Pt
*(c) CH3CH2CH = CCHO CH3CH2CH = CCH 3 CH3CH2CH2 CHCH 3
Wolf -Kishner reduction

CH 3 CH3 CH3
CH 3OH (i) H 2 / Pt
**(d) CH3CH2CH = CCHO CH3CH2CH = CCH(OCH3 ) 2 CH3CH2CH CHCHO
HCl (ii) HCl, H 2O
13. If a carbonyl compound has some other functional group which is stable to acids but react with strong base, then Clemmensen method
(Zn/Hg + HCl) should be used. In case, the carbonyl compound is sensitive to acid but stable in base, then Wolf-Kishner method
(NH2NH2, OH) should be used. Raney Ni desulfurization occurs under neutral conditions : however it cant be used with reactants
with good leaving groups because SH is an excellent nucleophile.
14. (a) BrCH2CH2CHO BrCH2CH2CH3. It should be carried out by Clemmensen reduction because strong base (used in Wolf-
Kishner method) causes dehydrohalogenation. Desulfurisation by Raney Ni cant be used because HSCH 2CH2SH, used for
converting C = O into thioacetal, can displace Br (a good leaving group), hence thioacetal will not be formed.
BrCH2CH2CHO + HSCH2CH2SH HSCH2CH2SCH2CH2CHO + Br
(b) Me 2C(OH) CH 2CH 2COCH 3 Me 2C(OH)CH2CH 2CH 2CH 3. It can be carried out by Wolf-Kishner reduction or
desulphurisation. Clemmensen method, using HCl, is not suitable because 3 alcohol is easily dehydrated in presence of acid.
(c) C6H5CH(OH)CH2COCH2CH3 C6H5CH(OH)CH2CH2CH2CH3.
Here again acid causes dehydration of an alcohol which is although 2 but produces quite stable alkene because its double bond
is conjugated with the benzene. Hence either of the other two methods can be used.
(d) Epoxides are very reactive, hence these are opened up by the reagents used in either of the three methods used for reducing
carbonyl group. Thus none of the three methods give good result for reducing a carbonyl group.

15. (a) [A] is ; [B] is CHO group is reduced earlier than keto.

2 Cl , OH -
LiAlH
16. (a) C6H5CH = CHCOCH3 C 6H5CH = CHCOOH (b) C6H5CH = CHCOCH3 4 C 6H5CH = CHCHOHCH3
(haloform reaction)

Li, liq.NH 3 , ether NH 2 NH 2 , OH -

(c) C6H5CH = CHCOCH3 C 6H5CH2CH2COCH3 (d) C6H5CH = CHCOCH3 C6H5CH = CHCH2CH3
Birch reduction

(i) NH 2 NH 2 , OH -
(e) C6H5CH = CHCOCH3 C 6H5CH2CH2CH2CH3
(ii) H 2 /Pt
17. Aldehydes are more easily hydrated than ketones. Further, presence of electronwithdrawing group increases hydration.
(a) HCHO > CH2ClCHO > CH3CHO > CH2ClCOCH3 > CH3COCH3

(b)

18. (a) All these compounds undergo Cannizzaro reaction (a characteristic reaction of aldehydes lacking a-hydrogen atom). Note that
compounds (iv) and (v) although do not have an aldehydic group, however, in presence of OH these are converted into aldehydes
lacking a-hydrogen atom, hence they also undergo Cannizzaro reaction.
OH - OH -
C6H5CHCl2 C 6H5CH(OH)2 C 6H5CHO; Me3CCHCl2 Me 3CCH(OH)2 Me3CCHO
Thus the products in these compunds will be

(i) and (iv) C6H5COONa + + C6H5CH2OH (iii)

(ii) and (v) Me3CCOONa + + Me3CCH2OH

 743
(b) All these compounds have a-hydrogen, so they will undergo aldol condensation.
OH
OH - H 2O
(i) 2C 6H5CH2CHO C 6H5CH2 CH CHCHO C 6H5CH2CH = CCHO

C6 H 5 C6H5
Highly conjugated system
(C = C is conjugated with CHO
as well as benzene ring)
(ii) In CH3CH = CHCHO, since the CHO group is conjugated with the double bond, hydrogen atom of the methyl group (allylic
hydrogen) becomes acidic, i.e., it is the allylic carbanion that will be formed rather than vinylic, hence in such cases aldol
condensation involves allylic hydrogen atom which is, of course, not the a-hydrogen atom.
OH

2 CH3CH = CHCHO CH3CH = CH CHCH2 CH = CHCHO CH3CH = CHCH = CHCH = CHCHO
H 2O

OH

OH - heat
(iii) C6H5CH = CHCHO + CH3CH = CHCHO C6H5CH = CH CHCH2 CH = CHCHO
(H 2 O)
C6H5CH = CHCH = CHCH = CHCHO
H H

(iv) H C = O + HCH2CHO H C CH 2CHO

OH
Here only CH3CHO has a-hydrgoen atom so it will be forming carbanion which then adds on carbonyl carbon of formaldehyde. The
process repeats till all the three hydrogen atoms of CH 3CHO are replaced by CH2OH group.

H CH 2 OH CH 2OH
CH 2O, OH - CH 2O CH 2 O
H C CHO H C CHO CH2OH C CHO
(aldol condensation) (aldol condensation) (aldol condensation)

OH H H

CH 2OH CH2OH
CH 2O
CH 2OH C CHO CH 2OH C CH 2OH + HCOO
(Cannizzaro
reaction)
CH 2OH CH OH 2

19.

[A] [B] [C] [D]

20. (a) Halogenation occurs at the a-position to the C = O group under free radical conditions, hence product will be C 6H5COCHClCH3.

(b)

21. (a) Only phenylacetaldehyde, C6H5CH2CHO responds Tollens reagent.

(b) Only 2-pentanone, CH3COCH2CH2CH3 responds iodoform test
(c) Only cyclohexanone gives crystals with 2, 4-dinitrophenylhydrazine
(d) Only n-valeraldehyde responds Tollens reagent.
(e) Diethyl acetal on treatment with acid regenerates aldehyde which responds Tollens reagent.
(f) Only propiophenone, C6H5CH2COCH3 responds iodoform test
(g) Only 2-pentanone responds 2, 4-dinitrophenylhydrazine, while 2-pentanol gives colour reaction with CrO 3/H2SO 4.
(h) Paraldehyde, a cyclic trimer of acetaldehyde, (CH3CHO)3, on treatment with acid gives CH3CHO which responds Tollens or
Schiffs reagent.
(i) Trioxane, (CH2O) 3 on treatment with acid followed by heating gives CH2O which responds Tollens reagent or Schiffs test.

Dioxane is a cyclic ether

 744
22. First step involves the conversion of COOH to COCl [A]. Conversion of [A] to [B] involves loss of HCl but without any change in
carbon number, it indicates that the reaction is intramolecular Friedel Crafts acylation. Thus conversion of [A] to [C] can be repre-
sented as below.

23. n-C 5H11C CLi n-C 5H11C CCH2CH2CH2Br n-C 5H11C CCH2CH2CH2 CHR

OH
[A] [B] [C]

[D] [E]

H+ + C6 H5 Cl
24. Cl 3C.C HOH
H 2 O

25. (a) Here either of the a-carbon can act as a nucleophile to form two possible compounds by intramolecular aldol condensation.
Et CHO Et a Et
base CHO base
a carbon CHO a as nucleophile
as nucleophile
a
CHO
(b) Here only one product will be formed by the aldol condensation since here only one a carbon (a' carbon) can form a stable
carbanion; in the second case (a carbon) +ve and ve charges will be present an adjacent atoms causing unstability.
a
+ CH2COC6H5 + C6H5
N base
N
N a' as nucleophile N COC6H5
CH2COC6H5
a .. . .+
O CH .OCH
. 3 CH OCH3
H
H 2O
Wittig
26. (a) + CH3OCH = PPh3
reaction
[A] +
OH 2 OH

CH OCH 3 CH OCH3 CHO

+
H CH 3OH

a [B]

(i) O3 O base
(b) (ii) Zn, CH3COOH
O O
(aldol cond.)
a
O