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21.1 Introduction Carboxylic Acids 21.1 Introduction Carboxylic Acids

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21.1 Introduction Carboxylic Acids 21.1 Introduction Carboxylic Acids 4/25/2012 21.1 Introduction Carboxylic Acids 21.1 Introduction Carboxylic Acids • Carboxylic acids are abundant in nature and in • The US produces over 2.5 million tons of acetic acid per pharmaceuticals. year, which is primarily used to produce vinyl acetate. – Vinyl acetate is used in paints and adhesives. • Carboxylic acid derivatives, such as vinyl acetate, are very common, and they play a central role in organic chemistry. Copyright 2012 John Wiley & Sons, Inc. 21-1 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-2 Klein, Organic Chemistry 1e 21.2 Nomenclature of Carboxylic 21.2 Nomenclature of Carboxylic Acids Acids • Monocarboxylic acids are named with the suffix • When the carboxylic acid group is “oic acid.” attached to a ring, it is named as an alkane carboxylic acid. • There are also many common names for carboxylic acids. • The carbon of the carboxylic acid moiety is assigned the locant position 1. Copyright 2012 John Wiley & Sons, Inc. 21-3 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-4 Klein, Organic Chemistry 1e 21.2 Nomenclature of Carboxylic 21.3 Structure and Properties of Acids Carboxylic Acids • Dicarboxylic acids are named with • The carbon atom of the carboxylic acid the suffix “dioic acid.” has a trigonal planar geometry. WHY? • There are also many common names for dicarboxylic • The acid moiety is capable of strong hydrogen (H‐) acids: bonding including H‐bonding between acid pairs. • As a result, carboxylic acids generally have high boiling points. • Practice with CONCEPTUAL CHECKPOINTs – Consider the BPs of acetic acid (118 °C) and 12.1 through 12.3. isopropanol (82 °C). Copyright 2012 John Wiley & Sons, Inc. 21-5 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-6 Klein, Organic Chemistry 1e 1 4/25/2012 21.3 Structure and Properties of 21.3 Structure and Properties of Carboxylic Acids Carboxylic Acids • Carboxylate ions end in the suffix “oate.” • In water, the equilibrium generally favors the acid . • pKa values mostly range btbetween 4 and 5. Wha t is pKa? • Compounds that end in the suffix “oate” are often found in food ingredient lists as preservatives. • NaOH is a strong base, so it is capable of reacting ≈100% with a carboxylic acid. Copyright 2012 John Wiley & Sons, Inc. 21-7 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-8 Klein, Organic Chemistry 1e 21.3 Structure and Properties of 21.3 Structure and Properties of Carboxylic Acids Carboxylic Acids • How does the pKa value for a carboxylic acid compare to • Let’s examine the equilibrium between the carboxylic a strong acid like HCl, or a very weak acid like ethanol? acid and the carboxylate at physiological pH (7.3). • The acid and the conjugate base make a buffer. HOW? H–Cl • Recall that the Henderson‐Hasselbalch equation can be pKa = -7 used to calculate the pH of a buffer: • How can induction and resonance be used to explain the acidity of a carboxylic acid? • Assuming the pK is 4.3, calculate the ratio of • Practice with CONCEPTUAL CHECKPOINTs 21.4 through a carboxylate/acid. 21.7. Copyright 2012 John Wiley & Sons, Inc. 21-9 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-10 Klein, Organic Chemistry 1e 21.3 Structure and Properties of 21.3 Structure and Properties of Carboxylic Acids Carboxylic Acids • Many biomolecules exhibit carboxylic acid moieties. • Electron withdrawing substituents have a great effect • Biomolecules such as pyruvic acid exist primarily as the on acidity. carboxylate under physiological conditions. • Practice with CONCEPTUAL CHECKPOINT 21.8. • WHY? Copyright 2012 John Wiley & Sons, Inc. 21-11 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-12 Klein, Organic Chemistry 1e 2 4/25/2012 21.3 Structure and Properties of 21.4 Preparation of Carboxylic Acids Carboxylic Acids • Electron withdrawing substituents affect benzoic acid as • In earlier chapters, we already learned some methods well. to synthesize carboxylic acids. • Practice with CONCEPTUAL CHECKPOINT 21.9. Copyright 2012 John Wiley & Sons, Inc. 21-13 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-14 Klein, Organic Chemistry 1e 21.4 Preparation of Carboxylic Acids 21.4 Preparation of Carboxylic Acids • Let’s examine two more ways to make carboxylic acids: • In earlier chapters, we already learned some methods 1. The hydrolysis of a nitrile can produce a carboxylic acid. to synthesize carboxylic acids. – The mechanism will be discussed later. – Carboxylic acids can be made from alkyl halides using a two‐ step process. Copyright 2012 John Wiley & Sons, Inc. 21-15 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-16 Klein, Organic Chemistry 1e 21.4 Preparation of Carboxylic Acids 21.4 Preparation of Carboxylic Acids • Let’s examine two more ways to make carboxylic acids: • This gives us a second method to convert an alkyl halide 2. Carboxylation of a Grignard reaction can be achieved using into a carboxylic acid: CO2. • Practice with CONCEPTUAL CHECKPOINT 12.10. + – The Grignard reagent and the H3O cannot be added together. WHY? Copyright 2012 John Wiley & Sons, Inc. 21-17 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-18 Klein, Organic Chemistry 1e 3 4/25/2012 21.5 Reactions of Carboxylic Acids 21.5 Reactions of Carboxylic Acids • LiAlH4 (LAH) is a strong reducing agent that can convert • LiAlH4 (LAH) is a strong reducing agent that can convert an acid to a primary alcohol: an acid to a primary alcohol: – The LAH acts as a base first. – The aldehyde is further reduced to the alcohol. – Then, an aldehyde is produced. – Can the reduction be stopped at the aldehyde? Copyright 2012 John Wiley & Sons, Inc. 21-19 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-20 Klein, Organic Chemistry 1e 21.6 Introduction to Carboxylic Acid 21.5 Reactions of Carboxylic Acids • The milder borane reagent can also be used to promote Derivatives the reduction. • The reduction of acids with LAH or borane result in a decrease in the oxidation number for carbon. HOW? • • Reduction with borane is selective compared to LAH There are also many reactions where carboxylic acids reduction. don’t change their oxidation state. • Practice with CONCEPTUAL CHECKPOINT 21.11. • What criteria must Z fulfill so that there is no change in the oxidation state? Copyright 2012 John Wiley & Sons, Inc. 21-21 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-22 Klein, Organic Chemistry 1e 21.6 Introduction to Carboxylic Acid 21.6 Introduction to Carboxylic Acid Derivatives Derivatives • When Z is a heteroatom, the compound is called a • Acid halides and anhydrides are relatively unstable, so carboxylic acid derivative. they are not common in nature; we will discuss their instability in detail later in this chapter. • Some naturally occurring esters are known to have pleasant odors: • Because it has the same oxidation state, a nitrile is also an acid derivative despite not having a carbonyl group. Copyright 2012 John Wiley & Sons, Inc. 21-23 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-24 Klein, Organic Chemistry 1e 4 4/25/2012 21.6 Introduction to Carboxylic Acid 21.6 Introduction to Carboxylic Acid Derivatives Derivatives • Amides are VERY common • To name an acid halide, replace “ic acid” with “yl in nature. halide.” • What type of molecule in nature includes amide lin kages ? • Many other compounds feature amides, including some natural sedatives like melatonin. Copyright 2012 John Wiley & Sons, Inc. 21-25 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-26 Klein, Organic Chemistry 1e 21.6 Introduction to Carboxylic Acid 21.6 Introduction to Carboxylic Acid Derivatives Derivatives • Alternatively, the suffix, “carboxylic acid” can be • Acid anhydrides are named by replacing “acid” with replaced with “carbonyl halide.” “anhydride.” Copyright 2012 John Wiley & Sons, Inc. 21-27 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-28 Klein, Organic Chemistry 1e 21.6 Introduction to Carboxylic Acid 21.6 Introduction to Carboxylic Acid Derivatives Derivatives • Asymmetric acid anhydrides are named by listing the • Esters are named by naming the alkyl group attached to acids alphabetically and adding the word anhydride. the oxygen followed by the carboxylic acid’s name with the suffix “ate.” Copyright 2012 John Wiley & Sons, Inc. 21-29 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-30 Klein, Organic Chemistry 1e 5 4/25/2012 21.6 Introduction to Carboxylic Acid 21.6 Introduction to Carboxylic Acid Derivatives Derivatives • Amides are named by replacing the suffix “ic acid” or • If the nitrogen atom of the amide group bears alkyl “oic acid” with “amide.” substituents, their names are placed at the beginning of the name with N as their locant. Copyright 2012 John Wiley & Sons, Inc. 21-31 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-32 Klein, Organic Chemistry 1e 21.6 Introduction to Carboxylic Acid 21.7 Reactivity of Carboxylic Acid Derivatives Derivatives • Nitriles are named by replacing the suffix “ic acid” or • In general, carboxylic acid “oic acid” with “onitrile.” derivatives are good electrophiles. • WHY? • Practice with CONCEPTUAL CHECKPOINTs 21.12 and 21.13. Copyright 2012 John Wiley & Sons, Inc. 21-33 Klein, Organic Chemistry 1e Copyright 2012 John Wiley & Sons, Inc. 21-34 Klein, Organic Chemistry 1e 21.7 Reactivity of Carboxylic Acid 21.7 Reactivity of Carboxylic Acid Derivatives Derivatives • Reactivity can be • Let’s examine the acid chloride: affected by – The electronegative chlorine enhances the electrophilic – Induction character of the carbonyl. HOW? – Resonance – There are 3 resonance contributors to the acid chloride: – SiSterics – Quality of leaving group – The chlorine does not significantly donate electron density to the carbonyl.
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