Concept Based Questions

oL Carbonyl compounds are more

between
C and O atonms is less thanpolar than alcohols although
O and H atoms. electronegativity difte
Ans. In the carbonyl
group (>C 0), the T-electron
=
Explain. ferna
the oxygen atom. It is
not the case with pair is loosely held and can be
compounds are more polar and have higher thealcoholic (0-H) readily shiítet
group. Therefore. carbom
(16- 1-8D). For more
details, consult sectiondipole
13.7.
moment values (2:3 2-8D) than the alcoho
Q.2. Dialkyl cadmium is used to
reagents. Assign reason. prepare ketones from acid chlorides
and not from
Ans. Grignard reagents do form ketones with acid Grignart HCN
Ketones further take part in the chlorides but the reaction
reactions does CK
Therefore, dialkyl cadmium is used which with Grignard reagents to givenot stop at this stage.
ketones. For details, consult section reacts WIn only the tertiary alcohols
acid chlorides
13.6. and not with
Q.3 In the
preparation of aldehydes from primary alcohols,
as soon as
they are formed. Why ? aldehydes formed must be distiled
wdiur
Ans. Aldehydes formed result of the oxidation of primary
and are
expected
as a

to form acids. Therefore, it is advisable

alcohols are nra
prone
Aiehy-
able to remove hthem to
further oxidation ite c
from the reaction -
 ixure by distillation in
anvert prinary case these
alcohols into dchyrler
are
low
OW
13.63
Boiling points of aldehydes. boiling,
boiling. Otherwise, other methods must
cohols. Justify. carbonyl compounds lie mu be usea to

between the
EWeen the parent alkanes and
AIka are non-polar in nature and parent corresponding
intermolecular
dipolar Torces exiSt hydrogen
in the
the
bonding isattractive forces are weak
arin Compounds are moleculee present
more than in alkanes
boiling point values
ent in
in the molecules.
molecule
van d
In the carbonyl compounds,
n

sction 13.6. in the and less vious that the ttractive forces
in
members of these
ODes aldehydes
of
and
DCTS comparison
families.
son to alcohols.
This justifies
families. For more details,
are formed ketones are not
consult
by
hile. In the reacting carbonyl prepared strongly acidic medium. Why ?
Hydrazonesa

in a
.
uen act strongiy acidic
to compounds with hydrazine (ÑH2-NH,) which acts
AS medium,
as
cridic 1 For nucleophile.
mediu ium. more details, consultresult, a hydrazine gets protonated and,
sectionaldehydes
13.8. and thero
ketones are
lodotor
is
prepared by reacting acetone with
for it ?
not
prepaic in strongly
gcrount
molecules,
one molecules, a-hydrog
the acetone
hypoiodite and not with iodine. How will
ayailable by hypoiodite d-nydrogen
hypoiodite (say
(say Naol). atoms
lodine
are to be
replaced as
you
e attack. being non-polar in
Ht ions by the It
ions
CHCOCH 3I0
nature, does not
provide I 10nma
tor
Acetone
Hypoiodite ion ClCOCH3 30H
Halogen acids readily
acids readily combin,
combine with Tri-iodoacetone
alkenes to form
rbonyl compounds. Discuss. addition products but fail
cids acids (HX) react with
Halogen to react with
alkenes to form
npOunds. In fact, the attack does take haloalkanes but they fail
carbonyl compounds.
onyl compound alongwIth place but the to react with
the
halogen acid. Thus, the product is unstable and decomposes
reaction becomes
reversible.
TH

-HX

ly does pure HCN fail to react with aldehydes and C0

ketones?
Wis mainly a covalent compound and can not
provide CN- ion readily for the nucleophilic
K on the carbonyl compound. The reaction is carried
ERISation of the acid to in the presence of base
liberate CN ion. which helps in
HCN +OH H20 +CN
um
phite is used to
purify aldehydes and ketones. Explain.
CslOnes (except benzophenone) react with a saturated solution of NaHSO3 to form
PECipitates which are filtered. These are easily decomposed by aqueous HCl or
gEDerate these
compounds in pure
form.
 13.64 OH C=0 + H20 .
N a H S O 3 -

soNa
C
NaOH
C=0 + Na,SO3 + H20

which is more reactive

TdsnluiccleTesulahdiliut .
p r o p i o n a l d e h y d e v

towart
and
benzaldehyde
towa
leophi
benzaldehyde

Out of reactive than

0 . 10
Propionaldehyde
is
more

aldehydic
group
nas
-M (mesomeric)eric) effect. As
Ans benzaldehyde the tends to increase
ncrease and the a
in
density

ditticult
n

as
the carbonyl
conmpared
to
carbon atom
propionaldenyde
section 13.8.
where Ikyl group is
alkyl
nuclattached
eophile a tuo
more details,
consult
isomerir. the
gayF
of ketones
are higher
than those of the
eric aldehydes. Aswigat
Boiling points > C 0 group by releasing
stabilise the
to
(R) tends
elec
The alkyl group
ards the sp hybridised
tow
carbon
atom.
AS a
result, the polarity of the
Ketones with two such pro
Dond is
ery
ectrons
and stability will therefore. increase.
oups are more
group. Consequen
corresponding aldehydes having only one alkyl he
For example, anal
boiling points of isomeric propanal and
and r boj
slightly higher.
329 K respectively.
propanone ae
gem-diol will you account
but stil stable. How
o1: Chloral hydrate is a
?
In chloral hydrate, the presence of three CI atoms with -I effect incraa
t reases
the positive charge on the carbonyl carbon atom. As a result, even a Weakg
H:0 attacks to form a hydrate. Moreover, there is weak intermolecular hude
the chloral hydrate which tends to increase its stability.

CI H

CIC+CK
H
+H0: Cl-¢- CH
C 0
or
CClCHOH
H
Chloral
Chloral hydrate
0.13, Ketones are less reactive than aldehydes in the
nuclephilic addition reactions. Justif.
An This is attributed to the (D.S3.
greater steric hindrance by the two
compared to one such
group in alkyl (or aryl) groups n E
also
tend to increase the electronaldehydesonto the
the attacking
nucleophile. Moreover, thes
to aldehydes. Ketones are density carbonyl carbon more in
substitution reactions. therefore, less reactive than ketones
9.14. Wby does not aldehydes in tne
n
Ans. olAidOl formaldehyde
take part in aldol
à condensation involves the nucleophile condensation ?
partucular
must have
atleastcarbonyl compound attack of carbanion one D
one
on the
other molecule. For generated rbonyl
0-hydrogen
present, t fails to take part in present. Since formal this, tne
r ich
Condensation alongwith aldol naldehyde (HCHO) has ate in cros
condensation. However,
formaldehyde
Q.15. Why and acetaldehyde.
another
carbonyl compound with it can paidrogen
is
ammoniait derivatives
necessary to? control the atleast one
onc a-hydrogen
Ans.
The pH during the aldehydes and keton

addition of
acidic medium ammonia reaction ot
au
ammonia derivative (NH,-G) to
(pH about 3-5).
derivative will In case
be also the aldehydes and k (pH
medium is strongly acidic
m is close
1).
protonated and will notstrongiy
be ablea
ucleophie

o
a
n h e n o nd
e oCS
not
not
react with NaHsOg. Explaln.
uSO on benzophenone (C6Hs}hC=0] involves the nucleophile attack of
n ofn
S 0 , )i o n . n The phenyl groups act as hindrance to the attacking nucleophile. Theretore,
react with NaHSO.
s formaldehr ith
not
does
r
Cannizzaro's reactlon whlle
adehyde undergo acetaldehyde gives aldol
(Haryana Board 2006)
eotion?

section
13,8,
consult
utf,
sdes and ketones undergo a number of addition reactions?
d oa
(D.S.B. 2009)
nfamilies
r ecommonly ascarbonyl
known compounds have a carbonyl group (>C=0). It
as well has a reactive pi bond. The compounds containing this group are
ake part in the adaition reactions readily. For more details, consult text part.