Carboxylic Acid

/H20
+

"Amide
Preparation b) ofAcid halide x
-Nie
R-40H
R-4
-
-

H +, Ha0
onidation Run KOH (Base)
1) By R x R
-
0H x- Acid Base
- +
SOA - -

kMnO4 H

R-CHz 0F

R-G-
-
H

, alcohol KOH (aq) R- NHK

okt
4-
R-4
-

2. Amide *
OxidationofKetones
c) ofAnhydride
R-G-NH-R B-G-OH
kMnOy/HT O 0
Acid Base Run KOH (Base)
CHz-CHz- C
- C1-CH CH3
C
= -

↓H **
C- 4-OH
ketone stable Ouidative Oxidative
CHy-4-0-4-crs R-4-niRK
KOH
Ozonolysis 3. Amide
CHOL Ozonolysis

R-Cre
kt *co of

R-G-
0
CH-4-0H e
CH--
+ =

4 No Acid

Side Chain Oxidation <-

Hydrogen d) of esters KOH

COOH
CH3 I
I
kMn8y, Ht HT, He0
OR R C - 0H
4-
t
R-4-0
R- -

3H
!
2x4
COOH KOH
He CH3 kMnOy, Ht
R okt
1) From
grignard Reagent-
B
- -

02H 12 H 200H
A
-+ 2 - CO2 Ht
amides
10
R- H
2) of RMgX 4
2 o

-
-
-

8.
2)By hydrolysis
1 Amida
R-4 Ntedic
-

a) of Cyanide
Partial Hydrolysis
-P-NH2
R C=
N R Amide -NH-R 2"Amide CH
-0-CH3
-

Complete R-4 Acidic

hydrolysis OH -
30 Amide
- 4- R-4
-

R - 2
or adic R
No

Hydrogen
 Amines
R-c**N
now,
LiALH4 0

Preparation O I
en.
R-CH-NH2 11
C KOH
C

- -
Nixt
I &NH
Ammolysis ofAlkyl Halide (R-X) 3) Reduction ofIsocyanides
OH-
1) 2 -

+ S.S R -X Reagent: 1) He/Ni, Pt, Pd - !

R-X H-NH2
+

R-NH2 R -
NH
2) LiALHy Phthalimide + S s
1 Amine ↓ eg. H2
R -
X
2Amine
CH-CHz-NEC
↑

R -NH-2 + X-R
CH-CH2-NH CH2
=

di 1 SN2

R-X

an
8 +
S-
R X
-R1)
-

RyN* x- Reduction ofAmide. R -NH2 KOH e

Quaternary Ammonium ↓ LACHy

Amine
Salt a R-CH
-N2
Run
+
3Amine 0

-
"-okt
LIACA
CH-NH2
G-Ng
-

Reductions Reaction -- okt

↓
Reduction of Nitro group
1) (-NO2)
x GABRIEL SYNTHESIS:
PHTHALIMIDE Salt

Reagent: 1) Sn+ HCL

COOH H-NHE -4 NH -H

Hoffmann Bromamide Degradation:

-

Fe
2) +
HCL NHS

He/Ni (excess) -
3) te
Sn
COOH H-NHy
- Buz
R-NH2
(H-CHy -NO2 CH-CH-NHe a Ne
4-
en. -

HCL KOH
A Step down Reaction

2) Reduction ofCyanides Reagent: KOH R-X

NE BE CHG-CH-Ne
CH-CH-4
-

19
Reagent:1) Hy Ni, Pt, Pd 1. Amines Aliphatic
-
2) LiAIHY Aromatic "Amine Nahi Banegi I H
-NH Bre
Cls--wi
-->-p-Ne
-

3) Na(Hg) /R-OH 4 24 KOH

Phthalimide
C13
dis
 He NH2 He
1) Basic Nature I Case 1:
Aliphatic 1"Amine
-

- N0y
i
↑

HC
NaNOz +

Base e donor
"NO2 V M
R-

NH2 or
R-Netc- RT (Rearrangement
ifpossible)
Carbocation
b>
-

a)
-
I 102 -
I
HNO2 Diazonium
H20
R-xis R-ni-R
R-nitz
salt
ad
I
R ↳ Ortho substituted anilines
*
are weakest R-OH
alcohol
1 Amine 2"Amine 3Amine bases

Basic
*
Strength
&
e-availability Aromatic 10Amine

2) Acylation + HCL

Rea-R
NaNOz H20 OH
Rise R-nit + I
Ph Pl
-N2
+
c-
-

+I
a
C--ch +MC
-NH2
HNO2
OR

R-NA-g-cty
I
R
-NH2 Diazonium
+

Benzene

+I Chloride

+C-4-cis Case
R-NH-N
Basic Nature: 2's 1" (in gas phase) 2 "Amine
3'x 2:
Aliphatic
R -N NO
Note:In aqueous phase R -N-H + HO -N 0 = -

·
Solvation R CH, 2x 1x3>NHs =

3) Carbyl Amine Test:

I ↳
R
I R 2" 3x1 Nits Nitrosamine
yellow oily
=CH CH,
·+

CHClz +
kOH
Steueric R R-NC
·

Reso
-

NH2
Aromatic 2"Amine
te CHz- itResoX
CHClz + kOH
- - Pb NC
Ph-NH2
-

-
-

TN
I No
H HO-N 0
socyanides
-

-
-N - +
=

smelling
↓
Foul

,
Nie
I z NHy
I
o yellow oily
↳ ReactionwithNitrous Acid (HNO2)
Case 3:Aliphatic 30 Amine
I
:
&

R
M
NO2 Reagent: -

1) HNO2
HNO2 N
-

+ M

R
1
R - NO
2) NaNOy +HCL NaCl + HNOz R -
-
I - -
-
I

a) d) - NO
↳ a
axc xb
 0 Nitration
11
Aromatic 3"Amine R -N-R+ Cl-S-PH No Run
NHy N2
R-N-R a I NH2 NH2
R-i-R
I I I
COMC. HNO3
- / /
I I
+ Not 3 Amine Conc
I

H2SO42
I -
2
2
electrophilic ho Mog 47%
6) Electrophilic
Aromaticsubstitution
Electrophilic Aromatic Substitution 2% 51%
0H

I I
BVz sulphonation
HINSBERG ~, HSO iM
5) TEST
CS2
Non-Polar Solvent
Mono substituted NH2
I
I

Zone.
453k -
473k
I Hesay
Bre H20 Polar
-> used to
distinguish 1, 2 and 3 solvent Be
2
It
A

amines
Br
** Base its sogt
-
Bu
2
Sulfanilic
Hinsberg Test: Benzene Sulphony( acid
Chloride Zwitter ion I
white
ppt
⑧
bu (Bipolarion) SO
- -
c
Ne Ne Ne
↓
it
I I
Bu does not Friedal
Brz CS
+

-
Bu Note:
give Craft

P-S-
- Acidic, ag. KOH
-

kt
02
Reaction
Brz He0
- Ph

R-NH H ↓ M-NH-S-PH-x
Base
+

Bu
-

↓ Reaction
Amine N-alkyl Benzene soluble Coupling
Trisubstitution
Sulphamide
0 Mono substitution o
nir--Hs PIN-H-Y- oH Orange
-H-c-c pit-l-cts
0

- - Ph 11 KOH
I henol Ph-N=N-YOH
ag Bre ~
R-N S Ph > Insoluble -I
I ozobenzene
P-hydrony
R-N - H
- -
~
-
↳

a
O
a Bu
He/H20 - nter
N,N-dialkyl PINCH -

2.Amine Benzene Sulphoamide ↑Ne Aniline

x
x
- Ph n N- NHz
-
- =

CHICOUNT
p-amino ozobenzene
Bu
yellow
 Netcl- i
NHy I CuCL+rich
I
NaNOw +HCL

of
Cur
HBs
+
Bu

HNO2
Cucx
*Cx CN
HI I
(u + HCl
HBF4 Cu + HB2

Be
F I Ch
Is I

Nach- Ol
I !
H20

in
H3PO2
NaNO2

,NOz
 Chemical Properties *
Dehydration ofCarbonylic Acids -
Decarbonylation Sodalime

1) Acidic Nature cone.

H2Soy or
HgPOy
-

NaOH/CaO
cone.

Alas
CH4
of

R Ht
cone. Heso
- Crg-4-or
R-4
R
4
-o 0
step down Run
4 Face 4 R-G-OH
- - -
+
=

Anhydwide
very stable & HELL VOLHARD ZELINSKY RXN
As 2 EnlG
R-
Equivalent
-OH Ho-4-R Run
RS HV2
EDG 2
i) Red P+ Xe
oH
CHI-CH
Cz-cy--or -
-

) NO
Na
x
Esterification
R-4-N R-G-oNat IH
+ Esterification
HO-R R R' H0
R-4-OH -
- +
+

ni He of Aromatic substitution:
R-G-0NaT NME
+

Hydrolysis Electrophilic -

Acid Alcohol C stee COOH

COOH
* -
P
meta ↑
R-g-oNat
NaH
He
+

R t
Rate ofesterification&
-

EDG +

ENG
-E

with PX, PX5, Rate ofhydrolysis ofester EWG

+CHg
sole
Run a

PC15 EDG Cl
e
R OH

-
-

NOe*
PCI A
withNHS
-

R
-
H
R-p-C+HCL+POLSRun C4,
-4
- -

Ch
Cl
--
P oH +
H-NH2 R- NH2
Heating effect
↳
R
4
- -
-

Cl CL
Acid Base Amide intermediate
CL
acids
socle ↳: AlH4 Alcohol
a) B-keto Carbanion
R x
sO+HCl R-CH-OH
- +

R R
-
OH
-

OH x

-
-
-

B
Thionyl
R-G--G-OH
chloride
cot
By products
a?-+
are
NaBHy
gases No Run

:. Forward

Direction
Alcohol
He Ni
R-CH-OH

B-position Ketone (Carbanion)

 COOH
A 4
acid CO2 CH-COOH
Heating effect. H Dicarbonylic
+

b) n1
CH2
=

(CH2 (n n
0,1,2,3,4,5
= COOH

it
COOH C OH CHa-C
r20
-
-

e(z) a
↳
n=
A D

ONSG AP or

↳- i
-

succinic acid
cool
0
n= COOH n3 =
Succinic
Onalic acid Anhydride
[CN2 13

queen--
⑧
COOH
glutamic acid COOH
his
COOH COOH
n1 n 4
=
=

Malonic acid
CH2 (He)+
COOH Adipic acid
cool

COOH
glutamate -
n 5
=

Glutamic
COOH
(2)5 Anhydride
e(r2)a CH2-COOH
n =

succinic acid COOH n4

=
1
Che
Pamelic acid -
H20 O
=

COOH
CHa
CO2
-

CH2-COOH

8
n0
=
COOH D
C0
He0 5 CHe
CO2 +
+
n =
COUH
Che A
O
CH2
=

COOH -
20

CH2 202
-

COOH
CHa