chapter 18 enols and enolates
DESCRIPTION
Chapter 18 Enols and Enolates. 18.1 The a -Carbon Atom and its Hydrogens. O. CH 3 CH 2 CH 2 CH. Terminology. The reference atom is the carbonyl carbon. Other carbons are designated a , b , g , etc. on the basis of their position with respect to the carbonyl carbon. - PowerPoint PPT PresentationTRANSCRIPT
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Chapter 18Chapter 18Enols and EnolatesEnols and Enolates
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18.118.1
The The -Carbon Atom and its Hydrogens-Carbon Atom and its Hydrogens
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The reference atom is the carbonyl carbon.The reference atom is the carbonyl carbon.
Other carbons are designated Other carbons are designated , , , , , etc. on the , etc. on the
basis of their position with respect to the carbonyl basis of their position with respect to the carbonyl
carbon.carbon.
Hydrogens take the same Greek letter as the Hydrogens take the same Greek letter as the
carbon to which they are attached.carbon to which they are attached.
TerminologyTerminology
CHCH33CHCH22CHCH22CHCH
OO
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18.218.2
Halogenation of Halogenation of
Aldehydes and KetonesAldehydes and Ketones
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XX22 is Cl is Cl22, Br, Br22, or I, or I22..
Substitution is specific for replacement of Substitution is specific for replacement of
hydrogen.hydrogen.
Catalyzed by acids. One of the products is an acid Catalyzed by acids. One of the products is an acid
(HX); the reaction is (HX); the reaction is autocatalyticautocatalytic..
NotNot a free-radical reaction.a free-radical reaction.
General ReactionGeneral Reaction
OO
RR22CCR'CCR'
HH
++ XX22
OO
RR22CCR'CCR'
XX
++ HHXXHH++
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ExampleExample
HH22OO
(61-66%)(61-66%)
ClCl22++
OO
HClHCl
OO
ClCl++
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ExampleExample
CHClCHCl33
(80%)(80%)
BrBr22++ HHBrBr++
HH
CHCH
OO
BrBr
CHCH
OO
Notice that it is the proton on the Notice that it is the proton on the carbon carbon that is replaced, not the one on the carbonyl that is replaced, not the one on the carbonyl carbon.carbon.
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18.318.3
Mechanism of Mechanism of Halogenation of Halogenation of
Aldehydes and KetonesAldehydes and Ketones
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specific for replacement of H at the specific for replacement of H at the carbon carbon
equal rates for chlorination, bromination, and equal rates for chlorination, bromination, and
iodinationiodination
first order in ketone; zero order in halogenfirst order in ketone; zero order in halogen
Mechanism of Mechanism of Halogenation Halogenation
Experimental FactsExperimental Facts
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specific for replacement of H at the specific for replacement of H at the carbon carbon
equal rates for chlorination, bromination, and equal rates for chlorination, bromination, and
iodinationiodination
first order in ketone; zero order in halogenfirst order in ketone; zero order in halogen
Mechanism of Mechanism of Halogenation Halogenation
Experimental FactsExperimental Facts
InterpretationInterpretation
no involvement of halogen until after theno involvement of halogen until after therate-determining steprate-determining step
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first stage is conversion of aldehyde or first stage is conversion of aldehyde or
ketone to the corresponding enol; is rate-ketone to the corresponding enol; is rate-
determiningdetermining
second stage is reaction of enol with halogen; second stage is reaction of enol with halogen;
is faster than the first stageis faster than the first stage
Mechanism of Mechanism of Halogenation Halogenation
Two stages:Two stages:
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Mechanism of Mechanism of Halogenation Halogenation
RCHRCH22CR'CR'
OO
RCHRCH CR'CR'
OHOHslowslow XX22
fastfastRCHCR'RCHCR'
OO
XXenolenol
Enol is key intermediateEnol is key intermediate
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first stage is conversion of aldehyde or first stage is conversion of aldehyde or ketone to the corresponding enol; is rate-ketone to the corresponding enol; is rate-determiningdetermining
second stage is reaction of enol with halogen; second stage is reaction of enol with halogen; is faster than the first stageis faster than the first stage
Mechanism of Mechanism of Halogenation Halogenation
Two stages:Two stages:
examine second stage firstexamine second stage firstexamine second stage firstexamine second stage first
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Reaction of enol with BrReaction of enol with Br22
BrBr BrBr•••• ••••
••••••••••••••••
RR22CC CR'CR'
OHOH••••••••
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Reaction of enol with BrReaction of enol with Br22
BrBr BrBr•••• ••••
••••••••••••••••
BrBr••••
••••••••
RR22CC CR'CR'
OHOH••••••••
++
carbocation is stabilized by electron release carbocation is stabilized by electron release from oxygenfrom oxygen
BrBr••••
•••••••• ••••
––
RR22CC CR'CR'
OHOH••••••••
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Reaction of enol with BrReaction of enol with Br22
BrBr BrBr•••• ••••
••••••••••••••••
BrBr••••
••••••••
RR22CC CR'CR'
OHOH••••••••
++
carbocation is stabilized by electron release carbocation is stabilized by electron release from oxygenfrom oxygen
BrBr••••
•••••••• ••••
––
RR22CC CR'CR'
OHOH••••••••
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Reaction of enol with BrReaction of enol with Br22
BrBr BrBr•••• ••••
••••••••••••••••
BrBr••••
••••••••
RR22CC CR'CR'
OHOH••••••••
++RR22CC CR'CR'
OHOH••••••••
••••
BrBr••••
••••••••
RR22CC CR'CR'
OHOH++
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Loss of proton from oxygen completes the processLoss of proton from oxygen completes the process
••••BrBr•••••••• ••••
––
OO••••
CR'CR'
BrBr••••
••••••••
RR22CC
••••
HH BrBr•••• ••••••••
HH••••
BrBr••••
••••••••
RR22CC CR'CR'
OO++
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18.418.4
Enolization and Enol Content Enolization and Enol Content
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first stage is conversion of aldehyde or first stage is conversion of aldehyde or ketone to the corresponding enol; is rate-ketone to the corresponding enol; is rate-determiningdetermining
second stage is reaction of enol with halogen; second stage is reaction of enol with halogen; is faster than the first stageis faster than the first stage
Mechanism of Mechanism of Halogenation Halogenation
Two stages:Two stages:
now examine first stagenow examine first stagenow examine first stagenow examine first stage
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Mechanism of EnolizationMechanism of Enolization(In general)(In general)
OO••••
CR'CR'
••••
RR22CC
HHOOHH
HH
••••••••
OO
HH
HH ••••••••
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Mechanism of EnolizationMechanism of Enolization(In general)(In general)
OO••••
CR'CR'
••••
RR22CC
HH
RR22CC CR'CR'
OO••••
•••• HH
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Mechanism of EnolizationMechanism of Enolization(Acid-catalyzed)(Acid-catalyzed)
OO
HH
HH ••••
HHRR22CC
HH
OO••••
CR'CR'
••••++
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Mechanism of EnolizationMechanism of Enolization(Acid-catalyzed)(Acid-catalyzed)
OO••••
RR22CC CR'CR'
••••
HH
OO
HH
HH ••••
HH
++
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Mechanism of EnolizationMechanism of Enolization(Acid-catalyzed)(Acid-catalyzed)
OO••••
RR22CC CR'CR'
HH
HH++
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Mechanism of EnolizationMechanism of Enolization(Acid-catalyzed)(Acid-catalyzed)
OO••••
RR22CC CR'CR'
HH
HH++
OOHH
HH
••••••••
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Mechanism of EnolizationMechanism of Enolization(Acid-catalyzed)(Acid-catalyzed)
HHOOHH
HH
••••++
OO••••
RR22CC CR'CR'
HH••••
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percent enol is usually very smallpercent enol is usually very small
keto form usually 45-60 kJ/mol more stableketo form usually 45-60 kJ/mol more stablethan enolthan enol
Enol ContentEnol Content
RR22CHCR'CHCR'
OO
RR22CC CR'CR'
OHOH
enolenolketoketo
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Enol ContentEnol Content
CHCH33CHCH
OO
HH22CC CHCH
OHOH
KK = 3 x 10 = 3 x 10-7-7
CHCH33CCHCCH33
OO
HH22CC CCHCCH33
OHOH
KK = 6 x 10 = 6 x 10-9-9
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18.518.5
Stabilized Enols Stabilized Enols
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2,4-Cyclohexadienone2,4-Cyclohexadienone
OO
HH
HH
HH
HH
HH
HH
OHOH
HH
HH HH
HH
HH
keto form is less stable than enol formketo form is less stable than enol form
keto form is not aromaticketo form is not aromatic
enol form is aromaticenol form is aromatic
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1,3-Diketones1,3-Diketones(also called (also called -diketones)-diketones)
keto form is less stable than enol formketo form is less stable than enol form
CHCH33CCHCCH22CCHCCH33
OO OO
CHCH33CC
OHOH
CHCCHCHCCH33
OO
(20%)(20%) (80%)(80%)
Example: 2,4-pentanedioneExample: 2,4-pentanedione
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Enol form of 2,4-pentanedioneEnol form of 2,4-pentanedione
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Enol form of 2,4-pentanedioneEnol form of 2,4-pentanedione
103 pm103 pm
133 pm133 pm
134 pm134 pm 141 pm141 pm
124 pm124 pm
166 pm166 pm
HH33CCCC
CCCC
CHCH33
HHOO OO
HH
C=C and C=O are C=C and C=O are conjugatedconjugated
intramolecular hydrogen bondintramolecular hydrogen bond