Carboxylic Acids Carboxylic Acids Nomenclature Properties Preparation reactions Typical...
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Carboxylic Acids Carboxylic Acids Nomenclature Nomenclature Properties Properties Preparation Preparation reactions reactions Typical Typical reactions reactions Spectroscopy Spectroscopy
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Transcript of Carboxylic Acids Carboxylic Acids Nomenclature Properties Preparation reactions Typical...
Carboxylic AcidsCarboxylic Acids
NomenclatureNomenclature PropertiesProperties Preparation reactionsPreparation reactions Typical reactionsTypical reactions SpectroscopySpectroscopy
NomenclatureNomenclature
Carboxylic acidsCarboxylic acids»IUPACIUPAC
»CommonCommon
Acid derivativesAcid derivatives»IUPAC IUPAC
»CommonCommon
RCOOH Preparation Reactions RCOOH Preparation Reactions
Oxidation of Primary AlcoholsOxidation of Primary Alcohols Oxidation of AldehydesOxidation of Aldehydes Oxidation of Substituted AromaticsOxidation of Substituted Aromatics Carbonation of Grignard reagentsCarbonation of Grignard reagents Hydrolysis of Acid derivatives and NitrilesHydrolysis of Acid derivatives and Nitriles Haloform reactionHaloform reaction Periodic acid Cleavage of Vicinal Periodic acid Cleavage of Vicinal
Dials/DiketonesDials/Diketones Oxidative Cleavage of Alkenes/AlkynesOxidative Cleavage of Alkenes/Alkynes
Carboxylic Acids via OxidationCarboxylic Acids via Oxidation
From Primary AlcoholsFrom Primary Alcohols From AldehydesFrom Aldehydes From Substituted AromaticsFrom Substituted Aromatics
RCH2OH RCOOHKMnO4
orK2Cr2O7
∆
R C
O
H RCOOHKMnO4
orK2Cr2O7
∆
RKMnO4
orK2Cr2O7
∆
COOH
Carbonation of Grignard ReagentsCarbonation of Grignard Reagents
Rδ
Mg
X
C
O
O
δ+
R C
O
OMgX H +
H 2OR C
O
OH
Hydrolysis of Acid Hydrolysis of Acid Derivatives and NitrilesDerivatives and Nitriles
R C
O
G
where G = X, OR, NH2 , NHR, NR2 , & O C
O
R- - - - - -
H+
H2OR C
O
OH +HG
R C
O
G H2OR C
O
O-OH-+G-
RC NH2O
R C
O
NH2 R C
O
OH R C
O
O-( )H+ OH-or
Haloform ReactionHaloform Reaction
Cleavage of methyl carbinolsCleavage of methyl carbinols
Cleavage of methyl carbonylsCleavage of methyl carbonyls
C
H
OH
CH3 RX2
OH-/H 2ORCOO- +HCX3
X2
OH-/H 2ORCOO- +HCX3CH3 C
O
R
Periodic Acid Cleavage of Periodic Acid Cleavage of Vicinal Dials/DiketonesVicinal Dials/Diketones
H C
O
C
O
H HIO4HCOOH2 +HIO3
HIO4C
O
C
O
HR RCOOH+HCOOH +HIO3
HIO4C
O
C
O
R R' RCOOH+R'COOH+HIO3
Oxidative Cleavage Oxidative Cleavage ReactionsReactions
Alkene CleavageAlkene Cleavage Hot Potassium Permanganate Hot Potassium Permanganate
Alkyne CleavageAlkyne Cleavage Hot Potassium PermanganateHot Potassium Permanganate OzonolysisOzonolysis
Alkene CleavageAlkene Cleavage Hot Potassium Permanganate Hot Potassium Permanganate
Alkyne CleavageAlkyne Cleavage Hot Potassium PermanganateHot Potassium Permanganate OzonolysisOzonolysis
R CH CH R' RCOOH R'COOH+KMnO4
∆
R C C R' RCOOH R'COOH+
KMnO4∆
ozonolysisor
R CH CH R' RCOOH R'COOH+KMnO4
∆
R C C R' RCOOH R'COOH+
KMnO4∆
ozonolysisor
Typical RCOOH reactionsTypical RCOOH reactions
Conversion to carboxylate salts Conversion to acid halides Conversion to esters Conversion to amides Conversion to anhydrides Reduction to alcohols Decarboxylation
Carboxylates from Carboxylic Carboxylates from Carboxylic
AcidsAcids
Reaction with Active MetalsReaction with Active Metals Reaction with Strong BaseReaction with Strong Base Reaction with Weak BaseReaction with Weak Base
RCOOHNa
o RCOO- Na+ + 12H2
RCOOHNa
RCOO- Na+ +OH
H2O
RCOOH NaRCOO- Na+ +H2OHCO3
+CO2
Acid Chlorides from RCOOHAcid Chlorides from RCOOH
Reaction with Thionyl ChlorideReaction with Thionyl Chloride Reaction with Phosphorus TrichlorideReaction with Phosphorus Trichloride Reaction with Phosphorus PentachlorideReaction with Phosphorus Pentachloride
RCOOHSOCl2
R C
O
Cl SO2 HCl+ +
RCOOH +3 3 H3PO3PCl3R C
O
Cl
RCOOH R C
O
Cl +PCl5
POCl3 +HCl
Ester FormationEster Formation Ester FormationEster Formation From Carboxylic AcidsFrom Carboxylic Acids
with ROH via mineral acid catalysiswith ROH via mineral acid catalysis
via the use of diazomethanevia the use of diazomethane
From Acid ChloridesFrom Acid Chlorides From Acid AnhydridesFrom Acid Anhydrides
R C
O
ClR'OH
R C
O
OR'+
R C
O
OHR'OH
R C
O
OR'+H+
R C
O
O C
O
RR'OH
R C
O
OR'+R C OH
O
HCl
H2O
R C
O
OHCH2N2
R C
O
OCH2 H +N2
Amide FormationAmide Formation Direct Conversion of Acids to AmidesDirect Conversion of Acids to Amides From Acid Chlorides From Acid Chlorides From Acid AnhydridesFrom Acid Anhydrides From EstersFrom Esters
RCOOH NH3
∆RCOO- NH4
+
∆H2O( ) R C
O
NH2
R C
O
Cl +2NH3 R C
O
NH2 +NH4Cl
R C
O
O C
O
R+2NH3 R C
O
NH2 +
R C
O
OR' +NH3
C
O
RONH4+
R C
O
NH2 +R'OH
Acid Anhydride FormationAcid Anhydride Formation
Via Dehydration of Carboxylic AcidsVia Dehydration of Carboxylic Acids Via Reaction of RCOCl with RCOOHVia Reaction of RCOCl with RCOOH Via Reaction of RCOCl with RCOONaVia Reaction of RCOCl with RCOONa
R C
O
OH2H2O( )
∆R C
O
O C
O
R
R C
O
Cl+HO C
O
R' R C
O
O C
O
R +HCl
R C
O
Cl + R C
O
O C
O
R +C
O
R'O Cl
'
'
Formation of Cyclic AnhydridesFormation of Cyclic Anhydrides
Formation of 5-membered cyclic anhydrides:
Formation of 6-membered cyclic anhydrides:
C
O
C
CC
O
OH
OH strong heatO
O
O
C
O
OHC
Cstrong heat
C
O
OHC
O
O
O
+ H2O
+ H2O
Reduction of Reduction of Carboxylic AcidsCarboxylic Acids
Lithium Aluminum Hydride reductionLithium Aluminum Hydride reduction Diborane reductionDiborane reduction
RCOOHLiAlH4ether
H+
H2ORCH2OH
RCOOHB2H6
diglymeRCH2OH
(selective reduction ofcarboxyl group in preference to carbonylof aldehydes/ketones)
RCOOHLiAlH4ether
H+
H2ORCH2OH
RCOOHB2H6
diglymeRCH2OH
(selective reduction ofcarboxyl group in preference to carbonylof aldehydes/ketones)
Decarboxylation of RCOOHDecarboxylation of RCOOH
Thermolysis of beta-diacids Thermolysis of beta-keto acids
CCOOH
COOH
∆ CCOOH
H+ CO2
CCOOH
C
O
∆ CH
C
O
+ CO2
SpectroscopSpectroscopyy
InfraredInfrared
PmrPmr
CmrCmr
