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25
ALCOHOLS
(R OH)
RX
||
ethylformate
ROH + KX
2 alcohol
(ii)
Moist AgOH
ROH + AgX
3 alcohol
OH
O
||
LiAlH 4
Aldehydes
1 alcohol
CH3CHO
CH3CH 2OH
acetaldehyde
ethanol
3 alcohol
LiAlH
4 2 alcohol
Ketone
OH
||
R - C - OC 2 H 5 + 2R MgX
R - C - R
(ii) Mg(OH)X
LiAlH 4
(ii)
H - C - OC 2 H 5 + 2R MgX H - C - R
(ii) - Mg(OH)X
H O / H+
2
Formic esters + 2RMgX
2 alcohol
OH
(i)
O
conc H 2SO4
RCH = CH 2 + H 2O
R - CH - CH 3
Anti Markownikoff rule
OH
LiAlH
4 CH - C - CH
CH3 - C - CH3
3
3
acetone
2-propanol
LiAlH4 / H2 - Ni
1 alcohol
(iii) Acid
LiAlH / Na - alcohol
4
(iv) Ester
mixture of alcohols
THF
LiAlH
4 RCH OH + R OH
RCOOR
2
(i)
1 alcohol
HCHO + RMgX
(ii)
2 alcohol
+
H 2O / H
(iii) Ketone + RMgX
3 alcohol
OH
H
1-methoxycyclohexene
Trans-2-methylcyclohexanol
RCH = CH 2 + B2 H 6
diborane
NaOH/H O
2 2
2(RCH 2CH 2 )3 B
Trialkylboron
RCH 2 CH 2 OH + 2H 3 BO 3
It
is
anti-Markownikoff
addition of H2O to alkene.
CH3OH cannot be prepared by Grignard reagent.
2
(iii) Oxymercuration demercuration reaction
RCH
Markownikoff addition
NaBH4 / OH
R - CH - CH3
R - CH - C H 2
|
OH
OH HgOCOCH3
propanol -1
glu cos e
fructose
Zymase
C6 H12O6
2C2 H5OH + 2CO2
ethyl alcohol
Starch
H2 O / Maltase
C12 H 22O11
2C6 H12 O6
Maltose
glu cos e
Zymase
C6 H12O6
2C2 H5OH + 2CO2
glu cos e
ethyl alcohol
Properties of Alcohols
(i) Boiling point of alcohols are higher than those of
hydrocarbons and isomeric ethers of comparable
molecular mass due to intermolecular hydrogen
bonding.
(ii) Reactivity of alcohols
ROH
R'COCl/Pyridine
(RCO)2 O
RCOOR
ester
R'MgX
R H + Mg(OR')X
alkane
R COOH
conc H2SO4
2C2 H5OH
CH3CH 2 - O - CH 2 CH3 + H 2 O
diethyl ether
443 K
H 2SO 4
C 2 H 5 OH
H 2 C = CH 2 + H 2 O
ethene
Cu / D
CH3CH 2CHO
CH3CH 2CH 2 OH
(f)
413 K
H 2SO4
ethyl sulphate
1 alcohol Aldehyde
H2 / Ni
propanal
383 K
H 2SO4
C2 H5OH
(C2 H5 )2 SO4
4
CH 2 = CH 2 + CO + H 2O
ethene
RCOOR' + H2O
Cu / D
2 alcohol Ketone
Cu / D
2 3RBr + H PO
3 ROH + PBr3
3
3
P/I
2 3RI + H PO
3 ROH + PI 3
3
3
2 3
CH3CH2 O CH2CH3+ H2O
2CH3CH2OH
513-523K
PHENOLS
3
Methods of Preparation of Phenols
(i) From benzene diazonium chloride
N2Cl
OH
D
+ H2O
Diazonium salt
+ N2 + HCl
Phenol
OH
H 2O/HCl
+ 1/2 O2 (air)
+ MgBr(OH)
Phenol
+ NaOH
+ Na2SO3
Properties of Phenols
(i) Physical properties: Phenol is a colourless crystalline solid
mpt. 42C and bpt 183C. It is deliquescent, becomes pinkish
on exposure to air due to oxidation sparingly soluble in cold
water.
(ii) Chemical properties of phenols :
(i) Acidity of phenols
phenol
OH
CH3
OC2H5
OH
(i) O2
+ CH3COCH3
Acetone
Phenetole
(ether)
Phenol
Cumene
(iii) Benzoylation
OH
Cl
+ NaOH
Chlorobenzene
573 623 K
200 atms
NaOH
+ NaCl + H2O
Benzoyl chloride
ONa
Phenol
OH
+ NaCl
Sod. phenoxide
Phenyl benzoate
Phenol
Cl
distil
+ Zn
+ HCl + O2
COOC6H5
+ C6H5COCl
HCl
+ ZnO
Benzene
Phenol
Cu/Fe
+ H2O
OH
ONa
OH
Cl
+ H2O
Steam
+ HCl
Phenol
Sod. phenoxide
OCOONa
OH
V2O5
+ CO 2 400 K
4 7 atm
+ NaOH
425C
(vii) Oxidation of benzene:
Anisole
(ether)
C2H5I
CH3
C
+ NaI
Phenol
Propene
Benzene
+ CH3I
H3PO4
+ CH3 CH = CH2
OCH3
OH
HCl
2
+ HCl
Sod. salicylate
Salicylic acid
315C
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+ O2
COOH
(CH 3CO)2O
OH
+ CH3COOH
+ conc H2 SO4
COOH
OCOCH3
COOH
OH
K2S2 O8
Catechol
(Minor)
OH
OH
Quinol
(Major)
COOC6H5
alkaline solution
Aspirin
(2-acetoxy benzoic acid)
Salicylic acid
OH
OH
CO
OH
COOCH3
CH3 OH (reflux)
OH
Phenol
conc. H2SO4
O
C
CO
Phthalic anhydride
Methyl salicylate
(oil of winter green)
ONa
ONa
CH
CHCl2
+ CHCl3
NaOH, 340 K
NaCl, 2H2O
OH
OH
NO
NOH
NaNO2
Conc H2SO4
NOH + H
ONa
CHO
OH
OH
OH
2NaOH
NaCl
OH
OH
Phenolphthalein
H2SO4
H2O
OH
H2 O
CHO
Dil HCL
NaCl
OH
Indophenol (red)
If CCl4 is used instead of CHCl3 salicylic acid is
formed.
OH
ONa
+ CCl4
Phenol
ONa
CCl3
2NaOH,
H2O NaOH
NaCl,
2H2 O
3NaCl
H 2O
ONa
OH
COOH
dil. HCl
COOH
NaCl
OH
OH
OH
+ Br2
O 2/CrO 3
Phenol
+ Br2(aq)
Benzoquinone
(pink colour)
C 2H 5N 2Cl
Coupling reaction
C6H5 N = N C6H5OH
p hydroxyazobenzene
(Orange red dye)
ONa
Salicylic acid
(vii)
C(OH)3
3NaOH,
OH
Br
OH
Br
CS2
+
Br
(Major)
p-bromo phenol
Br
Br
2, 4, 6 tri bromophenol
(white ppt)
(Minor)
o-bromo phenol
5
(ii) Sulphonation
OH
OH
OH
H2SO4
H2SO4
373 K
293 K
SO3H
Phenol
SO3H
(iii) Nitration
OH
OH
OH
NO2
OH
dil HNO3
conc HNO 3
H 2SO 4
H 2SO 4
NO2
NO2
NO2
NO2
2, 4, 6 trinitrophenol
(picric acid)
Test
Litmus test
Neutral FeCl3 test
Br2 + H2O
C6H5N2Cl
Liberman nitroso test
(H2SO4 + NaOH)
Phenol
Blue
red
Blue or violet colouration
White ppt
Orange red dye
Red colouration changing to
green and again red on dilution
Alcohol
No change
No change
No change
No change
No change
(ii) 1, 2 splitting products of glycol by reaction (oxidation)
with different compounds :
GLYCOL : CH2OH
|
CH2OH
Viscous liquid due to extensive hydrogen bonding due to
presence of two OH groups.
Preparation
(1) Hydroxylation of ethylene
CH 2 OH
1% KMnO 4
|
CH 2 = CH 2 + H 2 O + O
alkaline
CH 2OH
Cis addition
H2C = CH2
RCOO.OH
Peracid
CH2
CH2
CH2OH
H2O
H
CH2OH
CH2OH
Ethylene chlorhydrin
1
+ O2
2
CH2
CH2OH
Catalyst CH2
Ag
CH2
H2O
dil. HCl
CH2OH
CH2OH
Ethylene oxide
Properties
Chemical properties :
(i)
CH 2 OH + HOOC
COOH
CH 2 OH
phthalic acid
+H3PO3
CH2I
CH2
I2
CH2I
ethylene iodide (unstable)
+NaCl+CO2
Industrial method
CH2
PI3
CH2Br
CH2Br
CH2OH
NaHCO3
CH2Cl
PBr3
Heat
CH2
600C
CH2
CH2
ethylene
O + H2O
Ethylene oxide
O
||
anhy. ZnCl2
Tautomeris ation
CH 3 . C - H
CH 2
D
||
CHOH
vinyl alcohol
acetaldehyde
Conc. H2SO4
or Conc. H3PO4
CH2
CH2
CH2
CH2
Dioxane
CH3CHO
CH2O
(HCl)
CH2O
CH.CH3
Cyclic acetal
O=C
CH3
CH2O
CH3
CH2O
CH3
Cyclic Ketal
Heat
Glycol
H SO
2 4 Dacron (terylene)
CH3
6
(ii) Reaction with oxalic acid
HIO 4
CH2 OH
CH 2 OH
|
(COOH)2
CHO H
HCOOH +
383 K
formic acid
|
CH 2 OH
2HCHO + HIO3
formaldehyde
CH2 OH
glycol
HNO 3
COOH
|
+ COOH
CH 2 OH
glycollic acid
KMnO 4 / H 3O +
glycerol
COOH
503 K
CH 2 OH
CH 2 ONO2
|
|
conc H 2SO 4
CHO NO 2
CHOH
+ conc HNO3
|
|
CH 2 OH
CH 2 ONO2
oxalic acid
Lead acetate
Nitroglycerine
or glycerol trinitrate
or Nobel's oil
(iv)
Propene
Bismuth
nitrate
Allyl Chloride
CH 2 I
|
- I2
CHI
|
CH 2 I
CH3
|
+ HI
- I2
CHI
|
CH 2 I
CH 2
||
CH
|
CH 2 I
allyl
iodide
CH3
CH3
|
|
HI
CH CHI
||
|
CH 2
CH 3
propene
Isopropyl
Iodide
COOH
|
CHOH
|
COOH
tartonic acid
COOH
|
+ CO2 + H2 O
COOH
COOH
|
CO
|
COOH
KMnO4
glycerol
glyceric acid
Cl2
CH3 - CH = CH 2
500C ClCH 2 - CH = CH 2
glycerol
CH2 OH
|
CHOH
|
COOH
dil HNO3
CH2 OH
|
CHOH
|
CH2 OH
CH 2OH
|
3HI
CHO H
|
CH 2OH
allyl alcohol
COOH + 2H2 O
Formic acid
glycerol
(It is regenerated)
(COOH)2
CH 2 = CH - CH 2 OH + 2H2 O + 2CO2
oxalic acid
COOH
(CH 3COO) 4 Pb
CH 2OH
|
CHO H
|
CH 2OH
FeSO4 + H2O2
(Fenton's reagent)
or Br2 NaOH
CH2 OH
|
CHOH
|
CHO
glycreralaldehyde
(v)
C H2 OH
|
+ CO
|
CH2 OH
dihydroxy
acetone
CH 2 OH
|
CHOH + 2HIO4
|
CH 2 OH
glycerol
(vi) CH 2 OH
|
KHSO 4 or H 2SO 4
CHOH
or only ZnCl2
|
CH 2 OH
glycerol
CH 2
||
CH
|
CH 2
acrolein
(Bad smelling)
7
Uses of Glycerol
(i) Used in manufacture of dynamite, high quality soaps
and cosmetics.
(ii) Sweetening agent in beverages and confectionary.
(iii) As medicines. In treatment of heat disease and asthma.
RX
R - O - R + H 2O
alcohol
(ii)
ether
2RX + Ag 2 O (dry)
R - O - R + 2AgX
ONa + Cl CH 3
ether
RONa
mixed ether
conc H SO , 413 K or
Al2 O3 , 633 K
+ R ONa
R - O - R + NaX
methyl
chloride
sod. phenoxide
CH3+ NaCl
methyl phenyl ether
R - O - R + NaX
simple ether
Properties of Ethers
+ [R 2 O H ] Cl
+ [ R 2 O H] H S O 4
H2SO4
peroxide formation
air or O3
Cleavage by HX
R - O- R
HX / D
R - X + R OH. R X
Excess
X attaches itself to small R.Reactivly of HX
HI > H Br > HCl
R O R
F
Coordination complex
BF3
R
R
..
O
RMgX
R
R
..
O
Grignards reagent
H2O / dil. H2SO4
BF
F
Addition product
R
Mg
X
..
O
R
(R = C2H5)
R
ROH + ROH
Hydrolysis
PCl5 D
CH3COCl
Anhy. AlCl3
2RCl + POCl3
O
||
CH 2 - C - OR + RCl
Ester
alkyl chloride
8
O
||
2 CH 3 - C - OR + RCl
(CH3CO)2O
Anhy. AlCl3
Ester
Dehydration
Alkene + H2 O
Al2O3 300C
R O R'
Cl2 / dark
Cl
2
CH 3 - CHCl - O - CH 2 - CH 3
Cl
Cl
Cl
Cl
|
CH 2 - CH - O - CH 2 CH 3 + CH 3 - CH - O - CH - CH 3
a,b -dichloro diethyl ether
..
Cl5C2 O
.. C2Cl5
Cl2
light
Perchlorodiethyl ether
OCH3
CH2N2
+N2
OH
Properties
HI
OCH3
+ CH3 I
OCH3
OCH3
NO2 +
o-nitro anisole
OCH3
OCH3
Bromination Br2/CS2
NO2
p-nitro anisole
Br
o-bromo anisole
+
Br
p-bromo anisole