NAME REACTIONS OF THIS CHAPTER

Gutterman -

Koch reaction :
4110

☒ + CO + HCl
Allez

(2) Rosenmund Reaction :

R -

C -
Cd + Ha
É R -
§ _
µ

8 Benzaldehyde
Benzoyl chloride

③ Reaction :( from nitrites and esters) ( R CN )

Stephen ≈ R EN
-
-

R CEN
-
+ Snllz + Hcl - R -
G- N -
H ¥s R -
§ -
H
H2O
Imine t
also R C -=N
-
DHs R -
CHO
, H2O

(4) Clemmensen Reduction :

Amalgam
-

> C=0 ¥8s > CH2 +

H2O

(5) Wolff kishner Reduction :

Reagent :
Hydrazine ,
sodium / Potassium hydroxide Ethylene glycol
,
.

> C=NNHÉÉ%' N
"

> o_0 A
+

161 Aldol condensation :

2GHz -
CHO ( Hz -
CH -
CH2- CHO
¥0s ( Hz -

CHIH -
CHO

lots /Aldol condensation)

Ctlz CH3

2443 -
CO -

CH } ( Hz -

¢ -

CHIO Ctb -

-7%-2 Ctlz
-
É=CH -

CO -
CH}

OH / Aldol condemn )
(7) Cross Aldol condensation :(2 diff aide / keto reacts)

Ethanol ( Hz -
CHO CHz-ctt-CH-CHO-CHzctlz-CH-C-C.NO
µ,
+
" ☐ Études { µ, too
?} pmaonkaewleof
( Hz CHZCHO simple self aldol prodv _¥*
propanol
-

aldol CTFCHCHO
/
cross
CHO CHI Ha
Ctb
y-
CH
-

+
-

product
-

from 1- mole of Ethanol and propanol

 IT
☒
- CHO +
☒ § -
-

Ctb ¥3k -CH=cH-%

Benzalacetophenone
(8) Canizzaoo Reaction ( self oxidn) : (
major product)
Autooedox / disproportionation reaction
base
Reagent : conc .

condition : x H -
should be absent
H

H -
C -

H + conc . KOH - H - d- H + H -
% -
O -
K

8 Potassium formate

formaldehyde

of Ph PHCOONA
§
-
-

H Ph -

CHEON +

alcohol sodium benzoate

Benzyl
421 Etard Reaction :
→
by chromyl chloride ¢802 2)
clocroitclzz
* + Crack
Lot
Toluene chromium complex Benzaldehyde
CH(010113) 4110
→
A
] + GO } -16%020 ¥3k É
☒
(B) Decarboxylation : 3 : i

2- COOH R-
H
alkane

44 ] Hell volhaod Zelinsky Reaction :

R R CH COOH ( ✗ =ce Bo)

§
ctk OH
-
-

-
-
-
,

IT ) H2O
¥
acid
✗
Halocarboxylic
-

4-H should be
☆
present
-
 PREPARATIONS
PREPARATIONS OF ALDEHYDE AND KETONE :

C) By oxidation of alcohols
Aldehyde & ketone formed by 1° and 2° alcohol -
(ch ID -

(2) By dehydrogenation of alcohols

volatile alcohols Industrial
suitable for , application
Alcohol vapours metals ( ch -11)
passed by heavy -

③ From
hydrocarbons zinc dust , (ch -13)
Ozonolysis alkenes
of ,
to
get aldehyde and ketone -

(4) of alkynes
Hydration
addn of H2O to ethyne in presence of Hzsoy and Hgsoy to
give acetaldehyde ,

all
alkyne give ketone -
Ccn -

)
13

PREPARATION OF ALDEHYDES :

4) from chloride (acid chloride )

acyl
Rosen mund oxn ( already mentioned)

(2) From nitriles and Esters

→ In nitrile Stephan reaction
→ "
by DI BAL H
-

"

→ " "

by
: RCN
%s R
-
CHO

In esters :
%-06145 %
→

CHz(CHz)q -

CHz(CHz)q - -
H

(3) From Hydrocarbons :

Aromatic aldehydes prep by aromatic hydrocarbon
.

d) By oxidation of methyl benzene

a) Use of chromyl chloride Ccoozclz) lftard react ]
"

(0601411212
YH
÷ 1€
+ Crack
☒
oxidise methyl group to chromium complex .
 b) Use of chromic oxide
""
+ Coo, + (Cuzco), pcH(°Y¥¥
%) side chain chlorination followed
By by hydrolysis :

It is commercial method of manufacture of benzaldehyde .

[¥ᵗʰ→ ☒ 'ʰ¥o,s
CH CHO

,
Benzoel Chloride

Ii ) By Ga Herman -

Koch -

(mentioned earlier)

PREPARATION OF KETONE :

4) From acyl chlorides :

2 R ✗ cdcdz Rzccl 2mg G) Cl

Mg + - +
- -

'
Cl +
Rzcd
'
% Cdclz
§
2 R - - -
212 -
-
R +

② from Nitrites :
MY ☒
CH2- ( = N +6 Hsing Bo CH, CH,

)
Ctb
-

C6H5
-

GHS
-
C
µ,

Propiophe none
③ From Benzene or substituted Benzene .

Friede crafts
acylation %
"
aka ox

Ao / R É ce ¥
_
AHR

☒
-

+ -
 CHEMICAL REACTIONS
C) Nucleophilic Addition Reaction :

f) Add " Of hydrogen cyanide CHCN)

HCN :[ H2O
-

+ OH N +

/ Yµ )
tetrahedral
> ⇐◦ + EN =
Intermediate

% Add of sodium
"

hydrogen sulphite
→
forms addition products
converted back to
→

Theyare water-soluble and

mineral acid or alkali
can be
original carbonyl
with dilute
compound by treating .

→
Used for
separation and purification of aldehyde .

/ OSUNA
¥0 + Namsos =
%aH÷y Jc \ OH

"
BPsulphate add
ccoystalline)
compound

Elis Addition Of Grignard Reagent -

Ccm -11 )

Ev ' Addition of alcohols :

""
R
-
CHO
fr -

cuff! ) R -
ca
'
OR
'
+ H2O

Hldgas Acetal / gem

Hemiacetal /
alcohol intermediate
dial
Kong compound
alkoxy
R\C=o 4ᵗʰ
OH
Rlc 0 ctk
-
-

/
+ H2O
al
+

← [ Hz OH-

RI lo -

ketal
Ethyl glycol Ethyl glycol
4) Addition of ammonia and its derivatives

¥-0 +
Han -
2
/ ¥z / →
¥ N -
Z + H2O

other 8in in textbook (Table 122 )

② Reduction :
E) Reduction to alcohols
by } lialteyl catalytic EH "]
reduced to 1° alcohol
Aldehyde
→

NABH , /
-

alcohol
→ Ketone n n
2°
by hydrogen
 F) Reduction to hydrocarbons
Clemmensen reduction and Wolff Kish neo Reduction
③ Oxidation :
→

Aldehydes are
easily oxidised to
carboxylic
acid , potassium
acid on treatment with :
common
oxidising agents : Nitric permanganate
-

potassium dichromate
R CHO
-
R -
[ OOH

mild : Totten 's and Feb

lings reagent
ketone oxidase under condition i. e.
vigorous strong oxidising agents
→

and at elevated temperature .

R -

ith E- Étlz
-
-
R R -

COOH + R' CHZCOOH

bond)
(
by clevage of G -
Cz

*-
R CHz( OOH
-
+ R' COOH
( de of bond)
by rage
G- ↳

Totten 's test :

Warm aldehyde with ammonia silver nitrate Hollen 's reagent,

reagent
→

mirror is produced due to formation of silver metal

a
bright .

alkaline med aldehyde oxpdpse to ion

reaction in
carboxylate
→
occurs .

,
.

R CHO
-
+ 2 [ Ag ( Nhs)21++3015 - R COO
-

+ 2
Ag +21120 + 4MHz

%) fending 's Test :

↓ ↳
fending A fending B
alk sodium potassium tartar ate
aq copper sulphate
→ →
. .

1 Rochelle 's salt)

both mixed in heated aldehyde and brown formed
→
ppt .

→
Aromatic compounds do not show this .

R CHO 2 CU 2++5014 R COO Cuz 0 31420

-

+
-

-
+ → +

Red brown
ppt
 His Oxidation of halo form reaction :
methyl ketones by
R
-
%-
CH} s R -
% -

Na + CHX, (✗ = Cd , Bo
,
)
I

sodium
nypohalite
'

¥3
Ctb
/
= ,
- -
CH }
→
_
ON a +
ctlscd
Hzc § ( Hs
§
→
Iodoform reaction with NAOI use for detection of CHIO
gop
or

CHIH /OH) grp which produce CHIO by 10 ] .

(4) Reaction due to a- Hydrogen :

Aldol , cross aldol ( discussed earlier)
-

(5) Some other Reactions :

Cannizaro
%) Electrophilic substitution reaction :
""
-
CHO - CHO
273 -283K

→ Uses of aldehyde and ketone from Textbook

 Carboxylic
\ I \
Acid
\
-

PREPARATION :

(1) from aldehydes :

disused before

② from Primary alcohol :

R CHZOH
-
Éo RCOOH
2.
1130

Hasoy ( acidic med)

Jones Reagent Cross any
= -

↳ CHz(CHz)gCHz0H
Decanol
¥s CH3(CHz)g COOH
Decanoic acid

③ From
alkyl benzene :
oxidised
i and 2°
alkyl group are not 3°

◦ OH
'"

3-km.no#oy cookies

Ctbltbltts "
'
inks ☒
(4) from nitriles and amides :
Nitrites → amides - COOH

R -
CN ¥¥s R - É -

Nth É RCOOH

egg Hz CONHZ
( Hᵗ¥ (
Hz ( OOH + NH}

N#¥oH-s
'◦ ◦"
+ NH}

(5) From
Grignard Reagents
G. R .
reacts with CO2 (0--5-0)

R -

ing
-
✗ +0=0-0
÷ R-cd-f.mg#+sRC00H
(6) from
acyl halides and anhydrides :

-1¥
ce
-

RCOOH +

Rcocd
¥1120s RCOO + ( d- RCOOH

Hs ( 020 €0s 2 Cotes COOH

Benzoic acid
Benzoic anhydride

↳ Hs (00C OCH } ¥ 611s COOH + ( Hz COOH

Benzoic ethanol

anhydride
(7) from Esters :

Ester
ÑY ""

COOH + OH

ÉᵈÉ
Ester
carboxylate COOH

[ 004M¥ (°°"+GHsOH
benzoate
Ethyl

( Hzctkctkcoocztls - ( Hzctfzctlz (OONA + Cz Hs OH

↓ 1430
( Hzctlzctk COOH
 CHEMICAL REACTIONS OF Carboxylic Acid :

Reactions involving devage of O H -

bond :

4) Acidity
→
Reactions with metals and alkalies :

Nat
-

212 -

COOH +2 Na - ZR -
COO + Hz
sodium carboxylate
R COOH +
NaOH R COO Nat H2O
-

- - - +

Nai coz
-

R-
COOH + NAHCO} - R -
COO + H2O +

Reactions
involving derage of C- OH bond :

formation of
4)
anhydride
Cµ
Ht D "
°
Ctb
,
CH
+ Ctb
7g }
-

Hzc
-

}
-
-

, 1305
Ethanol is
Ethanoic anhydride
acid

(2) Esterification :

'
RCOOH + R' OH RCOOR + H2O

③ Reactions with :

RCOOH + Pcds - RCOCI -1 Pock + HCl

3. RCOOH + Pcd } -
3Rcocd + 431003
ROOM +
sock → RCOCD + 502 + HCl

(4) Reactions with Ammonia :

CHz(OOH + NH } ← CH} COO

-

ÑHY ¥0s CHzC0Ntk

Ammonium acetate Acetamide

Month CONHZ
Nts
☒ _¥s
Ammonium Benzamide
Benzoate
 COE NHI
COOH
/ \/ +
Nᵗʰ

]
'
Coo NHI
-

cool, Ammonium
phthalate
Pthalic acid ON H2

#
/
NH
heat
C- NHA
☒ 10MHz

" phthalamiae
◦

Phthalimde
Reactions
involving -

COOH
group
:

4) Reduction
→
Diborane do not
easily reduce functional group like ester nitro , ,
heal; .

→ sodium borohydoate do not reduce carboxyl gop .

R-foote-ketherr-ctgoHE.li
Hzot ,

(2)
Decarboxylation 3: I

R -
[ OONA Ñ R -
H + Nastos
also
→
Kolbe 's
electrolysis .

substitution Reaction in
Hydrocarbon Part

4) Halogenation
Hell V01 hard
Zelinsky Rxn

(2) Ring substitution cools

40011
A cone

☒ no.

COOH

É I -
Bo