22: Carboxylic Acid Derivatives and Nitriles

Last updated
Save as PDF

Page ID: 424405

\( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \) \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)\(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\) \(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\)\(\newcommand{\AA}{\unicode[.8,0]{x212B}}\)

learning objectives

After reading this chapter and completing ALL the exercises, a student can be able to

describe the structure and physical properties of carboxylic acid derivatives and nitriles (section 22.1)
determine the structure of carboxylic acid derivatives and nitriles from their elemental analysis and spectral data (MS, IR ¹H NMR & ¹³C NMR) (section 22.2)
predict the products and specify the reagents to interconvert between a carboxylic acid and its derivatives (section 22.3)
predict the products and specify the reagents to hydrolyze carboxylic acid derivatives (22.4)
predict the products and specify the reagents for transesterification reactions (section 22.5)
predict the products and specify the reagents for reduction reactions of carboxylic acid derivatives (section 22.6)
predict the products and specify the reagents for organometallic reactions with carboxylic acid derivatives (section 22.7)
predict the products and specify the reagents for the synthesis and reactions of
- acyl chlorides (section 22.4)
- anhydrides (section 22.5)
- esters (section 22.6)
- amides (section 22.7)
- nitriles (section 22.8)
- thioesters (section 22.9)
- step-growth (condensation) polymers via ester and amide bonds (section 22.10)
discuss the chemistry of beta-lactams and biological acylation (section 22.11 and 22.12 respectively)
combine the reactions studied to date to develop efficient and effective multiple-step synthesis

Please note: IUPAC nomenclature and important common names of carboxylic acid derivatives and nitriles were explained in Chapter 3.

22.1: Structure and Physical Properties of Acid Derivatives
A acyl derivative (functional derivative) of a carboxylic acid is a substance formed by substitution of the hydroxyl group of the acid by some other group such that it can be hydrolyzed back to the acid.
22.2: Spectroscopy of Carboxylic Acid Derivatives
While all of the carboxylic acid derivatives include a carbonyl group, the heteroatoms that characterize the derivative can be used to distinguish between the derivatives.
22.3: Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution
Carboxylic acid derivatives are electrophilic and can react with nucleophiles to form nucleophilic acyl substitution products.
22.4: Acid Halide Chemistry
Acyl halides (acid halides) are synthsized from carboxylic acids. Acid halides can undergo hydrolysis, nucleophillic acyl substitution, reduction, organometallic, and Fridel-Crafts acylation reactions.
22.5: Acid Anhydride Chemistry
Acid anhydrides are typically synthesized from acyl halides. Acid anhydrides undergo hydrolysis and nucleophilic acyl substitution reactions.
22.6: Ester Chemistry
Esters can be synthsized from acid chlorides, acid anhydrides, and carboxylic acids. Esters can undergo hydrolysis under acidic or basic conditions, trans-esterification, aminolysis, reduction, and organometallic reactions.
22.7: Amide Chemistry
Amides can be synthesized from amides, carboxylic acids, acyl halides, and acid anhydrides. Amides can be hydrolyzed under acidic or basic conditions and can also be reduced to amines.
22.8: Nitrile Chemistry
Nitriles can be synthesized from the reaction of nucleophilic cyanide with electrophilic groups, such as the carbonyls (aldehydes and ketones) and alkyl halides that are suitable for SN2 reactions. Amides can react with thionyl chloride to produce nitriles. Nitriles are electrophilic and can undergo hydrolyisis, reduction, and organometallic reactions.
22.9: Thioesters- Biological Carboxylic Acid Derivatives
Thioesters are biologically important carboxylic acid derivatives. Acetyl coenzyme A is an important thioester in metabolism and transports two carbon atoms to the Citric Acid Cycle (Kreb's Cycle).
22.10: Polyamides and Polyesters- Step-Growth Polymers
Bifunctional monomers can be used to synthesize a wide range of step-growth (condensation) polymers by forming ester or amide bonds.
22.11: Beta-Lactams- An Application
Many carboxylic acid derivatives are prevalent in biochemistry. This section introduces some of the notable compounds.
22.12: Biological Acylation Reactions
The reactions of glutamine, asparagine, and glycinamide ribonucelotide synthetase are introduced to illustrate biological acylation reactions.
22.13: Additional Exercises
This section has additional exercises for the key learning objectives of the chapter.
22.14: Solutions to Additional Exercises
This section has the solutions to the additional exercises from the previous section.