24.6 sources of phenols phenol is an important industrial chemical. major use is in phenolic resins...
TRANSCRIPT
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24.624.6
Sources of PhenolsSources of Phenols
Phenol is an important industrial chemical.Phenol is an important industrial chemical.
Major use is in phenolic resins for adhesives Major use is in phenolic resins for adhesives and plastics.and plastics.
Annual U.S. production is about 4 billion Annual U.S. production is about 4 billion pounds per year.pounds per year.
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1. NaOH 1. NaOH heat heat
2. H2. H++
1. NaOH 1. NaOH heat heat
2. H2. H++1. O1. O22
2. H2. H22OO
H H22SOSO44
IndustrialIndustrial
PreparationsPreparations
of Phenolof Phenol
SOSO33HH
ClCl
CH(CHCH(CH33))22
OHOH
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(81-86%)(81-86%)
OO22NN
NNHH22
OO22NN
OOHH
1.1. NaNONaNO22,,
HH22SOSO44,,
HH22OO
2.2. HH22O, heatO, heat
Laboratory Synthesis of PhenolsLaboratory Synthesis of Phenols
from arylamines via diazonium ionsfrom arylamines via diazonium ions
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24.724.7
Naturally Occurring PhenolsNaturally Occurring Phenols
Many phenols occur naturallyMany phenols occur naturally
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CH(CHCH(CH33))22
OHOH
CHCH33
ThymolThymol
(major constituent of oil of thyme)(major constituent of oil of thyme)
Example: ThymolExample: Thymol
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ClCl
OHOH
ClCl
2,5-Dichlorophenol2,5-Dichlorophenol
(from defensive secretion of(from defensive secretion of
a species of grasshopper)a species of grasshopper)
Example: 2,5-DichlorophenolExample: 2,5-Dichlorophenol
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24.824.8
Reactions of Phenols:Reactions of Phenols:
Electrophilic Aromatic Electrophilic Aromatic
SubstitutionSubstitution
Hydroxyl group strongly activates the ringHydroxyl group strongly activates the ringtoward electrophilic aromatic substitutiontoward electrophilic aromatic substitution
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HalogenationHalogenation
NitrationNitration
NitrosationNitrosation
SulfonationSulfonation
Friedel-Crafts AlkylationFriedel-Crafts Alkylation
Friedel-Crafts AcylationFriedel-Crafts Acylation
Electrophilic Aromatic Substitution in PhenolsElectrophilic Aromatic Substitution in Phenols
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HalogenationHalogenation
monohalogenation in nonpolar solventmonohalogenation in nonpolar solvent(1,2-dichloroethane)(1,2-dichloroethane)
++ BrBr22
ClCHClCH22CHCH22ClCl
0°C0°C
OOHH OOHH
BrBr
(93%)(93%)
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HalogenationHalogenation
multiple halogenation in polar solventmultiple halogenation in polar solvent(water)(water)
++ 3Br3Br22
HH22OO
25°C25°C
OOHH
FF
OOHH
BrBr
BrBrBrBr
FF
(95%)(95%)
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HalogenationHalogenation
NitrationNitration
NitrosationNitrosation
SulfonationSulfonation
Friedel-Crafts AlkylationFriedel-Crafts Alkylation
Friedel-Crafts AcylationFriedel-Crafts Acylation
Electrophilic Aromatic Substitution in PhenolsElectrophilic Aromatic Substitution in Phenols
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NitrationNitration
HNOHNO33
acetic acidacetic acid5°C5°C
(73-77%)(73-77%)OH group controls OH group controls regiochemistryregiochemistry
OOHH
CHCH33
OOHH
CHCH33
NNOO22
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HalogenationHalogenation
NitrationNitration
NitrosationNitrosation
SulfonationSulfonation
Friedel-Crafts AlkylationFriedel-Crafts Alkylation
Friedel-Crafts AcylationFriedel-Crafts Acylation
Electrophilic Aromatic Substitution in PhenolsElectrophilic Aromatic Substitution in Phenols
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NitrosationNitrosation
NaNONaNO22
HH22SOSO44, H, H22OO
0°C0°C
OOHH
NNOO
(99%)(99%)only strongly activated only strongly activated rings undergo nitrosation rings undergo nitrosation when treated with nitrous when treated with nitrous acidacid
OOHH
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HalogenationHalogenation
NitrationNitration
NitrosationNitrosation
SulfonationSulfonation
Friedel-Crafts AlkylationFriedel-Crafts Alkylation
Friedel-Crafts AcylationFriedel-Crafts Acylation
Electrophilic Aromatic Substitution in PhenolsElectrophilic Aromatic Substitution in Phenols
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OOHH
CHCH33HH33CC
SOSO33HH
(69%)(69%)
HH22SOSO44
100°C100°C
SulfonationSulfonation
OOHH
CHCH33HH33CC
OH group controls OH group controls regiochemistryregiochemistry
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HalogenationHalogenation
NitrationNitration
NitrosationNitrosation
SulfonationSulfonation
Friedel-Crafts AlkylationFriedel-Crafts Alkylation
Friedel-Crafts AcylationFriedel-Crafts Acylation
Electrophilic Aromatic Substitution in PhenolsElectrophilic Aromatic Substitution in Phenols
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Friedel-Crafts AlkylationFriedel-Crafts Alkylation
(63%)(63%)
(CH(CH33))33COH reacts COH reacts
with Hwith H33POPO44 to give to give
(CH(CH33))33CC++
OOHH
CC
CHCH33
CHCH33HH33CC
CHCH33
HH33POPO44
60°C60°C
(CH(CH33))33COHCOH
OOHH
CHCH33
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HalogenationHalogenation
NitrationNitration
NitrosationNitrosation
SulfonationSulfonation
Friedel-Crafts AlkylationFriedel-Crafts Alkylation
Friedel-Crafts AcylationFriedel-Crafts Acylation
Electrophilic Aromatic Substitution in PhenolsElectrophilic Aromatic Substitution in Phenols
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24.924.9
Acylation of PhenolsAcylation of Phenols
Acylation can take place either on the ringAcylation can take place either on the ringby electrophilic aromatic substitution or onby electrophilic aromatic substitution or onoxygen by nucleophilic acyl substitutionoxygen by nucleophilic acyl substitution
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Friedel-Crafts AcylationFriedel-Crafts Acylation
AlClAlCl33
OOHH
(74%)(74%)
CHCH33CClCCl
OO OOHH
CCOO CHCH33
++ ortho isomerortho isomer
(16%)(16%)
under Friedel-Crafts under Friedel-Crafts conditions, acylation conditions, acylation of the ring occursof the ring occurs(C-acylation)(C-acylation)
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O-AcylationO-Acylation
(95%)(95%)
in the absence of AlClin the absence of AlCl33, acylation of the , acylation of the
hydroxyl group occurs (O-acylation)hydroxyl group occurs (O-acylation)
OOHH
CHCH33(CH(CH22))66CClCCl
OO
++
OOC(CHC(CH22))66CHCH33
OO
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O- versus C-AcylationO- versus C-Acylation
OOC(CHC(CH22))66CHCH33
OO OOHH
CCOO CHCH33
AlClAlCl33
formed fasterformed faster more stablemore stableO-Acylation is kinetically controlled process; C-acylation O-Acylation is kinetically controlled process; C-acylation is thermodynamically controlledis thermodynamically controlled
AlClAlCl3 3 catalyzes the conversion of the aryl ester to the catalyzes the conversion of the aryl ester to the
aryl alkyl ketones; this is called the Fries rearrangementaryl alkyl ketones; this is called the Fries rearrangement
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24.1024.10
Carboxylation of PhenolsCarboxylation of Phenols
Aspirin and Aspirin and the the
Kolbe-Schmitt Kolbe-Schmitt ReactionReaction COHCOH
OO
OCCHOCCH33
OO
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how is salicylic acid prepared?how is salicylic acid prepared?
Aspirin is prepared from salicylic acidAspirin is prepared from salicylic acid
COHCOH
OO
OOCCHCCH33
OO
HH22SOSO44
COHCOH
OO
OOHHOO
CHCH33COCCHCOCCH33
OO
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called the Kolbe-Schmitt reactioncalled the Kolbe-Schmitt reaction
acidification converts the sodium salt shownacidification converts the sodium salt shownabove to salicylic acidabove to salicylic acid
Preparation of Salicylic AcidPreparation of Salicylic Acid
COCO22
125°C, 100 atm125°C, 100 atm
CONaCONa
OO
OHOHONaONa
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acid-base considerations provide an explanation:acid-base considerations provide an explanation:stronger base on left; weaker base on rightstronger base on left; weaker base on right
What Drives the Reaction?What Drives the Reaction?
++ COCO22
OO ––
•••••••• ••••
stronger base:stronger base:ppKKaa of conjugate of conjugate acid = 10acid = 10
weaker base:weaker base:ppKKaa of conjugate of conjugate acid = 3acid = 3
OO
––
•••••••• ••••CC
OO
OO
••••
••••HH
•••• ••••
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how does carbon-carbon bond form?how does carbon-carbon bond form?
recall electron delocalization in phenoxide ionrecall electron delocalization in phenoxide ion
negative charge shared by oxygen and by thenegative charge shared by oxygen and by thering carbons that are ortho and para to oxygenring carbons that are ortho and para to oxygen
Preparation of Salicylic AcidPreparation of Salicylic Acid
COCO22
125°C, 100 atm125°C, 100 atm
CONaCONa
OO
OHOHONaONa
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•••• OO••••
HH
HH
HH
HH
HH
••••––
•••• OO
••••
HH
HH
HH
HH
HH
––••••
•••• OO••••
HH
HH
HH
HH
HH––••••
•••• OO••••
HH
HH
HH
HH
HH
––••••
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OO
CC
Mechanism of ortho CarboxylationMechanism of ortho Carboxylation
••••
••••
••••
••••
OO
OO
HH
•••• ••••••••
––
OO•••• ••••
HH
––
•••••••• ••••
CCOO
OO•••• ••••
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OO
CC
Mechanism of ortho CarboxylationMechanism of ortho Carboxylation
••••
•••• OO
••••
••••
OO
HH
•••• ••••••••
––
OO•••• ••••
HH
––
•••••••• ••••
CCOO
OO•••• ••••
OO
––
•••••••• ••••CC
OO
OO
••••
••••HH
•••• ••••
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Why ortho?Why ortho?
Why not para? Why not para? OO•••• ••••••••
––
OO
––
•••••••• ••••CC
OO
OO
••••
••••HH
•••• ••••
OO••••
••••HH
CC
•••• ••••OO
OO••••••••••••––
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weaker base:weaker base:ppKKaa of conjugate acid = 3 of conjugate acid = 3
Why ortho?Why ortho?
Why not para? Why not para? OO•••• ••••••••
––
OO
––
•••••••• ••••CC
OO
OO
••••
••••HH
•••• ••••
stronger base:stronger base:ppKKaa of conjugate acid = 4.5 of conjugate acid = 4.5
OO••••
••••HH
CC
•••• ••••OO
OO••••••••••••––
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Hydrogen bonding between carboxylate and hydroxylHydrogen bonding between carboxylate and hydroxylgroup stabilizes salicylate ion. Salicylate is less basic group stabilizes salicylate ion. Salicylate is less basic than para isomer and predominates under conditionsthan para isomer and predominates under conditionsof thermodynamic control.of thermodynamic control.
Intramolecular Hydrogen BondingIntramolecular Hydrogen Bonding
in Salicylate Ionin Salicylate Ion
OO
OO
CC OO ––
HH