CH. 20 - CARBOXYLIC ACID DERIVATIVES: NASlightcat-files.s3. COOH DERIVATIVES AND NUCLEOPHILIC ACYL...

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Transcript of CH. 20 - CARBOXYLIC ACID DERIVATIVES: NASlightcat-files.s3. COOH DERIVATIVES AND NUCLEOPHILIC ACYL...

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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 -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.

    -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

    -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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