Alcohols, Phenols and Ethers

7
ALCOHOLS c) OMDM (oxymercuration demercuration)
(i) Hg(OAC)2/H2O
M.O.P 1. From Alkenes R–CH=CH2 R–CH–CH3
(ii) NaBH4
H+–OH MAR OH
a) Catalytic hydration OH
Mech R–CH–CH3
+
dil H2SO4/H (H2O)≡H3O + R–CH=CH2

+ – H+ + Hg–OAC
R–CH=CH2 R–CH–CH3
xx OAC H
e H2O
a ng OH
r
ar S б+ H2O
Re PO R–CH–CH3 Cyclic R–CH–CH R–CH–CH2
i f 2
OH mercurinium Hg +
Hg
ion
b) HBO (Hydroboration oxidation) OAC
OAC
(i) B2H6/THF
R–CH=CH2
(ii) H2O2/–OH
R–CH2–CH2–OH H3O+ HBO OMDM
#Carbocation # 4MCTS # cyclic
H+–OH Anti MAR mercurinium ion
THF→Tetrahydro furan #syn addition #anti addition
O +– +–
Role is to break dimer of B2H6 #H OH Anti #H OH MAR
B2H6 mar
BH3+ +
Q
O Electrophile O H
BH3 + +
б– б+ H3O
A
+ – H–BH2 +
R–CH=CH2 R–CH–CH2
OMDM HBO
–
H+BH2 H – –
BH2 H+OH H+OH
(major)
4 MCTS Syn addition MAR Anti. mar
OH
+ B C
–
б+ б– R–CH=CH2
R–CH2–CH2–BH–H
+– OH
R–CH2–CH2–BH–CH2–CH2–R
OH
+
б б–
R—CH=CH2 2. Reduction Rxn
A. Redn of carbonyl comp
HO OH
HO OH H H R
R–CH2–CH2–B–CH2–CH2–R C=O C–OH
OH
H
HO
CH2–CH2–R
R a) H2 + Pd/Pt/Ni
H2O2 (–H3BO3)
b) LiAlH4
3 R–CH2–CH2–OH c) NaBH4
 B. From acid Q.
H – 2+
O R OMgBr
R–C–OH R–CH2–OH CH3–C–H
HH H H+–OH
O– +
R 1) H2 + Pd/Pt/Ni
2+
(i) PhMgBr Ph OH2
CH3–C–H A
2) LiAlH4 + (ii)H2O Ph–CH–CH3
+
HCl/ZnCl2
C. From ester
H Alc.KOH
O R C B
α
Ph–CH–CH3
R–C–OR' R–CH2OH+R'OH Ph–CH=CH2 β
HH H Cl
Styrene
R 1) H2 + Pt/Pd/Ni
2) LiAlH4 CHEMICAL PROPERTIES
OH O 1. Acidic Nature
Q. OH H OH
H
CH2–C–OCH3 CH2–C–OCH3 –
ROH→RO +H
+
HH
Na
SBH a) ROH RO–Na+ + H2
LAH SA WA
NaOH
b) ROH RO–Na+ + H2O
OH Acidic strength CH3OH>H2O>ROH
CH2–CH2OH + CH3OH
AI
d) ROH –H2↑
(RO)3Al

Q.
H 1
O # Acidic strength α – I α
H OHH +I
H H
H
HO Q. OH OH
SBH (–I) F
H2+Pd 1 2 I
O A.S. 1 2
OH
HO HO OH

3. From G.R. Q. OH OH OH
– 2+
+ – RMgx – 2+
C=O C–O Mg X Cl NO2 CH3
1 (–I) 2 3 (+I)
R (–I)
+ –
H OH A.S
r1>r2>r3 2 1 3
C–OH
R
r1 2. Esterification #
H (i) RMgx
C=O R–CH2–OH
H (ii) H2O 1° Alcohol
– +
R'O H
RCOOH
RCOOR'
r2 R– O
R' (i) RMgx O C–+
C=O R'–CH–OH – O O
H (ii) H2O R–C–Cl –
–

R 2° Alcohol + C–
r3 O R
R' (i) RMgx O
C=O R'–C–OH 3° Alcohol R–C–OR'+HCl
R'' (ii) H2O R–C–OR'
R'' R + RCOOH

168
Organic Chemistry
3. Lucas Test R
Conc. HCl 1° Alcohol Aldehyde
R–OH anhy ZnCl R–Cl
2
R
ClCrO3–
H+ 2° Alcohol Ketone
Cl – N+
+
R–OH2→R+ R Mild Oxidising agent H

1° ROH, 2°ROH, 3°ROH R → 1 PCC (Pyridinium chlorochromate)

No turbidity turbidity in turbidity in 2 PDC (Pyridinium dichromate)
min sec 3 Collin’s reagent
CrO3.2Py
Q. Compare time for turbidity 4 CrO3+ acetone 2–
+N Cr2O7
OH 5 Cu/300°C
H 2
OH
βCH CH2
OH 3
α Cu/300°C
1 2 3 CH3–C–OH CH3–C
time CH3 CH3
1 2 3 (reactivity 1°<2°<3°)

**3° ROH and Resonance stabilised R

 1° ROH & 2° ROH 1° Alcohol Acid
give Immediate turbidity H OH
[O]
OH R–C–OH R–C–OH
+ H H
turbidity in sec Reso
R → Strong O.A O
+
CH–CH3 CH–CH3 a) KMnO4/H +
R–C–H
Reso
OH turbidity in sec or
KMnO4/Δ [O]
4. Rxn with PX3, PX5, SOX2, Red P/X2 (X = Br, I) O
b) K2Cr2O7/H+
R R–C–OH
R–OH R–X
5. Dehydration of Alcohol Allylic & Benzylic
Alcohol
H+ + Conc H2SO4 MnO2
R–OH R–OH2 alkene CH2=CH–CH2–OH CH2=CH–CHO
443K mild O.A.
or +
H /Δ
Q.
Δ
R+ Alkene OH
6. Oxidation of Alcohols
H OH O OH
[O]
R–C–OH R–C–OH R–C–H MnO2

H H PCC
O OH
H OH
[O] O O
R–C–OH R–C–OH
H H
R' R'
R' O
[O] R–C–R'
R–C–OH X
R''

169
Alcohols, Phenols and Ethers
 PSS CH 2 CH 2
+ +
Δ OH
+ + OH OH
+ OH2 2 1
H
H+/Δ NBS Aq. KOH
A B MnO2 LAH
Br C D K
OMDM Br
H+–OH Na/Δ
CrO3 J
OH

E 1 CH3MgBr OH H + x L gas H2 at STP

O Na+ 1
–
CHO 2 H O F PDC
2 HC–C G mol H2
H 2
3
PCl5 O C–CH i.e. 11.2 L
3
Cl
I
H C–CH3

PHENOLS CHEMICAL PROPERTIES

M.O.P 1. Acidic Nature
– +
1. from chloro benzene PhOH PhO + H
Carbolic
Dow's process acid
– +
Cl O Na OH
(a) Rxn with metal
NaOH HCl – +
623 K PhOH + Na PhO Na + 1 H2
300 atm 2
(b) Rxn with NaOH
2. from Benzene – +
PhOH + NaOH PhONa + H2O
SO3H OH
SA WA
oleum 1) NaOH (fuse)
+ (c) Rxn with NaNH2
2) H
– +
PhOH + NaNH2 PhO Na + NH3
3. from aniline SA WA
+ – (d) Rxn with NaHCO3
NH2 N2Cl OH
NaNO2/HCl H2O – +
OH ONa
0–5°C warm + –
+ NaHCO3 + H2CO3
4. from cumene
(mostly SA
WA
CH3
Me backwards)
C–H CH3–C–O–O–H
Me # Nitrophenol + NaHCO3 salt + H2O + CO2
O2
SA WA
O=O – +
OH ONa
H+
OH + NaHCO3 + H2O + CO2
O
SA WA
+ CH3–C–CH3 NO2 NO2

170
Organic Chemistry
Acidic strength 3. E.A.S
Nitration:
1
A.S α –I & –M α (a) In dil HNO3
+I & + M
OH OH OH
+
Q. 1 2 3 NO2 NO2
+
OH OH OH
NO2 A NO2
, ,
NO2 Intra B
–M & –I molecular Inter
–I NO2
H-Bonding molecular
P O M
–M & –I H-Bonding
3>1> 2
B.P B > A
volatility B < A
Q. OH
O2N NO2 OH (b) In conc HNO3
OH OH OH
NO2
1 , , conc HNO3 NO2
NO2 NO2
2 +
2 > 3 > 1 3 NO2
–M&–I –I NO2
2,4,6-trinitro phenol
or
Q. 1 OH 2 OH 3 OH Picric acid
(poor yield)

O2N NO2 , , Bromination:

–I CH3 (+ M& +I)
(a) In Br2/CS2
1 > 2 > 3
OH OH OH
Phenol > ROH
Br2/CS2 Br
+
2. Esterification
+
Br
minor Br
+ – O major
– + RCOOH (b) In Br2/H2O
=

PhOH R–C–OPh
H+ OH OH
O O
– Br2/H2O Br Br
=

=
+

+ – R–C–O–C–R +
RCOCl O Br
Br
O
=

R–C–OPh 2,4,6-tribromo phenol

=

R–C–OPh
4. Kolbe's Rxn #
– +
Aspirin formation OH ONa
NaOH
COOH
– + O O
OH + – H+ i) CO2(ii) H+
=

+ CH3–C–O–C–CH3
Salicylic COOH O OH
acid
=

O–C–CH3 COOH
O-acetyl salicylic acid
(Aspirin) salicylic acid

171
Alcohols, Phenols and Ethers
Mech O– O– OH
OH +
CH CHO H CHO
– +
OH +
O Na OH
+ –
NaOH 6. Rxn with Zn

Zn
Ph–O–H Ph–H
O=C=O zn
1
O O–
2 H 7. Oxidation
3
C O

OH O
OH OH Na2Cr2O7
COO –
H2SO4
H+ COOH
O
P-Benzoquinone
5. Reimer-Tiemann Rxn
Practice
OH OH OH Q.
CHCl3 CHO
+
KOH OH +M OH OH
salicylaldehyde
(major) CHO dil HNO3 O2N
+

Cl Cl +H
– NO2
OH –
Cl C H Cl C xx α-elimination
Cl Cl Q.

– +
Electrophile OH
CCl2 + – O
A.R CH3COCl HNO3
A B O C CH3
O H2SO4
xx major
– + (+M) O C CH3 (NO2)
1
OH OK O
2 H NO2
CCl2 –
+ KOH 3 CCl2

O–
OH
CHCl2 –
CCl2
–
2OH(SN2)

172
Organic Chemistry
 OH
OH OH
PSS Zn Br
G Br
1) NaOH Br2/CS2
oleum B C + D
A
2) H+ major minor
SO3H NaO +
NO3 PhONa
–
H
n cH E + H2O
co
i) NaOH salt
CO 3 F
NaH ii) CO2
H2O + CO2 + I OH

H
iii) H+

KO
O2N NO2 O

3/
O–Na+ H (CH3CO)2O
Cl O–C–CH3
CH
O2N – + Aspirin
NO2 OH OH+ H
NO2 COOH
CHO COOH
NO2 J + K O
+ –
OH Intra- CH3–C–O–COCH3
H Bonding

CHO

ETHERS 2. Williamson-ether synthesis

M.O.P (WES)
1. Dehydration of Alcohols R'O Na+
R–X
Conc. H2SO4
R–OH Alkene R'O /SN2 R–X
443 K 1°>2°
Conc H2SO4 R–O–R'
R–OH ROR
CH3
413 K
+
–

xx H+ R–O–H CH3–Cl + CH3–C–O Na

CH3
+

R–O–H
–

CH3 –
CH3–C–O–CH3
–

H
–

xx
SN2 ROH CH3
Q. β CH2– H
R–O–R ← R–O–R
+

–
–

H CH3–C–Cl + CH3–O Na+

α
–

conc H2SO4 CH3

C2H5OH CH3–CH2–O–CH2–CH3
E2
+
H CH2
+

CH3–CH2–OH2 CH3–C isobutene

–

xx
CH3
CH3–CH2OH
Q. A + B Ph–O–CH3
Salt R–X
– +

CH3–CH2–O–CH2–CH3 –
– a+ CH3–X Ph O CH3–X
H
conc H2SO4 PhON –
R–O–H+H–O–R R–O–R CH3 O Ph–X
413K x

173
Alcohols, Phenols and Ethers
Q. O–CH3 CH3
HX

–
A + B Q. CH –O–C–CH
3 3
XX
Salt R–X

–
– + CH3
O Na –
O H+
+ CH3–X CH3
CH3–X +

–
CH3–O–C–CH3
X

–
–
– H CH3
CH3O
CH3

–
Q. ? Ph–O–CH=CH2 CH3OH + +C–CH3
– CH3

–
No Rxn – X CH3 X
Ph O

–
X –CH=CH2 X–C–CH3
xx
–

–
CH2=CH–O X Ph–X CH3
xx

HX
O Q. Ph–CH2–O–CH3
A + B
+
Q. Salt R–X H
– + – +
ONa X O Ph–CH2–O–CH3
X
X

–
H 2 – H
PhC X
+
CHEMICAL PROPERTIES Ph–CH2+CH3OH

1. Rxn with HX HX
Q. Ph–O–CH
3
HX H
+
R–O–R' Reactivity
XX + –
+ of HX Ph–O— CH3 X PhOH+CH3–X
H
HI > HBr > HCl
–

H
+ X
–
R–O–R' # Rxn with Excess HX
–

H
δ+ δ– δ+ Excess
*∞ R–O–R' R–X
# if R or R' 3°, 1° & 2° Resonance stabilised H+X–
X HH X +
e.g., benzyl allyl SN1 R'–X
∞ CH3
#* if R or R' 1° & 2° SN2 Excess
–

CH3 — O — C —CH3
HX
X HH X
–

HX CH3
Q. CH3–O–CH2–CH3 CH3
XX
+
– –

H CH3–X + X–C–CH3
+
CH3–O–CH2–CH3 CH3
–

H
– xx Excess
X SN2 Q. Ph–O–CH3 PhOH + CH3X
H X HX
CH3–X + CH3–CH2–OH

174
Organic Chemistry
2. EAS Na/Δ –
Q. PhOH A PhONa+
CH3Cl
x
x OR +M (O,P directing) – Br PhOH CH3–Br
OR OR Excess
Ph O — CH3 B D + E
E+ E H HBr
+ Alkyl
+
Br2/CH3COOH Halide
Br
Minor E
OCH3 C major
Major

A. Bromination
Br
OCH3 OCH3 OCH3
Br3 Br Practice
+
CH3COOH
+ Minor OCH3
Br
(Br)
Major Q. A + B
Salt RX
B. Friedel crafts Rxn
NO2
– +
(a) Alkylation O Na

+ CH3–X
OCH3 OCH3 OCH3 NO2 x
CH3Cl CH3 x
X
+ X
Anhy AlCl3 – +
+ Minor + CH3O Na
CH3
CH3
Major NO2

(b) Acylation

O O–C2H5
OCH3 OCH3 O OCH3 HBr
–
–

CH3–C–Cl C CH3 Q. 2 PhOH + C2H5Br

Anhy AlCl3 + SN
Br
+ Minor
x
x

CH3–C=O O=C–CH3 Ph–O–C2H5

Major H

C. Nitration

Q. OC2H5 OC2H5 OC2H5

OCH3 OCH3 conc HNO3 NO2
OCH3
conc HNO3 NO2 +
conc H2SO4
conc H2SO4 + + minor
NO2 NO2
+ Minor major
NO2 NO2
Major

175
Alcohols, Phenols and Ethers
 I I
PSS O
conc H2SO4 Excess
OH 413K A B
HI
2CH3–CH2–I
conc H2SO4 Na/Δ – +
443 K C2H5ONa

F C + 1
H
+ 2 2
CH3–CH2–OH2
PhCH2Cl CH2OC2H5
+ + Cl
CH3–CH2
Anhy AlCl3 E
HSO4– major
D
CH2=CH2 Ph–CH2–O–C2H5 H +
(+M) +

Apni kisi bhi mehnat ko bekar mat maan

Manjil tumhe jaror milegi bs haar
mt maan.

176
Organic Chemistry