Carboxylic Acid Derivatives Overview
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Questions and Answers

What is the product formed when nitriles react with Grignard or organolithium reagents?

  • Aldehyde
  • Amine
  • Ketone (correct)
  • Imine

    • The hydrolysis of an imine involves replacing a C=N bond with a C=O bond.

    True (A)

    What reagents are required to convert a nitrile into a ketone?

    Grignard reagent or organolithium reagent

    In the reaction of nitriles with organometallic reagents, the polarized C—N triple bond is subjected to __________ addition.

    <p>nucleophilic</p> Signup and view all the answers

    Match the following processes with their corresponding products:

    <p>Hydrolysis of imine = Ketone Action of Grignard on nitrile = New C—C bond Protonation of anion = Imine Reaction of nitrile with DIBAL-H = Aldehyde</p> Signup and view all the answers

    What is formed when a nitrile is treated with LiAlH4 followed by H2O?

    <p>A primary amine (A)</p> Signup and view all the answers

    DIBAL-H treatment of a nitrile yields a primary amine directly.

    <p>False (B)</p> Signup and view all the answers

    What is the general structural formula of nitriles?

    <p>RC≡N</p> Signup and view all the answers

    The mechanism of nitrile hydrolysis involves replacing three C—N bonds with ___ C—O bonds.

    <p>three</p> Signup and view all the answers

    Match the reagents with their corresponding outcomes when reacting with nitriles:

    <p>LiAlH4 = Primary amine DIBAL-H = Aldehyde Water and acid = Carboxylic acid Water and base = Carboxylate anion</p> Signup and view all the answers

    Which of the following statements about nitriles is true?

    <p>Nitriles contain a carbon-nitrogen triple bond. (D)</p> Signup and view all the answers

    Imidic acids and amides can interconvert by treatment with either acid or base.

    <p>True (A)</p> Signup and view all the answers

    What is the result of hydride addition to a nitrile using DIBAL-H?

    <p>Imine</p> Signup and view all the answers

    What is the main purpose of using DIBAL-H in organic synthesis?

    <p>To reduce esters to aldehydes (A)</p> Signup and view all the answers

    Lithium Aluminium Hydride (LiAlH4) is a strong reducing agent and can reduce nitriles to primary amines.

    <p>True (A)</p> Signup and view all the answers

    What is the product formed when a Grignard reagent reacts with a carbonyl compound?

    <p>Alcohol</p> Signup and view all the answers

    The reaction of an aldehyde with ammonia forms an ______.

    <p>imine</p> Signup and view all the answers

    Match the reagents with their corresponding reactions:

    <p>DIBAL-H = Reduces esters to aldehydes LiAlH4 = Reduces nitriles to primary amines Grignard reagent = Forms alcohols from carbonyls Ammonia = Forms imines with aldehydes</p> Signup and view all the answers

    Which of the following reactions does not lead to imine formation?

    <p>Reacting a carboxylic acid with ammonia (C)</p> Signup and view all the answers

    The reaction of a nitrile with Grignard reagents results in the formation of a ketone.

    <p>False (B)</p> Signup and view all the answers

    What is a common application of reducing agents like LiAlH4 in organic chemistry?

    <p>Reduction of aldehydes and ketones</p> Signup and view all the answers

    In the presence of water, the reaction of a Grignard reagent with an aldehyde produces a ______.

    <p>secondary alcohol</p> Signup and view all the answers

    Match the following reduction reactions to their respective reagents:

    <p>DIBAL-H = Reduces esters LiAlH4 = Reduces nitriles Grignard reagent = Forms alcohols</p> Signup and view all the answers

    Flashcards

    Hydrolysis of Imine

    The process of breaking down an imine using water, replacing the C=N bond with a C=O bond, forming a ketone.

    Nitrile Reaction with Organometallics

    Organometallic reagents (Grignard/organolithium) react with nitriles to form ketones, creating a new carbon-carbon bond via nucleophilic addition, followed by hydrolysis.

    Nucleophilic Addition to nitriles

    Organometallic reagents add to the polarized C-N triple bond of nitriles forming an anion, subsequently protonated with water, forming an imine.

    Reagent Reaction (Sodium Bicarbonate)

    Sodium bicarbonate (NaHCO3) reacts with a certain compound, but the reaction is unknown in the provided context.

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    Reagent Reaction (Ammonia)

    One equivalent of ammonia reacts with a certain compound, but the reaction is unknown in the provided context.

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    Amide hydrolysis (acid)

    Amide hydrolysis in acidic conditions follows the same mechanism as ester hydrolysis in acid.

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    Amide hydrolysis (base)

    Amide hydrolysis in basic conditions involves two steps of nucleophilic acyl substitution, plus a proton transfer step.

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    Nitrile structure

    Nitriles have the general formula RC≡N.

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    Nitrile preparation

    Nitriles are made by SN2 reactions of unhindered methyl and 1° alkyl halides with cyanide ions.

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    Nitrile hydrolysis (general)

    Water and an acid or base breaks down nitriles into carboxylic acid.

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    Nitrile hydrolysis mechanism

    The process involves amide tautomer formation, similar to keto-enol tautomerization.

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    Nitrile reduction (LiAlH4)

    LiAlH4 reduces nitriles to amines by adding two hydride equivalents, sequentially.

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    Nitrile reduction (DIBAL-H)

    DIBAL-H reduces nitriles to aldehydes, adding only one equivalent of hydride.

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    Grignard Reagent with Nitrile

    A Grignard reagent (RMgX) reacts with a nitrile (RCN) to form a ketone after hydrolysis. The Grignard reagent adds to the nitrile's carbon, forming an imine intermediate.

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    Lithium Aluminum Hydride (LiAlH4) with Nitrile

    LiAlH4 reduces a nitrile (RCN) to a primary amine (RCH2NH2). The hydride ion attacks the nitrile's carbon, breaking the triple bond and forming an imine intermediate, which is then further reduced.

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    Hydrolysis of Nitrile to Carboxylic Acid

    Hydrolyzing a nitrile (RCN) with acid (H3O+) produces a carboxylic acid (RCOOH). The nitrile's carbon is attacked by water, forming an amide intermediate, which is then hydrolyzed further.

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    Acid Catalyzed Ester Hydrolysis

    An ester (RCOOR') reacts with an acid (H3O+) producing a carboxylic acid (RCOOH) and an alcohol (R'OH). The acid protonates the carbonyl oxygen, making it more susceptible to nucleophilic attack by water.

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    Base Catalyzed Ester Hydrolysis

    An ester (RCOOR') reacts with a base (NaOH) forming a carboxylate salt (RCOO-) and an alcohol (R'OH). The base deprotonates the alcohol formed in the initial nucleophilic attack, driving the reaction forward.

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    Amide Hydrolysis with Acid

    An amide (RCONH2) reacts with acid (H3O+) producing a carboxylic acid (RCOOH) and ammonia (NH3). This reaction requires heating and is an equilibrium process.

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    Amide Hydrolysis with Base

    An amide (RCONH2) reacts with a base (NaOH) producing a carboxylate salt (RCOO-) and ammonia (NH3). The base deprotonates the ammonia formed in the initial nucleophilic attack.

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    Conversion of Carboxylic Acid to Acid Chloride

    A carboxylic acid (RCOOH) reacts with thionyl chloride (SOCl2) to form an acid chloride (RCOCl). The reaction involves the formation of a reactive intermediate and releases HCl gas.

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    Conversion of Carboxylic Acid to Ester

    A carboxylic acid (RCOOH) reacts with an alcohol (R'OH) in the presence of a catalyst (H2SO4) to form an ester (RCOOR'). This reaction is reversible and requires heat.

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    Conversion of Carboxylic Acid to Amide

    A carboxylic acid (RCOOH) reacts with ammonia (NH3) or an amine (RNH2) to form an amide (RCONH2 or RCONHR). The reaction requires heating and removal of water.

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    Study Notes

    Carboxylic Acid Derivatives

    • Carboxylic acids have a general structure with a carbonyl group (C=O) and a hydroxyl group (OH).
    • Acyl group: The carbon chain attached to the carbonyl group
    • Electronegative atom (Z): The atom bonded to the carbonyl carbon in derivatives, impacting acid/base properties
    • Common derivatives include: acid chlorides, anhydrides, esters, amides, and nitriles.

    Types of Carboxylic Acid Derivatives

    • Acid Chlorides:
      • General structure: R-C(=O)-Cl
      • React readily with nucleophiles, forming substitution products.
      • Often form HCl as a byproduct which must be neutralized.
    • Anhydrides:
      • General structure: R-C(=O)-O-C(=O)-R
      • Formed from the dehydration of two carboxylic acid molecules.
      • React with nucleophiles, resulting in the carbonyl group of the anhydride breaking the bond
      • The nucleophile attacks one carbonyl group and the carbonyl from the other part is the leaving group
    • Esters:
      • General structure: R-C(=O)-OR'
      • Formed by the condensation reaction of a carboxylic acid with an alcohol.
      • Hydrolysis can be performed by acid or base, to form a carboxyl and alcohol.
    • Amides:
      • General structure: R-C(=O)-NR'R"
      • Formed by the reaction of a carboxylic acid with ammonia or amines
      • Exist in two tautomeric forms that interconvert, with the amide form usually being more stable.
    • Nitriles:
      • General structure: R-C≡N
      • Prepared by SN2 reactions of unhindered methyl and 1° alkyl halides with CN.
      • Involve hydrolysis reactions to form carboxylic acids.

    Reactions of Carboxylic Acid Derivatives

    • Nucleophilic Acyl Substitution:
      • Characterizes the reactions of carboxylic acid derivatives
      • Involves the nucleophilic attack at the carbonyl carbon, following by loss of the leaving group.
      • Oxygen nucleophiles: Can react to form anhydrides, carboxylic acids or esters
      • Nitrogen nucleophiles: Can react to form amides.

    Anhydrides

    • Types of anhydrides:
      • Symmetrical Anhydride: "Two R Groups are the same."
      • Mixed Anhydride: "Two R Groups are different."
      • Cyclic Anhydride: "Cyclic" structures.

    Amides

    • Types of amides:
      • Primary Amide: One C-N bond.
      • Secondary Amide: Two C-N bonds.
      • Tertiary Amide: Three C-N bonds.

    Cyclic Esters and Amides

    • Lactones: Cyclic esters.
    • Lactams: Cyclic amides.

    Structure and Bonding

    • The carbonyl group (C=O) is sp2 hybridized, making it trigonal planar
    • The electronegative oxygen atom polarizes the carbonyl group, making the carbonyl carbon electrophilic
    • Three resonance structures stabilize carboxylic acid derivatives by delocalizing electron density.

    Stability of Carboxylic Acid Derivatives

    • Stability increases with increasing basicity of Z

    Acid Chlorides Reactions

    • Acid chlorides readily react with nucleophiles to form nucleophilic substitution products.
    • A weak base (like pyridine) is usually required to neutralize the byproduct strong acid HCl.

    Nomenclature

    • Specific names and abbreviations exist for different types of carboxylic acid derivatives and nitriles.

    IR Spectroscopy

    • Provides characteristic absorption frequencies for carbonyl groups. Frequency data varies by derivative type

    Acid-Catalyzed Hydrolysis

    • Mechanisms for converting esters and amides into carboxylic acid involve protonation and loss of an OH or NH2 group.

    Base-Promoted Hydrolysis (Saponification)

    • Base-promoted hydrolysis results in the formation of a carboxylate anion.

    Reactions of Nitriles

    • Hydrolysis reactions form carboxylic acids or carboxylate anions
    • Reduction with LiAlH4 forms a primary amine.
    • Reduction with DIBAL-H forms an aldehyde.
    • Organometallic reagents add to the nitrile group resulting in ketones.

    Carboxylic Acid Reactions

    • Carboxylic acids behave as acids in water, neutralizing bases to form carboxylate salts.
    • Other reactions form functional derivatives from the carboxylic acid.

    Resonance Stabilization of Carboxylates

    • Resonance stabilization plays a crucial role in the equilibrium of the reaction.

    Summary

    • Carboxylic acid derivatives, such as acid chlorides, anhydrides, esters, amides, and nitriles, exhibit distinct properties and reactivity patterns.

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    Description

    This quiz covers the fundamental aspects of carboxylic acid derivatives, including their structures and properties. Learn about various types like acid chlorides, anhydrides, esters, and amides, along with their reactions and applications in organic chemistry.

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