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Culture Documents
• KMn04 / H -1/0 :
strong ( typical) 0A
or 54
003/420/4-1 = 42004 :
strong 0A
Jones 0A
1- = 35°C
: :
good but
HNO
}@
one
) :
very strong 0A
•
KMn0y
-
-
-
OH
/A
-
OH
2
,
UNO
3 }
4^103
'
COOY
'
'
-
50%
.
.
Oy
.
50% 4
-5004
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Mild Oxidising Agents:
1° of
Pcc :
Pysidinium chloro chromate • oxidised to
aldehyde
Ñ↳ " " °ᵗ "" "" ""
↳ ᵈ"
IDC ;
Pyridinusm dichromate
• do not oxidise
¥=cf bond
also oxidise 2° ol to ketones
cnzclz
•
Acetic
cross / in Aczo =
anhydride
•
003 / Py (Collin's reagent )
•
Cu
/ 573 :
Dehydrogenation = oxidation
◦
Mn0z : mild 0A : used for allylic & benzylic alcohols
(ONLY)
NO z
Mn 02
3¢
2
-1
3
1
04 • ✗
,p
- Unsatd carbonyl compds .
alcohol
•
fail to oxidise
\g=c{ bond
allyl
@ cry / aldehyde)
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
?⃝
9. Dehydrogenation Cu at 300°C = Cu at 573K
2° CU
RC4zOy RCHO -1 Hz
573K
2°
CU
Rzch OH Rzco + Hz
573K
3°
Rzc -04 No reaction
CU
an alkene ( dehydration )
573K
Cu
*
Meg C- 04 MezC=C4z + H2O
573K
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
10. Lucas Test Lucas HCl
/ Znclz L R
Reagent : = -
.
@ hydrous,
T = 25°C
< ' R
Roll Rct ( Alkyl chlorides are insoluble in L - R
giving
white lis
a
turbidity the solution)
* Lucas Test
helps in
distinguishing a saturated alcohol (CnH2n -120)
whether it is 1° 2° or 3°
,
.
t R
A white
Rzc turbidity instantly 3001
-
Rzc OH CI :
-
-
3° of is
confirmed .
"R
Rzcnon Rachel : A while
turbidity is observed after
◦
of 2° ol
confirmed
2.
3 -5 min a is .
L -
R
RCHZOH Rcuzcl is NOT formed .
No white turbidity is
1001 observed a I.
◦
Roy
is confirmed
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
H
RÉH
¥
1- Znclz @ nhy ) .
-
lewis Acid) zinclz
{ RDS
bond weakens
8-1
HCl
8-
if 12=30/20
2-1
-
1° Rt
stability)
• R = 1° ; is NOT formed ; No RCI is formed
No white
turbidity !
Note : If Temp is increased with 101204 ; then a while
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
As Temp (60-702) (a ) becomes
-
• . is raised ; CI weak Nu
high in
energy and is motivated to do an SNZ attack .
SNZ
H
12£ # Inch
-
C1
+
-
{
Cl -
R + Enloe)ck]
1° ↳
bond weakens alkyl halide
good
Note
↓ leaving group
benzylic allylic alcohols obviously
,
: &
a white
turbidity
react faster with Lucas reagent
(due stable carbocation but do not Lucas
to
) ; we use
•
DO NOT USE LUCAS TEST FOR ALLYLIC & BENZYLIC ALCOHOLS ,
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
11. Victor Meyer Test To make distinction 2° 2° & 3°
among ,
P/ Iz As N°2
Roy RI RNOz
HNOZ
p
↳ N°2
•
RCHz0H RCUZ -
I Renz -
NO
,
Iz
HNOZ
blood NaOH R
R -
C -
Noz -
C -
11102
11 Red alkali 11
Nitro / ice Acid
µ -5m£ colour N -
OH •
t,
soluble salt
↓ acidic -
H
•
This confirms that alcohol
is 1004 .
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
P AS " " 4^102
• RZCHOH
Iz
Rz -
ch -
NO
,
k -
CR,
-
Moz
1
NO
insoluble NaOH Pseudo mitral -
in NaOH
( to acidic -
4)
↳
blue colouration
↓ alcohol
confirms 2°
P AS " "
•
Rzc -04 Rzc -
NO
,
KNOZ No reaction
Iz
confirms
◦
• 3. ol
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
12. Other Tests
• CAN = Cervia ammonium nitrate :(V44)[ce(Nos) ]
2
,
CAN
A obtained
Cseltyo red colouration is
" Ma
Hz ↑
° "
Cnttzntzo _
compound is Alcohol
Metal
Ethers effervescence
R5N+a ( an alkoxide
Note : Always remember that ROH
or
NO Rxn .
NaOH
?
Note : Phon
Ma
PhÑÑa akkoy or alc Noon
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
•
Iodoform Test :
04
only
1° alcohol : [ 211-504 =
cnztcnz
&
Methylated 2° alcohols =
cuz
-
CH
'
-
R ( Phi cydoalkyl)
on
NaOH/ Iz
CH
Izt, + sod . salt of an acid .
yellow ppt
a 04
- +
Ch3CUz0U Ch -1-3 + H ◦ Na
§
• -
-
±,
R
-ENa+
' '
Ch
cuz ch Is +
- -
a-
§
'
on
:
gives + ve
iodoform test
Identify ×
, y
:
forms a
rearranged product ,
4 on
°"
8-1
Ei Hyo
8- Et -
-
1,0 %
.
- - - -
\
CI C C H
(chloral hydrate )
- -
-
Ninhxdrin / \
Eli +9¥
tot
.
_
. _
intramolecular
chelation)
it
bonding (
-
ViccinalI I -
Cf
/
I 1 :
Glycol
OH OH
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Glycols:- • 91-204
Ethylene Glycol •
Cltscltcltz
{ HZOH bit bit
Ph -
CH Chiou
-
Me - d- d- Me : Pinnacol
bit bit ( 2,3 Dimethyl butan -2,3
-
diol
-
• Other Pinnacols : Ph
2
-
C -
g- Me , ; ph -
F- e- ph
bit OH ① It '
OH
D- bit GHz Q¥ OH
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
OH
Cyclo-Alkandiols:-
'
OH
i
it-AND
HO OH
_rans-l,2-CycWhe✗andi#
--
x Trans
¥+10
cis
11-0 OH
1+0 It
cyclopentamdioks,
Glycerol
CHZOH
A tri -
hydric { non
alcohol
{ 420th
• also known as
Glycerine
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Preparation of Glycols:-
1. Hydroxylation of Alkenes
2. Hydrolysis of Viccinal Dihalides
3. Hydrolysis of Viccinal Halo-hydrins
4. Hydrolysis of Oxiranes
5. Reduction of Glyoxal(s) ✗ dicarbonyl compounds
-
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
1. Hydroxylation of Alkenes
alk cold dit
.
KMn04
° °
↳
's
Baeyer
'
1 1
reagent 40 OH
vicinal diols
addn)
( syn
(Glycols)
2 .
Halt 503
CUZ =
cuz
KMn04@iY7.Ph
cnzcu =
cuz
cold 1204
Cn cuz
.
-
=
Me
,
C =
cuz
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) 7 C̲ i ̲r ̲c̲l ̲e̲
Kinnock ')
* cuzcn __ Cn -
cnz ?
Cold .
KOH
cis / Trans
syn
cis Meso
Trans Racemic Mix
KMn04@iyHHCold.K
OH
cis -
product
Synaddn 40 OH
H no Trans = ?
Pg . 22
how to ?
no H
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
2. Hydrolysis of Viccinal Dihalides
✗
OH
✗2
c -
c aq .
C=c
C C
CC / 4 KOH
-
×
✗ ≠F 04
I vicinal di halide
( glycol)
Ctntiaddn)
✗z
aq .
CCl4 KOH
✗z aq .
✓ Cag
KOH
✗z aq .
Ph -
Ch =
cuz KOH
cc , ,
✗z aq .
KOH
ₕydᵣₒcₐᵣbₒₙₛ
CC / 4
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
3. Hydrolysis of Viccinal Halo-hydrins
OH HO 04
✗2 / THF aq .
[ = a c- a
C -
C
H2O Koy
✗ I
×
( glycols)
7- F
✗z
/ THE aq .
Hzo KOH
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
4. Hydrolysis of Oxiranes
PHCOOOH
C=c C -
C
Peroxy 1 .
H+
benzoic acid 2 .
Uzo
Hao :
◦
SNZ type of attack c -
c
-% +
c
( anti -
type
+
2 ring opening H
H protonated
Oxiranes
+
0h2
OH
C -
C
C- c.
-
h -1
OH
OH
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Phcoztl
•
(cyclohexane oxide
I. Ht
2 .
Uzo
" ◦ "2
H backside attack
yo
.
antitype ring
H
+ opening
H -
n -1
"
(
Trans -
product
H
PHCOZH Ht
•
Product
420
c
ₕydᵣₒcₐᵣbₒₙₛ
Me
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
5. Reduction of Glyoxal(s) Cho :
Glyoxal
Kuo : Ethan dial
NaBH4
CHO CHZOH
{ yo { 4204
•
H2O
@ lyoxal)
a NABH "
Me Cho Me Cy cuz
g
- -
- -
104
"
0 H2O OH
Methyl glyoxal
( ✗ keto aldehyde)
-
NaBH4
Ph cuo Ph CH -
cuz
§
-
° -
-
' '
Hzo on on
Phenyl glyoxat
" AB " "
Ph Pb ( Denzil) Ph
gu cnn.ph
-9g §
- -
- -
•
H2O on 10h
Di -
phenyl glyoxal
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
6. Reductive Hydrolysis of Carbonyl Compounds
(Bimolecular Reduction)
1.
My
2.
H2O (ex)
Mg
2 C -55
↓
2é +
Mg2+
dimerisation nngzt C C
C
E C
-
-
-
2 -
o
O O
-
O
-
Cradical anion)
,
,
_
- -
-
-
H2O Mg
-
C C
( glycol ) OH OH
-
Mg( OH)z
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
◦ For Pinnacle) :
cuz Chs
.
Mg d- d- cuz (Rinnacol)
cuz
§ cnzz.gg ,
2<43
- -
-
tou Ion
Mg Ph in
the e- Me
g-
•
-
•
2 Me -9T
-
Ph
2 .
Hzo 04 but
0
2cm
cnzcllz
•
Mg Et Ine Ie Et
§
-
3-
- - -
•
2.
H2O 04 104
.
Mg
• 2
2.
H2O 404
"" Me Me
9
Ph come + Me come
d (Mixed)
•
d
a
ph - - -
me
2.
H2O ↓
toy by cross product
.
Mg
Note : ZHCUO Cuz -
cuz
2.
H2O 6h by
2cnzcno.MG ₕydᵣₒcₐᵣbₒₙₛ
cuz -44 cuz -24
Alcohol(s),
H2O Phenol(s), Ether(s) & Glycol(s)
-
2.
104 On C̲ i ̲r ̲c̲l ̲e̲
Chemical Properties (Reactions)
1. Reaction with Phosphorus Trichloride & Thionyl chloride .
2. Reaction with Organic & Inorganic Acids
3. Polymerisation
4. Condensation
5. Acetal Formation
6. Oxidation
(A) Simple Oxidation (B) Oxidative Cleavage
7. Pinnacol-Pinnacolone Rearrangement
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
1. Reaction with Phosphorus Trichloride & Thionyl chloride
Pas vicinal
94204 GHz CI
-
1 Dichloride
CUZOH or DCI }
cuz -
Cl
( Plas)
p
Iz
-
-
-
-
0¥
.
cuz -
-
-
-
-
SOCK cuz -0
= ,
1 - -
-
-
I 5--0
< 42° "F Cuz
-0
cyceicsulphilé
, .
.
. .
.
.
5=0
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
2. Reaction with Organic & Inorganic Acids
Chio -
% -043
↳ +
CHZOY { Uz-ON
Luzon
+ Cuzco 04
25°-40°C festers
Ht cuz -0
-
É cuz
-
+ 2043004
Lugo cus
-9g
-
11 Ht
c- 04
+
I 25740°C
on
g-
☐
430-1
(Ethylene oxalate)
can
•
€4204 H+
HNO cuz-0 Noz
{ 420K
-
+
}
I
cuz-0 NO,
-
•
Ethylene 2 CUZOY
di -
nitrate { 4204
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
3. Polymerisation H+
2 ( Glycol) + Terepthalic acid
Polyester
- -
gnz-cnso.iii-iio.IE '
E-ioi-i-iiiio-cns.in " ,
- - -
by
'
- -
-
-
y
-
-
-
◦
-
-
H -1
É É cuzcilz
oh
o o
cuz cuz-0
-
- - -
- -
- -
• A polyester
polyethylene Terephthalate ↓
Terylene
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
4. Condensation
dit
2
CUZOH .
?
{ 4204 42504
dit
Note : ROH R -
O -
R
42504
(12-+30)
cuz -04 n -0 -
CUz-oycnz-pt-e.com
-
(dioxane)
Luzon 42504
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
5. Acetal Formation Acetals : Gem dietbers
-
acidic
hydrolysis
HCl
(9) 04
+ ROY
¥0
= 0
hemi acetal
-
dry
ether
R
gem hydroxy
- •
OR ROY
• Acetal
C
HCl
•
gem OR (g)
di ethers
-
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
HCl OR
(g) Acetals
=0 + ROY C
@ ✗ cess] dry OR
against 1 .
Reducing agents
Note : How to recover carbonyl compds ? 2 . Alkaline medium
OR 430-1 04
c , 1- 2 ROY
OR
04
diols
gem
-
H2O
-
C.
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
HCl Ome
≠
/
C -0 1- 2 Meon acetal
dry none
CHZOH 0 Cuz
+
I C
CUZOH 0 cuz
(di→xa1an)
glycol
acetal
¢420M )z cyclic
Hcno ( More stable)
H+( dry)
Me
¢4204)z
Chino "
Htcdry)
Me
@nz0U)z
Meco me
H+(dry] Me
n
to
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
6. Oxidation (A) Simple Oxidation (B) Oxidative Cleavage
(A) Simple Oxidation
oxalic acid
CUZOH (O) COOH
Luzon { 00h
PCC Cno glyoxal
Chzclz { HO
0
2° 10
É- Coon
4- keto acid
)
cuz -44 cuz cry
-
-
on 6h
:
Pyruoic acid
PCC
cuz
-
§ -
Cho (methyl glyoxal)
CHZCIZ
HzCN4
cuz
-É -
Coon
( Pyritic acid)
acetone
35°C
JonesReagent
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Ph -
ch -
ch 2
ton £4 PCC
CHZCIZ
HIM 4
acetone
35°C
n n
H H PCC
CHZCIZ
HIM 4
acetone
35°C
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
(B) Oxidative Cleavage HI0q Periodic Acid
Reagent :
:
% ¢
'
OH OH
,
Y=o + o=c
\
(carbonyl compds)
Éuz0H
- -
Me -
Ch :-C Hz HI°4
Me Cho + HCHO
"
10h "
OH
ph _±- me
Ph -0=0 + 0=c -
me
1
Ph
it
Me
th the
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
:
1--04
•
/
04
149
OH
2 .
H2O
4. 3
5 I - 2
H µ
i H Ho
'
o 1
;
H H 4
HO
HIO4 HI 04
611 ' ?
◦ 8 •
because 2- 0h
group are
Ether(s) different
in
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), plane
& Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Action of HIO4 on 9-Hydroxy carbonyl compounds:
✗
! HI 04
c :
cut E- on
-
! _
-9=0
(acid)
(carbonyl)
'
1-
1=04
cuz c CH
cnz Cuz COOH 1- cuz CHO
- -
-
!
¥ on
'
2-
2
3
3 HI 04 1
COOH
°
4 £ .
4
CHO
51 g
OH
of acids
" "
ₕydᵣₒcₐᵣbₒₙₛ
◦ O
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
2
3
I
I. HI04
COOY
' 0
glutaric
.
i
2
'
.
=
Me - C :-c -
Et Mecom
11
◦
ill 0
0
+ ETCOOH
04 0
Note :
' 2 ( glutamic
anhydride)
. "
. '
3
'
-
1 04
xHI04
-
yo
_
-
- - -
-
5 HCOOH
- -
! fur
-
Huon
5
4
04
(x=5) >
40
<
lookout
'
n
t,
,
Hcno
hcno
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
04
3-
? /
'
1 hI04
•
-
-
4
-
-
_
.
,
1
5
04
40
2
Éoz
CHO 5
1- MCOOH +
3
4 CHO
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
OH
: £
2 ,
' coz
[
•
: HI04
Eno
- - - -- - -
¥6
'
I
3
4
•
'
g. /
4
'
"
C. 004
OH
• H COO Y
u
n @ 004
Than
'7
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s)
;
Bpg
.
C̲ i ̲r ̲c̲l ̲e̲