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ALCOHOL
Hydroxy derivatives
OH OH
(iiii) Trihydric [three –OH] CH2 CH CH2
OH OH OH
(iv) Polyhydric [n –OH] CH2 CH ------------- CH2
OH OH OH
(b) Classificat ion accordi ng to nature of carbon :
(i) p or 1° – alcohol CH 3CH 2 – OH
(ii) s or 2° – alcohol (CH 3 ) 2CH – OH
(i) t or 3° – alcohol (CH 3) 3C – OH
Str ucture of alcohol : :O:
3
sp
sp
3
3
Alcohols are bent molecules. The carbon atom (linked with 108.5° 1s
sp
O —
Non - bonding e pair
2s 2px 2py 2pz
sp3 hybridisation
OH
(ii) By hydroborat ion oxidat ion :
BH
CH 3 —CH CH 2
3
CH3 CH2 CH2 (1° alcohol)
H 2 O 2 HO
OH
(iii) By oxymercurat ion demercurat ion :
(i ) Hg (OAc ) , H O
CH 3 —CH CH 2 2 2
CH3 CH CH3
(ii ) NaBH 4 ,HO
OH
(c) From alkyl halide s (By hydrolysis) :
Aq. KOH
C H 3— C H 2— C l C H3C H 2—O H
or Moist Ag2 O
NaBH
R C R
4
R CH R
H
O OH
LiAlH 4
CH3 C CH3
?
H
O
Mechanism :
H H
H H
CH3 C CH3 CH3 C CH3 CH3 C CH3
LiAlH4
O O OH
OD
H
LiAlH4
O
D
OH
D
NaBD4
H
LiAlH
C H 3— C H CH—CHO
4
C H 3— C H C H— C H 2— O H
H
Crotonaldehyde
LiA lH
Ph—CH CH—CHO
4
–
P h — C H 2— C H 2— C H 2— O H
H / OH
Cinnamaldehyde
(e) From et her s :
R—O—R dil.H SO R—OH + R—OH
2 4
LiAlH
R C Cl
4
R—CH 2 —OH + HCl
H
O
LiAlH
R C OR
4
R—CH 2 —OH + R—OH
H
O
LiAlH
R C O C OR
4
R—CH 2 —OH + R—CH 2 —OH
H
O O
LiAlH
R C NH2
4
R—CH 2 —NH 2 +H 2 O
H
O
(g) From e ster s (By hydrolysis) :
(i) By alkali ne hydrolysis :
NaOH
R C OR R C ONa + R OH
O O
(ii) By acidic hydrolysis :
H
H O (excess)
R C OR R C OH + R OH
2
O O
18 H O 18
CH3 C OC2H5
3
CH3 C OH + C2H5OH
O O
This reaction is reversible reaction and it's order is 1 and it is also called Pseudo-Unimolecular reaction.
(h) From p-ami ne s :
NaNO HCl
R—NH2
2
R—OH + N 2 + H 2 O
or HNO 2
CH 3 CH 2 — N H 2 HNO CH 3 CH 2 —OH + N 2 + H 2 O
2
Mechanism :
NaNO 2 HCl
CH 3 CH 2 — NH 2 CH 3 CH 2 — N 2 Cl CH 3 CH 2 N 2 Cl
(Unstable)
OH
CH3CH2 OH [major]
Cl
CH3CH2 Cl
CH3CH2
O N O
CH3CH2 O N O
H
CH2 CH2
NaNO 2 HCl
CH 3 CH 2 CH 2 —N H 2 CH 3 CH 2 CH 2 — N 2 Cl CH 3 CH 2 CH 2
HO H
CH3 CH CH3 CH3 CH CH3
OH
HNO 2
E x c e p t io n : CH 3 — NH 2 CH 3 — O — CH 3
R R
HO
R Mg X + H C H H C H H C H 2
R R
HO
2
R Mg X + CH2 CH2 CH2 CH2 CH2 CH2
O OMgX OH
[two C more p-alcohol]
(ii) s-alcohol :
R R
H2O
R Mg X + R C H R C H R C H
O OMgX OH
R
R MgX
R Mg X + H C OR H C R
HO
H C R
2
O O OH
(iii) t-alcohol :
R R
2 HO
R Mg X + R C R R C R R C R
O OMgX OH
R
R MgX
R Mg X + R C OR R C R R C R
H2O
O O OH
Physical proper t ie s :
(i) C1 to C11 are colourless liquids and high alcohols are solids.
(ii) Density of monohydric alcohol is less than H2O.
(iii) Density mol. wt. (for monohydric alcohol).
(iv) Solubility : C 1 to C3 and t-butyl alcohol is completely soluble in H2O due to H–bonding.
1
solubility No. of side chainsc molecular weight
CH3
CH 3 CH 2 CH 2 CH 2 OH < CH3CH2CH OH < CH3 C OH
CH3 CH3
CH3CHCH
2 2
< CH3 CH CH2 < CH2 CH CH2
OH OH OH OH OH OH
[Number of —OH increases, H-bonding increases]
(v) Boiling points : B.P. molecular weignt
1
If molecular wt. is same then B.P.
branching
CH3
CH 3 CH 2 CH 2 CH 2 OH > CH3CH2CH OH > CH3 C OH
CH3 CH3
CH3CHCH
2 2
< CH3 CH CH2 < CH2 CH CH2
OH OH OH OH OH OH
[Number of OH increases, H-bonding increases]
Ex. Boiling point of alcohol is more than corresponding ether. Why ?
S o l . Reason : H-bonding in alcohol.
O H O
R C C R
OH O
Chemical proper t ie s :
Monohydric alcohol show following reactions
(A) Reaction involving cleavage of O H
(B) Reaction involving cleavage of C OH
(C) Reaction involving complete molecule of alcohol
O O
(Acetylation)
OH O C R
CH 2 COCl O
COOH COOH
R OH + Cl C Ph R O C Ph
O O
(Benzoylation)
(vi) Esterification : Conc. H 2SO 4 is used as catalyst and dehydrating agent.
conc. H 2 SO 4
R C OH + R OH R C OR + H2O
O O
Mechanism :
H2SO4 H+ + HSO 4–
::
+
R—C—O—H + H R—C—O—H
O OH
OH OH OH OH
+
–H
R—C—O—H + ROH R—C—OH R—C—OH2 R—C R—C R—C—OR'
OH O OR' OR' OR' O
H R'
O O
18 18
Example : Ph conc. H 2 SO 4
C OH + H OC2H5 Ph C OC2H5 + H2O
O O
1
(i) Reactivity for esterification .
Steric hinderence
(ii) Reactivity of R – OH [If acid is same] : CH3 – OH > 1° > 2° > 3° alcohol
(iii) Reactivity of RCOOH [If alcohol is same] :
CH3
BF3 / HgO
OCH3
CH CH + 2CH 3 —OH CH3CH
OCH3
Methylal
Ethylal
( v i i i ) Reaction with carbonyl compounds :
OR
R—CHO + 2R—OH H
R CH
OR
Acetal
R OR
R C R + 2R OH H
C
R OR
O Ketal
OCH3
H
CH 3 CHO + 2CH 3 —OH CH3CH
OCH3
Methylal
(ix) React ion w it h Grignard reagent :
X
R—Mg—X + H—OR H
R H + Mg
OR
(x) Reaction with Ketene : Ketene is used as acetylating agent.
OR OR
OC2H5 OC2H5
OC2H5 OC2H5
NH C O + H—OC2H5 NH C
OH NH2 C O
Ethyl urethane
(xii) Reaction with oxirane :
OR
H+
R OH + CH2 CH2 CH2 CH2
O
OH
ZnCl2
R2CH—OH + HCl
R 2 CH—Cl + H 2 O
2 0 alcohol
R e a ctiv ity o f th e a cid s is HI > HB r > HC l > HF
(ii) React ion w it h i norga nic acids :
R OH + H O N O R O N O + H2O
O O
Nitric acid Alkyl nitrate
R—OH + HHSO 4 R—HSO 4 + H 2 O
Alkyl hydrogen sulphate
(iii) React ion w it h phosphorous halide s :
3R—OH + PCl 3 3RCl + H 3PO 3
R—OH + PCl5 R—Cl + POCl3 + HCl
(iv) Reaction with thionyl chloride (SOCl 2 ) :
(gas)
(v) Reaction with NH 3 : Alumina (Al 2O 3 ) is used as dehydrating agent.
Al O
R OH + HNH2
2 3
R—NH 2 + H 2 O
250 C
(vi) Reaction with halogens : Oxidation and chlorination takes place simultaneously.
CH 3CH 2OH + Cl 2 (dry) CH3CHO + 2HCl (Oxidation)
CH3CHO + 3Cl2 CCl3CHO + 3HCl (chlorination)
chloral
(C) Reaction involving complete molecule of alcohol :
(i) Dehydration : Removal of H 2 O by two type
(a) Intermolecularly removal of H 2O [form ether]
(b) Intramolecularly removal of H 2O [form alkene]
0°C
(C2H)
5 2SO4
100°C
C2H5 OH + H2SO4 C2HHSO
5 4
(conc.) 140°C
C2H5 O C2H5 (Williomson's synthesis)
170°C
CH2 CH2 (Elimination)
250°C
C2H5 OH +Al2O3 C2H5 O C2H5
(Alumina) 350°C
CH2 CH2
Ease of dehydration follow the order : 3° ROH > 2° ROH > 1° ROH > CH3 OH
(ii) Catalytic Dehydrogenation : This reaction is useful in distinction of 1°, 2° and 3° alcohols.
Cu
CH 3 CH 2 OH
300 C
CH3CHO + H2
(p- alcohol ) (Acetaldehyde)
Cu
CH3 CH CH3
300 C
CH3 C CH3 + H2
OH O
(s- alcohol) (acetone)
CH3 CH3
CH3 C OH
Cu
CH3 C CH2 + H2O [dehydration]
300 C
(Iso - butylene)
CH3
(t. alcohol)
H KMnO or [O ]
R —C H 2—O H 4
H / K Cr O
RC HO
Room temp.
RCOOH
2 2 7
R
[O]
R C R Room temp.
No reaction
OH
high temp.
(t-alcohol) Acids (less carbon)
[O ] [O]
CH3CH2 CH CH3
high temp.
CH3CH2 C CH3 CH 3 COOH + CH 3 COOH
OH O
Carbonyl group goes with smaller alkyl group
(iv) React ion w it h phosporous pentasulph ide :
R—OH + P 2 S 5 R—SH + P 2O 5
Thio alcohol
(v) Reaction with salts :
CuSO4
CuSO4. 2CHOH
3
CaCl2
CH3OH CaCl2. 4CHOH
3
MgCl2
MgCl2 . 6CH3OH
P + I2 P + I2 P + I2
R — C H 2— I R 2C H — I R 3C — I
AgNO2 AgNO2 AgNO2
R C H 2— N O 2 R 2C H — N O 2 R 3C — N O 2
HNO2 HNO2 HNO2
R—C—NO2 R 2C — N O 2 No reaction
N OH N
NaOH
NaOH NaOH
[green]
H K Cr O
2° Alcohol
2 2 7
6
Ketone + Cr +3
orange [Cr ]
[green]
H K Cr O
3° Alcohol 2 2 7
No oxidation, No green
orange [Cr 6 ]
1
R—OH Na
R—ONa + H
2 2
[effervesence of H2]
PCl 5 NH 3
R—OH R—Cl + POCl 3 + HCl NH 4Cl
[White fumes]
R—OH Cerric ammonium nitrate Red colour
(ix) Distinction between CH3 – OH and C 2 H 5 OH
C H 3O H C H 3C H 2O H
B.P. 65°C 78°C
I 2 + NaOH No ppt Yellow ppt of CHI3
Cu/300°C Smell of formalin [HCHO] No smell
Salicylic acid Smell of oil of wintergreen No smell
OH
CH3OH COOH3 Methyl salicylate
(Oil of wintergreen)
OH OH
Ph—OH COOPh Phenyl salicylate
COOH
Salol (Internal antiseptic)
O C CH3
Aspirin
CH3COCl O (Analgesic)
COOH
HIO 4 3H 2 O
CH2 CH CH2
HO CH2+HO CH OH + HO CH2 HCHO+HCOOH+HCHO
OH OH OH OH OH OH
(Glycerol)
O
HIO
Example : CH3 C CH CH2 C 4
H CH3COOH + CHO CH2 CHO
O OH
Example :
Pinacole Pinacolone
Mechanism :
OH OH OH
CH3 COOH
OH
OH OH
OH
OH OH
catechol resorcinol quinol
All phenolic compounds give characteristic colour with neutral FeCl3.
PHENOL (C 6 H 5 OH)
Phenol is also known as carbolic acid or Benzenol or hydroxy benzene.In phenol —OH group is attached with
sp2 hybridised carbon.It was discovered by Runge in the middle oil fraction of coaltar distillation and named it
carbolic acid (carbo = coal; oleum = oil) .It is also present in traces in human urine.
General Met ho ds of preparat ion :
(1) From benzene sulphonic acid :
When sodium salt of benzene sulphonic acid is fused with NaOH phenol is obtained.
C6H 5SO 3Na + NaOH C6H5OH + Na2SO3
(2) From benzene diazonium chloride :
When benzene diazonium chloride solution is warmed, phenol is obtained with evolution of nitrogen.
N2Cl OH
(Steam distilled ) H O
2
+ N2 + HCl
(3) By distilling a phenolic acid with sodalime (decarboxylation):
OH OH
COOH NaOH CaO
+ Na 2 CO 3
Salicylic acid
(4) From Grignard reagent : (The Grignard reagent on reaction with oxygen and subsequent hydrolysis by acid
yields phenol)
Br
[O]
C6H5MgBr H2 O
C 6H5OMgBr C 6H 5OH + Mg
OH
OH
V2 O 5
+ [O]
300 C
Order of NSR :
Cl Cl Cl Cl
NO2 NO2 NO2 NO2
< < <
NO2 NO2
max. –I, –M
Aq. NaOH min. ed Aq. NaOH
300°C min. ESR 25°C
max. NSR
OH OH
NO2 NO2
NO2
2, 4, 6–Trinitrophenol (Picric acid)
(7) Industrial preparat ion of phenol:
Phenol can be prepared commercially by :
(a) Middle oil fraction of coaltar distillation
(b) Cumene
(c) Raschig process
(d) Dow's process
(a) Middle oil fraction of coaltar:
Fractional
Coaltar Middle oil (170-230°)
distillation
(Phenol, cresols, Naphthalene)
Coal
Naphthalene liquid
(Solid crystals separate out) NaOH (dil.)
C6HONa
5
C6HOH
5 + Na2CO3
(b) From cumene (Isopropyl benzene) : Cumene is oxidised with oxygen into cumene hydroperoxide in
presence of a catalyst. This is decomposed by dil. H2SO4 into phenol and acetone.
O OH
CH3 CH3
CH C(CH3)2 OH
O
2 H SO ,H O
4 2
+ CH3 C CH3
2
130 C
H / 100 C
O
Cumene Cumene hydroperoxide
o
(c) Raschig process : Chlorobenzene is formed by the interaction of benzene, HCl and air at 300 C in
o
presence of catalyst CuCl2 + FeCl3. It is hydrolysed by superheated steam at 425 C to form phenol and
HCl.
1 CuCl FeCl
C6H6 + HCl + O
2 3
C 6H 5 Cl + H 2 O
2 2 0
300 C
0
C 6H 5 Cl + H 2 O 425 C
C 6 H 5 OH + HCl
(super heated steam)
(d) Dow process : This process involves alkaline hydrolysis of chloro benzene-(large quantities of phenol
formed).
OH
Cu — Fe
C 6 H 5 Cl + NaOH + NaCl
300 0 C
Physical proper t ie s :
(i) Phenol is a colourless, hygroscopic crystalline solid.
(ii) It attains pink colour on exposure to air and light. (slow oxidation)
C 6H 5OH-------- O O----------- HOC 6H 5
Phenoquinone(pink colour)
(iii) It is poisonous in nature but acts as antiseptic and disinfectant.
(iv) Phenol is slightly soluble in water , readily soluble in organic solvents.
(v) Solublity of phenol in water is much lower than alcohols because of larger hydrocarbon part in the
molecule.
(vi) Due to intermolecular H-Bonding, phenol has relatively high boiling point than the corresponding
hydrocarbons, aryl halides etc. but intermolecular H-bonding in o–derivatives is used in the preparation
of dyes, drugs, bakelite and it's melting point (MP) is 43° C and boiling point (BP) is 182° C .
Chemical Proper t ie s :
(A) React ions due to –OH group :
Acidic Nature : Phenol is a weak acid. The acidic nature of phenol due to formation of stable phenoxide
ion in solution. The phenoxide ion is stable due to resonance. The negative charge is spread through out
the benzene ring which is stabilising factor in the phenoxide ion. Electron withdrawing groups
(–NO 2, –Cl) increase the acidity of phenol while electron releasing groups (–CH 3 etc.) decrease the
acidity of phenol.
C 6 H 5 OH
C6H5 O H3O
Phenol is stronger acid than alcohols but weaker than the carboxylic acids and even carbonic acid
The acidic nature of phenol is observed in the following:
(i) Phenol changes blue litmas to red.
(ii) Highly electro positive metals react with phenol.
2C 6 H 5 OH + 2Na 2C 6 H 5 ONa + H 2
(iii) Phenol reacts with strong alkalies to form phenoxides.
C 6 H 5 OH NaOH C 6 H 5 O N a H 2 O
(iv) However phenol does not decompose Na2CO3 or NaHCO3 because phenol is weaker than carbonic acid.
C 6 H 5 OH + Na 2CO 3 or NaHCO 3 No reaction
Ph—OH + NaHCO3 Ph—ONa + H 2 CO 3
Acid-I Base-I Base-II Acid-II
O O
Acid-I Base-I Base-II Acid-II
(vi) Acetic acid reacts with NaHCO3 and gives effervesence of CO2.
Reaction with PCl 5 : Phenol reacts with PCl 5 to form chloro benzene. The yield of chlorobenzene is
poor and mainly triphenyl phosphate is formed.
C 6H 5 OH + PCl 5 C 6H 5Cl + POCl 3 + HCl
3C 6 H 5 OH + POCl 3 (C 6H 5) 3 PO 4 + 3HCl
Reaction with Zn dust: When phenol is distilled with zinc dust benzene is obtained.
C 6 H 5 OH + Zn C 6 H 6 + ZnO
CH2 OH
Ex. Zn
?
S o l . No reaction
CH3
OH Zn
Ex. ?
CH3
Sol.
CH3
CH3 Zn
Ex. ?
S o l . No reaction
COOH
OH Zn
Ex. ?
COOH
Sol.
Reaction with NH 3 ( Bucherer reaction): Phenol reacts with NH 3 in presence of anhydrous ZnCl 2 to
form aniline.
Anhydrous ZnCl or (NH ) SO / NH 150 C
C 6 H 5 OH + NH 3
2 4 2
300 C
3 3
C 6 H 5 NH 2 + H 2 O
Reaction with FeCl 3 : Phenol gives violet colouration with FeCl3 solution (neutral) due to formation of a
complex.
C 6H 5 OH + FeCl 3 Voilet colour
This reaction is used to differentiate phenol from alcohols.
Acetylation (Schot ten-Baumann reaction) : Phenol reacts with acid chlorides or acid anhydrides in
alkali solution to form phenyl esters.
NaOH
C 6 H 5 OH + ClCOCH 3 C6H5O—C CH3
HCl
O
NaOH
C6HOH
5 + Cl C C6H5 C6H5O C—C6H5
HCl
O O
Ether formation (Alkylation) : Phenol reacts with alkyl halides in alkali solution to form phenyl ethers.
(Williamson's synthesis)
alkali solution RX
C 6 H 5 OH + NaOH C 6 H 5ONa
NaX C 6 H 5 OR
Sodium phenoxide
C 6 H 5 OH + CH 2 N 2 C 6H 5OCH 3 + N 2
Reaction with P 2 S 5 : 5C 6 H 5 OH + P 2 S 5 5C 6 H 5 SH + P 2 O 5
(B) Reaction of Benzene Ring : The —OH group is ortho and para directing. It activates the benzene nucleus.
Halogenation : Phenol reacts with bromine in CCl 4 to form mixture of o–and p–bromo phenol.
OH OH OH
CHCl 3 or CS 2 or CHCl 4 Br
+ Br 2
low . tem p.
+
Br
Phenol reacts with bromine water to form a white ppt. of 2,4,6 tribromo phenol.
OH
OH Br Br
+ 3Br2 H O + 3HBr
2
Br
Nitration : Phenol reacts with dil. HNO3 at 0°–10° C to form o- and p- nitro phenols.
OH OH
OH
dil. HNO
3
NO2
0 10 C
+
When phenol is treated with nitrating mixture to form 2,4,6- trinitro phenol (picric acid)
OH
OH NO2 NO2
Conc. HNO 3
Conc. H 2 SO 4
[2, 4, 6–Trinitrophenol (Picric acid)]
NO2
Sulphonation: Phenol reacts with fuming H 2SO 4 to form o–and p–hydydroxy benzene sulphonic acid
at different temperatures.
OH
25°C
SO3H
OH
+ conc. H2SO4
OH
100°C
SO3H
Friedel-Craft's reaction : Phenol when treated with methyl chloride in presence of anhydrous AlCl 3
p-cresol is main product.
OH
OH OH
Anhydrous AlCl
CH3
+ CH 3 Cl
3
+
CH3
o-cresol p-cresol
OH OH
COCH3
OH +
+ CH 3 COCl Anhydrous AlCl
3
COCH3
o – and p – hydroxy acetophenone
Gattermann aldehyde synthesis : When phenol is treated with liquid HCN and HCl gas in presence
of anhydrous AlCl3 yields mainly p- hydroxy benzaldehyde (formylation)
HCl + HCN AlCl HN CHCl
3
OH OH OH
AlCl3 H O
+ HN CHCl
HCl 2
NH
3
CH NH CHO
Riemer-Tiemann reaction : Phenol on refluxing with chloroform and NaOH (aqueous) followed by
acid hydrolysis yields o–hydroxy benzaldehyde. When CCl4 is used salicylic acid is formed.
CHCl3
OH ONa + OH
NaOH H
60°C NaOH (aq.) H2O
OH CHCl2 CHO CHO
Salicylaldehyde
CCl4
OH ONa + OH
NaOH H
60°C NaOH (aq.) HO
CCl3 COONa 2
COOH
Salicylic acid
OH O O O
H Cl
HO
:CCl
2 C
–H2O Cl
OH O O
CHO OH Cl
H CH OH CH
Cl
–H O 2 OH
Kolbe 's Schmidt reaction : This involves the reaction of C6H 5ONa with CO2 at 1400 C followed by
acid hydrolysis salicylic acid is formed followed.
O Na OCOONa OH OH
COONa COOH
140° C Rearrangement H+
+ CO2
6 atm. pressure H2O
Sodium phenyl carbonate Sodium salicylate Salicylic acid
Hydrogenation: Phenol when hydrogenated in presence of Ni at 150-200 0C forms cyclohexanol.
OH OH
Ni
+ 3H2
150 – 200° C
Cyclohexanol. (C6H11OH)
(used as a good solvent)
OH
60°C
OH
Phenyl ester (acetate)
COCH3
Duff 's reaction: This method gives only the o-compound which is hindered by the presence of a –I
group in the ring.
OH OH OH
Glycerol
CH NCH3 H O CHO
+(CH)
2 6N4 2
Boric acid
NaOH
N2Cl + OH
–HCl
N N OH
p–hydroxy azobenzene (Orange dye or Red dye)
Phenol couples with phthalic anhydride in presence of conc. H2SO4 to form a dye (phenolphthalien)
used as an indicator.
O O OH
O C C OH OH H SO
O C C
2 4
+ OH
–H2O
H OH
Lederer Manasse (Condensation w ith formaldehyde) : Phenol condenses with HCHO (excess) in
presence of NaOH or weak acid (H+) to form a polymer known as bakelite (aresin).
OH OH OH
CH2OH
NaOH
+ HCHO +
(20%)
CH2OH
(40%) Polymerisation
condensation with HCHO
HO CH2 OH
CH2 CH2
OH CH2 OH
CH2 CH2
OH OH O
HONO 6 5C H OH H2O NaOH
Green phenol Red Blue Sodium
H2SO4
or blue colour Indophenol Salt (original
H NO N OH ion green or blue
colour is restored)
Reaction with acetone: (Condensation with acetone)
OH OH OH OH
con. HCl
–H2O
H H CH3 C CH3
O Bis - Phenol-A
p-p'– Isopropylidene diphenol
CH3 C CH3
Oxidation:
Air [O]
O O + H2O p-Benzo quionone (Red)
CrO2Cl2
OH COOH
H OH
(O) H/KMnO4
Meso tartaric acid
H OH
(Phenol)
COOH
K2S2O8/KOH
HO OH (Quinol)
(Elb's persulphate reaction)
1, 4 – Dihydroxy benzene
Te st of Phenol :
(i) Phenol turns blue litmus to red.
(ii) Aqeous solution of phenol gives a violet colour with a drop of ferric chloride.
(iii) Phenol gives Lieber mann 's nitroso test.
NaNO 2
Phenol in conc. H2SO4
excess of water
Red colour
NaOH excess
Blue colour
(iv) Aqeous solution of phenol gives a white ppt. of 2,4,6 tribromophenol with bromine water.
(v) Phenol combines with phthalic anhydride in presence of conc. H2SO4 to form phenolphthalein which
gives pink colour with alkali.
(vi) With ammonia and sodium hypochlorite , phenol gives blue colour.
Difference s bet ween phenol a nd alcohol (C 2 H 5 OH) :
(i) Phenol is more acidic than aliphatic alcohol due to resonance in phenoxide ion.
(ii) Phenol gives violet colour with FeCl3 while aliphatic alcohol does not give.
(iii) Phenol gives triphenyl phosphate with PCl5 while aliphatic alcohol gives alkyl chloride.
(iv) Phenol has phenolic odour whereas alcohol has pleasent odour.
(v) Phenol on oxidation gives quinone while alcohol gives aldehyde or ketone and acids.
Uses of Phenol : Phenol is used :
(a) As an antiseptic in soaps and lotions. "Dettol" (2,4-Dichloro-3,5-dimethyl phenol)
(b) In manufacture of azodyes, phenolphthalein , picric acid (explosive), cyclohexanol (Solvent for rubber),
plastics (bakelite) etc.
(c) In manufacture of drugs like aspirin salol, phenacetin etc.
(d) As preservative for ink.
ETHER
R—O—R (Dialkyl ether), alkoxy alkane. It's General formula is C n H 2n + 2 O.
CH 3 —O—CH 2 CH 3 (Methoxy ethane) or ethyl methyl ether or 2–oxa butane
Ether is monoalkyl derivative of R–OH and dialkyl derivative of H 2 O
H 2H
R—OH
R R—O—R
2R H—O—H
Mechanism : [ S N 2 Reaction]
C2H5ONa C2H5O + Na
H H H H
Slow Fast
C2H5O C— I C2H5O------ C ----- I C2H5—O—CH3+ I
H H
Na + I NaI
CH3 CH2
CH3 CH3
Example : CH3
C ONa + CH3 CH2 Cl CH3 C O CH2 CH3
CH3 CH3
Example : 2CH 3 —CH 2 —Cl + Ag 2 O CH 3 CH 2 OCH 2 CH 3 + 2AgCl
250°C 140°C
CH3CH2 O CH2CH3 CH3CH2 O CH2CH3
Al2O3 conc. H2SO4 (Willomson's synthesis)
CH3 CH2 OH
350°C 170°C
CH2 CH2 CH2 CH2
(Elimination)
(ii) Reaction with CH 2 N 2 (diazomethane) :
R—OH + CH 2 —N 2
BF R—O—CH 2 —H + N 2
3
Physical Proper t ie s :
(i) CH 3 OCH 3 , CH 3OCH 2 CH 3 are gases and higher are volatile liquids.
(ii) Ether are less polar [=1.18D].
(iii) Ethers are less soluble in H 2 O.
(iv) Ethers have less BP then corresponding alcohol.
Ex. Ethers are less soluble in H 2 O . Why ?
S o l . Reason : Due to less polar, it forms weaker H–Bonding with H 2 O.
Ex. Ethers have less BP then corresponding alcohol. Why ?
S o l . Reason : No H–Bonding in ether molecules.
Chemical proper t ie s :
Ethers are less polar so less reactive and do not react with active metals [Na,K], cold dil. acid, oxidising and
reducing agent.
Reason : They do not have any active functional group.
1. Basic nature : Due to presence of .p on oxygen atom ether behave as lewis base
Ethers react with cold conc. acid and form oxonium ion
.. cold ; conc.
.. C2H5
Example : C2H5 O H SO
C2H5
2 4
O C2H5 HSO4 (diethyl oxonium hydrogen sulphate)
H
Ether form dative bond with Lewis acids like BF 3, AlCl 3 , RMgX etc.
R R
..
O
..
R .. F
Example : O: B F R Mg X [Ether is used as solvent] for Grignard reagent.
R F ..
O
..
R R
2. Halogenation :
Cl2/dark
CH3CH O CH CH3
Cl Cl
CH3CH2 O CH2CH3
'–Dichloro diethyl ether
10 Cl2 light
C2Cl5 O C2Cl5 + 10 HCl
Perchlorodiethyl ether
3. Formation of peroxides : Ether add up atmospheric oxygen or ozonised oxygen. It is explained by Free
radical mechanism as intermediates is free radical.
O (nonpolar )
C 2H 5— O — C 2H 5
Long contact
2
CH3CH2 O CHCH3
(Non polar) sunlight or UV O O H
.. .. ..
C2H5..
OC2H5 + O
.. C2HOC
5.. 2H5 or (C2H5)2O
O
..
:O
.. :
O
CH 3 CH 2 —O—CH 2 —Ph 2
long contact
CH —CH —O— CH —Ph O2
CH3 CH2 O CH Ph
3 2
stable by resonance O O H
Peroxides are unstable and explosives.
Test for peroxides
FeSO / KCNS
ether (peroxide)
4
Red colour
ether (Peroxides) + Fe + 2 Fe + 3
CNS
Fe(CNS) 3
(Red)
hot dil
4. Reaction with hot dil. H 2 SO 4 : R—O—R
H 2 SO 4
2R—OH
cold dil.
No Reaction
cold conc.
Oxonium salt
H2SO4
CH3 CH2 O CH2 CH3
hot dil.
Ethyl alcohol
hot conc.
Ethyl hydrogen sulphate
CH2CH2 O CH2CH2 + C2H5
10. Reaction with C 2 H 5 Na : CH 3 CH 2 OH + CH 2 CH 2 +C 2 H 6
H H Stronger
base
Re d P HI
12. Reduction : CH 3 CH 2 OCH 2 CH 3
heat 2CH 3 CH 3
13. Oxidation :
H / K 2 Cr2 O 7
CH 3 CH 2 —O—CH 2 CH 3 [O] [O]
2CH 3 CH 2 OH 2CH 3 CHO 2CH 3 COOH
14. Combustion : C 2 H 5 OC 2 H 5 + 6O 2 4CO 2 + 5H 2 O
(explosive mixture)
CH3
Cold and conc.
Ex. CH3 C O CH2 CH3 HI ?
CH3
Sol. Mechanism
CH3 CH3 CH3
..
CH3 C O CH2CH3 H+ CH3 C
O CH2CH3 CH3
..
CH3 CH3 H CH3
(Oxonium ion)
CH3 I
CH3 C I + CH3CH2OH
CH3
If oxonium ion gives more stable carbocation [ Ph CH 2 , CH2 CH— C H2, (CH3)3 C ] then SN1 reaction occurs.
If oxonium ion gives less stable carbocation [P h , CH 2 C H, CH 3 C H 2] then SN 2 reaction occurs,
and X attacks at less hindered carbon.
Cold con.
Ex. CH 3 CH 2 —O—CH 2 Ph
HI CH 3 CH 2 —OH + PhCH 2 —I, write mechanism of given reaction.
S o l . Mechanism :
.. H
I
CH3CH2OCH
.. 2Ph CH3CH2 O CH2Ph CH 3 CH 2 OH + Ph CH 2 PhCH 2 I + CH 3 CH 2 –OH
H
anhy.HI
Ex. CH 3 CH 2 —O—CH 3 ?
.. HI I
Sol. CH3CH2 O CH3 CH3CH2 O CH3 CH3I + CH3CH2OH
..
H
Oxonium ion gives less stable carbocation
SN 2 reaction I attacks at less hinderd carbon.
(aq.)HBr
Ex. CH 3 —CH 2 —O—Ph
?
.. +
S o l . Mechanism : CH3 CH2 O H
Ph CH3 CH2 O Br
Ph CH3CH2Br + PhOH
..
H
SN1 2°
CH3CH2OH + I CH CH3
HI HI
CH 3 CH 2 —O—CH 2 Ph CH 3 CH 2 OH+PhCH 2 I CH 3 CH 2 — I PhCH 2 — I
S o l . C 2 H 5 —Br + C 2 H 5 — Br
Uses of ether :
(i) General anaesthetics agent.
(ii) Refrigerant a mixture of ether and dry ice gives temperature as low 110°C.
(iii) Solvent for oil, fats, resins, Grignard reagent.
(iv) For providing inert & moist free medium to organic reaction example : Wurtz reactions.
(v) In perfumery.
(vi) Di-isopropyl ether Petrol as an antiknock comp.
(vii) Mixture of alcohol and ether is used as a substitute of petrol. Trade name "Natalite"
(viii) Halothane (CF3CHClBr) used as an anaesthetic because it produces unconsciousness without affecting
lung and heat.
Preparat ion of Epoxide s :
(i) Epoxidation of alkenes by reaction with peroxy acids
(ii) Base-promoted ring closure of vicinal halohydrins
(iii) Epoxidation of alkenes by reaction with peroxy acids
Epoxidat ion of alkene s by react ion w it h peroxy acids :
O O
C=C + R–C–OOH C—C + R–C–OH
O
Peroxy acid Epoxide
Example :
O O
(a) CH2= CH–(CH2)9–CH3 + CH3–C–COOH CH2–CH(CH2)9CH3 + CH3–C–OH
O
O O
C6H5 O O
H C6H5 H
C= C + CH3–C–OOH + CH3–C–OH
H C6H5 C6H5
H O
Mechanism :
H
O C O O
C
CH3–C O CH3–C H +
C CH3–C O O––C––
O C
O O C
O
HO X
Vicinal halohydrin Epoxide
Mechanism :
R X R X
R C––C R R C––C R + HO—H
Step I
–O
..
O
..
..
.. – .. R .. R
HO
.. H
R X R R
..
Step II R C––C R –
R+X
..
..
R C––C ..
–O
..
..
O
..
..
.. R
Example :
H H
OH
NaOH
O
(i)
OH
Br H
trans-2-bromocyclohexanol 1, 2-epoxycyclohexane
H3C Br
H3C
H H
H3C H
Br2/H2O inversion of
Anti addition configuration H3C
(ii) H3C H3C H H
H
OH O
cis-2-butane cis-2, 3-epoxybutane
H Br
H
CH3 CH3
H CH3
Br2/H2O inversion of
Anti addition configuration H3C
(iii) H3C H3C H H
H
OH O
trans-2-butane trans-2, 3-epoxybutane
Reaction of Epoxides :
Wit h Grignard reagent :
(1 ) diethylether
RMgX + H2C––CH2 (2 ) H 3 O
RCH CH OH (primary alcohol)
2 2
(i) diethylether
CH2MgCl + H2C––CH2 + CH2CH2CH2OH
(ii) H3O
O
Benzyl magnesium Ethylene 3-phenyl-1-propanol
chloride oxide
Nucleoph i lic ri ng openi ng react ions of epoxide s :
Y Y
OH
..
..
.. ..
KS CH 2 CH 2 CH 3
H2C–––CH2
ethanol water, 0 C
CH ––CH CH ––CH SCH CH OH
3 2 2 2 2 2
O
2-(butylthio) ethanol
Note : Nucleophilic ring opening reactions of epoxides is the characteristic feature of S N 2 reaction.
H OCH2CH3
NaOCH 2 CH 3
(i) H H
CH 3 CH 2 OH
O H
OH
CH3
H3C
H OH
NH3/H2O
H
O
H3C H2N H
H
CH3
H O CH3 OH
1, diethyl ether
C6H5MgBr + H2C–––CHCH3
C6H5CH2CH––CH3
2, H 3 O
O OH
R R R
R
.. – ..
O
..
.. OH
..
–
Y: – ..– Y
Y O Y
O ..
epoxide transition state alkoxide -substituted alcohol
1. LiAlH 4
CH2–––CH(CH2)7CH3 CH3––CH––(CH2)7CH3
2, H 2 O
O OH
HBr
(i) H2C–––CH2 BrCH2CH2OH
10 C
CH 3 CH 2 OH
(ii) H2C–––CH2 CH3–CH2OCH2CH2OH
H 2 SO 4 , 25 C
O
Mechanism
+ H ..
H2C–––CH2 + H—O: H2C–––CH2 + H2O:
Step-1 :
H :O+
:O:
H
H2C–––CH2
H .. + H
Slow
:O: + O+ .. ..
..
Step-2 : H—O
H
H
..
CH2–CH2–O–H
+ H
H—O ..
..
H H .. ..
Step-3 : :O: + ..
CH2–CH2–O–H +
.. 2CH2..
O—H + HOCH OH
..
H H
H
Example : H
OH
HBr
O
OH
H H
1,2-Epoxycyclohexane trans -2-bromo cyclohexanol