IITIIT-J EE ChE ChEm mist r y by N. N.J . sir
or ga nic chem chemist r y
Alcohol and Phenol
Al co h ol
acid catalysed hydration
CH3 – CH = CH2 + H+
: O R : H
CH3 + CH – CH2 – H
1. Lewis Base 2. Nucleophiles 3. Polar protic solvents
R I S . J . N CH3—CH CH— —CH3+H O–H
Difference between alcohol & phenol
O–H
(a)
high boiling point & water solubility due to Hydrogen bonding.
CH2 — CH CH2 — OH OH
CH3—C —CH—C H—CH H3 2°– alcohol (Secondary alcohol)
1 alcohol (primar (primaryy alcohol alcohol))
(c)
OH
OH
Cl2 / h
(1)
aq.KOH
CH3 — Cl
Me
Br2 / h
Me—C—H Me
CH3
Me—C—Br
(2)
Me
H
2. NaBH4
1. Hg(OAC)2 H
OH
CH3—CH —CH—C —CH H3
1. Hg(OAC)2 R
H
O
H
2. NaBD4
CH3—C— —C—CH CH = CH2 CH3 CH3 OH
CH3
O
2. NaBH 4
CH3
(3)
CH3—C —C—O —OH H
OH H
OR D
1. Hg(OAC)2 H
O
H
2. NaBH4
CH3—C — CH — CH3
from alkenes OH +
(i) CH3 — CH = CH 2
O
1. Hg(OAC)2 H
Features:– (1) Markownikoff addition (2) No. Rearrangement (3) Non – classical carbocation
from alkanes
CH3 — OH Me
(2)
(c)
(n – hexane or paraffin solvent)
General Methods of preparation
H
OH
(b)
CH3 — CH = CH2
CH2 = CH – OH (vinylic alcohol) CH2 = CH – CH2 – OH (allylic alcohol)
H
H
Oxymercu ratio n – Demercur Demercur ation (O M D M)
CH3 3°– alcohol (tertiary alcohol)
O
H/ H2O
H
CH—C—OH 3
CH4
H
Ans .
CH3
(1)
O
H+ H
(a)
O
(b)
OH
3
O+ H H
H+ H
Classification
3
CH2–O –OH H
Phenol alcohol partial double bond character between C & O
H
CH —C —CH— H—CH CH
+
O
H
H H
O
CH3
H CH —C —CH— H—CH CH3 3
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1
CH3 OH Ans .
(3)
(5)
CH3—C — CH — CH3
Conversion of lower alcohol into higher alcohol
HI CH3 – I CH3 –MgBr CH3 – CH3 CH3 –OH
CH3
SO2Cl2 /h CH – CH KOH(aq.)CH –CH –OH 3 2 2 3
Hydroboration – oxidation
| Cl CH3OH CH3 —CH2 —OH
1. BH3 THF CH3 — CH = CH 2 – O–O H OH 2. H CH3 — CH2 — CH2 — OH
(6)
Features 1. anti markownikoff addition 2. No. Rearrangement Ex:–
2.
R I S . J . N
5. 6. Ans .
(1)
H
OH
H
D
D
H
H R–CH –CH –OH 2 2
(7)
from primary amines H
(2)
NaNO
2 HCl
R — N:
R — N2 Cl — (diazotisation)
NaNO HCl
2 R — N:
H
Mechanism:– 1.
D
OH
:
R—NH2
+
+
+ R—N—N=O
NO
D
+ H R—N = N—O H
H
CH2—Cl
O
H
(8)
aq.KOH
H
O
+ R—N—N=O—H :
H
(5) CH3—CH—CH2 D
H
H
H (3)
from alkyl halides aq.KOH R — OH R — X SN2
:
C=O
H2 /Hi
Na/EtOH
R’
H
:
+ R—N = N D +
H R—N = N—O—H + + R—N
N
from Carbonyl compounds
R
CH2—Cl
H
R — C — OH R’
Sn/HCl
(4)
from grignard reagent 1. O2 2 R mg × 2 R — OH 2.H /H2O Mechanism:–
: – R +
R — OH
H H
(6) CH3—CH—CH2
(3)
OH
2.H /HO–H
O
OH
(4) CH3—CH—CH2
R
1. RMgX – R–CH 2 –CH2 –O MgX
2.
1.B2H6 / THF CH3 — CH = CH 2 2.CH3 –COOD 1.B2D6 / THF CH3 — CH = CH 2 2.CH3 –COOD 1.B2H6 / THF CH3 — CH = CH 2 2.CH3 –COOH
4.
2.H /H2O
O
1.BD3 /THF 2.HOOH/OH
3.
1. RMgX
1.
1. B2H6 THF – O–O H OH 2. H 1. B2H6 THF – O–O H OH 2. H
1.
from epoxy compounds
Zn/ACOH Fe /H O
2
. . R
— O = O R—O—O
H /H2O R — O + RO — R— OH + R— OH
LiAlH
4
(9)
MPV – Reduction:– Meerwain pondorf werley reduction)
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2
1.
R C=O R’ (10)
CH
3
CH
3
CH—O Al R 3 +
2. H3O
CH — OH
R
CH3 (6) + Al(OH)3 + 3 C = O CH3 (7)
Oppenaur Oxidation CH — OH
O
— H+ CH3MgBr CH4 + R—O MgBr : O H : H
CH2 = C = O
(CH )3 COAl 3. R 3
R
R
O —
+ O—R H
C=O
R
R
O (11)
from Carboxylic acid
LiAlH4
(8)
Reacti on d ue to C — O bond Cleavage
(b)
4 R— CH2OH R — C — OR
R
(c)
C
O
O
C
LiAlH4 R— CH2 —OH R
LiAlH4 R — C — NH2 R— CH2 —NH2
(13)
from hydrolysis of ester.
(a)
C R O
(b)
C Me
OR’ +
H
HI R — OH
O
H
(2)
2 R — OH R — Cl.(Lucas Test) 1 2
(3)
SOCl2 R — Cl + HCl + SO R — OH 2 SN1
R — C — OH + R’OH
(4)
3R — OH
O
(5)
R
HCl/ZnCl SN or S N
18
2 4 CH3 — C — OH+ MeOH OMe
18
R—H
Re d P
H2SO4 (d il) dil H SO
C
(1)
O
OR’
OR’
R—O—H
O
(d)
O
R'OH H R
LiAlH
R— CH2 —OH
R — C — Cl O O
C
LiAlH4
(a)
(acetal)
O
(9)
R
OR’
R'—OH/H OH R — CH
O
from Carboxylic acid derivatives
O
C
R I S . J . N
R — COOH R— CH2OH (12)
R
CH3 — C — OR
CH2 = C — O
O
PCl SN
3 2
3 R — Cl + H3PO3
PCl5 R — Cl + HCl + H SN1 & SN2
O
General Reaction of alcohol s
(a)
P
Reactions sue to O — H bond Cleavage
Cl
R—O—H
(6)
(1)
R
O
Na
R—O — Na+ + ½ H2 H
(E1CB)
O
ThO2
+ Blue litmus Red litmus (Alcohols are weak acids)
(3)
R
R
R
O
O
R
O
OH
1
Conc. H2SO4(E ) 170°C
H
H
+
NaOH
Oxidation of alcohol
H
+
O
NaHCO3 1.
(5)
Conc.H2SO4 CH — CH = CH CH3 —CH2 — CH 2 3 170C | OH
(acidic nature) (2)
(4)
Cl
Cl
H
+ CH2N2 R
O
CH3
Red hot
R1 — C — R 2 R1 — CH — R2 CuTube OH
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3
O
CH2–OH
Red hot R—C R — CH — OH CuTube H
H
K MnO4 /H OH
(1° – alcohol to aldehydes)
O
Q.3
Red hot R — C — CH3 R — CH — CH3 CuTube
OH
CH3
Ans .
1.
OH
(3)
Red hot Cu
Ph—CH—OH 2
Red hot Cu
Red hot Cu
Q.3
OH
/CrO3/HCl
1: 2 : 3 1 aldehyde 2 ketone no.effect) 3
OH
CH3
3.
P.C.C.
CH
2.
: N
(3° – alcohol – dehydration to alkenes)
Q.2
—C—H
R I S . J . N Red hot R — C = CH 2 CuTube
R — CH — CH 3
Q.1
O
O
(2° – alcohol to ketones)
CH3
KMnO
4 H
Q.2
OH
P.C.C.
1.
O
Ans .
1.
C—H
OH P.C.C.
2.
O
3.
Oxidation of alcohol + (2) Oxidi sin g agent KMnO 4 / H
1.
R — CH2 — OH
or
4.
K MnO4 /H R—C
O
R1 — C — R2 R1 — CH — R2 OH
(2° – alcohol ketone)
R1 — CH — CH3
O
R1— C = CH 2 K MnO / H 4
OH (3° – alcohol alkenes)
OH Q.1
K MnO4 /H
OH
O
H
P.C.C.
1.
OH P.C.C.
2.
5.
6.
O C
H
John ’s Reagent (H2CrO4 in anhydrous acetone)
1° aldehydes 3° alkenes
CH3
3.
: CrO3 : CH 2Cl 2
H
K MnO4 / H
CH3
C
Colli n’s Reagent
+
K 2Cr 2O7/H
(1° – alcohol acid) 2.
O
: N
—C—CH3
2.
O
MnO2
2° ketones
Weak oxidizing agent
MnO
2 CH2 = CH — CH 2 — OH
O CH2 = CH — C
H
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4
Ans .
MnO2
— CH2 — OH
Q.1
O — C — H
Q.1
Ph H
Me — C —O — C — Ph
Me
Et — C — OH +
H
—C—OH
H—O
OH
O O
—C—OMe
Q.7
OH
Q.8
—COOH Q.8
C–O–Me
Q.9 H
Et
O
O
+ Ph
OPh
Me O
H
+ Me — OH
O C
H
(Methyl Salicylate)
OH
R — O — C — R’ OH O
H
+
H—O—C—R’ O C
C—O
Q.6
—C—OH H—O O O R — OH +
Q.5
OH
O
Q.7
Me
C—O
H
Me — C — OH + CH2 — CH3
OH
Me
Me — C —O — CH2 — CH3 O
3
CH — OH
Me
O
Q.6
H CH OH
H — C — OH + CH3 — OH
Q.5
Ph — C —OH Ph
R I S . J . N O
Q.4
O
Q.4
+
H — C — OCH 3 O Et — C — O — CH
2
O
Q.3
Q.3
HO
Ph
Q.2
Me — C —OH O
Q.2
O
Ph
O
H
H
Q.10
CH3
H
Me–C–O
Me
(Phenyl Salicylate )
Me Q.9
H
MeOH
COOH + H
Et O Q.10
CH3 H
Me — C — OH + HO
H
Et
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Cl : O : — H
Phenol:-
OH
NaOH
2.
OH NO2
OH
+ – H O H N2 Cl
3. Phenol
R I S . J . N
1-Napthol -Napthol
2- Napthol - Napthol
(Benzene diazonium chloride)
OH
OH
OH
OH
COOH
4.
OH
NaOH/CaO
(Soda lime decarboxylation)
Catechol
Resorchinol
OH OH Quinol (hydroquinone)
5.
Hydroperoxide Method:-
H PO
CH3
3 4 -----+ CH2 = CH — CH 3
CH3
CH3
O2/air
OH
O-cresol
m-cresol
OH
p-cresol
--------
OH
H SO /(conc.)
2 4 --------------
6.
Napthalene
H /H2 O ----------
+ -------
1. NaOH(molten) ----------------------
Anthracene
2. H
Reaction of Phenol:-
(1)
Electrophilic aromatic Substitution:-
OH
Phenanthrene
Methods of pr eparation:1. Dow’s Prcess:-
Cl
NaOH 360C/320atm
HNO
3 H SO
(a)
2
----------- +
-----------
4
OH
Br
2 CS
(b)
----------- + -------------
2
OH
(Follow’s Benzyne Mechanism)
(c)
Br
2 --------------------HO 2
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COOH
OH
—O—H
NaNO2 -------------------HCl
(d)
+
OH
(f)
R I S . J . N CHCl
1.
-------- + ---------
2.
Kolb’e Reaction
OH
O : — H
+ ------------
Reimer Tiemern Reaction:-
3 KOH
(g)
O ----- + ------
:
------
OH
CH3 — C O
Phenol as Nucleophile:-
Conc.H2SO4
(e)
O CH3 — C
NaOH
---------------
O : O: C6H5 — C — Cl Ph H + O C6H5 — C — O — Ph + HCl O : CH3 — C O: + O Ph H CH3 — C O O O Ph— O — C — CH 3 + CH3 — C — OH
1. CO (high P) 2. H
2 --------------
(h)
Hydrogenation:-
Fries Rearrangement:-
OH
O O—C—CH3
H /Ni
2
---------------
AlCl
3 ------ + ------------
Reduction:-
OH
(i)
HO
+
-----
N=N +
Zn/dust --------------
Coupling Reaction:-
(j)
Oxidation:-
Leaderer marnase reaction:-
OH
H
O C
H / H+
OH — CH2
OH
CrO
CH2
---------------
(Quinone)
OH CH2
—
3
---------------
CH 2—
CH2
B alkaline polymer
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R I S . J . N ---------------------------------------------------------------------------------------------------IIT-J EE ChEmist r y by N.J . sir A-833, Indr a VIha r , near IL ba ck door , Cont a Ct : 9414969800, 9549908816 web : symmet r yii t j ee.com
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