Carboxylic acid should not cause a heart udj

oxylic acid should not cause a hear

Carboxylic acid should not cause a heart udj
oxylic acid should not cause a hear

Haloalkane haloarene
oxylic acid should not cause a hear
Carboxylic acid should not cause a heart udj
oxylic acid should not cause a hear
Carboxylic acid should not cause a heart udj

For this chapter this Tist-color

imp pointcolor
color side concepts.
MOP

Alkyl halides from Alcohol

1. ROHwith cans. HX

crs- x -

R-OH S R -x + Has

Hoo x
+

mechanism > H curbocation (after rearranys.)

④
xxpt Ro-H
R 0
=
-
H S > R t H20
ot
it loving
x X
⑦ very good Grp.
nu X
W

R-

Rearrangementin carbocations

Why-to
gain stability

a) hydride shift? It shift to make ac with mass d-H

⑰
Hg) C CHa 7
(3(stub)
-

Itz
-
- -

Cis Cit3

12 -H & GH -

a) methyl shift:me
⑭
Priority:(H) me]
1
-

⑰
It, - CHa > Hz CHaCH3
-
-
-

cits 2-H 0 =
Citz 2 18
- =

harimithi
 ⑦
2) Ring Expension:don'texpand Cla
Ring stability
I

diz B(y6)7)57433
-

X state, asing X

How to DOS 1,2 Gond thodo, 2 Ko & So Jodo, 1 ko do

&

⑰
⑰ ⑰
A
Cla -

↳ 7 I

⑰
⑰
CH2

↳ 2
7

Extra 3C-h

Special case :H
⑰ CH3
⑦ ⑦!
2 Back Banding CH2
y
-
I' cla t 3
1, Ec
lit

a
Ring contraction:when (*onring (
④
CH2
⑰ I

t...
⑰

.......
⑰ 3
a
3 CH2
O.I

Ring contraction/Expansion I've me shifting

0H Cl
R-OH with ItX
I +
3
eg
I,
I - I
eg. 7
. L
I
H
↓ t
H20

ox",
,0*
-

0H
Br

09 HB
>

:It
2.
-
120
⑰ Ba
 Nort

R-Br -

her can also use NaBe+Hesop -> HBR+ NaHSOn

For in Alcohol catalystInCly is used

ROR of ROH:3° 2% (stability)

-ROR of HX:H-I)HBe)HU
(Size/Band Broaking)

imp. Notapplicable for Arge halides due to partial double Band Glu c=0
-

⑰
t =0.H
-H.....
↓
-
4 22.
-)

Far RC use it on
day Id a canc. He

R-BR constant
boiling HBe (48%)
with
-

R-I NaI + HyPop ->

HI+NalaPOy

& Why Hasoyis notused for HI

NaI HaSon It
->
+ NaHSOp
Strany excusing agent

HI H2SO4+ <
I2 +H20 + SO2

Luca's test -

Difference Glu i, 2"3" ROH

Ragint-conc. HC 1zucle
imp. When carbocation is
stubalised by
BackBonding, Aro, Riso thin ROH will
R-ON ? RU (tubidity) immediate
give the bidity of R.Cl

1 ROH ·
iRU Long time
O

2 ROH > a "RU Sow min

3"ROH -
3RU immediate

eg. Alcohol Chick C.C.

Turbidity
Stability
Ph-CHa-OH SiC
t

Ph-CH2 (R(s0)
OH
I

(aso) Si
 2. Run of ROHwith PX, (U,Br)
PX3
3 ROH >3R-X + HsPos (Phosphonous Acid)
x C, Br, I
=

R-OH

:**T**
p

Paints

rearrangement
->
no

->
PBMs and PIs are madein situ by the rich
of RidP + Xa

Ridp + Ca ->
PUs

of C
OH
PCI,

OH
PBR3, Be

Rod P
>

BR2 I
di Br

3. Rn" with PCI5

PC5
R-OH >R.C +

HC POUs
+

R 0
= -

H no
passangement
C-Pdz-c

4. Run with Soca (Thiong charido)

Soda
R-Ol > R-U+ SO2HU

R-0-H * Bust Bay. Son and Id and gas

C-So. C they separts out
easily
and economically

Alkyl halides from hydrocarbon

1. Alkans fero radical

a.
Halogenation - R H
-

s R-X H-X
+
R-X
 Ra da
g. CHY CAC no <Halle > CHU nu
C4

g. Hy)-CAs e CH3CH2C (monohalogenated product)

BR2
3

↳or
br
eg. hV

-
Br

Bra
by >

hu

- Br
↓Be I I
by Bra -Be
7 t t t t
Gr W
Br
Be
ncet
de Dark
-
no su
(51,0
Calnr

only
our mana chloro derivatio

Find
major product
a. Chlorination rp:: Rs 1:3.8:5
=

Up:R.OR at IC Up:no of lit

1.1 npUp =

x100 Us : 2 Us:" "2"H

'
3° :3
UpUp +hsRs + NtRe Ut At
-
'I

Easy way

UpUp
%01: x100 ->
since every thing castantonly ruminates it
UpUp +hsRs + NtRe
%02 = nsUs x100 See UpUp, DsUs, not which value grat
UpUp +hsRs + NtRe thatis
major.
%03: n t Wt
x100
UpUp +hsRs + NtRe
e
C I
Ca S

S (major)
⑨ LV
3 t
⑨ Op

Up 3x2 6 npUp:6X 1
= =

ns:2 nsUs:2x3.8 iT (magon)

 S P
calau
⑨ > I
·
⑧
C
P
be
Up:6 UpUp 6
=

ng:4 ng5g 15.24 (minor) (major

=

O
dc/ar, C t -
C

(major) (minor)
ApUp P
=

n 5.2
2
=

C
I
Sun
Cl
imp. of a

da/hr, I t t
I
C

P: P C
Gang -> Up Up:1 x

UpAp:1x
us:38x?:26 Uphp':/x 3:3

P
c
c
9 ·
t
C2/hu
-

I a
so
3 I I -

j
man o
be
20 up: I x 3
minor
major
3.8 x4
③
ns:
ng: 2
x
3.8

2) Pt
=

5 x I

G. Bromination

Same formula Mp: rg:RE:1:82:1600

Always 3% 2%, for Bromination.

Mechanism:Fr Radian substitution Ru CA, eT CH-C+H-C

i chain initiation s cette zi

man voild is chain propogation (a) CHy H , CHy+HC
a) "CAs+UIC >CH-c i
+

this
iii chain teemination >da

3
3 as

a) small amount
-
(Itz(Hs
C) its +'c ->
CHzC
 Imp. point:1. ROR Fz Ca) Brc) Ic - slow and for an

anothemic
W

Highly more reactive dies bractive

and uncontrolled in less selective more selective

2. For iodination
~securit
R-H + Is -R -

1 HI
+

Bragent:OA-HNog on HIOs
II HI
W W

IatNo2 +H20 Iz tHa0

R-HEz/hr, RI
HNO3
3. FRSR

2.From Al Kene

(don'tuse
1.
of
Addition AX. M.N Rule

HX
R CH (H2
·-R-4H- (s
-
=

x Ht
+

HX H X
W

R -

CH-CH3 (Rearrange if pass.)

HI
eg.
7
I I
I
H
W

=
④

Imp. ↓ Elictrophic addition an" (H) (EAR)

2. C*will
decide major product

3. don'tuse M.N Rule to make major.

 2. Addition of HBR/Por
Phys.R
oxide (0-0)
Hatz or

->
follow rule
Anti mark (-to more H) (Benzay provide

+
R -

CH (H2
=
S
R-CHz-CHeB
1 202

mechanism: O

--8
Ph
--o-ph G
aPh

Oh -"-8
1Br Br + Ph-cooH
·
Stot-1 R-CH Ha >
R-iH-CHee
mase stable for
radion
Stop -
2 R-c-(He >R-CHaCHar
it
Ph--o:
key paints
HF/PR ->
Both 1&2 Step Ondo (noma")

HU/Pe-> any and stop endo (noen")

HB/Per -> Both anothermic (praction happen)

AI/Pm ->
any abstip endo (no evil

Cl
HCl
by S

H202
Br
-

⑰
by >

-d
7

<
HB
He BR

HBr
7

H202

-
c, io-o-o-g e
 3. Addition of Xa/cdp
X Test for unsaturated
-x2 (14
I I hydro carbon

ic
+

c
= S -
C-C-
↳ I L
X Br =

X
Bra/4-Brown

sing under
mich. X
Brown, colorless
I o

, -x
X
7
-I
-
- C-

x
E

From Allylic substitution

1.
Allylic substitution. (Remous Allylic-H and + Br(u)

-> G-c of alkene called

is
Allylic carbon.

-> 2-2 of Bengine is called Benzylis carbon.

↑
②I3
->

<
-
c)
=
- cAlglic
Alliglic Ha-[Ha)g-[Hs
He

Chlorination Bromination

Ragents :all gives free radical

Reagents all gives free radical

1. da1500 1. Bra/hr

2. da 1hr 2. BR2/500c

3 AQuoc (tertiary butys ony 3. NBS (N. Gomo succinamide)

Br
chlorid
·

·
O 0
of
=

4. Da (Low conc.) 1 Br, (Law can)

itis
 Clz-(H (H2
NBS, BR-CH2-CH CH =

ey. =

Be
moch
Ca-CH CH2 =
>
CHa CH
=
-

(H2

Br
eg NBS -
7

imp point: I more stable fell radical makes

major (no Roso.)
2. Rearrangementif possible (Reso.), then mass stale Altrine
major.
is

by 2.
CHz CH2 -CH (H2 =
t6OC, A B
+

CHz-I-ca
·
c
CH-CH=CH-CHa
CHy-CH-CH
>
CH2
=
+

i
⑧

CHz-CH-CH-CH2
........

>
CHy-CH CH
=
-

CH2

91. i
tBuOC, ⑧

= >
2.
-
O
Ce
1.
2CH
⑧

2 Allylic 2
H 03
·

5-
It
22 H -

It (Stalli)
"Y i

application X
CH3 62 -H
19
⑧
⑧

of rule or
C
(major)
(main four radical selected) rule I.

Calsoo
CHz-CH CH-CH-2Hs =

·y CHz CH (Itz
>
CH CHa
-
- = -

&
Cl

radical i
W

cHz-CH CH
= -

CHaCHs CHz -CH CH = -

CH -

(H3 (Hz -(H -CH CH

= = -
CH
3
y Liss Stabl

Sam after riso.

Br
·y ⑧
·

NBS
7
ir
E Br
3 -
-

14-H 32H
2.
Brngylic substitution:

-> same as Allylic

-> Resonce hog;not sig.
->
Directfree radical
CH3 CH2-C
I
py. ABMOC
3

ce

CA
of
I WrangeHar I
CHa

NBS, AGOC
7
c

-8

Ring
eg 02H
CH3 CH3 CHach
I I I

2 F.R. tBuoc
NBS 3
S
·
Br Br
Ring
- Br
42H
-

(mar)

Br Br
eg.

Bra/ho C21500
> S

Cl

Halogen Exchange no
ronggarmint

1. Finkelstein Praction: (for R-IS imp.- When Nace or NaB

it forms pptwith
acctone dry acetone
R -x NaI
+ 3 R-I +Nax
(UarBr) DMSO ->
Reaction favour product
↓
8 formation
Il
C1z-S CH3 -
2. Swarts Reaction:(R-F) Reagent- HgaFz
10 F2

inorganic (AgF) 36 F3
R -
X S
R -
+
F Agx
fluoride
x C, Br, I
=

ey HBR NaI
I >
DMSO I
Ha02 Br

H92F2
S
F

↑Mp. I HI
vicinal di iodides
3

Ex less
1

Ht I
relius.
HI

~I In
I
-
I2
>

I
I
Ol
Encess
~ I2
>
ey Ol S I S
IfI won't stop
0H I

OH
Br
I Lukasfistin min's
9
OH HB Rid
3 ↳
BR2

we
sochz
F V I
a
I
I NaI
saw S

70 =
 [It- Cl
C13 OH
.

by I I
Turbidity
I

221500° PC5 in siz Moso. Stab.

> L

HBr

I NaI
Br CoF2 I

L
7

S0 =

JEE
HB BR COF2 I
7 3

202
I I I

NO2 NOz NOz

etyl halide
ESR
Electrophilis Ru
substitution

->
also writin as ·
E.A.S (earomatic substitution)
ArgE
·

S.
·

EAR

I
It
7

1. Halogination:Reagent -

XatF0/XatFoxs (n 2,
=

Br) (n 1
=
with (Noz)
0
+ ⑦

xox1F3
+

S x Foxy

I
X
>
H8
+

Frx48
FoXs
P

+HX
X
 Directive
influnce of Groups

-> th gives to
I
ring at0.4 Position
⑦O H
ey
-
H
11
itup
-

⑦ ⑦
far directing
-

NH2
:... -

CH3
⑦

-> -

M
gives take I from ring and generates & at0,P

:moth directingfar
-
+
t
EN
-

c 0
-
=

t it

By Itz 13 CitB
I Cl
Cat
Fras, t
-

minor

a major
·

Melting paint a Lattis enthlpy a symmetry. C.L. EN

Imp. points
->
we can easily
separts o, pisame due to diff. M.P.

->
R2" with
II are reversible: Sequine (o] agintto and HI

Ph-H 3
Ph-I HI
+

Fat H90+Noz
HNog
->
Fluor comp, have high reactivity:notused
 mich. It complex
>
all is- are + Et > E

delocalized they all

gotattracted to E
E
E t Ht
↳Got Stop-1 -> R.D.S (Attackof Et
main
·. Et
+

⑰
> Stop-2-> Fast (Rimoval of it)
S
I 2

aromatic non Aromatic

Diazonium Salt

1. Benzene diazonium chloride is prepared by reaction of aniline with nitrous acid at 273 to 278
kelvin
2. Nitrous acid is produced in the reaction mixture by the reaction of sodium nitrite with hydrochloric
acid.
3. The conversion of primary aromatic amine into diazonium salt is known as diazotzation
4. due to its Instability diazonium salt is not generally stored and used immediately after its
preparation.
 Chemical properties

NNSR
nudiophilic Rn"
substitution

R -

x
vei, R-Nu +
x

Sn' and Sn
(R-X + hel R8 + x8 n8R-Nu +x*

Sn'
Sn yO
+

(nut nut
1. unimolicular nucliaphlic substitution
x*
X
au

R. D.S
⑦ R Rarsocation. R

R-X R*x
t
Rx+ hut
R-Nu x*
Slaw NU: s
+

XO
⑦ s
nu
nu
~ X
RI
R R
R-Nu

Point
->
a Stip run
->
carbocation formation
-> 1 Stop is R.D.S
> Rate K [substrate]
=

->
R.ORX (*Stability
(Before rearrangemont) (1(*)
R.O.R
->

E dreusing,
R I) R-Br > R-US R-F
-

of R.OR towards In'

1: Ph-CHa-Ce iiPha-CH-C ii
PhyC-Cl
Stop- I make c

i Ph-cit"(i Pha-CH*L i Phyc

ring Stale
brings Cring 3
 I I I

2.
I I I
i
i iii

at
Stability of

R-X >R +x Back. Bonding) Aromacity Riso

>Hyper Bonding 7 Induction
⑰ ⑰ ⑰
r

I
i iii
tM of

no Ars No Aro Anti Asanatic OCHz7 -CHz

-

1 Reso NO RISO 2 Reso

ROR Sn'

Sn'= is ii) i

a ->

Energy profile diagram Sa

High CH3
CH3
T.S 1 1
= + Because +- Bu are
beltiygrp.
therefore due to replaision of
you
EI

ER -

Ep

When Sn
Alcoholysis
->
Solvalysis to, Rot its (weakhil
Hydrolysis

- 3t, Riso stalised

Yas?.R*
->
Lewis acid

->
Moist AyaO (AgaO tHa8 S
AyOH Ag +ON
|x-
presitations Ru" (Sast))

2
SU Bimolocular nucliophilic Substitution 1-Stip

intermitte nota Stop

nu aus-
 imp 8. if all of same" and x thin on-cHax carbon

-
Itswy for the win.

St

CAs-CHz-C
si
i ins ,
eg.

cia-ca-a-cl
i
CHy-I,Gest
I
-

St
ii Ph-CH2 -

in its--cHall
St
is

When Su,
->
stage nut 1. ag KOH /KSH

2.
KCN/NaCN

3.
AgCNY

4. K
5.
Agios
6. NaI / 30
=

a Ys:0

who won'tunder
go in"

1. : due to Parial-character
-

2. cit=CHE, . .
...
 3. Breat'srule:sphycleiisnotpossible at Bridge headed position in bridged
Gi cycle comp. C non planner)

other
Chalogon should notbe
Gidge had to
in
⑧ on
plan
by
⑧ ⑧ do Sn?)
I
⑧ ⑱

Bridge had ⑧

-
CH3 Sn Bulky
4- I

Hi -
-

CHa
-

X Sn' +
no x-H

City

same

j
all-
She

Suz

Suz
..

Sne
Sn2

Os
Ambient nucleophile-are those notwho have more than I

nucleophilic center

-One
less EN give
Easily R-nu

KCN KiCEN: ionic R -

CEN

↑
↓

AgCN Ay -
N.
C= covelt R -

NEC

0 0.

KNO2 kt 0 -

N0 = icnic R -

0 N0
- =

↑ ↓

Ag-NOz Ay -0 -i 0 =
covelent R-NOL
d CEN

eg. si
I

+KIN
Br Br
by Ph-OH + CH3CHal CH3CHO'Nat
SNE

Acid/Baso -> Ph-ONa + CHyCHaH

Sp2 -
CHzCH20 (Ha(H3