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Chapter 20 Notes

This chapter discusses carboxylic acids and nitriles. It outlines the intended learning outcomes, which include understanding their structures, properties, acidity, preparation methods, and reactions. Key topics covered are the acidity of carboxylic acids, the Henderson-Hasselbalch equation, substituent effects on acidity, spectroscopic characterization by IR and NMR spectroscopy, and common reactions such as hydrolysis, reductions, and additions to the carbonyl group. Practice problems are provided at the end.

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Tiffany Yeh
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56 views

Chapter 20 Notes

This chapter discusses carboxylic acids and nitriles. It outlines the intended learning outcomes, which include understanding their structures, properties, acidity, preparation methods, and reactions. Key topics covered are the acidity of carboxylic acids, the Henderson-Hasselbalch equation, substituent effects on acidity, spectroscopic characterization by IR and NMR spectroscopy, and common reactions such as hydrolysis, reductions, and additions to the carbonyl group. Practice problems are provided at the end.

Uploaded by

Tiffany Yeh
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Chapter 20

Carboxylic Acids and Nitriles

Intended learning outcomes:


1. To understand the structure and properties of carboxylic acids
and nitriles.
2. To understand Henderson-Hasselbalch equation.
3. To understand the effect of substituent effects on acidity.
4. To understand the preparation methods for acids and nitriles.
5. To understand the reactions of carboxylic acids and nitriles, and
the mechanisms mentioned in class.
6. To understand the spectroscopic characterization of carboxylic
acids and nitriles
Introduction to Carboxylic Acids and Their Derivatives

Carboxylic acids

Esters
fragrance

Others
Structure and Properties of Carboxylic Acids

Carboxyl carbon: sp2 hybridized hydrogen bonds: cyclic dimers

~120° ~120°

~120°

high boiling points

Acidic

https://www.youtube.com/watch?v=DoYcn09sxM4
Acidity Constant Ka and pKa

Ka acidity constant

Ka ~ 10-5 carboxylic acids


pKa ~ 5

https://www.youtube.com/watch?v=rKqYE5sZi1s

high pKa
low acidity

stable conjugate base


high acidity
Substituent Effects on Acidity
Inductive effect

Question: compare acidity

poll
In-Class Practice Question

Compare acidity:
Substituent Effects on Acidity
Henderson-Hasselbalch Equation
Interpretation of the Equation

[A-] [A-]
pH = pKa + log or log = pH - pKa
[HA] [HA]

• When pH =pKa, then [HA] = [A-].


i.e., 50% of HA remains as HA, and 50% of it is A- .
• When pH < pKa, mainly in the form of HA.
• When pH > pKa, mainly in the form of A- .
• The exact ratio can be calculated.

Physiological pH: 7.4; pKa of acetic acid: 4.8

That’s why biochemists speak of acetate instead of acetic acid.


Preparation of Carboxylic Acids (1)

A. Oxidation of a substituted alkylbenzene

B. Oxidative cleavage of an alkene


The alkene should have at least one vinylic hydrogen (see Section 7.9)
Preparation of Carboxylic Acids (2)

C. Oxidation of a primary alcohol or an aldehyde (Jones oxidation)

D. Hydrolysis of Nitriles (hot acid or base )

E. Carboxylation of Grignard Reagents


Reactions of Carboxylic Acids: An Overview
Preparation of Nitriles: Dehydration

• Primary amides RCONH2 with SOCl2 or POCl3


• Not limited by steric hindrance or side reactions
Reactions of Nitriles
Nitrile Hydrolysis: Conversion to Carboxylic Acids

acid or base catalysis

For practice:
draw the mechanism
for acid-catalyzed
hydrolysis.
Reactions with other nucleophiles
1. Hydride (H-) : Reduction to amine

2. RM (Organometallic reagents):
Spectroscopy of Carboxylic Acids and Nitriles

IR of Carboxylic Acids
• O–H bond: a very broad absorption 2500 to 3300 cm1
• C=O bond: sharp between 1710 and 1760 cm1
(Free carboxyl groups:1760 cm1; dimeric carboxyl groups: 1710 cm1)
IR of Nitriles

• Intense CN bond absorption:


 near 2250 cm1 (saturated CN)
 near 2230 cm1 (aromatic and conjugated CN)

• Highly diagnostic:
13C NMR

 13COOH signals are at 165 to 185


 Aromatic and ,β-unsaturated acids are near 165
 Saturated aliphatic acids are near 185
 13C  N signal 115 to 130
1H NMR

 The acidic CO2H proton is a singlet near  12.


 When D2O is added to the sample the CO2H proton is replaced by D,
causing the absorption to disappear from the NMR spectrum.
Practice Problems

7th Ed.
20.1-20.16, 20.25, 20.26, 20.27, 20.34,
20.35, 20.39, 20.43, 20.48

8th Ed.
20.1-20.16, 20.28, 20.31, 20.37, 20.29,
20.32, 20.42, 20.48, 20.53

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