carboxylic acids and their derivatives - جامعة...
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Carboxylic acids and TheirDerivatives
Carboxylic acids and TheirDerivatives
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Diacids
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Physical Properties of carboxylic acids
Hydrogen bondingSolubility in water(lower acids)
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Acidity of carboxylic acids
pKa = -log Ka
As Ka increase or pKa decrease, the acidity increase١٣
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Resonance and Inductive effect
Conversion of acids to salts
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Preparation of carboxylic acids
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From Alkenes• Oxidative cleavage of an alkene with KMnO4 gives a
carboxylic acid if the alkene has at least one vinylichydrogen (see Section 7.8)
Based on McMurry, OrganicChemistry, Chapter 20, 6th
edition, (c) 2003
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20.6 Preparation of Carboxylic Acids
• Oxidation of a substituted alkylbenzene with KMnO4or Na2Cr2O7 gives a substituted benzoic acid (seeSection 16.10)
• 1° and 2° alkyl groups can be oxidized, but tertiarygroups are not
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Carboxylation of GrignardReagents
• Grignard reagents react with dry CO2 to yield a metalcarboxylate
• Limited to alkyl halides that can form Grignardreagents (see 17.6)
Based on McMurry, OrganicChemistry, Chapter 20, 6th
edition, (c) 2003
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Mechanism of GrignardCarboxylation
• The organomagnesium halide adds to C=O of carbondioxide
• Protonation by addition of aqueous HCl in a separatestep gives the free carboxylic acid
Based on McMurry, OrganicChemistry, Chapter 20, 6th
edition, (c) 2003
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Hydrolysis of Nitriles• Hot acid or base yields carboxylic acids• Conversion of an alkyl halide to a nitrile (with cyanide
ion) followed by hydrolysis produces a carboxylic acidwith one more carbon (RBr RCN RCO2H)
• Best with primary halides because eliminationreactions occur with secondary or tertiary alkylhalides
Based on McMurry, OrganicChemistry, Chapter 20, 6th
edition, (c) 2003
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• Hot acid or base yields carboxylic acids• Conversion of an alkyl halide to a nitrile (with cyanide
ion) followed by hydrolysis produces a carboxylic acidwith one more carbon (RBr RCN RCO2H)
• Best with primary halides because eliminationreactions occur with secondary or tertiary alkylhalides
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From Alcohols• Oxidation of a primary alcohol or an aldehyde with
CrO3 in aqueous acid
Based on McMurry, OrganicChemistry, Chapter 20, 6th
edition, (c) 2003
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Reactions of carboxylic acids
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EstersNomenclature
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Examples
O
OMe H
OO
OPh
O
OEt
CH3 O
O
Cl
OEt
OH
CH3CH3 O
O
O
OMe H
OO
OPh
O
OEt
CH3 O
O
Cl
OEt
OH
CH3CH3 O
O
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Lactones (Cyclic Esters)
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Reactions of Esters with Grignard Reagent
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Formation of Amides (Ammonolysis of Esters)
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Reduction of EstersEsters can be reduced to primary alcohols
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The Cliasen Condensation
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Acid HalidesThey are prepared from the reaction of acids with thionyl chloride or
phosphorus halides
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Reactions of acid chloridesAcid chlorides react rapidly with most nucleophiles such as water,
alcohols and ammoniaAcyl halides have irritating odors. Benzoyl chlorid is a lachrymator(tear gas)
CH3 Cl
O
CH3 OH
O
CH3 OR
O
CH3 NH2
O
H2O
EtOH
NH3
+
+
+
HCl
HCl
HCl
CH3 Cl
O
CH3 OH
O
CH3 OR
O
CH3 NH2
O
H2O
EtOH
NH3
+
+
+
HCl
HCl
HCl
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Reaction with Grignard Reagent
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Preparation of mixed anhydrides
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• Mixed anhydridesCH3 O
OO
Ph
Acetic benzoic anhydride٤٣
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Nucleophilic substitution of anhydrides
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Amides• Nomenclature
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• Properties of Amides
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Amide Resonance
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Reactions of Amides (Hydrolysis and Reduction)
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