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ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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:

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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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

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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PRACTICE: Provide the IUPAC name for the following compound.

PRACTICE: Provide the IUPAC name for the following compound.

OH

Br O

OH

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: CARBOXYLIC ACID NOMENCLATURE

Diacids:

Memorize the first 3 common names

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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PRACTICE: Provide the common name for the following compound.

PRACTICE: Provide the IUPAC name for the following compound.

HO

O

O

OH

O

O

OH

O

HO

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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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

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: NITRILE NOMENCLATURE

Add suffix _________________ to the alkane name

● Do not drop the ”e”

● Substituents are located using _______

EXAMPLE: Correctly name the following structure.

EXAMPLE: Correctly draw the following molecule.

2-amino-4-bromohexanenitrile

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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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.

EXAMPLE: Correctly draw the following molecule.

γ-ethylvaleryl chloride

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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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.

EXAMPLE: Provide both the correct name for the following molecule.

Formic anhydride

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: AMIDE NOMENCLATURE

Replace “e” with the suffix _______________

● R groups on the nitrogen are named as substituents on the

--N or –N, N positions

EXAMPLE: Correctly name the following structure.

EXAMPLE: Provide both the correct name for the following molecule.

N, N-dibenzylacetamide

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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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

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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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.

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: SPECIFIC CARBOXYLIC ACID CONVERSIONS

Synthesis of Acid Chloride:

Synthesis of Amides:

Dehydration of Amides:

Hydrolysis of Nitriles:

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: FISCHER ESTERIFICATION— MECHANISM

Also known as acid-catalyzed esterification, this is one of the more important mechanisms in this course.

General Reaction:

Mechanism:

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: FISCHER ESTERIFICATION— MECHANISM

Also known as acid-catalyzed esterification, this is one of the more important mechanisms in this course.

General Reaction:

Mechanism:

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: ACID-CATALYZED ESTER HYDROLYSIS— MECHANISM

The exact reverse of Fischer esterification.

General Reaction:

Mechanism:

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: BASE-CATALYZED ESTER HYDROLYSIS— MECHANISM

Also known as saponification, this is one of the more important mechanisms in this course.

General Reaction:

Mechanism:

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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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:

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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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

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: CARBONATION OF GRIGNARD REAGENTS

Grignard reagents can react with dry ice (frozen CO2 gas) to create carboxylic acids

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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PRACTICE: Determine the major product for the following reaction.

1. Br2 , hv2. Mg, ether

3. CO24. H3O+ workup

 

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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CONCEPT: DECARBOXYLATION

β-carbonyl carboxylic acids easily decarboxylate when heated, producing CO2 gas.

Mechanism:

EXAMPLE: Predict the correct structure for the final product.

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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PRACTICE: Provide the mechanism for the following reaction.

O

OH

O O

 

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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PRACTICE: Which carbonyl group will undergo decarboxylation most readily?

HOOC

C

C

C

O

OHO

O OHO

OH

 

ORGANIC - CLUTCH

CH. 20 - CARBOXYLIC ACID DERIVATIVES: NAS

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