Aldehyde ,

Ketones $
Carb Acid
.
.

D19l-ALN0-E
Prepared By Bharat
- Panchal Sir

chemistry Guruji to

bharat panchal 92

Bharat Panchal Sir

?⃝
 General Formula : -

cnn.no having > Eogp .

Aldehyde : ketone :

R ,
R- where
⇐o
,c=o where ,
µ R R alkyl
-

or
R
alkyl aryl
-

-
H

aryl
-

, ,
.

COMMON Name -

→ CHO
lol CHZCHO Cuz
-
CO -
CH
,
→

Benzaldehyde Acetaldehyde Acetone

o
11 By
a- C CHS
'll
-

CHU
④ HE c EH
-
- -

,
N B L

Acetophenone
p -

bromo butyraldehyde

EXAMPLE FROM NCERT : # STRUCTURE OF Carbonyl Gb

Hybridisation and geometry

-

20
carbonyl carbon
'

no
.

4=0
f
,
is spa hybridized
H2o
Trigonal planar
.
•

9ns Shake
.

•
It contains 3r and IT bond .

Polarity > E' IES

-

Highly
polar in Nature

Resonance Nucleophile
centre

>c o←→ > f- o

'

E
trophikentre
 duo 'T
methoxy propionaldehyde ?q
ci , a -

ctg H
-
-

OH

ciis 3 -

hydroxy butanol Ctb - du -

Ch - CHO
CHO

f
OH
( iii ) L
-

hydroxy cyclopentane carbaldehyde

STRUCTURE OF CARBONYL GROUP

PRE PARA TON OF ALDEHYDE $ KETONE

A- FROM ALCOHOL

By Oxidation of Alcohol

R CHO-

ftp.0
R CH OH
- -
+ co]
,
" alcohol aldehyde

RICH -

on + cog
'
Rico + tho
l l
R R ketone
alcohol
'
L .

By Catalytic Dehydrogenation
R CHO + Hz
R OH
-
-
CH -

,
" alcohol Aldehyde

Ry →Cu/573K Ry 1- Hz
C=o
CH -
OH l
l

R R
2. alcohol
ketone
he FROM CARBOXYLIC ACID :

a) By passing vapours of Mn O

H COOH t H COO H HI - o + thot Cq

H
formaldehyde
Mn 0,573 K CHS,
Cuzco OH + H COO H
-7 1-
f thot CO2
-
- o

"
Acetaldehyde .

b) By dry distillation of calcium salt of fatty acid

H COO
,

ga Eg H CHO + Ca coz
H COO

* CH
,
COO
Ica + ca
If 't A- 2%7=0
CH,
'
Coo n
+ 2cal Og

(
Hz COO
(
Hz COO
I ca t { ⇐ o + caco
,

I FROM HYDROCARBONS
•

By Reductive ozonolysis of Alkenes

-
O-

cha
-
-

cuz 9¥, c

Offcuts &
H
7=0
/
H
 " ''
=
to ' 's
, n

"
c - O
Acetaldehyde .

"

:÷c=e :* i' is
c
.io . #
.

Zulte
→ ethic = O
Zno
of Acetone
-

By Hydration of alkynes

{In.in#megrismGHsCH=o
'

II + HOH

( unstable

CECH HE, (
pity ,

CHS + HOH
Hz Ctf
-

-
C =

Hg Sog
Cuz -
di -

CHS

ROSEN MUND REDUCTION

•
Acid chloride Aldehyde
Il
1-- C Cl Hu
Choi
-

14 HU
-

FEI
RCOU TH ¥04,
RCHO + HCl
,
.

boiling xylene
 FROM Di halides
gem
-

* CHI CH, CHI

- -

Ye t2 NaOH
?
cutout Iif CHS CH CHO
- -

CHI -
CH -
,
,
Acetaldehyde

i:* :
* "

.
HC
'
→ 4=0
-

Hao '
g

STEPHEN REDUCTION

R CEN-

Eg R CH-
- NH 1¥, R -
CHO
HU imine Aldehyde
ET Gtf
.

↳ Hs CIN
÷gg ↳ Hs CH NU Cleo
-
-
- -
-

1-
NHS

* DIISOBUTYL ALUMINIUM HYDRIDE

or E kHz), CHCH,] ,
Al H or A- IH Ci -

Bula

orDIBAL-HR.CN#l-He,R-CH--NHiilH-R-CH0tNHz Hydrolysis
CHS CH, CN Di¥→ CHS Cha CHO
- -
- -

Hao

[TARD REACTION
' "'
tcro.ua ±
-
CHT 8%8418:* euo '

Chromium complex .
Benzaldehyde
GAITER MANN KOCH REACTION

a CHO

④ AEE,
-

1- cot HCl
Benzaldehyde
F@InmYrmyWjn
FRIEDEL CRAFT REACTION

COCH
,

←÷g
+ CH, U + HCl

Acylation
+ Econ
¥÷ EI thee
,

PREPARATION OF KETONES

From Acid Chlorides

chloride , treatment with
-

Accel
- -

on
dialkyl cadmium
given ketones .

IR -

Mg -
X + Cda
,
0¥ ,
R Cd
,
t
2mg 'T
2 RI U Deng
Cq Rg Cd Cd U ,
-
t R
ar '
-

c
-

- -

ether if
From Nitriles
- -

Colts Mg Br - - t CH, -

Ctf
-

CIN Ethers

!µ,MSB -9=0
'
CH, -

Ctf
-

c Ets CH
,
-
CH
,

GHS-
 PHYSICAL PROPERTIES
✓ PHYSICAL STATE :

At temp methanol is a
ethanol is a volatile
room ,
gas ,

liquid .

other aldehyde and ketones are liquid or solid .

✓ Odour .The lower aldehydes have sharp

pungent odour .

•
The odour becomes less pungent and more

fragrant as the size of molecules Increases .

These are used in her fumes and

flavouring agents .

✓ BOILING DOING
b.pt of aldehydes and ketones
The
are higher than that of hydrocarbons and ethers due to
stronger dipole -
dipole interactions in them but
lower than alcohols due to the absence of inter -

molecular H
Bonding
-
-

Ketones are more polar than aldehyde

the b.pt
Therefore of ketones are
higher than
that
of aldehyde .

✓
SOLUBILITY
• Lower
aldehydes and ketones are
miscible with water in all proportions due to
their ability to form H -
bond with water .

with increase
solubility decreases
in size
of alkyl group .

and ketones
Aldehyde are

soluble em
organic solvents like benzene
,

ether , methanol , chloroform .

 CHEMICAL PROPERTIES

✓ ADDITION OF AMMONIA $ ITS DERIVATIVES

> Its ten H2O

C=o HAN 2 Z +
-

+
-

✓ Reduction

R - I '
-
H + Hz Kds R -

Cha
-

OH Clealcohol )
e
liAlH4
R -
d
'
-
'
R > R CH-
-
R' ( Iealcohol )
GH
R -
ch - H ¥70 R -
CH
,
o
HI, Red P
R - E -
R
,
> R -

Cha - R
" "
CLEMMENSEN RED WOLFF -
KISHNER RED
Zn
Hgltlcl Aldehyde / ketone KOH, that
Ntlg
-
-

1
Y

Hydrocarbon Hydrocarbons
✓ ADDITION OF GRIGNARD REAGENT

>c -
- Ot R -

Mgx -7
75piM9× + Hao
Ht

\ - OH
c e
l
ar
one of the best method to prepare ie
, 253 alcohol
.

✓ ADDITION OF HYDROGEN CYANIDE CHCN )

CN
IC >
-
-

-
O + HCN of c '
OH
cyanohydrin

✓ ADDITION OF SODIUM HYDROGEN SULPHITE

05024
I >
-

> CIO t Na HSO

,
c
'
ON a
* Na
= > CTOSO ,

Hansa , OH .

✓ Mech . OF NUCLEOPHILIC ADD . REACTION

a) ALDOL CONDENSATION :

CHS -

CIO
TH -

Ctf CHO EICH, CHO .¥ocH5cn -

- en cao
-

b) CROSS ALDOL CONDENSATION :

% E %
cuz
-
- H t H - -
H
÷÷ ,
Ho -

cuz Ctf
- - - H .

c) BENZOIN CONDENSATION :

In die,
"

⇐ In + n -
Eee, takin '
,
- -

Benzoin .

d) CANNIZZARO REACTION
CF Ona
:

LCH c'IH )
-

+ NaOH → CHGOH t H - -

I CHO + NaOH → -

CHIH tf -

COO Na
Benzoate
Benzyl alcohol .
Sod .

* Resonance in Benzaldehyde I Acetophenone

meta directing
NITRATION

SUL PHONATION

CHLORINATION
 so

f.test

IODOFORM TEST give positive result for

ethanol and -
F -

Ctg ( methyl
ketone)
 CARBOXYLIC ACIDS
carbon compounds containing
acids
carboxyl group c- COOH)
are called carboxylic .

-
I '
-
OH C carbonyl group -1
hydroxyl group
=

carboxyl group )
(
Hz CIC CH - CH -
COOH Ncert
↳ ex
-
-

2- en -
4- ynoic
Hex -

L -
en -

4- ynoic acid .

acid .

C.
Hz -
CIC -
cnet.CH Coon -

Methylbenaouifd
cook 2-

Draw Sto -

of 4 -

hydroxy pentomic
NCERI
1¥73 OH

acid
cyclopentane
.

2. Methyl
( Hg -
CH -

CHA -
CH -
COOH carboxylic acid
,
.
.

GH NCERT CH -
CH -
COOH
I , , ,
e-
"
ctegive IUPAC Name of hot
(CHS), CCH
,
COOH 3-
Phenyl
brobanoic acid
3,3 Dimethyl-

batanoic acid .

NCERT NCE tycoon

Tis 3- Bromo -
4- phenyl pentomic Lod NE
-

acid .
Nf ,

Go
OH
cha
-4¥ Cubs
cus
-

Trinian
-
- -

a. e. co -

benzoic acid .

Structure of carboxyl group .

Resonating ship .
-0
° e

no:*
. .

"
r
no
-
c :

'
OH '
c g→ c
-
-
-

→ Spr hybridise d lo -
H -70 -
te
"
o -
H

Trigonal
- -
e

)
.④
.

planar
. .
-

7120
.

✓ bond angle
METHODS OF PREPARATION OF CARBOXYLIC ACIDS
@
From I Alcohols $ Aldehyde
•
KMn0g in neutral , acidic or alkaline medium
•
K Crag In acidic medium
,

•
Chromium trioxide ( Cros ) in acid .
med (Jones
kMn041H+ Reagent )
R -
CH -
OH -7 R -
COOH
, carboxylic acid .

Kmn -041Mt R COOH

R CH -
-

O
carboxylic
-

acid
-
-

%h%K ¥90
°
" on .

•
Aldehyde can also be oxidised by mild oxidising
agent like fencing solution or Totten 's Reagent .

from ketones
under drastic conditions , ketones can
be convened into acid
carboxylic .

City -
di -
CH
,
H Coote +
cuz Coote .

( Hy -
CH, -
di -

CHS
HMNB > CH, COOH -
+ CHS -
COOH .

Popoff 's
unsymm .
Ketones Rule

From Alkyl benzene

c. chain on benzene ring is
oxidised to -
COOH
group by using strong
oxidising agent like acidic or alkaline kMn0g
R ON
,
a KMn04 1Mt
LT t
v
FROM ACID DERIVATIVES

acid derivative Hydrolysis carboxylic acid

> .

✓ From Acid Halide

R CO Cl t
Hao → R COOH + HCl
- -
-

CH , CO Cl t
H2O → Ctf COOH t HU
-
- -

✓ From esters

R CO OR
-
'
-
+ H2O RCOOH + R' OH .

✓ from Amides

R -
& -
NH
, ¥I> CH, COOH t NH
,

u from Nitriles
R CN-
R -
di - NH
,
R -
COOH .

FROM GRIGNARD REAGENTS

carboxylic acids are prepared by the action of

Grignard Reagent on CO2 followed by hydrolysis .

0€ O t R Mgx 17¥ R
E°omg×T Hao #
-

>
-
-
-

- O
R c
-
-

'
OU .

PHYSICAL PROPERTIES OF CARB ACIDS .

✓ PHYSICAL STATE
•
Aliphatic carboxylic acids upto 9 C -

atoms are colourless liquids .

°
The
higher Acids are wax like solids .

✓
ODOUR :

The lower carboxylic acids have

unpglaenq
•

Higher carboxylic Acids are odour

odour, egg .
✓ BOILING POINT
•
For the compounds of comparable Mol .
mass ,

the increasing order of B. Dt is . . .

Hydrocarbons L Halo alkanes L Ethers L Aldehyde

{ Ketones
4 Amines 4 Alcohol 4 Carboxylic
Aid
B. Pt
Reason of
higher of carboxylic Acid .
.

cis carboxylic acid molecules are more extensive

associated through intermolecular Hydrogen bonding .

ciii The
group
electron
withdrawing
increases the
nature
polarity of
of
O -
H
carbonyl
bond,
makes H than
which the
bonding stronger
-

alcohol .

DI MER FORMATION

most of the carboxylic acids exist as dimer

in the vapour phase or in the aphotic
solvents
Onc
.

H -

fo
-

R
- -

C
R -

- o H
-
H - - -
o

✓
SOLUBILITY
•

Aliphatic carboxylic acids

having upto 4- e- atoms
are miscible in water in all proportions due to the
formation of H -
Bond with water .

•
The
solubility decreases with increasing no .

of carbon atoms .

•
Aromatic carboxylic acids like benzoic acid
is nearly insoluble em cold water .

• As Hydrocarbon increases , solubility of

carboxylic acid decreases em water
✓ CHEMICAL PROPERTIES OF CARBOXYLIC ACIDS

✓ ACIDITY OF ALCOHOLS / Rxh with Metals

LCR -
COOH ) t 2Nd → LR -
COO Na + H2
sod .

Carboxylate .

R COOH
-
+ NaOH R COO Na
→ t H2O
-

Natl cog Test

R COOH 1- NAH coz R COO Na +
-
→ -

thot CO2
sod .
carbonate CNAH COs) is used as a
Hydrogen
characteristic test for carboxylic acids All .

carboxylic acids give brisk effervescence of CO2 gas .

✓ FORMATION OF ANHYDRIDE

% di
O

R E out Ho
"
c R ¥e R R
o t
H2o
- -
-
. - -
- -

or 105 ,
A

✓ ESTERIFICATION
Ht
R -
COOH + R '
-
OH I R COOR ' TH O
,

✓ Reaction with PUS, Pelz and sock :

R -
& '
-
on + pees -7 RCOU + Polls + HA

d '

RCOU
R - -
OH +506
,
7
-150g + HCl

3 RCOOH t Dd , 7 3. RCOU + Hypos .

✓ Reaction with Ammonia :

NH,
a
7
R -

CON Hz
R -
COOH + H -

Amide .
✓ Reduction

R -
COOH
H4 R - CH, OH

R COOH - ¥9 R -
CH
,

✓
Decarboxylation Rxh

R -
COO Na + NaOH EA> R -
H t Naa
ATRA he
"
H.KZ REACTION .
HELL VOL HARD ZELINSKY RX

Y
R Coon
Ctf
- -

R - -
cook

* ELECTROPHILIC SUBSTITUTION REACTION

deactivating ring
The carboxyl grouts on benzene acts as a

and meta electrophilic

directing group for
substitution Rxn due to its -
R effect .

Ifs
"

+ Bq
Es ,
BROMINATION

+ conc . HMOs IYmq NITRATION

l¥%gµsuLDno
° "
NATION
t conc .

tgsog →

Mole
Aromatic
carboxylic acids , however do not
undergo
Frieldal craft reaction because the carboxyl
is
group deactivating and catalyst

anhy Allez bonded to the carboxyl grouts .