Download - Chapter 17 Aldehydes and Ketones
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Chapter 17Chapter 17Aldehydes and KetonesAldehydes and Ketones
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17.117.1NomenclatureNomenclature
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4,4-dimethylpent4,4-dimethylpentanalanal 5-hex5-hexenalenal
Nomenclature of AldehydesNomenclature of Aldehydes
HH
OO
OO
HH
OO
HCCHCHHCCHCH
OO
2-phenylprop2-phenylpropanedialanedial
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when named when named as a suffixas a suffix
when named as when named as a substituenta substituent
formyl groupformyl group carbaldehydecarbaldehydecarboxaldehydecarboxaldehyde
CC HH
OO
Nomenclature of Aldehydes Nomenclature of Aldehydes
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Substitutive Nomenclature of KetonesSubstitutive Nomenclature of Ketones
CHCH33CHCH22CCHCCH22CHCH22CHCH33
OO
CHCH33CHCHCHCH22CCHCCH33
OO
CHCH33
3-hexanone3-hexanone 4-methyl-2-pentanone4-methyl-2-pentanone
HH33CC OO 4-methylcyclohexanone4-methylcyclohexanone
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Functional Class Nomenclature of KetonesFunctional Class Nomenclature of Ketones
CHCH33CHCH22CCCHCH22CHCH22CHCH33
OO
ethylethyl propylpropyl ketone ketone benzylbenzyl ethylethyl ketone ketone
divinyl ketonedivinyl ketone
OO
CHCH22CCCHCH22CHCH33
CHCH CHCH22
OO
HH22CC CHCCHC
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17.217.2Structure and Bonding:Structure and Bonding:
The Carbonyl GroupThe Carbonyl Group
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planarplanar
bond angles: close to 120°bond angles: close to 120°
C=O bond distance: 122 pmC=O bond distance: 122 pm
Structure of FormaldehydeStructure of Formaldehyde
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1-butene1-butene
very polar double bondvery polar double bond
propanalpropanal
dipole moment = 0.3Ddipole moment = 0.3D dipole moment = 2.5Ddipole moment = 2.5D
The Carbonyl GroupThe Carbonyl Group
OO
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2475 kJ/mol2475 kJ/mol
2442 kJ/mol2442 kJ/mol
Alkyl groups stabilize carbonyl groups the sameAlkyl groups stabilize carbonyl groups the sameway they stabilize carbon-carbon double bonds,way they stabilize carbon-carbon double bonds,carbocations, and free radicals.carbocations, and free radicals.
heat of combustionheat of combustion
Carbonyl group of a ketone is moreCarbonyl group of a ketone is morestable than that of an aldehydestable than that of an aldehyde
OO
OO
HH
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Heats of combustion Heats of combustion ofof
CC44HH88 isomeric alkenes isomeric alkenes
CHCH33CHCH22CH=CHCH=CH22
2717 kJ/mol2717 kJ/mol
ciscis-CH-CH33CH=CHCHCH=CHCH33
2710 kJ/mol2710 kJ/mol
transtrans-CH-CH33CH=CHCHCH=CHCH33
2707 kJ/mol2707 kJ/mol
(CH(CH33))22C=CHC=CH22
2700 kJ/mol2700 kJ/mol
2475 kJ/mol2475 kJ/mol
2442 kJ/mol2442 kJ/mol
OO
OO
HH
Spread is greater forSpread is greater foraldehydes andaldehydes and
ketones than for alkenesketones than for alkenes
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nucleophiles attack carbon; nucleophiles attack carbon; electrophiles attack oxygenelectrophiles attack oxygen
Resonance Description ofResonance Description ofCarbonyl GroupCarbonyl Group
CC
OO •••• ••••
CC
OO
++
––•••••••• ••••
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Carbon and oxygen are Carbon and oxygen are spsp22 hybridized hybridized
Bonding in FormaldehydeBonding in Formaldehyde
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The half-filledThe half-filledpp orbitals on orbitals oncarbon andcarbon andoxygen overlapoxygen overlapto form a to form a bond bond
Bonding in FormaldehydeBonding in Formaldehyde
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17.317.3Physical PropertiesPhysical Properties
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boiling pointboiling point
––6°C6°C
49°C49°C
97°C97°C
Aldehydes and ketones have higher boilingAldehydes and ketones have higher boilingthan alkenes, but lower boiling points than alcohols. than alkenes, but lower boiling points than alcohols.
More polar than alkenes, More polar than alkenes, but cannot form but cannot form intermolecular hydrogen intermolecular hydrogen bonds to other carbonyl bonds to other carbonyl groupsgroups
OO
OHOH
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17.417.4Sources of Aldehydes and KetonesSources of Aldehydes and Ketones
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2-heptanone2-heptanone(component of alarm pheromone of bees)(component of alarm pheromone of bees)
OO
Many aldehydes and ketones occur naturallyMany aldehydes and ketones occur naturally
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transtrans-2-hexenal -2-hexenal (alarm pheromone of myrmicine ant)(alarm pheromone of myrmicine ant)
Many aldehydes and ketones occur naturallyMany aldehydes and ketones occur naturally
OO
HH
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citral (from lemon grass oil)citral (from lemon grass oil)
Many aldehydes and ketones occur naturallyMany aldehydes and ketones occur naturally
OO
HH
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from alkenesfrom alkenes
ozonolysisozonolysis
from alkynesfrom alkynes
hydration (via enol)hydration (via enol)
from arenesfrom arenes
Friedel-Crafts acylationFriedel-Crafts acylation
from alcoholsfrom alcohols
oxidationoxidation
Synthesis of Aldehydes and KetonesSynthesis of Aldehydes and Ketones
A number of A number of reactions alreadyreactions alreadystudied providestudied provide
efficient syntheticefficient syntheticroutes to routes to
aldehydes and aldehydes and ketones.ketones.
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CC
OO
RR OHOH
aldehydes from carboxylic acidsaldehydes from carboxylic acids
HHCC
OO
RR
What about..?What about..?
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CC
OO
RR OHOH
aldehydes from carboxylic acidsaldehydes from carboxylic acids
RCHRCH22OHOH
1. LiAlH1. LiAlH44
2. H2. H22OOPDC, CHPDC, CH22ClCl22
HHCC
OO
RR
What about..?What about..?
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benzaldehyde from benzoic acidbenzaldehyde from benzoic acid
1. LiAlH1. LiAlH44
2. H2. H22OOPDCPDCCHCH22ClCl22
COHCOH
OO
CHCH
OO
CHCH22OHOH
(81%)(81%) (83%)(83%)
ExampleExample
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CC
OO
RR HH
ketones from aldehydesketones from aldehydes
R'R'CC
OO
RR
What about..?What about..?
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CC
OO
RR HH
ketones from aldehydesketones from aldehydes
PDC, CHPDC, CH22ClCl22
R'R'CC
OO
RR
1. 1. R'MgXR'MgX
2. H2. H33OO++
RCHRCHR'R'
OHOH
What about..?What about..?
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CC
OO
CHCH33CHCH22 HH
3-heptanone from propanal3-heptanone from propanal
HH22CrOCrO44
1. 1. CHCH33(CH(CH22))33MgXMgX
2. H2. H33OO++
CHCH33CHCH22CHCH(CH(CH22))3 3 CHCH33
OHOH
OO
CHCH33CHCH22CC(CH(CH22))3 3 CHCH33
(57%)(57%)
ExampleExample