Aldehydes and Ketones Nomenclature Properties Preparation reactions of Aldehydes and Ketones ...
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Transcript of Aldehydes and Ketones Nomenclature Properties Preparation reactions of Aldehydes and Ketones ...
Aldehydes and Aldehydes and KetonesKetones
NomenclatureNomenclature PropertiesProperties Preparation reactions of Aldehydes and Preparation reactions of Aldehydes and
KetonesKetones Characteristic reactions of Aldehydes and Characteristic reactions of Aldehydes and
KetonesKetones Carbanion related reactionsCarbanion related reactions Spectroscopy Spectroscopy
Aldehydes and Aldehydes and KetonesKetones
NomenclatureNomenclature IUPACIUPAC CommonCommon
PropertiesProperties
Preparation of Preparation of Aldehydes and Aldehydes and
KetonesKetones Oxidation reactionsOxidation reactions Hydrolysis of Geminal DihalidesHydrolysis of Geminal Dihalides Hydration of AlkynesHydration of Alkynes Reactions with Acid Derivatives and Reactions with Acid Derivatives and
NitrilesNitriles Reaction with Carboxylic AcidsReaction with Carboxylic Acids Reaction with ThioacetalsReaction with Thioacetals
Aldehydes/Ketones via Aldehydes/Ketones via Oxidation ReactionsOxidation Reactions
From Alcohols via PCCFrom Alcohols via PCC From Alkenes via OzonolysisFrom Alkenes via Ozonolysis From Glycols via Periodic Acid CleavageFrom Glycols via Periodic Acid Cleavage
RCH2OHPCC
R C
O
H
R2CHOH PCC R C
O
R
ozonolysis R C
O
HR'CH CR2' +R C
O
R
R C
OH
CH2OH
R'
HIO4R C
O
R' +H C
O
H
Hydrolysis of Geminal Dihalides
Formation of Aldehydes or KetonesFormation of Aldehydes or Ketones
Cl2H2O
∆+ HCl2CHR C
O
HR
R2CCl2H2O
∆+ HCl2C
O
R R
Hydration of Hydration of AlkynesAlkynes
Markovnikov Addition Anti-Markovnikov Addition
R C CHH2O/H 2SO4
HgSO4R C
OH
CH2 R C
O
CH3
R C CH RCH CH
OH
R CH2 C
O
H1.
2.H2O2/OH -9-BBN
Reactions with Acid HalidesReactions with Acid Halides
Aldehydes via Selective ReductionAldehydes via Selective Reduction Lithium tri-tert-butoxyaluminum hydrideLithium tri-tert-butoxyaluminum hydride Rosenmund reduction Rosenmund reduction
Ketones via Friedel-Crafts AcylationKetones via Friedel-Crafts Acylation Ketones via reaction with OrganometallicsKetones via reaction with Organometallics
Gilman reagent (organocuprates)Gilman reagent (organocuprates)
Aldehydes from Acid Aldehydes from Acid ChloridesChlorides
Lithium tri-t-butoxyaluminum hydride reduction
Rosenmund reduction
R C
O
Clether
R C
O
H
R C
O
Cl R C
O
HH2 / Pd / S
BaSO4Rosenmund catalyst
LiAlH(O-t-bu)3
Aldehydes from Esters and Aldehydes from Esters and AmidesAmides
Diisobutylaluminum hydrideDiisobutylaluminum hydride
(DIBAH or DIBAL-H)(DIBAH or DIBAL-H)
R C
O
OR'or
R C
O
NH2
R C
O
NHR'
R C
O
NR2'
or
or1.Diisobutylaluminum
hydride
2. H3O+
R C
O
H
Ketones via Friedel-Crafts Acylation
R C
O
ClAlCl3
benzene C
O
R +HCl
R C
O
O C
O
RAlCl3
benzene C
O
R +RCOOH
Ketones via Reaction Ketones via Reaction with Organometallicswith Organometallics
Use of Lithium dialkylcuprates
R C
O
Cl(R')2CuLi
R C
O
R' + +LiCl
where R' can be alkyl, aryl, or vinyl
R'-Cu
Reactions with Nitriles
Grignard Addition to give KetonesGrignard Addition to give Ketones DIBAH Addition to give AldehydesDIBAH Addition to give Aldehydes
R CNR'MgX
R C
R'
N MgXH+
H2OR C
O
R'
R CNdiisobutylaluminum hydride
R C
H
N Al(i-bu)2
H+/H 2OR C
O
H
DIBAH or DIBAL-H
Ketones from Carboxylic Ketones from Carboxylic AcidsAcids
Attack by Alkyl Lithium reagentsAttack by Alkyl Lithium reagents
RCOOH RLi RCOO- Li+ + RH
RCOO- Li+ RLi CR
R
O-
O-
Li+
Li+
CR
R
O-
O-
Li+
Li+H2O C
R
R
OH
OH
CR
R
OH
OH
H2O( )C
O
RR
Ketones from Ketones from ThioacetalsThioacetals Thioacetal formation from an aldehyde precursor
Alkylation of the thioacetal intermediate using alkyl lithium reagents
Hydrolysis of the alkylated thioacetal to give ketone product
R C
O
HHSCH2CH2SH
BF3
S SC
R H
(a thioacetal)
S SC
R H
C4H9Li S SC
RLi+
R'CH2XS S
CR CH2R'
+ LiX
S SC
R CH2R'
HgCl2 / CH3OH / H2OR C
O
CH2R'
( C4H10)
( )HSCH2CH2SH
Characteristic Reactions of Aldehydes and Ketones
Characteristic Reactions of Aldehydes and Ketones
Reduction reactionsReduction reactions Alcohol formationAlcohol formation Alkane formationAlkane formation
Oxidation reactionsOxidation reactions Nucleophilic addition reactionsNucleophilic addition reactions
Grignard additions to form alcoholsGrignard additions to form alcohols Addition of water (hydration) to form gem-diolsAddition of water (hydration) to form gem-diols Addition of alcohols to form acetals/ketalsAddition of alcohols to form acetals/ketals Addition of HCN to form cyanohydrinsAddition of HCN to form cyanohydrins Addition of ammonia and ammonia derivativesAddition of ammonia and ammonia derivatives
Reduction Reactions of Reduction Reactions of Aldehydes and KetonesAldehydes and Ketones
Alcohol formationAlcohol formation HydrogenationHydrogenation Hydride reductionHydride reduction
Alkane formationAlkane formation Clemmensen reductionClemmensen reduction Wolff-Kishner reductionWolff-Kishner reduction
R C
O
HH2 / Pt
R CH2OH
R C
O
H R CH2OHLiAlH4
etherH2O
H+
R C
O
H R CH3conc. HClZn(Hg)
R C
O
H R CH3
NH2NH2
OH- / H2O
Oxidation of Oxidation of Aldehydes and Aldehydes and
KetonesKetones Conversion of Aldehydes to Carboxylic acidsConversion of Aldehydes to Carboxylic acids Oxidation of Aromatic Aldehydes/Ketones to Oxidation of Aromatic Aldehydes/Ketones to
Benzoic acid derivativesBenzoic acid derivatives Haloform reaction of methyl carbonylsHaloform reaction of methyl carbonyls Periodic acid cleavage of vicinal dials/diketonesPeriodic acid cleavage of vicinal dials/diketones
Aldehyde / Ketone Aldehyde / Ketone OxidationsOxidations
HIO4C
O
C
O
HR RCOOH + HCOOH +HIO3
R C
O
H RCOOHAg(NH3)2
+
(Tollens reagent)
C
O
H
or
C
O
R
COOHKMnO4 or K2Cr2O7
∆
CH3 C
O
RX2
OH- / H2OHCX3 + RCOO-
Ar C
O
Hor (ArCOOH)
Aldehyde / Ketone Nucleophilic Aldehyde / Ketone Nucleophilic Addition ReactionsAddition Reactions
R C R'
OR"MgX
H+
H2OR C
OH
R'
R"
R C R'
O
R C R'
O
R C R'
O
H2OC
R
R'
OH
OH
dry HClR''OH
CR
R'
OH
OR"C
R
R'
OR"
OR"
hemiketal ketal
H+ or OH-
gem diol
HCN CR
R'
OH
CNcyanohydrin
R C R'
OH2N G ( H2O)-
C N GR
R'
Carbanion Related ReactionsCarbanion Related Reactions Aldol CondensationAldol Condensation
Self vs. CrossedSelf vs. Crossed Claisen CondensationClaisen Condensation
Self vs. CrossedSelf vs. CrossedDieckmann cyclizationDieckmann cyclization
Reformatsky ReactionReformatsky Reaction Wittig ReactionWittig Reaction Carbanion Carbanion
Alkylations/Acylations/ConjugatAlkylations/Acylations/Conjugate Addition reactionse Addition reactions
Aldol Aldol CondensationsCondensations
Aldol Aldol CondensationsCondensations
Self CondensationSelf Condensation Crossed CondensationCrossed Condensation
RCH2 C
O
H2OH- or H+
RCH2 C
H
OH
CH
R
C
O
H
RCH2 C
O
H +R' C
O
HOH- or H+
R' C
OH
H
CH
R
C
O
H
Claisen CondensationsClaisen Condensations Self vs. Crossed CondensationSelf vs. Crossed Condensation Dieckmann CondensationDieckmann Condensation
R'O-
R'OH2RCH2 OR'
O
C RCH2
O
C CH C
O
OR'
R
RCH2 OR'
O
C +R" C
O
OR' R'O-
R'OHO
C CH C
O
OR'
R
R"
+R'OH
+R'OH
R'O C
O
(CH2)4 C
O
OR' R'O-
R'OHO
C
O
OR' +R'OH
R'O C
O
(CH2)5 C
O
OR' R'O-
R'OH+R'OH
O
C
O
OR'
Reformatsky Reaction
Reformatsky Reaction
R C
O
R +Br CH2 C
O
OR'Zn benzene/1.
2.
R C
O
H +Br CH2 C
O
OR'Zn benzene/1.
2. OH
C OR'
O
CCH2
H
R
OH
C OR'
O
CCH2R
R
H3O+
H3O+
Wittig ReactionPhosphonium salt formationPhosphonium salt formation
Ylide formationYlide formation
Alkene formationAlkene formation
RCH2X+Ph3P Ph3P CH2R+
phosphonium salt
Ph3P CH2R+ NaH Ph3P CHR
+ -+NaX+H2
ylide
CHR
P
CR'
O
R'
Ph3+
-+
(R')2C CHR
O PPh3
C CHR'
RR' +Ph3P O
oxaphosphatane alkene+
triphenylphosphineoxide
SN2X
X
Carbanion Carbanion Alkylation/Acylation/Conjugate Alkylation/Acylation/Conjugate
Addition ReactionsAddition Reactions
Malonic Ester Synthesis Acetoacetic Ester Synthesis Stork Enamine Synthesis Michael Addition / Conjugate
Addition
Malonic Ester SynthesisMalonic Ester Synthesis
Formation of Formation of alkylatedalkylated acetic acid acetic acid derivativesderivatives
C2H5O CO
CH2 CO
OC2H5NaOC2H5
C2H5OHC2H5O C
OCH C
OOC2H5
Na+
C2H5O CO
CH CO
OC2H5
Na+RCH2X C2H5O C
OCHCH2R
CO
OC2H5
C2H5O CO
CHCH2R
CO
OC2H5
H+/H 2O CO
OHCO
CHCH2R
HO
CO
OHCO
CHCH2R
HOstrong heat + CO2CH2COOHRCH2
Malonic Ester Synthesis Acylation/Hydrolysis/Decarboxylation
C2H5O C
O
CH2 C OC2H5
O
NaOC2H5
C2H5OHC2H5O C
O
CH C OC2H5
O
Na+
C2H5O C
O
CH C OC2H5
O
Na+
R CO
X C2H5O C
O
CH
COR
(-NaX)C OC2H5
O
C2H5O C
O
CH
COR
C OC2H5
O
H+/H 2O C
O
OHC
O
CH
COR
HO
C
O
OHC
O
CH
COR
HO strong heat R C
O
CH3 +2CO2
Acetoacetic Ester SynthesisAcetoacetic Ester SynthesisFormation of Formation of alkylated alkylated acetoneacetone derivativesderivatives
CH3 C
O
CH2 C
O
OC2H5NaOC2H5
C2H5OHCH3 C
O
CH C
O
OC2H5
Na+
CH3 C
O
CH C
O
OC2H5
Na+
RCH2X
(-NaX)CH3 C
O
CH
CH2R
C
O
OC2H5
CH3 C
O
CH
CH2R
C
O
OC2H5
H+/H 2O CH3 C
O
CH
CH2R
C
O
OH
CH3 C
O
CH
CH2R
C
O
OHstrong heat
CH3 C
O
CH2 CH2RCO2(- )
Acetoacetic Ester SynthesisFormation of Formation of acylated acylated acetoneacetone derivativesderivatives
CH3 C
O
CH2 C
O
OC2H5NaOC2H5
C2H5OHCH3 C
O
CH C
O
OC2H5
Na+
CH3 C
O
CH C
O
OC2H5
Na+
(-NaX)CH3 C
O
CHC
RO
C
O
OC2H5
H+/H 2O
strong heatCH3 C
O
CH2 C
O
RCO2(- )
R CO
X
CH3 C
O
CHC
RO
C
O
OC2H5 CH3 C
O
CHC
RO
C
O
OH
CH3 C
O
CHC
RO
C
O
OH
Stork Enamine SynthesisStork Enamine SynthesisFormation of Formation of AlkylatedAlkylated Aldehydes/Ketones Aldehydes/Ketones
R' C C
O
H
H
+R2NH R' C C H
OH
NHR2
H
aminolan
(-H2O)
( )
R' C C H
NR2
H
H+( )
R' C C H
NR2
(an enamine)
R' C C H
NR2
(a disguised carbanion)
R' C C H
NR2
R"CH2X
S N2R' C C H
NR2
CH2R"
R' C C H
NR2
CH2R"hydrolysis R' C C H
CH2R"
O
+R2NH
+
+
+
+ +
+
Stork Enamine SynthesisStork Enamine SynthesisFormation of Formation of AcylatedAcylated Aldehydes/KetonesAldehydes/Ketones
R' C C
O
H
H
+R2NH R' C C H
OH
NHR2
H
aminolan
(-H2O)
+
( )
R' C C H
NR2
H
H+( )
R' C C H
NR2
(an enamine)
R' C C H
NR2
(a disguised carbanion)
R' C C H
NR2
R' C C H
NR2
CO
R"
hydrolysis R' C C H
O
CO
R"
+R2NH
R" C
O
X
R' C C H
NR2
CO
R"
+
+
+ +
+
Conjugate Addition to Conjugate Addition to Unsaturated Unsaturated
SystemsSystems
Nu C C C
O
+ CNu C C
O
CNu C C
OH+
CNu C C
O
H
where Nu = CN-1, NH3 , RNH2 , & R2NH
Michael AdditionMichael Addition Michael DonorsMichael Donors Michael AcceptorsMichael Acceptors
Michael Product
C C C
O
C
C
C
CH C
O
H2O
(Michael donor)
CH(COOR)2malonic ester
CH COORC
O
R'
-ketoester
CHC
O
R'
C
O
R'
-diketone
R2CuLi dialkyl cuprate
RCH CH C
O
H
,− unsaturated aldehyde
RCH CH C
O
R'
,− unsaturated ketone
RCH CH C
O
OR'
,− unsaturated ester
RCH CH C N,− unsaturated nitrile
RCH CH NO 2,− unsaturated nitroalkeneN C C
enamine
Michael AdditionMichael AdditionRobinson AnnulationRobinson Annulation
OC
CC
OMichael donor
C
CC
O
H3C
Michael acceptor
CC
CC
O
H3C
CO
CO
Michael product
OR-
ROH
OR- ROH
CC
CC
O
CO
CO
H2C
CC
CC
O
CO
C
H2C
HO
Aldol
CC
CC
O
CO
C
C H2O
Direct vs. Conjugate Addition to Direct vs. Conjugate Addition to Unsaturated Carbonyl SystemsUnsaturated Carbonyl Systems
C C C
O
+ Nu
H+
H+
C C C
OH
Nu
conjugate addition
C C C
OH
Nu
direct addition
Conjugate addition Direct addition
NH3, RNH2, & R2NH
CN-1
R SH
R2CuLi− carbanions
( )Michael addition
LiAlH 4
RLi or ArLi
RMgX)considerations
(subjecttosteric
Spectroscopy of Spectroscopy of Aldehydes and Aldehydes and
KetonesKetones Mass SpectrometryMass Spectrometry Infrared SpectroscopyInfrared Spectroscopy Pmr SpectroscopyPmr Spectroscopy Cmr SpectroscopyCmr Spectroscopy