CoD Alcohol Ether 8x Phenol

- -

Monoshydric CH3 CHOM Trthydtrtc ch CH CHZ

→ -
-
-

Dihydric - OH 2- CHI oh tore toy

In '

on

R
t
I ( primary ) → R -
c- OH 2
'

(secondary) R -
d -
OH
µ 4
tertiary) '
'

3 ( → R Furan :

p , g -

on
£ FHF : tetrahydrofuran
preparation ↳
Éi
Nii
Erm alkyl halides R Nii
:
R -
✗ + - - -
✗

Where Nu = OH
-

( SN , / snz in haloalkanes / haloarenes)

/ Agon / H2O
¥-9,0M
Nii used : aq Kon moist
.

aq
.

Agro =

hydration E-Athene :
I metal → breaks c-✗ bond

> c- =D ¥0 > c-CT

' '
( not possible)
( both e- rich)
| /
"
n n

, n -11ns 0+1 Mason I ✓

me
E- of = y%Ée '
yÉ%- '
( forms 2° alcohol)
n n

H-ydmbora-t.com Oxidation
t
:
Thus we use

t
or Blts THF - :

:
ntsc -
o

Insert hydrogen ,
borane ( BHS) / diborane ( Balto) in an alkene .

↳ causes
reduction ↳ lewis acid - not stable
 ÉH CHÉ
-

Chs -
= Terminal alkene - s on outside as if

on us
.
-

inside then destabilised by +I .

I. is -
n
T
CHS -
ÉH = CHÉ CH } -
CHZ CHL -

go ,
.

→ -

1-1 a ÷ ! I

T.sn BINH THF→BHz

9
nydtoboration a + CH } -
cH=cHz
it
mechanism
CTHF still exists not written)
-
(CH] -

GHz cHz)zBH
-
+ CH } -
CH =CHz → GHz -
Chi -
CH 2) 3B

on 39th on

Oxidation :
CMS -

CHz-cni-B-cm-c.hr -

ons
+
( *
Hzoz / OH
-
→
4th 3GHz
CHz-cnz-OHC.tk
+ → -

1- H3B03
( forms primary alcohol) I
cnz

syn addition Product shows

→ →

- Reduction of alkene antimarkonikov addition

→
Peroxide / Kharasch effect of H2O ( H -10h)
BHS , THF

Summey :
Ats Ch __ cm
-
-

Hzoz /
-
GHz -
CH -
cnz
µ
OH

µ
oh
HB°_ non

"" Ctwo stereo

-
In +
Y on products)
É
CH] -
CH cuz 42021 OD
-

cnz -
CH -
GHz

h '
on
ÉaIo_n Demercuration
:
( of alkenes)

t t ( OMDM) Hg
Add Oz , Mg remove Hg OAT \OAc
HGCOAC)z →

É
Hgl0A42 / H2O

µ
0
, 11
NABHN
CH} - É -
o -

Ag
-
O - -
cry
(no -
rearrangement major y

Yi lens ? )zAg-0
i.
ng
-
tix ]
+

oA Yt
-

Ac Entire 3 member ring shares

OAC +ve
charge → called Ncc
t
Enzo
yÉ%
:

,
Non-classical carbocation
7¥
-

TH
+
ng HGOAC S

GAC
Bond breaks where c④ stable
HGOAC
+ steric hindrance less

^
Demercuration :
on

Hr
-

NaBHu OH,

↳ ,

HGOAC

→ Markovnikov addition of water without rearrangement .

-
Anti -
Phenomenon
→ Ncc intermediate formed .
 j-0-hj.IT - ons -0min ion

fit }
creon
lwro "%gYj ?
£10m KM ( intramolecular attack

Reduction of carbonyl compounds : ( next chapter

-

details )
-

" AMN" """ "

R H 2h R cuz OH
§
-
-
+ ) - -

① alcohol )
in
" " " " "" """ "

R R 2h R CH R ( 2 alcohol )
§
-
-
+ s - -

Reduction of Coon , acid anhydride ether , ,

ester, by
LIAIHN all give Alcohol . Done in detail in later chapters .

Reactions :

(prev. chapter
AMH" " ""

HX 's
dry ux : R on- +
☐ , 300 C
'
R ✗
-
+ Hz

-
Darzen Reaction ( SM) (sock → R X)
-
)
A
of Alcohols Ht Hsoui
Dehydration
- - -
Mason → + Ccb)

-
✗ ÉH
conc . Hzson
OH '
or conc .
nzpon tnz

kiss
""

+ Huson ¥i¥E
 +
- c- formation is RDS
- Rate of dehydration ✗ stability of Ct
→
Rearrangement possible 372° > lot

E mechanism →
saytzeff product ( major )
'
→

for i ↳ hofmann product ( minor)

⑦ 5th HC 9×4 HC

Yyon
" ""
oh
E-
☒
-

☒ ☒
→
+
|H
"
3×4 2am
u

( Hofmann) Csaytzeff)
Ht
(minor (
major)

I:{ ¥-1M -
on
Red ct
④ . -

I More stable alkene attacks

fconanzson
*
¥n -
-
OH

I
At low temp rearrangement of alcohol

Agi n g
→ .
or

ether formation takes place .

ri
or
Hom
-
Hain n¥ [ +
- H -
H
nzÉ

¥f÷+¥n ¥ Y
-
-

0
n

h
( ether)
 Important :( NCERT data)

conc -

Arson
s
1101C 0503M
NOH conc Hoon

NON
-

,
Cethanol) 1h0 c
-

conc .H2S0n
,
180C 3 alkenes formed
f
on ( CIS) (trans)
É
4- a
+ A- + d-
( major) ( minor
H thats
# +✓
Et
Et
×o→
Ms"
s ( stabilised by
µ,
resonance)
(major
F- OH (methyl shift
- -
A- - A- + Yu
( major) (minor)

partial reduction
a t % (poisoned
¥-_ Pd Bason Quinoline
-

*mnoniexass
,
"

catalyst
y 273k

F-on 1-1
OH
( Alkyne -y
Alkene only)
-1
µ

on neat
→
EFI → (mound

# Kmnoncaotoc
,§¥¥g;
-1
if attack on -3°C -
no
(excess)
double bond → Tax
Combination of isomeric alcohols of CNHIOO
°"
I
~- on =
ltisomers DO0--0
'
on
z 2

c. in
C- on bond length :
phenol C C methanol
clocks

final to Pinane reaf

: → find most stable C+
t -
migrate group ace . to
"
"" " "

vicinal diol s ketone migratory order .

- anti migration

t.IR#1lonouF →
¥¥ →

# #
→ →

Cpinacolone = ketone)
1)+0
H+
Ph ph
migrates faster

phµ
eg
:
Ph
t
hydride shift occurs

( left a stabilised by Ph)

Ethers CR ) sodium Alkoxide treated with

-

: ONat

substrate .

-
WÉn Ether synthesis ,
 ( R - É É -
+ Noon → Ro Nat
-

+ Uno )

→ g.
+
g
-

'
Nat R 't,X R O R Wax
-
+
RO + - -
-

tether
- SNZ mechanism / Eh

100% SNZ CH} ✗ 3° Éh major SNZ minor

[
-
V.V
/
← -
.

R -
O -
R pyx c=C
SN major
'
/ \ 2
. '
minor
← I → E major snz
E- 2 minor

me
Obo Nat -7 → ( major)
-

+ me - ✗
me

me
Me ( 100%3
me
-4-0 Nat
-

+ on]X → me
#0 -

Cms (major)
the
me

cleavage of Ethers : cold HI / dit

- . MI / 11m HI / HI

t
R -
O -

R on rxn with HI
gives R I + R OH
- -
or only R I -
.

T
CR's > R size) excess HI / hot HI / HI / A / cone .
HI
'
R -

G
-
R
↳
HI → H+ + I
-

→ R - É -
R' → if R or R
'
Is 3° → SN
'

'
n t
R' I
-

R' ( 3- will easily form I

24/-0In
+

(
'
+ ROH ←
carbocation and R'I) ← -
R
'

stereo -

products
 "p¥
If no 3- R ( I attacks from
±
→

group SNZ -
pi side with less stork hindrance)
In → RION + RICinverted

→
Even if 2°C with resonance stabilisation it will

go with
'
SN
→
If any 3° / Tw . resonance - I goes to bigger R

goes to smaller
↳ else → I R .

If HI Is hot
✓ ok 9¥ t
-

R OH
-
+ I
cold HI cold HI
t

cuz I + HO -4 CHZOH -1 I -
⇐ RI

'
* ✗ ether breaks in
HEIs 1- Ethers :
R -
O -
R
R O R
' * ✗ acidic medium only
f
- -

É
EIR =É '
RTT
'

R -
o -
R R -

R ont
-

4 ton
-

'
→
R OH-
+ R -
on

(retained) ( both)

→ carbocation intermediate formed

SN mechanism
'
-

/ ME cuz -
OH -1 CH] -
GHz -
ÉH ( SM)

443
/
0 É CHZÉH + chs OH ( 5N "
g
- -

CHS
 alcohol
✗ oh ne÷=s
=
Mon
☐ Huson

at ni
← -1
←
y

¥5s EÉ¥ -
E¥ ,
Br

°"

→ '

- ammo. THO
tsrtsr
OH

on, -
cn cuz
¥
cuz - CÑ -
PH
one
→
Chs - CH - dHz
Clmethyl ethylene oxide tsr
gym, any

CH , UH cuz CH,
qn
-
cuz
-

→ -
-

Dr Ipr Br Br

Total No . of stereoisomers of cyclic ether cnH80

↳ DOU -1
101 -0

1-1 To, CGI) (2)

g-

CGI ) y \ : -

Ans -
☒
(2) 3
CGI) ⇐
 partial DBL dgY¥L
4¥04
's I
cone .HBr (excess )
1 heat
,
4¥04 + cus Br

on = Cuz Dre -

GHz
Kr
phenols
-

Methods of
- -
preparation :

→ sodium salt of Benzene sulphone acid + NaOH

503N a

y + NaOH -
§% Nazsos +

( F- ]
-

N" aka super

→
Benzene diazonium chloride LG

HNOZ
,Ñ=na OH
-
or

,NHz
{
NAN 02 / HCl
O -
g
-

c
'
no
warm or aqnaon
, 1¥ + N2 -1 HCl

(aniline) (benzene diazonium salt ( phenol)

Grignard 's RH base →

-

R gets
→ : →
awesome H

-4in:*
to become alkane
EE
.

↳ -1mg
electrophile
( ntucleophtle
Hid > R H - +
Mg (on)✗

" H"
R
R Mgbr s
OmgBr s R OH +
MgBrOH
- -
-

OH
+ Co]
V05

30oz
s 1④-
 DOWIS Process : (
High temp .

req ) .
( not
favourable method

K¥ ↳ -
Fe 104
+ NaOH
300C
s
④ + Nad

Em Eumenes (Isopropyl benzene)

j
:
→

← peroxide linkage

CHS
% Gt3 ch
pore
cuz
(not
stable on
g-
- -
-

a
02

catalyst
s no

H+
, 1¥ +
Gt3 -

§
-
Ms
T
Kunene hydroperoxide) (acetone)

Phenol reactions
-

Acidic Date : Phenol is a weak acid .

HA n'+ A- → if stable acid strong and

4
conjugate base vice versa .

→ More stable the conjugate base, stronger the acid

t

pKa log Ka Pta ✗

higher the Ka
¥
= -

µ
lower the pKa
in g- Nat
?
Nao

④
an
NaCl
-

it
Decently stable cb phenol break) acid

Reactions -01-01 groupie

?⃝
→
Reaction with pots
-

in
-

④
+
Pas →
ÉÉ + Pools + Hcl

CP loves oxygen) on

É ¢64s) Pon
,

→ Reaction with-
7h Dust
-
+44
-
-

ON
Ctrl -

phenyl
+ Zn →
☒ + 2-no phosphate)

used for distinction

→
Reaction wth felt cnevtral → of alcohol and phenol

4¥ +
Fears →
Violet coloured
complex

Reactions of Pee ring :

( ortho, Para directing)
- -

i
+94
i
.in?pc-i&iI-c-F.g6lTe-
¥
pH
: oh

-0¥ p Site
→
c-
,,

(It activates
the benzene
ring) (major) (steric

in hindrance)

4¥ + Brz
"-

or can
s ÉÑIBR +
F¥Br
 ѥ
Br water Br Br
,
or Br + Hzo Cwhite + 3HBr
§ , ppt) .

Nitration : as highly activated → dit HNO] sufficient

-

in
mail.MG 110%7
④ 5-10
-

c
, so +
④
Cho't) doz
Unlike other here to intramolecular
cases para is major due
Hydrogen bonding forming 6 membered
ring .

( very)
"
T concurs no N°2 ( picnic acid) (good acid)
④ cone -
Hzson
,
I
→
NOL
c. B is very good as it
is both resonance stabilised and other Noe groups are good EWG
v. .

Sul phonation : (minor) (major)

qn
in and hydroxy
1¥
o
p
- -

pm son +
Musou
, \ SGH
benzene
acid
sulphone
.

Frid/ Crafts reactions :

co -
cresol) ( p cresol)
-

Cmain)
it in
Ñ + Chzcl
A' "
s
rats +
Fog
In, 0
-
and p -
hydroxy
acetaphenone

iy¥
Akb "
+ cnzcocl s coats +

,
Practice Questions Observed pattern
explained by ?
OH
I
aq
. Brztseq)
9
Bry Br
steric effect of

tosh Br t -

butyl group
+

9N → mono .
subs w/ Iz
.
→ electronic effect
""
¥
of phenolic group
.

d di subs w/ Br,
.
.

' +
"
ch,
}
→ tri subs . w/ d- steric effect of
halogen

"

f° Noons = 9 resonating
structures

↳ Hiooz → Rotates PPL pink with fears

Dou - h n

É" 1 chiral

+
2+2Meta

2 Para =
II
R
OH
9h
E% t.ci#iiiEq+
pm
-

a ' .
•
.
D ome

3 1 2 h

acidity pKa → BECCA CD