Carboxylic Acid Derivatives - NAS

Organic Chemistry
20. Carboxylic Acid Derivatives:NAS
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Organic Chemistry
CONCEPT: COOH DERIVATIVES AND NUCLEOPHILIC ACYL SUBSTITUTION

Carboxylic acid derivatives are defined as any carbonyl with a single electronegative group (-Z) in the α-position.
● These follow unique nucleophilic mechanism due to the presence of a leaving group, called NAS.
● By definition, they can ALL be hydrolyzed to a carboxylic acid using water with acid or base.
□ Nitriles also fall into this category due to their ability to be hydrolyzed
= -Cl, -COOR
-OR, -OH, - NH3
General Carbonyl Mechanisms:
Page 1
Organic Chemistry
CONCEPT: CARBOXYLIC ACID NOMENCLATURE

IUPAC: Replace alkane “-e” with ________________________
● Substituents are located using ____________
Common: Memorize the first 5 common names
● Substituents are located using _____________
Negative anions (deprotonated) are named using the suffix _____________
EXAMPLE: Give both the correct IUPAC and common name for the following molecule.
( ) Formic Acid
( ) Acetic Acid
( ) Propionic Acid
( ) Butyric Acid
( ) Valeric Acid
Page 2
Organic Chemistry
PRACTICE: Provide the IUPAC name for the following compound.
Br O
OH
OH
Page 3
Organic Chemistry
CONCEPT: CARBOXYLIC ACID NOMENCLATURE
Diacids:
Memorize the first 3 common names
Page 4
Organic Chemistry
PRACTICE: Provide the common name for the following compound.
OH
HO
O O
OH
HO
Page 5
Organic Chemistry
CONCEPT: ESTER NOMENCLATURE

The word “ester” is not found in ester nomenclature, making these difficult to recognize.
● Name as an ________________ + ___________________________
EXAMPLE: Correctly name the following structure.
EXAMPLE: Correctly draw the following molecule.
Isopropyl formate
Page 6
Organic Chemistry
CONCEPT: NITRILE NOMENCLATURE
Add suffix _________________ to the alkane name

● Do not drop the ”e”
● Substituents are located using _______
2-amino-4-bromohexanenitrile
Page 7
Organic Chemistry
CONCEPT: ACID CHLORIDE NOMENCLATURE

Common: Replace “ic acid” with the suffix -yl chloride
IUPAC: Replace “e” with the suffix -oyl chloride
EXAMPLE: Provide both the correct IUPAC and common name for the following molecule.
γ-ethylvaleryl chloride
Page 8
Organic Chemistry
CONCEPT: ANHYDRIDE NOMENCLATURE
Alphabetize acids, then replace the word acid with ___________________

● If you have two identical –R groups, name as alkynoic anhydride
EXAMPLE: Provide both the correct name for the following molecule.
Formic anhydride
Page 9
Organic Chemistry
CONCEPT: AMIDE NOMENCLATURE
Replace “e” with the suffix _______________

● R groups on the nitrogen are named as substituents on the
--N or –N, N positions
N, N-dibenzylacetamide
Page 10
Organic Chemistry
CONCEPT: NUCLEOPHILIC ACYL SUBSTITUTION – THE THREE RULES

Most of the formulas governing the conversion of carboxylic acid derivatives can be simplified into the following 3 Rules:
RULE #1 The general reactions for these conversions are as follows:
RULE #2 More reactive acyl compounds can be easily _______________________ into less reactive ones.
The reactivity of carbonyls toward NAS depends upon the strength of the __________________________
RULE #3 The Carboxylic Acid Conversions
Page 11
Organic Chemistry
PRACTICE: Determine the major product for the following reaction.
Page 12
Organic Chemistry
CONCEPT: SPECIFIC CARBOXYLIC ACID CONVERSIONS

Synthesis of Acid Chloride:
Synthesis of Amides:
Dehydration of Amides:
Hydrolysis of Nitriles:
Page 13
Organic Chemistry
CONCEPT: FISCHER ESTERIFICATION— MECHANISM

Also known as acid-catalyzed esterification, this is one of the more important mechanisms in this course.
General Reaction:
Mechanism:
Page 14
Organic Chemistry
CONCEPT: ACID-CATALYZED ESTER HYDROLYSIS— MECHANISM

The exact reverse of Fischer esterification.
General Reaction:
Mechanism:
Page 15
Organic Chemistry
CONCEPT: BASE-CATALYZED ESTER HYDROLYSIS— MECHANISM

Also known as saponification, this is one of the more important mechanisms in this course.
General Reaction:
Mechanism:
Page 16
Organic Chemistry
CONCEPT: BASE-CATALYZED TRANSESTERIFICATION— MECHANISM

Occurs when an ester is exposed to an alkoxide base with a dissimilar alkyl group.
● Can be avoided by only exposing esters to alkoxides with the same –R group as the ester
General Reaction:
Mechanism:
Page 17
Organic Chemistry
CONCEPT: LACTONES, LACTAMS AND CYCLIZATION REACTIONS

Hydroxycarboxylic acids and aminocarboxylic acids can be made to cyclize, forming lactones and lactams, respectively.
● 5 and 6-membered rings can cyclize spontaneously
Lactones and Lactams:
EXAMPLE: Provide the correct structure for the following cyclization reaction and name the new functional group.
Formation of cyclic anhydrides and imides:
Cyclic Anhydrides and Imines
Page 18
Organic Chemistry
CONCEPT: CARBONATION OF GRIGNARD REAGENTS

Grignard reagents can react with dry ice (frozen CO2 gas) to create carboxylic acids
Page 19
Organic Chemistry
1. Br2 , hv
2. Mg, ether
3. CO2
4. H3O+ workup
Page 20
Organic Chemistry
CONCEPT: DECARBOXYLATION
β-carbonyl carboxylic acids easily decarboxylate when heated, producing CO2 gas.
Mechanism:
EXAMPLE: Predict the correct structure for the final product.
Page 21
Organic Chemistry
PRACTICE: Provide the mechanism for the following reaction.
O O O
H
O
Page 22
Organic Chemistry
PRACTICE: Which carbonyl group will undergo decarboxylation most readily?
O OH
C O
HOOC C OH
C
HO O

Page 23

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Organic Chemistry

20. Carboxylic Acid Derivatives:NAS

CONCEPT: COOH DERIVATIVES AND NUCLEOPHILIC ACYL SUBSTITUTION

General Carbonyl Mechanisms:

CONCEPT: CARBOXYLIC ACID NOMENCLATURE

Negative anions (deprotonated) are named using the suffix _____________

PRACTICE: Provide the IUPAC name for the following compound.

PRACTICE: Provide the IUPAC name for the following compound.

CONCEPT: CARBOXYLIC ACID NOMENCLATURE

PRACTICE: Provide the common name for the following compound.

PRACTICE: Provide the IUPAC name for the following compound.

CONCEPT: ESTER NOMENCLATURE

EXAMPLE: Correctly name the following structure.

EXAMPLE: Correctly draw the following molecule.

CONCEPT: NITRILE NOMENCLATURE

Add suffix _________________ to the alkane name

EXAMPLE: Correctly name the following structure.

EXAMPLE: Correctly draw the following molecule.

CONCEPT: ACID CHLORIDE NOMENCLATURE

EXAMPLE: Correctly draw the following molecule.

CONCEPT: ANHYDRIDE NOMENCLATURE

Alphabetize acids, then replace the word acid with ___________________

CONCEPT: AMIDE NOMENCLATURE

Replace “e” with the suffix _______________

--N or –N, N positions

EXAMPLE: Correctly name the following structure.

CONCEPT: NUCLEOPHILIC ACYL SUBSTITUTION – THE THREE RULES

RULE #3 The Carboxylic Acid Conversions

PRACTICE: Determine the major product for the following reaction.

PRACTICE: Determine the major product for the following reaction.

PRACTICE: Determine the major product for the following reaction.

PRACTICE: Determine the major product for the following reaction.

CONCEPT: SPECIFIC CARBOXYLIC ACID CONVERSIONS

CONCEPT: FISCHER ESTERIFICATION— MECHANISM

CONCEPT: ACID-CATALYZED ESTER HYDROLYSIS— MECHANISM

CONCEPT: BASE-CATALYZED ESTER HYDROLYSIS— MECHANISM

CONCEPT: BASE-CATALYZED TRANSESTERIFICATION— MECHANISM

CONCEPT: LACTONES, LACTAMS AND CYCLIZATION REACTIONS

Lactones and Lactams:

Formation of cyclic anhydrides and imides:

Cyclic Anhydrides and Imines

CONCEPT: CARBONATION OF GRIGNARD REAGENTS

PRACTICE: Determine the major product for the following reaction.

EXAMPLE: Predict the correct structure for the final product.

PRACTICE: Provide the mechanism for the following reaction.

PRACTICE: Which carbonyl group will undergo decarboxylation most readily?

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