ALDEHYDE AND KETONE Rosenmund's reaction

H2
:
(Partial Reduction (

R-G Pd/BaSO4
R-G
R C H
Aldehyde Etard Reaction
-
-

of Alcohols
! Dehydrogenation Dibal-H (Reduction (
H2/Pd Complete Reduction
CU/A
CrD2C12
Di-isobutyl hydride
Of
CHE aluminium
Mo
Ketones
R-G-R Aldehydee
X ↑ alcohol CH3-CH-OH
I /
CS2
H
Of
CH3-G-H V

reduced Alcohol
CU/300'C
Benzaldehyde
R-4
. H
Y
solvent Al
B Px Mass & I
.

Non-polar R-CH2-OH
CU/300
'

Branching .
2 AlCOhOl CH3-CH-CH3
CH3-G-CH3
> Ketore
e
H
on
R-CEN R-CHO
N

L
>
CH2
CHE
Cu/300c
R-G
I II Re > R-CHO
Alcohol CH3-C-OH CH3-C Alkene
.

3
Oxidation of Alcohols >

-
ins

-
Elimination in
R CH2-OH strong >
R-COOH Acid

y
.A
0
& alcohol

strong or mild Mild Ozonolysis

>
103

-
R

R-G
R-CH-R R-CHO
-

CH3 +

-
7 > , CH3 -

on O A
Preparation
-
.

O A
.

CH3- II) Zn/H20

Aldehyde
Ketone
, CH CH3
= -

Reductive

↓
↓
CH3
CH3-4
1) 03

strong Oxidizing agents

Kuchevoy's Rxn CH3-Q-CH

NITESH DEVNANI
11) H20 Ketone
+
1) KMnOy /H Oxidative
weak
oxidizing Agents Hgt/H20 or
C
+

CH3-C
/Ht
R-
R-C

Haso =
2) K2C8207
= CH CH -

1) CU/A or (U/300' or Cu/573K

3) Cr03 + H2SO4 (Jones Reagent) 2) PCC
dil
legsou/dil
Reaction Ketone
Stephen's

G-OH
4) HNO3 3) PDC
Ade
+
snCIz H30 Markovnikov Addition of water
R-CEN
R-C
R-CH NH
4) Collin's
Reagent
=

>

HCI Tautomerism
HT/H20
5) Savett's
Reagent Nucleophilic Addition of water
6) MnOz Trick-R-CEN > R-CHO

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

ALDEHYDE AND KETONE Reaction with NaHSOs / Sodium bisulphite l

Ry /OH
NaHSOz R
side chain oxidation Nucleophilic Addition Reaction
Grignard with cyanide O
=
>

CHE CHO O
NU
I R R 503H
H NO R-C-H
RMgX
R
+ >
I I
B-R'
-

Cl2/hU
17 17 OH
R-C = N
3 >
and methyl ketones
2 times
Note-Test for all
aldehydes .

Ketone From chloride

COOH
Acyl Nu
I
N ,e

R-G-R'
CHE
+ R-C-R
I
C2/hr
I CaCl2
R2Cd bH
17 2RRgX Mack
+
Reaction with
Grignard
7

17
,

3 times

(
I
carbona
Rate of Rxn
charge
R-G-d
R2Cd
Ri-C
+ <
Benzoic Acid < the on CeH5
1)
C2H5MgCl
CH3-4
-

H I
sterric hindrance > CH3-C-H
Ketone
2) H /H2D +
de

↑-
RORd
ENG Aldehyde 2
.

alcohol

-
- CH3-4
-

CH2CH3
1) CH3MgBt
>
CH3
-
CH3

C
I
-

C2H5

Preparation chemical properties 2) H+ /H20 ·H

ketone

↓
I
-
3 alcohol

Reaction with HCN/NaCN

Reaction with Alcohol

NITESH DEVNANI
CN
HCN ON I
Friedal Craft Acylation Cyanohydrin
B-G
H R C H

RYOR
R-OH
- -
-

R
>

Gatterman Koch Reaction

⑥
NACN di =
0
, Actone
II O CN
CH3-C-CI
- - CH3
HCN ON I
Aldehyde
Cyanohydrin
R-G
R R-C-R
-
-

1) CO + HC I 7
I > .

19 di
- / / NACN
AlC13
Ric
I
RicOR
3
0 R -

Off
Keto
=

/
Acetophenone
7
2)
Arky AlCIs Lewis Acid R/
ROR-NACN > HON Ketone
Lewis Acid Benzaldehyde

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

ALDEHYDE AND KETONE Clemmenson Reduction
/only for
Aldehyde / Ketones (

CH3 INING
CH3-c
↑

R-G
-H

N-NH-TEX
R CH3
-N-NH-LX-NO2
-

0
=
= > 7

H H NO2 H conc .

HCI/Acidic Alkane
2
. 4-Dinitrophenyl Aldehyde
NH2-0H
(Hydroxylamine) (2 4-DNP)
Hydrazine Yellow
Orange Red zn(HG)
R-G-R
,

R1- CH2-R2

CH3 PN-OH <R3-c

>
Braddy's Reagent
- 0 + , N e
=
=

Conc HC
H'
.

Alkane
oxime Ketone
a

I
f

Hydrazine NH2-NH2
2 y Wolf Kishner reduction (only for Aldehyde/Ketones /
>
CH3
Y CH3-CIN-N
: Reduction Reactions -
nitrogen containing compounds
=
0 + N-NH2 <
Reaction with Hydrazine NH2-NH2
H/
& R-G
-

H
KOH + HO-CH2
7 R CH3
-

Alkane

Hydrazone

6(
.

HO-CH2

/
&

RI-C-R2 >
RI-CH2-R2 Alkane
Phenyl hydrazine
!
19

R =
0 +
M N-NH-Y 'RYIN-NH -
H

NITESH DEVNANI
LIA/HY ON NABHY ON
Phenyl hydrazone. L R H R-CH2-OH 1 Alcohol
C
- -

>
Oxidation Reactions
H2/Ni ,
Pd Pt ,

Weak Of
LiA/Hy or NaBHy Or
oxidised (Acids)
easily
R-G
R 2 Alcohol H

R-CH
R R

-G
- -

> >

Semi carbazide Pd Pt
H2/Ni , ,

StrongOA Difficult to oxidize

RY +P YN-NH-P-NH2 >
RY N-NH-G R-G-R
a
,
M i NaBH , cannot reduce "Ester 2) Acid 3)
Anhydride
= :
=
0

semi carbazone

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

 ALDEHYDE AND KETONE Bendict's solution test

Reagent-Cusoy (aq) + Sodium citrate

Fehling's
Reagent
-
solution test

Mild
oxidizing agent
Mild
Oxidising agent Fehling A
Febling B
Tollen' Test / Silver mirror test) Oxidation of Ketones
Bendict CusOn(ag) Roschelle's salt

R-
R-COOH + CU2O
strong Oxidizing Agents >

Reagent-AgNOs NHGOH+ Ammonical < Silver nitrate .

Red ppt
Mild
oxidizing agent
-

> Stablend
Ketone Oxidative
Ozonolysis. Bendit Fehling
R-G-H R-G-OH
+ Cu

R-G-R
>
NO RXN >

AGNOs KMnO4
Red ppt
R-G-4 CH3-G-C CH3- H-G-H
+

R-C-OH HO-C
0
+
A >
=

, >

Ht
NH4OH
Fehling

y
Silver mirror

R-G-R
, NORM
AgNOs
R-C
NO RXM

(
>
A

>
NH< OH

↑
& -
Cannizaro reaction

Reaction Aldehyde-Ketones having zero

-hydrogen
Reagent - conc NaOH or conc Kot
- .

Reaction
-

/
CONC
H H-c-ONAT CH3-OH
H-G

/
+
7
Aldol Condensation
NaOH !
Aldehyde and Ketone
having X-hydrogen CONC
Coo-Nat
/
Ex KYCH2-TH
X

Reagent-dil-NaOH or dil-KOH V >* +

dif NaOH
L NAOH

NITESH DEVNANI
.

Cross Aldol

Trick-CH3-C
CH3-CH CH

4
= -

>

OH

CH3-G-H CH3-G-H CH3-CH-CH2-

<

-B unsaturated Aldehyde CH3-c 'CH3-CH

H-CH2-G-Cs CH2-G-C
=
0 Cross-Cannizavo
-

dil Nota H
CH3-G-CH3
C43

-4 Ck-
self Aldol
=

>
CORC -

Y CH2
O

H-G-H YTG H-G-ONa

+ +

CH3-c CH3-4
>
Of

H-cH2- -
<
↑
=
0 -

CH2
NaOH
< Bunsaturated Ketone . /
·
CH3-4-Ck3 CH3-P-CH3
CH3
-C-CH2
CH3
-

> -

CH3

HG-R ETNPHCONC XCH-G-OTA

+
,

2 cross Aldol
self Aldol

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

ALDEHYDE AND KETONE
RDS is carbanion Formation
compounds which
gives this test :-
Reagent -

X2 + NaOH Oy

of carbanion is
NaOX or KOX or CaOCI Stability 2 > 3.

"I Methyl Ketones C

CH3-P
Rate of formation of Haloform is
-

same

I -
CHF3 CHCIs CHB03 CHI3
X
= = =

2) Alcohol
CH3-CH-
2'

3)
Only one 1 Alcohol CH3-CH2-OH
↑
-
Oxidation
Baeyer Villiger
O
O
R-"-0-0-H If
R2 0-R2
RI-G
-

3
RI -

C -

Haloform test
Ester

R-G-CH3E2 R-G-O'Nat
-
> +He
Priority
Yellow ppt # 3> 2 / >
ph > / CH3

Ce
12
-
cooNat
# & I
-

, /
+
CHIs
NaOH

NITESH DEVNANI
Yellow ppt Se02 Oxidation

Cl2 0 O
O
CHCIs
CH3-C
CH2 a + O CH
=G-
-

3
II Se02 II /I
NaOH CH3-C-CH3 CH3-C-CH

G
BUZ O

NORXR I If O

CH3-CH2-CH-CHEC
> - Se02 I-/
1 I >
I I
NaOH / L

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194