REAGENT MARATHON

2 24PY is
 Reduction 12/Pto Pda Ni :
Catalytic with

PdoPt >
4 4
-

(c c = + H2 o

Ni
>

Raney
divided Ni
finely
x- ch -

↑ -sameide
-j= =
eH-Legas =;
.

i
Hydrogenation of alkenes is a addition
syn
-

H2/Pt
Uz
-

CH =
CH2 >
-
Utz-CH2-Cz

& [bi
Pt
- -
4 Cz
-9
+

Deuterium)
addition
mero
compound
ci-2 Butene syn Ch3
(optically
inactive)

CH3 ! CH3
Pt

5
i
H- DD -

H
7
+
Dz
addition H
eyn D -

H -
D
trans-2 Belene
CH3 - CH3

optically
inactive , Paisofenautores
a
 trical alkene Addition Product
Type
symme
type Type
cis
syn meso
compound
trans anti Meso
compound
trans Racemic mixture
is synanti Racemic mixture

C A R

R-CEC- R # R CH2 CH2-R

+
2H2

From reduction alkene di-imide :

of
2

using
Nath
> c) ->
4 4
+
-

C =

H2Og
addition
-
syn -

H2O
NgHy + H2O2 > Natz +

di-imide

hydrazine this also does

ryn-addition
-

From reduction
3
of alkynes using
Lindlar's
Catalyst
RCEC-R +

. Ha

stainaine
Pd-BaSO4
7
P =
/R
is alkene
-H

catalyst
Lindlas's
BaSO4 /Quinoline used
poisoninagents
g
or an as

cis alker is
formed
#
 CHz-CEC-Utz ...
H2/Pd
BaSO4
7

u =as
Lindlar's
catalyst
4 From reduction
of alkynes using
Birch Reduction

NaKigNHy
,R <
R-CEC-R
tiaddition
=

trans alkene -

JEE
IIT
-
-
solution
/higNH
paramagnetic
I Na is a blue coloured
G
-
& this Blue color is due to ammoniated is -
As the
the
conc
of
Na increases
paramagnetism decreases
.
.

Nakig NH3 CHE

-N
CHz-CEC-Ctz >

nx -
Uz
2

= gite
*i
3
-

is H/

↓ H2/Pd BasOn
H

Ei
E Clemenson's Reduction : (Acidic Medium)
RI -
R In(Hg) > R-CH2- R' + Zul2 + H2O
Conc HB

it is
zu(kg) amalgam
Zinc
of
- - a source is .

<
II
zn(Hg)
[] conc. Hll
>

- zn(kg)
->
-
-
! conc .

HU

⑥ Reduction (Basic medium)

Wolf-kishner
:

N2H4/h
O
i
R-K R -

> R-CH2-R' + N2 T
(ii) NaOH) A
O

II
N2H4/H
&
(i

<ii) NaOM) D
>
[]

general WolfKishnerreductionis better ga

* In a

reducing
better
Y ield
aldehydes
- gives
 Decarboxylation (O2) rim)
: (Removal
F From
(step
of
down

O
↑ *
R-c-ONa + NaOH + CaO -
> R-H + NagCOg -

-
-
- - -

↳ salt
Sodium of soda lime

Carboxylic O
and
-H
EO>
COONG
/ NaOH +CaO

[0 A
<

-oNa
O
I alime CHz-CHz

C
CCONG
I

<T >
-
soda lime
A
[]

Carboxylic having electron

withdrawing group
* ands

at 2-carbon wort to and

rapidly catoxylic decarboxylate

p
O
O

C--chz
. O

CHz
-
c-c-k-oH-
1
↑
A
+ co2t
- -
--

B-Keto acd
 Imp
g Wurk Reaction :

&NATX-RR-R 2NAX
Rx + +

X = 4 , BU .

U-CH2-4 + No CHz-MHz Me CH3 + 2NaU

ether
+
underived
products
Characteristics reaction
of wurte :
-

is Methane not he wart reaction

can
prepared by
.

symmetrical
(ii) It
gives
better
yield with
leven
alkan
carbon)
formation
.

oftwo
no

at leat three
products allys
(iii) It when
halidesgive are used (alkanes)
different
+
- -

CHz -
1 + Uz-CH2 CH3-Uts + Cy-CH2-C2-C3 C3-Y
alkyl
(iv) We can not use there halides that contain acidic H.

(the which connected to (FONX) because

Hydrogen
is ·

in that care an intramolecular substitution reaction will

reacts with
place rapidly
take as Na acidic-H

⑦
-
3 I
NA
-- -
Na -x
na
no ether

t
 :
9
Corey-House Synthesis
ether
RX +
Ryluhi 7 R-R' + R-L + Lix .

e
(allimani unsymmetrical
--
alkane

from unymmetrical
* We can alkanes
-

Rx
preferablyCH-X ortalkyl
* should be hidioa
avoid the chances
of
CH3
-
[↳
↳

4)
ether
Ludi + Up -

- A ether
[Cz-C2) luhi +
Cz-X
>
CHz C2 C3
-

10
Halogenation of alkanes :

nO
CH4 + C2 <
CH3
-

H + HU

& Us/hV
HU +
(chlorotom)
CHU3
h
Callz + HC

↓ Arthr (DCM)
+HR
(dichloromethane)
CU4
 :
Nitration Lower alkanes do not nitration at
11
undergo ordinary
long
but nitration
temp chain alkanes
undergo
.

Nitration bond well bond also cleaves

During
C-H as as c-c -

450°
CHr + HNOz 3
④NO2 + H2O

450°
-M2fcy Cy-CH2-CH2-NO2
>
-

t
propane CH3
C3-4or
-

-
CH-CH2-NOC + CH-NO2
-

:
2
phonation lower alkanes do not
undergo suphonation
.
-

namal
n-hexane emallest alkanes
is the which
undergo
can
n

sulphonation
.

40 C
CoHIn +
H2SzO7 > CoH13SOgH + H2O
-

(olum)
 alcohols
13
Dehydration of the
Removal
ofis 120
from
Dehydration
↓
-
molecules called
dehydration
.

Removal -
> To
H/A
7
CHz-CH C2
CHz-at a =
Conc HISON/D
·

conc .

HyPO4/D alkene
Al2Oz/D
Rule :-
saytel's substituted
majo product
More alkene will be
a

major product
more stable alkene will be

* To
form saykelf product remove the that

from gen
,

which has leat atoms

B-calbon of
no -

as

becomes
Poor
pooser

dehydration goesviaEl
The

alonos
* mechan a
of
through
the

Note
- -

carbocation is
famed it can
>
-

Whenever
to
fom
undergo
calbocation
rearrangement
more stable -
 L
T
-
Obta
. ->
-

-I
3 : d
to
I

7
-

h 5 shift
↳ [
I Voigt Eg
[
&
↓ /

-
*
Of

-
E
-H2O
↓

·
q
/I

& d↳
2 I L

shift

it3in
E &I
-
[TIS
 halides :
Dehydrohalogenation of alky
14

intrast
Alcoholic
7
CH2 CH-CH3
Chz-CH-Ce
=

KOH
g

-
KOH)D X = U Br
,
.

the
rxn via E2 mechanism
goes
.

major product formed by saytzelf's Rule

* The is

* More stable alkens will be the

major product
st-
ekospecific -C
He
L L
BH
- H
alc Koll
- -
+ X

↳ majorstable
mind

more -
. - -

vicinal dihalides (Bromides) :

Dehalogenation of
15

↓
↓

vicinal dihalides (1 2) dihaledes

,

morally
-

<-

-
B - d
Nazlactone
(c c)
7
=

as
-
zn/deut
-

By -

me

Ran via E2 mechanism

goes
-
 Reaction :
lig
16

>( C2 PhyP
7
+ 0
PhsP CH2
= =
.

-
C= 0 + =

Phosphorous
ylide

&
.

CH-R .

O II

# + PhgP = M R- ->
[]

17 Acid
catalyzed hydration of alkenes
(formation of alcohols) : -
↳ /H20
y c) =

Hot
>
>Y On
* H30
e
C37CH CH2
CH-Of
= >
-

Addition ↳ &O
of
the
* takes
place according
Rule the double bond
Markornikoff's across .
↓

,thenegativepartof reagenta
Accordingtothis rul o be

of hydrogen
-
atoms

.
RAM
i
via
formation
be wed of
carbocation That means this
callocation
blinty-Meansdiffer
rule not Since

canundergoreallangementhe from
the
markovnik
may e e.
18
Oxymercuration -
Demercuration : COMDM) :

2/THF H2O
Y c) Hg(0ad ·> -
,

c =

(ii) NaBHG/OT

-acelye group--on-C
-

OAc

THE
e tetrahydrofran [ (pas t) .
O
<i.

--
HqSOAd2) THE H2O,

,
(ii) NABH4)oH
Note :-
- *
- In the addition H20 (H ) takes
place
4
ofwith out
OMDM
Rule
markonikoff's anyissearrangement
with
because in the mechanism carbocation not
formed
possibility of rearrangement
therefore
no

* HgLOAD
<i
-
2/THE H2O -
& o
, ,
3

(ii) NaBH4)on H

Lo-
I
&
be *

and
H
OmDi the OH comes
from
in the
the H20 in
first step
step
comes
from Nabley second
19
Alkoxy
mercuration demerculation :- Lethers are
formed)
iingCoAd2/THEOn ROM
>
<

y c
,

= >

(ii) NaBHa)
ether .

Mechanism is same as OMDM

H
PUTs
ingloAd2/THE CH3OH
I <
H ,

dis NABHF
-
-
Tn 7

H& OR with Rak

Addition
of markornikoffle
 Oxidation
20
Hydroboration : (HBO) :-

IBgH6/THF
Y c=
c ii More
>

on
hal .

-
-
di BeHGITHF -oh
(ii) H2O2) Of

*
Note ⑭ addition On) takes
-
-
The
of H2O (4 4
place with
Rule
antimarkornikoff's .

↳ ruk the
the
According to that to this ,

negative part
bonded carbon
of whichreagin goes
double

of hydrogens
.
more no

/ (i) BgH6/THF
[T -H
>
-

(ii) H2O2) On & on

-
↳
(i) By H6/THF
(ii) H2O2/OH
-X on

ful
-
-
& * Since there is no callocation
formed in the mechanism
the
o Rule
exe so we can
directly me
antimankornikofis

21
Hydroboration reduction :
-
(alkanes are
fored)
(i BgH6/THF
> = dis ch, con >q-
alkane
22
Hydroxylation of alkenes with
Bayer's Reagent
(cold-alk KMnO4):
.

Bayer's Reagent
y =
C
cryn
addition) >
dist
syn
CH3
cold alk H-OH

I
W
-

>

-----matically
-

KMnOH H-ol
inactive
Cz

CH3

I I
Of

agent
H Ho n
-
-

en
HO -

CH3

para a

[TK #To e
cold all
-
-

KMnO4

↑
 Monpyridinoy this allodoa
23 Ran alkens with
of
ci ,
Y c=
c ii)
<
eco4/pyridine
Malesogl H20
,
7C

24 alkene with peracids - (epoxidation alkenes)

of
Rxn
of & others
formed)
clic
are

i
M-CPBA
> C =
c) >
> c -C
N
o --

epoxide
M-CPBA -
meta-Chloo
U
pertenzoic and

[ - -o

H2203 ->
per famic aid

↳ He-o-o-M
magnesium monoperoxy phthalate
MMPP ! -

-
--

or)
-it-o-o-H

[
o

&3 ing
--
 conditions :
Mydoxylation
alkenes
25
of by prevent
CH3
H-OH
↳
(i , CHz
(NA) =2 >
[U4
in ↑= Of mao
-
--

ziil H2O
Utz
It is trans addition the
of two-of
groups
across

double bond .

26 :
Woodward condition

<CoAglFe a
ci ,
>n
CH,

y =
c) H20
>

addition)
(syn
e OH
I
H
<,
& -

CHICCONgl
H2O
F2 s H-OH

CHE

Rxu alkenes with hot acidic KinOL -

27
of
The oxidative
is same
ozonolyris
exp as

jifis, audic JC <

c =0

addee
He

#OH
 Ozonolysis of alkenes :
28

c
&2 -7
(i 03 = 0 + o=

dis zu/t
o

meas

Uz-ch-ch
03
+ 0 = Ufey
CHz-CH = 0

(ii) MzS

<7 -o
O
(is 03

dis zallg
> E B
↑
-H
-
-

29 Addition
of
Hx on alkenes :
Ext
> - (rearrangemen
④

a
↓
79 -
#
CHz-CHICHy
CHz-c-he
rate
of
Rxn - HIT HBUTHU .
30 Rxn alkenes with HBU : (Kharsch effect
of provide
--
HBG -Br
.
peroxide hap
: Peroxide effect is not

E
-

R-o-o-R
--

in care Chlorides &

applicable
Hoz zodides as one
of
the chain
propagation
steps endo themic
become

be care
ofMBr/ peroxidetheaddition of Ho Byee

placeThe
famation
I
radicals
zn
goes via nee I fre therefore
rearrangement
The

31 Rxu allrenes with :- (Used

of NBS
for allylic and benzylic
Bromination).

-N By n -

(NBS >
-
N-Bromo succinamide)
NBS
CH2 = CH-CH2- Cy =
C-CH2-By
↓ can

Benzyl ic T allylic hydrogen

CH2-Br
.

⑭ I

[5 I [

reaction
*

The ge
at
a
via
formation of fle radicals

positions
.
 Halogenation of
E
32 Alkenes :

( c)
=
-
Brakln
7-Buy o
Range ne e e

anti-addition
.

-
trans
-
Bra/Un
-Mr
I Meso

CH3

Be i
CH3

!
-
Brz/Un >

H Bu
Anti
-

is
Br-H H-By

Cz - Ut3

Racemicmixture

33
formation
alohydain : (Addition X2/H20)
of Bra/H20 or Uz/10-
④
In this addition oh & Br
rxn the
of
takes
place with
Markovnikoff's Rule .

It is also an anti addition

-

<= L-K
 It is medfor
unsaturation
I
test
of
& the
:Whichof decolorize
will
fol owing
e ee
Bl
=
-

th Reddish Brown

①
[ X -xn)
4
(no

·
[T] [Fiji
↳ I
-

E -

By
-
-

Brc/Un
· L&
-
-

EE & --
i -
-
I
I -

e -Bu

④
[Dun &But
Un X
⑤[
.

Bra/Un -
⑥ >
-

br Br
↓

* clopropane only Cycloalkanewhichgive

is he is
&
test unsaturation
of
 :
Chlorination
Allylic Benzylic
34 or

SO2U2 -
- - -

is
-
Ur/D

CH2-H
I
42-4 .

soallz
[O]
-
LU/A [s
(fee radical path)
35 Calbene insection reaction i

(c c) + Cl, 7 -c
af-
=
A
-
-Kon -
22
mination Echtuo carbend
:

36 Wacker's Process"
---

PdUz/H2O
CHz-CH2-CH CHy ·
=

Wll2/02
 vicinal dihalides
debalogenation of
38 :-
dihalides
geminal
.
4

NaNH2
CH2-Br alckot CH2 = CH-By >
- CHICH .

> ↓

· -Br A

↓ Alcoh
sodamide

.
X
NaNH2(excers)
④
-Na
-
NaNH2
MEM

alckot
Cz CH-Br U2 U-Bu
-
>
- =

-Br
↓ MaNH2
CHECH
--
-

Dehalogenation of tetrahalides :
39 -

By
Br
Up-c-k-cy (5C = C-Hz-

Bu Bu

of Haloform Agi-CHX3 Thalofom

40 Rxx with

CHU -> chloroform sweet

Liquid.
smelling
-

CHE3 +
yellow solid -

LCHU CHECH
GAgUwhite↓
+
bAg
+ >
-
.

-
-
 14 4
Ballz
4) CHECH +H - CH - CH- CU CH =

i Westrosol
Weston

42 CHECH + Asly >

- CHU =
CHASH2
Lewisite
used in I world war)
(poisonous gas .

↳ Addition
of
water !
O

R-CECH RgSOn/H2SO4 R-K-C3

>
-

CHOO
↓ iBcH6/TRF (Addition ofmarkovinikoff's Rub)
wate

R-CH2
-
( Addition water (4) OH)
with of
antimarkovinikoff's Rul)

. ·
reductive ozonolysis
Ozonolysis of alkyne
44
-

G O

I II ↑
s
R-c-R R -
C - C -
R.
B 4
Liie Zu/H20
B-diketones -

10
L ,
Oxidative
(ii) H2O2)
Ozonolysis
42O
O
O
II
R-C-OH + R -OH
 t
Polymerization
45
-

Lup
3cH = M [
-
-
#
U
4 CHECH- Tublike
structure
-
-

(COT) -
-
Mon aromatic .

-
Ze Cz
3 -
-
- &

E0 -

chz
un

46 2 MECH CHEC-CH C =

vinyl acetyle
↓ chech/Cull/NHU
C = CH-C = C-CH = C2

divings accty leve

O
47
galkyne
Reaction with Tollerie
Reagent (AGCNHb2]
CECH +
2AgCNH3)2]On Ag-EC-AgL
- +

+ NH3
He

↳
is
given only by
this text terminal
alkynes
-

H-CECH + at2 +N - C-GEC-Cut

ppt:
48
Decarboxylation
[] ada0 <G
) + Na2103 +He

49 From Reduction :

- zu/dult
2 + To

50 From
Benzemeulphonic and

/SOgH

[0]
H20/HU
under
i [0]
Pressure

5/ From Benzenediazonium Chloride ! -

ENG [
O
[_
 He
FeXz) X2 Eb
O x = 0, By

Chalogenation)
NO2
I
H2S Eob
juring HNOz Y

KE
,
>
(nitration)
SOzH

<ob
H2S207
>
deum

(sulphonation)
R
I
R-U/A1U3
Friedel
> [0]
craft
alkylation O
7
c- R
I
R -4/Al3
3
[Ob
Friedel
craft
acylation
 ④
M R

↳
-

4 R
E7
↑
-
-
-
+ - I
LI

E
Y
+ [0] ER
[]
commene
-

[ -
-
4 - nin
.

-
,
+

*
- ge
- ↳
↓
shift
- k
[0
utnos
90 +
[03-uh #
#
-

[0b-uk -
[8] + (o)
<3 -
+] 4
-
AlU3
[
3
-
"
"O
[] [ E
-

[
7
↳B + 2
()
es ④ O

[Ob
·

t Call C2-C Allz

9
-

4
i
i
[0] +
[0] + E 4

LAlls [0]+

- a
-
E
 52 "
From Alcohols

ROH + PU5 >

R-U + POUz + HU

3R-OH + PUz >

-
3R-U + HyPO3

Best method R-OH + SOU2 R-U + So24+ HuT

>
-
-
-

& becaueachof formatiof Thionylc

Unide
method
Pezen's
areous

CH3
CH3
SN2 D
u
PU5/PUs
-

D OH + -

immerston
H

o configuration
Ni
↓ SOUlz

CH3

D
IH
U

(Retention)
of configuration
53 ① Reaction
Finkelstein
only for
the
preparation of R-2)
R-U + Nat R-I + NalI
m

d ↓ ppt
-

more
covalent
polar a
profic
solvent
-

This reaction
path
*
of
via SN2 So inversion
goes
.

configuration
will be there .

(only for allyl flacsides

54
Rn:

13-x
Agxh

nir
B

+ addre +
legzxzf
cok
--
55 Borodine Hunsdieker Rxm :

-OAg +
Buy R-But
AgBuL
+ Cont

M: O O

Ruk-o-Br
R-K-0-Ag
-

AgBrL
-
+
Bug
>
-
+

R-C
&A -
0 -

B =
↓
Rif + Br

homolysis t
CO2 + R

R + Bi - R-Br
fe radical (Planar)
->
-

Bry *
II

O-Ag AgBr
+ o
Utze -

-But

C3

D
Long ~
can ,

i motoris a

enantiomer
H

O
1

Ph-c-o-Ag
+
Bug A PK-Br
56 SN2 Rxn : Substitution
nucleophilic Bimolecular 24d orde :

ack
Beide E
A N/polar
R-
X > N-R ↑ x
aproticnolvent
=

altack
-
-

alkyl
halide
-
-

↓ #
-
L I
d
-
8 -

N- - - .

R--. X .

transition state

rate law R(R-x]' [N]

of SN2 exn W =

ra(R x] -

2 (Na-]

solvent
polarity
C

X ↳
steric hinderence

owding -
 of reactivity ofs
write down the
& increasing order
one

Rems
of
the
following
① > 3 24-C3 > Up as
a
CHz -U CH5-CH2-U
Us-
methyle i
O

I 20 30

I
-Y 20
I I 14 30

Ez 7 [
② >
[]
: BEL FO
leaving group ability
③ CH3-H2-F < CH5-UIU <Ulz-Utz-Br < Us-CH2
4
.
Tc
④
Up
-
CH2 -
4 < che = M CH2 4
- -
<
[0]
IIT JEE ADVANCED
③
CH2 CH CH2-4
CH3-U CH3-CH2-4
= -

200 ·
of 79 O
4 I
L ·
/CH - -CH2-4
Utz-0-CH2-U
920
↳ EO3 EG3 1 , 00 , 000
200

L-halo
calbongls
-

↓
is
Si2
fastest
 a
q-KOH R-OH
>
-

KSH R-SH
-
1
RNat R-S-RI
-
R'S H

En
7
R-I

N5 R-Nz
>
-
O
II
Cl R-OAC
->
-

age halides moist

->
-

Ages
R-OH

R-0-R
-
auf .

Agro RECO
Again ·

KCN R-CN
->
-

O2 R-NO2

KNOZ R-ONO
7

↳
Rige R-R

↳
LiAlH4
ether
R-H

NABHH X-
>
ether
57

Reactions Substitution unimolecular 1st ordee:-

SN :
nucleophilic
-

④ Net-neutral nuckophile
R-
X polar protic > R > R-Nu + H
solvent
Carbocation
CH3
43 the OH
CH3
I MeOH I

CHz---- Cz-C#
-
Cz-c-oMet
its cnz che
(Planas sp2) ,

(Partial racemization

Relative
rate : takes
place as

3° 2
°

>1) -CH3
inversion
product) Retention
ylhalidesi- product
-

-Box - U)-F
halogen
:
different
--I3
.

wate = RCR-x]' (NH]

rate x (R-x]
<
leaving group ability
< dielectric constant the medium
of
 of reactivity of
the
0:
=
Write down the
SN Rxni-
order
following compounds
for
C3
① 454 < ch5-454
<UB-M-Co <Up inse
2
4
ins
+>
Upd a)
Up Lug-cis Br -
I

Y
Photo o e
<
-"
<
③
[8) < <
Ph-d-ph Ph
 Rxus: (substitution aromatic
58 SNAr
nucleophilic
↳
(SNAE)
Gian due to this resonance (treffect)
oUnder
U-
-

[F this does not

undergo
, 5x2 rem .

normal condition as there is

wond character is
partial double

developed 6/1 C-U bond

.

Dow's
process :-e

-dark
I
e i
SNAy
↓

4
) Ph-UY Ph-Br > Ph-E
-

Reachily i Ph-F -

- -
,
OH

SN2 < R-F <R-U (R-BU (R-I

F-z
6+4

· F
I NOZ

T
/
(order rate)
d3 of
ex
<
.

how hor
59 : Substitution
nucleophilicanim
SNEA :-
SNBenzyne
(Benzyne
Ety -
100 Bond

sp2-sp2 hybrid
3A bod
astital interaction .

↓
X X
L&
I H =

&·
OH
-
X

24 2,
NH2

H
-[Ob.
KNH2

E3
-

&

.
S Lig NHz

I - NH2 rH
N

ki
60 SNNGP : (Substitution nucleophilic Neighbouring group
participation)

mi
N
-e - w
SN2

Ni
q7
-
-

-u
-

E 600 times
· O

↓ farter
.

↓
internal
nucleophile -
Mu

In SNNGP two times

place that
* SN2 takes means

takes
retention
of configuration place
.

Internal nucleophiles can be

of three
types
:

① It be lone
can a
pair
-

② It be
can a ve
change
-

③ It can be a -Bond -

sing formed
* In Nap the mot common intransition state

ring
345 membered membered
rings
are 6 ar

less .
common
Gl From Benzene diazonium chloride ! -Q
NH2
NENC
I I
NaNO2/HC
E3 O
0-
°

5 C
>
[Ob
Aniline Benzene diazonium chlaide .

[ii iH
Bu
4
I I

[07
Br

lamelling
Can zo
>
[0]
(Sandmayer's
exn)
(Sandmayer's exn) Hs PO2
MBEG/D
I
K (Balz Schiemann)
A

-[O]
[0] 120
(Rxn)
F
I

[0]

koi
On
 Process
Raschig's
62
I
I

[ O + HU +O °
[
wll ,
258 C

langl anglhalides
Rxn : a
63 warth
Filtig
as
fol
-
R
R-X +

Che

+
Cs-x [be
Toluene
-

64 RXn :
Filtig e

<
[6] Nalether ,
[ E -

Phenyls

Biaryl Synthesis
65 Ullmann's !

= (-

(
-
-
&

-
of
[0)
~O
L I
66 Formation DDT :
of
La
T O

cap-1-1 +
< ms
in
Chloral
Lob
i Y
DDT-Insecticide .

pp-dichloss dipheny
--- - -
chluss ethane
67 Reaction :
of Aldehydes & kitones with
Grignard Reagent
kmgt
-H e -Omgx
-
other
⑭ Bra

Mo
Pomehyd .

R-CH2-OH
(alcohol)
⑦
omgt
Maldehyde
20 OH

* + R
+ K # Ruc-H-
H20 I
R
+ -R
Rigx
-

R 2 alcohol

R
-
Ringx
+ R-c-1'
Ketone
-

R
Ho
of
Rtk RI

e
-

i alcohol)
°
(3
68 and & their derivatives-
Carboxylic
Rxn with
O

R -OH +
Imgx
-

(Bane)
RH +
MglOcoR
Gomgx
za
20 ether
1
R1 R
R-MgX
- c I
+ c
-
-

↳
& -

U
easter
-OR -0-C
O
I
-
R
↓
R
, , &
d ↓ II
R
anhydride
C
and chluid acid
-

--- &
↓ Ringx letters
oR
of
my e
R1 O R R

↑ (3 alcohols)
: ↓

22 II43
O

-6
ether
-
img Cz 4 -ch3
+ c

excess
↓ Using X/ether
7

"mgx
Ch-it -Ch3 <20 Cty-C-ct
is Liz
④

Z
ether H20

Rog
X + CO2

&G
-

R-comgx >
- R-COOH
>
-
-

II
69 Reaction
with NHi-

Al2O3
R-MHz
R-OH +
NHz

Rxn alcohol with !

diazomethane
of
70

Bot
= ④
R-OK + CH2-NEN -

↑ diazome than

-
M2
==
Basin
-

Lap
Fl - Pinacol-Pinacolone :-
- Rearrangement
CH3
1 43 Mz
I H ④ 43
-
-C -
CHz C C H3
ab
-
- -
-

di de che
(Pinacol) Pinacolone
-

↓
CH3 CH3
13 (Ct3 -

H2O ↑ I
Uz -C-c-C3
>
Cz-C-C-C
O
on Goril tion
 CHz CH3 M3
CH3
I
1 I -

>
Uz
C CH3
Cz -C
CHz
40 -H
- -
-

migration
-

Chz
Tion ·

-
C3

Uz-K-K-U3
Lay
-
-

OH

·
no
Iπ 7
EXTR
i t
-1T
[& xt
S m
- H+
·
c- m

z 2
m
3
-

-
5

Ro
OH
OH H
-k-S
7
uo-L-k
0 -
-NO
② >

upas a
43-0-4-8 on

NOz

- ·o mon

= ---O-NOz
25-0 7
L -

Coun
-
-
 :
of migratory Aptitude
order

-
Ar 3: 2 %1
-
ArL-H > -R
↳ It is not
fixed
.

different angls
:-
Am
[0] [] []
I

[03-0 , 90b > > <

To i 's

do locks
72 Lucas test. !

R-OH - Inte
archy > R-C ti
conc -
HU

e
SNI turbidity.
↳
goes formation of
via carbocation
-

turbidity appears
:
* In care alcohol immediate
of
3 -

"20 a
turbidity appears
* n in 5 to coming
.

"appear" after
*

turbidity
either do not
appear a

long
time .
&

13 victor Test :
Mayer
Teapot R-CH2 - I E-C2-NOz
↓ HNO2
OM
R C-NO2
R-G-N
im nibolic acid
(Red)
 RedP Is
An
+
R-CH-R
R-C-B R-CHe
->
-

OH
2 alcohol
-

- -
↓To
R
K
- R- - NO
y

-
Noz
nitrole
preedo
(Blue C

R R R
I

RK-E
I
③ R-C-O4 R-C -
No

R R
cotourless

↓ HNOL

* 4/20
X
Th From Cummens
hydroperoxide : (Best method
for the /reparation
-

W
I of Phenal) .

+-
2 [OT
(commene)
us102/120 3
°

OH 4-k-o -
0 -
H
O I I

Up-t-C LoT [0]

Mason
t >
- -

I
Phenol
I

autom Commenc
hydroperoxide
.

75 Formation
of Aspin :

i
OH
I -cool O -i d
3 acticanhydride
Cho
O +i
.

--

↓ HzPO4/A
salicylicaid o-ki-CH3
I

[co
prin
76 Schotton-Baumann Reaction

-on +
pri E-o--
↓ NaOH T
-[] ooh
*
↳)
 Kaisen
RearrangementWhen
78

anyl allyl
other are

heated
of any catalyst
at about 200 in abrence

undergoes rearrangement form -ally phench

It to o -

-C2-CH =
172 OH
o I CH2-CH C2=

I /

[0] E3
O

is

Och2-(Pericyclic
h
4

Ein F

gua
&

[ I
:
E7 - 2 -

↓
P -C2-CH
= CH2
& M = CH2
Factomerism ch2

[b O =
# []
79 Likermann's Nitro test or (Rxn) : O

o Tasmani ie
King /Mason
↓
N
- on
(thei will
generate NO) , = 0

Benzenoid
form) quinoid
form
(p-nitrosophenol)
.

6
ei e
o so
,

ID
E-
<
4 -on in of
7
a

&
43
--
- kit ki
!

↓
i
Kin
fautomerism
=

i
dys(indophenol)
(Blue dy)
colour
80 Formation
of alkyl-anyl :
other

0-Cz
OH

o
I

[03
>
-

0-Uz

I
↓ NaOl
I id]
[b
+
14

TcT
Rxu with :
diazomethane CHIN2 of
-

- I
⑭H ④
E-NEM [T
[O]
-
+

↓
Q-Utz
[b
=

8 Rxn with Indust -

OH
[0]
dust + 20

[0b
·

-
+I

82
Hydrogenation H

[ + 3H2
Ni-Cat

150
°

-
250
: [T
 :
83
of Phenophthalin
-peration
-

Co
PH
<]
+
·

phthalic anhydride
L
↓conc H2SO4
O

-
&o Eb
Tec
o

On o

Phenolphthalin (pH range 83-103. nk

(colourless)
84
phenols
xidation :
of
-

oxidation"
(a) Elb's
persulphate on

Cook
I on
Of ,

[
K2S208
Alkaline
>
[0] +

medium
no
H x

[OT
kaC8gO7
H2SO4
7
KD
·
-
quinone
85 Bromination
of Phenol : OH

OH
[0] + By -
CS2
Lib
Br

↓ Brain o

B ph ,
Bu

ET
-
Buz/H2O
Br
ON
I

opp
com
,
t Buy [Ob

,
sol Of
+ Bug &
↓ Bralle
OH Bu
Bar

ET
O

Br
86 Reimer Teimann Reaction- de to
intramolecular
OH ...
H-BondingOff
I
on I HO
= [ +
[b
[] + CHU + 104

(major)
iro
minas

salicyladehyde
.

OH O
JEEADVANCED

ID c
CHO
- Ion 1/

*
KOH/CHU3
A
> E
I↳
- +

Chz
is ming
-

87 Kolbe's
--
Reaction

it +com t cool

Rin :
88
Diazocoupling
on oat [] I
-
N = N -

Lot

P-hydroxy azobenzene .

(a20dye) .

our
⑭ N = M-Ph

dojo
I on

>
on

P
for E -
OTO
-
- -

(B-naphthal)
 :-
89 Dienone
Phenol Rearrangement
que ↳ -n
-
&

KB >
-
#
i
Dienonl
H
↓
-

OH

<F In

mannasernoo(famation Balelisae
90
Ladder of
[0] 'OH
-
excess

PhOHT
of HMHO
Ht/on
Of
/04
W

[0]-m-6]
E
-
-

Ce

in in
I

-
--Cob -
a -[0] -an

On
on
resin
>
-
Bakelite Phend
fromaldehyde
 :
9) Test
of phenols -

* neutral fells (F(0-2)(6)

)
-
-on +

violet colour
-
--
92 intermolecular
dehydration of alcohols :
H2SO4
R-CHz- OH °
> R-CH2 0-CH2 R .

140 C

M: -

I
R-FTHQ -
④
R-Otz ->
-
R= 30
R
④
4
+ H2O

E ↳ !
↓
:

01/SN2
R-OH
R ④
R-O-R
↓. In

RO-R R-O-R

H2SO4
CHz-CH2-OH Cy-Ut2-0-Utz-CHy

Demercation
Alkoxymecuration
93 :

/THE RON
Y c) <IHglOAd
c= >
>q
(i) NABH/O
For
RgCoAd/THY
/ <i ROM

# 4
,

o H
-

wil NaBhy) -
-

*
Addition * & OR with malkownikoff's
of4
takes
place
Rule .
 * <i
Hgl oAc)
2) THE UsOH
,
&
-
-
(ii) MaBMa/ Oc
94 Williamson's Ether
Synthesis. -

④
R-Na + Rx
- -
-
SN2
R-O-R
-

i
askyothers
- -

R-x should be either

-

for -X better Y ield

of
the

allyl
halide
-

. To avoid the
Ut chances
of
or

E2 rxn .

1 -

E Na + Uzx -
&
L o -chz

Si
*
Exa + E-4

E-o-5
E this not be
formed
-
can .

CHz-k
C3
-

o -
CH3 E
CHz
-
Fis
X t Ctz
-
CH3
I
C- Na
④

asa
- -
=
-

E
an
I
U-c-0-C-cy = this also can not be

is knz femed by Williamson s

othersynthemt
s

possible)
 95 Rxn Rex with :
of dry Ag20
1
dy Agro
Ro-R
RAg
+
CR-X + >
-

96 !
Grignard reagent
From

- ·
4 -OR
-
-

SN2
-

97 RXN with HX :

fel
f

RIx
-
- RO-R' + HX >
-
ROH +

<excent
↓
x

R-X + H2O
-

Reactivity of
Hx ! -

HIT HBV) HUY HF

>

-che
--
HI
*0
Uz-0-CH2-Hz
-

↳ e

E
↓
Utz -
= + Uz-CH -OH
2
 CH3

Up As
I HI
② U-0-c -ch3

j
-
e

The
↓ Sal
PH3
Uz-0H + Cz-CQ

↳ 'z

< (IUes-s ie
- I

ins
·
ht

[c

e
ast
-

Frompermeationengaiat of
mal+co2+ Goo-

99 iodides
of glycero
RXU with Hi :
not stable
vicinal
.

are -
- -

· CH ,-OH CH2-F
I2
CH2

in-1 -
-

in-on + 3H1 >

-

Cc-on CH2 - I -z

He

is e 4 is
E

inz

100 with HNOz

&

CH2-OH CONCI
CH2-0-NO2
CH-on +
SHNO
- H2SO4
In-0-MOz

CH2-
04
-0MOS
col
gly
10) with oxalic aid :
&
O
II
°
CH2-0-C -COOH
CH2-OH COOH 120 C

it-of ↑
look CH-OH
CH2-OH Citz-on
↓
↓
A -
Coz
260
↑
CH2-0-C-H
U2-o-di ch-on
in-o
in or CH2- Of

1/ -
CO2
glycomonofrmate

icon
Sallye alcol e

102 Rxn with knson/conc H2SO4 /P205 (dehydration)

* COH knSO4/ CH2
In
o
3
on PgOj
in on acoline

aldehyde)
--
 From alcohols
103 oxidation
of O O

He R- He "-OH
R-C
R-CH2-04 -H

R-CH-R He R-K-R He X at normal

OH conditions
-

R
I
R-C ~
OH ,
# X

R
104 Dehydration heated !-
over
copper
R-CHG-OH R -H
c
O

R-K-R
R-CH ,
ME /
CHz-Cook As Ctz =,
E
43.
is
105 Oxidation with PCC : -

Chloro chromate
Pyridinium
PCC -

I&
I (Cl
=. cros

It i alcohols
aldehydes
oxidises - .

2 alcohols >
- Ketones

:
3 alcohols >
-
X -

general)
(in
allylicbenzylic aldehydes/Ketos
- a

ce
e stint
*

Itdoesnoteffect the multiplrons

PCC
CHz-C2-CH2-OH >
Cz-CH-M 0 -

E DCM

5)
PCC
+ +
& =0
on
DCM

#)-on -Ec PCC

0
DCM
=

E E
 dichromate (DCM) :
106 From PDC
Pyridinium
-

L) crgop27/Cel
T

It i alcohols
aldehydes
-
oxidizes >
-

2 alcohols -> Ketones -

30 alcohols >
- X -

It does not
any
effect other
functional group .

> -04 > -

ch = 0

o Mo
=
on -
CH2C2
-
-

Non-conjugated alcohols (1)areoxidizedtocaligee

*

alids

d Lap [The -

-
Of
-
PDC
->
-

Moist DMF
- -
E L

k
cool
-
=

--

⑰
the conjugated l'alcohols aldehyde
are oxidized to e

Go
zo E>
=

moist DMF
 From Collin's
Reagent
107 -

+ Cros + Ul
e
It oxidizes
i alcohol
aldehyde
-

2" alcohol - Ketones

30 alcohol -

multiple ronds -> not

effected

108 From Jones

Reagent
! (H2C204 in
anhydrows actone)
(cros + Hrson) in autone -

1 alcohol-
It oxidizes
2 alcohol-ketone
aldehyde
3" Alcohol - X

bonds
multiple X
->
 109 :
Manganese Reagents
From

(i) It
acidified Mno4 :
From is a
strong oxidising
-

F
agent
H
+

+2

MnOG- >
- Mn

colorless
purple pink
a

It oxidizes

1 alcohol
Carboxylic ad
- -

2" alcohol
kinnon/ acids
>
- Ketones -
A

Kalboylic)
(Poppof's Rule)
30 alcohol >
- X

bond oxidative
very
-
*
Multiple are oxidized as
cleavage
.

ful 10
T
7
From
Muoz) actoneThis
is
specific for venzylic
and

allylic oxidation
.

CH2 =
CH-120H >
-
MnO2
CH2 = CH - -
H
autore
alcohol
allyl acrabety
de O

accolime
 #) at-c E) i
MnO2 -

o
MnOz

T7an CH2-CH2-OH >

-

↓
-

w
-
-

actone .

on &
②h
.
I
Q E c-CcCH2-OH

Benzylic up - o
- .

phongl
I - -
↑

MnOz
Ph-ch =
Ch-C204 P h-CH = CH-CHO
e

unamaldehyde
- -

Laon X-co
CHO MnOz
X
autore
III Oxidation with Se02 :

Allyli
Oxidation alkenes
of
take
place & the
produc he
allylic
s
alcobs

carbonys compounds
o
-

R-CHICH-C R-M =
M -

CH, O
↓ Se02
R-CH =

-
-
O
CH-CHO

methylene carbonyl group

* Se02 Oxidizes to
a
go Ked
when
two
especially
aromatic
fan by
O

Ph-CH2-Ph
Se02
/
> Ph-K-Ph
-
-

-°
-

Oxidation
of alkynes with Se02 :
*

R-CEC-P -
Se02
R Li -pl
o o

Se02 II I
Ph-C = C-Ph ->
- Phe-c-Ph -
⑭ Oxidation
of ketones at
2-position :
p
·
O O

Et-o-k-chi-k-oft--
SeOz II

Eto-c-
-
C-oft

ki - Chz
O
SeOz I
↳ >
- R-C-CHO
-
-
-

O O O
O

-M-M2-K- R-K -R
SeOz
R- R -> -

- -
M = CH- .

-
-
-
-

12
oppeanaur Oxidation. :
Aluminium Test-Butoxide
.

faul
&
↓
T ph
Up-Pk-CH R1 Ki B
, Mess
,
+ R-CH-R
-

(excess) 2 alcohol
↓ +
ch
-C
L
reverse rxn is known as

reduction)
Meerwin Ponds
of Verley
L MPV reduction)

113 Severn Oxidation :

- i i
U
arc c -

R-CHyOH
-

+ Me-S-Met

L ④) LETgN
DMSO xalgechloride .

↳ >
-
R-CHO + M2S
+
O +
Co2 +
H
Dos
-
-
114 From
AG2 C03/C6H6 !

Econ
*
s [
ono
I/5 OmNBSi-
i alcohol-
aldehyde
.

2 alcohol - Ketone

offected
O

34 - not

alkenes
allylic
- Bromination
-
116 Oxidation acid) -
with HIO4 (periodic :

OH HIO4
X
-

--On
- 0 + >c 0 .
= =

-
Of

Cz

H-OH
Of
- HIOH M
it
- on
EC-ik-n
OH
H
-
On
HO OH
H-P-ot
- -

-ofn OH
I
~

-
H20

H H-0-C-4
-

on
CH3

117 LTA <head tetra actate) : -

TSCHC04 -
+2

P6 (cuto inest
pain
works same as HIO4
effect)

-
OH --
LTA
(c = 0 + >c =0

-
-

o Of I
-
-

Ammonium nitrate) :
118
from CAN (Ceric

(NHAlz Y"(NO)s -Ct3

o >( >C
+ =
= 0

HIOG O

2) 0

#D]
=
>
Lia ~

CAN
 Oxidation Ketones :
119
of
① Oxidation
Bayer Villiger
o

O
O
II
R-c-R
I MCPBA
>
-
R-K-o-R
ester
- -

peracid
O

Chy--chz Up-k-Oly
O

O
O I

# Laid [g
O
I
-

y peacia > Ei
 O O
M(PBA II
Ubi-Cz Uz ->
-
Utz-C-0-UICz

CH3
O
CH3
19 I MCPBA
un-k-o-k
C-c-Ct3 CH3
CHz
-

--

is
-

CH3
O

C-i-Ph -
M(PBA
Cs-k-o-Ph

-
O

1
[ m

order
Migratory Aptitude
20317-cy
30 >
for alkyl group
43
Ph > C2-Utz) -Cz
U
C > =
Uly C-Hg
-
- -
- -
-

ins
O
↑ 413
CoH5-1-4/473 ~
MCPBA
-- CoH5-0-C - /
-
CH3
Cly of
CH3
CoHs-k-o-ch/chy
O O
MCPBA
R-C
II
-
H --
R-K-OH
peracid --

Oxidking agent
 Rule"
120
Popoff's ④
i
C-18-cky Alt
A Utz-2-04 + H-c-H

. Cz-

*
-C2-U13
I
Kino4/
A
>
:CH3
-

*
-
-Y
i
C-OH + Cz-COOH
-
121
Effect -
Heating of dicarboxylic
aids

I
0 oxalic and O

con
n = >
-
-

1 Malonic and

e
n = >
-

Succinic aid
com n= 2 +

n = 3 -
Glutaric
-
and
4 +
acid
n
Adipic A
=

n = 5 >
-
Pimelic and P
-

COOH A CO24 + CO4 +H2O

->
-

Con
Oxalalic and

1024
CCOl
A
CHz-COOH +

in2 ->
-

Soon
Malonic ad
con
COUH ,
[
~

5
coun => + CO2

·
-
-OH

Succinic arch
succinic
anhydride .
 &-
O
-COOH

coon
-
A

bo
[O
phthalic ad
phthalic anhydride .

-
5)
1) -
-

is

oe
A
X

4)
-

-ko
H
COUH
- >
-
A

/
- con
H
-

i
Maleic and maleic
anhydride
.

H
i Colt

- X
,
O
-
H
noos

jemaric aid
CCON

[chals -
A
[
Econ
O
II
COUH
A + Con + 120
[chzl4 >
-

Cost
COOH
I + Cort H
23
[I 4
>
-

corn

cost
X
E3
A
->
-
O

Coote
Terephthalic and

COOH

(2H2)5 s i
dotH
 :
*
Heating effect of
B-keto aids

u-c-c-i-on
"E
B -
>
-

e
A

walm
-

-
C-K-c -
-
+ cost

:
- 1472
C-c
Ce Chz-
>
-

on (end)
·
Ed I

I
1) tautomerism
UB
-,
O

& N + CH2-K-04 >

-
A
U-NO2 + Co24
- I

Ap
>
- greater
the
-Iel fect at -position greate
will be The rate
of decarboxylation
.

O
O
cool con cook II -COOH
II 4

ETo 2]
&O < B 2 CO2
-
COM +

MOOC
D
->
-

B-repaid
O

# + a con
=>
 head
paning vapours of carboxylic and
122 e
By
over

R-OH A °
30 C
RU-R
O

RLOH RK-OH+
MnO
R "-R
c
I

O
+ RK R -

+ R + -R -

R-K-OK H-4-on
+ >
-
Mno
°
REM R -H
30 C
+ -M
H-4
.

123
Heating effect of calcium o Barium salt
of Carboxylic
ands !
- -

(R--olgla = R4 R
-
+ CaCOs

(R-ojBa = Bacost
RR .

* -I
(-i 0 - I
-

-
 processi carbonyl
124 dicobalt octa
>
-

(ar((0) 8
R-CH =
Uz 7
R-CH2-CH2CHO
+ CoH12
↓
water
gas
125
Cyano Hydrin formation : Y Kyanohydrin)
.
> 20 + HIN -
Y N

↓
y c = 04
④
/ -
/ot
-
CN

e ↓ Mot (hydrolysis of
of Cyanide
/-COOH -

RCET &
O-OH +
④
N

Mi ↓ ④
↳i
R-CEN-H -

Mo
v

LIMPT
R-P-NH *
automatic *
O
12-C
R- =
NH =

↓
o
iminal
hydrolysis
ial

Reint
Pitts a
O
Ron
do ④
II
R-C-OH + NHG
126 with Ammonia :
of formaldehyde
Rxn
1
↳ 6 H-1-H +
4NHz
-
KH2)sNn
HMTA

hexamethyle(Urotropine)
ne tetraamine

/Uz -

cx
M
-

ech (asotropine)
 Reaction
carbonyl compounds
127 with Ammonia derivatives :
of
-
H2O
Y = 0 +
HN -1 >
-
Y = N-2

H2O N/04
Y
-

Y
HIN-O
= 0 + =

oxime .

He
Y C= 0 +
HaN-NH2 YC =
N-NM2

hydrazine hydrazone
H20
N-NH-Ph
-

& c=0 + HgN-NH-Ph > =

phenyl hydrazine phenyl hydrazone

O O

Y N-NH-K-MHz
T
Y c= 0 +
BN-N--NH2 =

semicalbazide Semicalbazone .

NO2
I

7C = 0 +
MN-MH-E-NO2 (Brady's Reagent)
Test of 12 .

4-dinitrophenyl hydrazine) (24DNP-H)

Ketones ↓ 10

di n i t rophenyl )
-

- (2
NO2 4

-
.

I -

-LO 7 hydrazon)
YC M-NH NO2
-

(2 4 (orange-Red) /hello
DNP)
e
, ,
 ⑭ It is used
for the test
of aldehydes
& Ketones
.

128 Reaction with PU5 :

ill
(c = 0 +
PU
>
-
7 -
+ POUz
-
-

129 Formation actals hemiactals :

of
and

O
< = 0
-y R &
themiacetals)
(theyareunstablein as a
acidic

> = 0

+Ro Yo i

(actals)
* Unstable in acidic medium)
* stable in basic medium)
very
 Reduction
Carbonyl
-
of compounds
130 Reduction :
metals
by dissolving
PH
O
II si Na Prot
>
- lene
-
xy ,
Reflex
i Ho
OH
O
I
II

[ "Malf to e ->
[]
-

:
Pinacole
formation
131

magnesium Amalgam O-

I inglng ,
---
odimerization
I
I

-
--- H
Pinacol
di -
-
-

Bouveault-Blanc Reduction
-
132

O
II Na/EtOH
R-c-oR -
R-CHyOH + RLOH
133 Reduction with Lilly (LAH) -Lithium Aluminium
hydride"
Sup THE

X ↳ Lift Allz >

Hist
Lilly + Shill

hydride
very good
a dono

&
therefore very good reducing
is a

.
agent
LAH can Reduc :

O OH
II
(i) LAM) ether I
>
- -
(ii) Ho

-
Cool
-

CH2-OH
O

- -
OR & -

CH2-OH
O
I
-
C-H & -

CH2-ON
O

- k-U - -

CH-OH

19 O
4

R-c -
0 - -
R >
-
R-C,OH
O

= RK-NMy >
= R-H2-NH2 O
amim

NO2 >
-
-NH2 =

R-CEN -
R-CH2-NH2
-
 -
CH = CH- X X

-
CE -
= X4
C

-
CH2-B M
-

Cly

alkyl
3 halide =is alke =

Questions:-
-

④ H-[CH2a-K -4
CAMlether
Li HO
> L (4-CHOM
Uz-CH2

Oft
②
T
4
> -CHOH + EtOH
↳

o
- OH
③ =

④ R-CH2-C2-COOH me R-CHIU2 U2OH

⑤ C-CH
= CH-COOH e CHz-CH = C-U,Oh

fo
=>
PO Ph -CH = CH-COOH
9
Ph-CH2-CH2CH2OH

T
134 Reduction with LTTBAH :
Lithium Tritert
Butoxy aluminium
hydride .

[LiHAl(OMez)3]

It is much weaker
compared to LA
reducing agent
a as i

[O]
GEN
LTTBAH

[ diglyme-8s
u-k = H -
k = 0

CHz-0-42-CH-0-CH2-CH2-0-CH
glyme : -
,

(
135 Reduction with Sodium
Borohydride !BH4) :(SBH) .

* It isaweaker reducing agent than LAH But

a
etrog

Itreduces : -

-k -
H >
- -

M2
-
OH

H
O

II
- --

CH2-Mg CH-CHz
-

-> -

W Oh
O

4
- CH2
>
-
OH
-
-
-

3 R-X >
- alkane

& it does not reduces : -

-On
O

--OR ,
- -NH2
, ,
-NO2 ,
-CEC-
,
-
- halides-
i
alkyl
- c = C
,
 of

d [i-
<Is LAH
+ EtOH
-
~
CHIOH
(ii) H20
-
oft
CH2-CoH5
'CH2-Cots
NaBH4) ether
Ki
is

Ho

of

# oft

cons
136
Reduction
with By16'
It reduces
v
-
COOH --C-OH

70
>
-
>-042
I

-
CIN >
- -
CH2-NH2
-

CHICH2 - H2-Hs (Hydroboration

reduction)
↓ HBO ( .

CH2 -CH2-OH
--

137 Reduction with DIBAL-H !

(Diisobutyl Aluminium
hydride)

AlH)-CH-d e
-

I -H On w
-H A -H

O
of
# -
4

-
I -

O O
II 4 II
-OR -
-H
-
+ ROH
O

RK
U

R-CEM - -
H
O
4

R- -U
9
-
R-CHO-
E
138 Reduction with 9 BBN (3 13 nonque :
-9-Borobigelo
,
3,

↳ a

(
3

-
2

-
4

x 8 76
I

,
O
I BN
of
-

reduction"
139 ch

[0]
altignt
- D
=> (Radical anion)
s t
i &
[b
②

45 -
C
-
&B
E
i
-

radical

is
amon

ET
O

4 M's

IT
&

I
 It
93/EDG
Tight E
# Coul

cook/Waltig
[T
-
N
ED

Reduction !
140
Phen's O

R-CEN I
R-C-H

Sn + HU >
-
suC2 + 2 /H]
2 (H)
R-CEN ->
-
R-CH = NH

imine

↓ bot
R-K-H
O 3
14 Rosenmund Reduction !

o
R- -U Ald
Bason
R-CH =0 -

or

S-Quinoline
Lindlar's
catalyst
142 Aldol reaction and condensation :

usci-Ech-H
O -

II OH

-carbon
-

H-CH2-C-H -
-

Ok
-H
Ips B-hydroxy adily e
-
-
a
-

1) /A

B
CHz-CH =
L
CH -
* -H
B-unsaturated
aldehydes
4
,

crotonaldehyde) .

&h
Ii O
↳ it o
t
-
-

CH2 - k -
H -
- -
-
U-c-H =
O

OH
- H
-

12-dit c H
=> as
-
t

-
-

·
H2O
Uz CH
-
-

OH
aldot U
on ar t O
I
rich -H
↳ CHz -
CH = CH
- C

->
-
 -che -Pl -chz
c -c
* Cle
Us
n
Ch
-

i H
LH
-
OH
E↳
Eit -o
-

[
=

=
-

Eb
Openchaielersdo e ee
* not m T

143 Clairen Condensation

O
Et/EtOH _-oft
Uz--oEt A
,
Cz
B

B-Ketoester
&
EtoNa /Etol ⑰ 10
④
Y, H
Oft O -, &

-
9
-
- -

*of - -oft

Bl
-

-[2
Ut e
un-C-Ct -To ↓ Hot
B

Uttar tes -

U
a - -

~
CO2
- core
 Reanangement
144 Beckmann :

B
R' (i,
>
-
* o Lewis arid
R-B-NK-R'
i ps/H20
(oxime)
on (N-alkylamide)
: B
RL RL R
,
M
i-on .

Ca
I
? I

that e
which
groupwillantimigito H
--
~

Q
R' -- R-CE R
On
= N- N-

e
I
I
,

H
I
-

O
V

R N -
tautomerism R-K-NH-R'
C
- =
-- -
< --
Y

⑭ H30
- HpH3t05 A ⑬
majo
④

Cin
-
U
-
C = N-CH2-Uty
>
-

di
on Mod
CH -Yk-MH- C-Uz
-
- -
 Benzil-Benzilic :
Acid
Rearrangement
145

Of
Ph-ki -Ph si, on
-
- Ph-c-Ph
I

ii. Hot Corn

Benzil
Benzilic Acid -

S o
: ii
3

Ph-c-c-Ph >
-
OH
Pht-k-Ph 2

OH

Ph-k-cro" EMPT Ph
-- :
I
-
O
I
c-of

in in
↓ Hot

Ph-bot cook T

Q:

< sob)
E
or
=

④
ot
youcon

②
o
EY-kit ot
OH

LoD-c ↓
T
I I
-

doon
146 Cannizalo Reaction
Thisrxn is shown those
which do not have 2-H-
by aldehydes
It is a
disproportination
↳
ran

reduction
O -
Oxidation self
-
oxidation
O
II OH
2 H-C -
H >
-
CH5-OH + H-K-o
conce
-
- -

reduction

& slids
or
G

-
·

I
: - ,P
-
CONC OH I
c-n
.

H-C-H
- H C -
H
H
-

ion

-
+
2=
He -F +CHOH
M - -OK + H-c-H
In

* Ph-1P -M >
-
conce
Ph-k -
of + Ph-UzOH
NaOH

at home
Try
.
 147 Perkin Reaction'
The reaction comatic
of aldely
des

with
anhydride in sodium salt
of
and the
presence q
is called Rou
and
Perkin's
G

Ph- -H + U
-- o-* -M >
-
C3 (CONG
A
Ph-CH = CH-CC07
↓ H2G
Ph-CH = CH-ICOH
Cinnamic and
O

--Of C -o
PhX
Ph-CH =

HgCH
-
=0
+ -
-

Reaction:
148
Haloform
in
Ran
presence of
-
X/ Reaction mmyl
of Ketones oractade
See

CHU-Chorm-
sweet
smelling Liquid
CHES
-

odoform >
- yellow solid (ppt) ·

O
. Cz
-
O
" -
R +
x2
Naon
s
CHX
haloform
+ R-Ex
↓
methyl
Ketone
which
oxidising agen
this is a mild can convert

inc to
calbonyl compounds
alcohols
respective
149 Tischenko Reactionin
O

2R-K -H Rt-o-CHc-R
Mi I
= ④ COEt
0: Al(OEH1z z
Ell
II
R - C -
H & > R - C -
H
vacent i
partital R
-
H

t
⑦
Al 10ft)z
-

c
o
O
R-
R-K-o-CH2-R -
I

mid
3

150 Benzoin Condensation :

Ph-on--Ph
O &
KCN
2 Ph - -
-

on

S
..
MH
I
I
: I goI KCN I II
I of 2

PK-C-H - Ph-c-F Ph-c 2 C

-
H
IN
-

kN in
↓
of &

Phel-CH-Ph
on

E Ph-C
I
-
1 I
C -Ph EMPT Ph-* M

dN3
↳ con
151

Reaction Ne
smiat H2SO4
7 R-NH2

heydrazoic and
④ O
H-N = N = N

Roth 20
B-c-olmfEN
Mi ④
-
-
II
-

E -
-

N3

H &.. ↓
D
-

12C Hot
hydrol og
I

- R-N -

-
= 0 < -
R-N = C= 0

!i
Q
alkylisocyanate
④ i ·
II
R-N·-of t
I IMPF
- R-N c C

&
-
-

ot
2

R-NH2 + CO2 T

1S]
Curtins Rearrangement
R-K-N3 A RuNH2 + CO2
ilHot
< *
↑ H30
19 f
=

C
M: - ④
N-N EN
R-N = C = 0
- R-
C -
-
-
>
↳
-
-
153 Lossen
Reanangement
G O -

R-K-MN-O-K-R e
A R-NHz)

Got
hydroxamic
.

ester
&
I

/D
I L4

Ci REN-o--R-
O
-
R-N = C = O
2 ↳
-
--

154
Hoffmann Bromamide
Degradation
O
were
↓
fup decrease in
length of calton chain -

R-K-NH2 +
Buy T R-NH2 + KBU + K2CO
t H2O

D
I
Mi
= 24 &
R-C-NH-H
2

I OH >
- R-C = NH

↳
Br-Br

migration gR3
this ↳

↓
-

inf
&akela Dis
G
I

one RC N-By E

R-K-M By
-
-

&
tion I

If
- ON
#
R-N = C=
A REM :
&
isocyanate - -
 i
C3 O

D C-NHOP
II
D-MHz

H H

_ -NH ,
on
[0)
155 Gattermann Koch Reaction
CHO

[0b 20
+ + 4 -
[0
= = :* + HU -
H-c =

.-
Q

E]
I
E
L
-
H
H
- Kee
↓
und

[]
156 Gattermann Reactioni

[0-den
A
[O] + HCM

name
Skom u

I ④ O
H-CENIS Ally >
- H-CENAIUz
↳

·
[b
LOb
-
40
[]
157 Condensation :
ocyloin
R-dP-4
.

I
<is Malether
R-C
I
-
Op' ,

-
Lil H20

2-hydroxy carbonyls
of
#
Se
2
&O

-os anions
II
R-C-OR' >

R-kPe E R-c
~or
of7
↓ dimerization
-
C R

edite
2

↓
of

Rek
on
--

& -
R -
↳ -

O
To
-

1
tautomerism ino
en
- - R
- -

v
-
--
158 :
of Rearrangement
-"-c
O

R-LP-CH-NH2 -
MNO2
um
R =

BL

& Ag20/A
in
O I

R CH C =O 2
-
j
= -

↳
-

C
3
Ketone
:

↓ ↳zo

R-CH
Go
H

-UC
=
-

④ 2

1 tautomerim
H -

R-CH2--OH
Ketone O
ROH
R-CH = C = 0 > R-CH2-K-OR
O

NH3
> R-CH2-K-MHz
O

R-NH2
> R-cHz- -NH-R
-
159 Gabriel Reaction :
Phthalamide This is the best method
1 amines
to
prepare .

do -Po
O

L e ↳

too
phthalic ad
ie

phthalamide
- & Kimk*
?
kok
[8)
-

[b WH
-
,
- / =
the

- i 2
SN2

↓-x
alkyl
natide
·

31
2

-Niof14
-di-on
2

C-N-R
-

[↳
O
-
NR
I -
db-
q
-

IMPT
↓ O kno
-
II
Son EO-- - + R-NH2

[
-
-

-
NHR
lamine
-
↳ =
C zu
 Carbyl amine Reaction'
160
1° amine
of
Test
↳
.

R-NH2 +
CHUy + KOH E R

alkylisocyanida
hi
cust
-
-
Us + OH

↓ (4 elimination)
,

· Cl2 + CO
(dichlorocarbene)
is
R-Nitz + :Cl - R-N ·,
in 4
·
for
of

↓
R-NECE
④
4 -↳ = C
- q 3
161 Ren
of CHz-P-H with conc. Hason :

OH ,
z

3
O

i
Conc H2SO4
CHz-K-H
.

-
3 3

HOL cons
un
para aldehyde .

ch--H
-o - &
conc

che
.

4 -

Mason Ho-
S
of
Hork-o -
/ Chz
Ctz
meta
aldehyde
.

O
O

-Cz
conci
CH-K-cec
de
--
162 CHz
- =

H2SO4
an s

Phosone
- -
-

C
(3)
E
=
Hg 0 + -

LoI /
CH-K-U-1 -
=
-

Cly
Cz
163 Silver Mirror test (Tollen'stat) : -

R *
-] som
2/AgINH3)
-
H + +

↳ R-coF
LAgh
+
+ GNkz
silver mirror
Black
Lgrey to
the
sticks to the wall
felt take-
of

solution :
164
bling
+2 O-R-co
R-CHO +
Mod + 3 H0
+ 2u +

165 :
Benedict's solution
It is
2
alkaline solution cut
of
an

citrate
complexed with ion -

R-CHO +2Cutt + 50 - RCF + Carof + 3H

Red
167
it's Reagent
NH2 NH2

< colorlesssolutioniso
I

(schiff's
⑮ ,
R-C-H/D

q
Rosaniline
hydrochloride)
color)
(mgentaconeene
coregenta
⑭
Aldehydes restores the
megenta of schiff's reagent
colour

do not
* Ketones
which
respond
it
to this tat
except autore

gives very .
slowly
168
Carboxylic
Rxx
of RLi
acid with
of
excess

*
organometallic
compound .

& -OH + EL -Eri + RM

3 *
covalent character

Raid
↑

of lit
&
Ol

gendi ol
I

-do
R-C of
- i
-

mutable
- *
1 H20 -

R- R ~ - ~
-
--

Reactivity order
of organometallic compounds
:-
--

R-Li > RgluLiL R2Tn7 Rald

R-MgX
> .

RK-R-X
O
ReCd Rald
R-K-1 - .
 and derivatives !
Carboxylic
Conversion into

169 I
B
I
R-C-OH + PU5 -

4
-

I soe

:
170
Eterification
R-4-OR + H-OR' RK-OR
O O

R K-OH + CH2N2 >

-
RuK-OcHs + N2T

diazomethane

IT Conversion into amides :

O O
II NH3/A e
R-C-OH > R-C-NH2
excess

↓ Pas
R
O - NH3
-
U
172 Rxu actic acid with Hason :
of
conc ·
-

O
II conce
nort
CHz-C-OH-
-

H2SO4
O

CHz-K-OH H
conce
- CH2 = C= 0 +

H2SO4
(Glacial) Ketene
(no water
O
present)
H-K -H -
Conce
204 + H2O
H2SO4
Burns

Jame
with Blue .
173 &8
Heating effect of
<, B ,

-hydroxy carboxylic
ands :-

X O
it
:b
1 A
H O
C-Of >

C5-A
-

intermolecular
c
-

in
dehydration of i
C-hydroxy
acid.
(lactide)

Bx
O B <
II A
CH-C-OH CHz-CH CH-COOH

C3-4
- - =

He O
in
-

in <
,
B umaturated
.-
and

B
Y C2 D
Cz- Cinc
-

⑤ n
no
k ( = o
n =0

V-lactones

Un-d create= aTo

h
no -
=0
G-lactone .
 :

Test
of carboxylic
acids -

174 Rxn With NaHCOz :

U Carboxylic acids on exn with NaHCOs

give 2024 ·

phenols which are

stronger
and than p-nit (shenol
also CO2 with Nattlos-
give
on ran

Nanos-R-K-Ex +Oct
O

R- -OH + H,0

175 Test :
of famic
Acid
Famic and reduces both

Telling
Tollen's solution
Reagent
due to the
precede
of
# &
O

H-K-OH +
Hgdz Hgzll2f CO24 +HU
>
- & .

white
carbosit Calomel .

sublimate
 telt :
codyl
176
Acetate salts on

oxide which have

heating with solid As 203
-

order cacodyl
gives is in nature
extremely nausiating
poisonous
a .

4 CHzCOH + Al2O3 -
C /
3
As -
o -
As -

Uz- U

acodyloxide
+ 2N92CO3 + 2 CO2 T

177 Rxn Acid Chlorides :

of
O

R-4 -
01 + PUzIPU5/SOK - B- K -
y

on O
"
> R- C v
O

NH3
>
R-K-MH2
O

O R-o R-OR
RK -U
7
-

O O O

Ro R-c
x II
0-c-R
-

R-K-R
>
-
Ringx O
II
KCN R-C-CN
7
NHIOH
>
R-G-NH-
 19 i
Cz-*-04
D
178 + U = C= -
U5-C -
O-C -
CH3
Ketene
-
anhydride .

O G
NH3
R--NH + R-OH

nei-o-pr-fas
--

O O

R-K-U R--Ol
I
+

tO R-CCH
>
179

20-k
R-OR' + RION.

180 Amides
-

O O

R-" -OH A R-K-NH2

O O

R--ORI T R-K-MH2 + R'

8
P2O5 R-CEN
R-NH2 9 V205
>

↓ MNOz O

NANOLIHC

R-I-OH .

-
-
181
Alkylation of NHz M A
A
eiR-x
R X
R-R)H
. -

t
>
-
R-NH2 >
- R
SN2
1
alkyl lamine
halides
Lexcen
Rit
if EN
-
R

RQxO
L

Amonium Salt
Qualinary
182 RxU R-X with azide (N5) ion :
of
NaN3
R
-
X 7 R-N3
SNL
↓ LAH O MalEtOH

R-MH2
-
--
183
From
the reduction Nitro
compounds
:-
of
I R-NO2
H2/Ni > R-NH2 +
=
2 H2O

184 Reduction in audic medium :

R-NOS
- -
>
-
-
Sn/HU
ROH

on An Clie
a
185 Reduction in neutral medium :

[Ob
- NO2
>
-
Fe/steam
[
nitrosobenzene .

In INHaU)
°
H20
50 C

-of Phenyl hydroxyl amie

My /
NOz PH3 ,
NOz 43 /
NHL

[bO C
NHUHS
[↳
O H &O3
NH2 Nos hoz
=
186 Hottmann Mustard oil ran :
S

RNGK
+$
BNH2
dithio caltamic aid
- -

carbon
disulphide .

↓ ngC

E
this sells
liked R
E -
M = C= S

mustard oil
alkyl isothiocyanate
187 MNO2 with
with Primacy amines

NANOL/HG
Ri
&
R-NH2 + HNO
-
↓ HO
R-OH

188 RgNH + HNO - RgN-N = O

N-nitrosamine
-

4STAR
R -
N-NO
I
+ MNO -
[b
189 RyN +IN x (noRxn) b
NR2
<ob + MNO2 -
Sit 3
in = 0
-

=
 Oxidation amines :
of
Primary
."
amines 3
-

190 With Kinnon

R-CH2-NH2
KMnOn
> R-CH = NH >
-
H20
R H +
NH
10]
Aldimine

R-CH-NH2
4(0] A Re
R
- R- INH + NHz-
Ketimin

(H2S05)/H202 peroxy
carboxylic
191 With Calo's acid and :-

R-M2NH , H R-CH ,-NH-OH

L(0)
R-CH = N-OH

Aldoximes
.

He RgCH-NH-OH
Col
Rg C M-OH
RECH-NH2 - =

Ketoximes
.
 Oxidation !
of secondary
amines

nknow aBN -is a

192

Tetraalkyl hydrazine
-

Caro's and (H2SOs

193
With operoxy and : -

RINH
HeRYM -O

dialkyl hydroxyl
N-N' amine .

Oxidation amines :
194
of Tertiary ④
He RyN-O
RyN
L .
amine oxide

H2SOs) H2O2 peroxy

acids ·

195
Diazocoupling'
- NH -
NaNOL/HU
on
on OH
,

ob
[ ↓0
N= N-Ph
L
-E)-M =
-
[
= M
-Of no

ye .
196 test:
insberg's O
II u=
↑
S
TR
-

i p-NH-R I
T
u =

C
[O]
0 = S -

[0] CH3
(
R-NH2

Lob
-

Ch in
insoluble
4 .
soluble

↓ RgNH
R3N

O
I & 201X .

o = S-N-R -

I
-
-
R
KOH
[b -
*

Ens
(insoluble)
 diethyl
197 Reaction with :
oxalate
O

-NH-R + 2 EtON
O = C-Oft
+ 2R-NH < -
ok-oEt of
-NHR

(solid)

I <
Rol
RaNH

X
R
O
I
c
N-R
-

of
k-oft (Liguid)
Oxamic enter

HNO3
198 (CH2)gN4 >
-
Rox
explosive
NHnNOz
usotropine
CH2 NOz

-Cnz
& /
ON -

[RdX)
Loz
.
 DMethods
of preparation of Amino Acids :

U-C"
L-halo
!
aids
199 O
HVZ &
-on
CHz-C2-COOH e
-

p + BVz
- E

↓ - .
--

C-Bromination excess N
HVZ ↓
Hell-Volhard-Zelenskii *
-o
.

P + By

R-C-Cot
U i
-

R-CH2-COOH -

④It
He -

Alanine (Ala) .

S
X P
20 Strecker's
Synthesis &En CN

R-H + NH RCHINH
↳
-
R-K-x
imine H

fe
COOH

O
CN
4)
=

R-C-NH2 O -

O
NH2
H
-

x-amino aid