chapter 20: carboxylic acid derivatives - nas all closely related and made from carboxylic acids...
TRANSCRIPT
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Chapter 20: Carboxylic Acid Derivatives - NASChapter 20: Carboxylic Acid Derivatives - NAS
• All closely related and made from carboxylic acids• most are interconvertable
Acid anhydrideAcyl (or acid) chlorideCarboxylic acid
Ester Carboxamide
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20.1 – Carboxylic Acid Derivative Nomenclature20.1 – Carboxylic Acid Derivative Nomenclature
Acyl Chlorides
Acid Anhydrides
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20.2 – Carboxylic Acid Derivatives - Structure20.2 – Carboxylic Acid Derivatives - Structure
Extended system – like carboxylic acids
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20.2 – Structure and Reactivity20.2 – Structure and Reactivity
Fig. 20.2
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20.2 – Structure and Reactivity20.2 – Structure and Reactivity
Resonance possibilities - acid chlorides and anhydrides
Acid chlorides and acid anhydrides are not stabilized significantly by resonance – quite reactive towards nucleophiles
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Resonance possibilities – esters, amides, carboxylates
Increasing delocalization leads to increasing stability and decreasing reactivity
20.2 – Structure and Reactivity20.2 – Structure and Reactivity
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20.3 – General Mechanism for Nucleophilic Acyl Substitution20.3 – General Mechanism for Nucleophilic Acyl Substitution
Tetrahedral intermediate
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20.4 – NAS Using Acid Chlorides20.4 – NAS Using Acid Chlorides
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Tetrahedral intermediate
20.4 – NAS Using Acid Chlorides, e.g. Amide Synthesis20.4 – NAS Using Acid Chlorides, e.g. Amide Synthesis
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20.5 – Acyl Substitution in Carboxylic Acid Anhydrides20.5 – Acyl Substitution in Carboxylic Acid Anhydrides
Maleic anhydride
Synthesis of anhydrides
Acetic anhydride
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20.5 – Acyl Substitution in Carboxylic Acid Anhydrides20.5 – Acyl Substitution in Carboxylic Acid Anhydrides
Lab experiment
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20.5 – Acyl Substitution in Carboxylic Acid Anhydrides20.5 – Acyl Substitution in Carboxylic Acid Anhydrides
Lab experiment
3720
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20.5 – Acyl Substitution in Carboxylic Acid Anhydrides20.5 – Acyl Substitution in Carboxylic Acid Anhydrides
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100 200 400 800
Reciprocal of Antibody Dilution
Ab
sorb
ance
at
450
nm
50 µL EtOH
1 µL MV-II-065
0.1 µL MV-II-065
0.01 µL MV-II-065
50-75% decrease in S. aureus CP
construction
Selective inhibitor of
endothelial cell proliferation
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20.5 – Acyl Substitution in Carboxylic Acid Anhydrides20.5 – Acyl Substitution in Carboxylic Acid Anhydrides
• “N-Glycoside neoglycotrimers from 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl azide,” D. P. Temelkoff, M. Zeller, and P. Norris, Carbohydr. Res. 2006, 341, 1081-1090.
• “Application of Bis(diphenylphosphino)ethane in Staudinger-type N-Glycosyl Amide Synthesis,” D. P. Temelkoff, C. R. Smith, D. A. Kibler, S. McKee, S. Duncan, M. Zeller, M. Hunsen, and P. Norris, Carbohydr. Res. 2006, 341, 1645-1656.
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20.6 – Sources of Esters20.6 – Sources of Esters
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20.7 – Physical Properties of Esters20.7 – Physical Properties of Esters
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20.10 – Reactions of Esters20.10 – Reactions of Esters
Acid-catalyzed hydrolysis
Basic hydrolysis –
saponification
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20.12 – Thioesters20.12 – Thioesters
Acetyl coenzyme A
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20.13 – Amides20.13 – Amides
Hydrogen bonding
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20.11-13 – Amides – Structure and Synthesis20.11-13 – Amides – Structure and Synthesis
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20.14 – Intramolecular Amide Formation – Lactams20.14 – Intramolecular Amide Formation – Lactams
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20.15 – Hydrolysis of Amides – not covering20.15 – Hydrolysis of Amides – not covering
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20.16 – 20.17 – Preparation and Hydrolysis of Nitriles20.16 – 20.17 – Preparation and Hydrolysis of Nitriles
• Protonate nitrogen, attack C with water
• Proton transfer to nitrogen followed by enolization
• Rest of mechanism the same as the amide hydrolysis
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20.18 – Addition of RMgX to Nitriles – Not Covering20.18 – Addition of RMgX to Nitriles – Not Covering