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    Solomon ch16 PDF

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    shah khisarw
    This document summarizes nucleophilic addition reactions of aldehydes and ketones. It discusses how addition of nucleophiles like hydrides occurs at the carbonyl carbon due to its partial positive charge. Aldehydes are generally more reactive than ketones in these reactions. It also describes the formation of hemiacetals, acetals, imines, enamines and cyanohydrins from aldehydes and ketones, and how these products can be further transformed.

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    Solomon ch16 PDF

    Uploaded by

    shah khisarw
    108 views15 pages
    This document summarizes nucleophilic addition reactions of aldehydes and ketones. It discusses how addition of nucleophiles like hydrides occurs at the carbonyl carbon due to its partial positive charge. Aldehydes are generally more reactive than ketones in these reactions. It also describes the formation of hemiacetals, acetals, imines, enamines and cyanohydrins from aldehydes and ketones, and how these products can be further transformed.

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    This document summarizes nucleophilic addition reactions of aldehydes and ketones. It discusses how addition of nucleophiles like hydrides occurs at the carbonyl carbon due to its partial positive charge. Aldehydes are generally more reactive than ketones in these reactions. It also describes the formation of hemiacetals, acetals, imines, enamines and cyanohydrins from aldehydes and ketones, and how these products can be further transformed.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    108 views15 pages

    Solomon ch16 PDF

    Uploaded by

    shah khisarw
    This document summarizes nucleophilic addition reactions of aldehydes and ketones. It discusses how addition of nucleophiles like hydrides occurs at the carbonyl carbon due to its partial positive charge. Aldehydes are generally more reactive than ketones in these reactions. It also describes the formation of hemiacetals, acetals, imines, enamines and cyanohydrins from aldehydes and ketones, and how these products can be further transformed.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 15

    Chapter 16

    Aldehydes and Ketones I. Nucleophilic


    Addition to the Carbonyl Group
    ⧫ Nucleophilic Addition to the Carbonyl Groups
    Addition of a nucleophile to a carbonyl carbon occurs because of
    the d+ charge at the carbon

    Addition of strong nucleophiles such as hydride or Grignard


    reagents result in formation of a tetrahedral alkoxide intermediate
    The carbonyl p electrons shift to oxygen to give the alkoxide
    The carbonyl carbon changes from trigonal planar to tetrahedral

    Chapter 16 2
    An acid catalyst is used to facilitate reaction of weak nucleophiles
    with carbonyl groups
    Protonating the carbonyl oxygen enhances the electrophilicity of the carbon

    Chapter 16 3
    ⚫ Relative Reactivity: Aldehydes versus Ketones
    Aldehydes are generally more reactive than ketones
    The tetrahedral carbon resulting from addition to an aldehyde is less sterically
    hindered than the tetrahedral carbon resulting from addition to a ketone
    Aldehyde carbonyl groups are more electron deficient because they have only one
    electron-donating group attached to the carbonyl carbon

    Chapter 16 4
    ⧫ The Addition of Alcohols: Hemiacetals and
    Acetals
    ⚫ Hemiacetals
    An aldehyde or ketone dissolved in an alcohol will form an
    equilibrium mixture containing the corresponding hemiacetal
    A hemiacetal has a hydroxyl and alkoxyl group on the same carbon
    Acylic hemiacetals are generally not stable, however, cyclic five- and six-
    membered ring hemiacetals are

    Chapter 16 5
    Hemiacetal formation is catalyzed by either acid or base

    Chapter 16 6
    ⚫ Acetals
    An aldehyde (or ketone) in the presence of excess alcohol and an
    acid catalyst will form an acetal
    Formation of the acetal proceeds via the corresponding hemiacetal
    An acetal has two alkoxyl groups bonded to the same carbon

    Chapter 16 7
    Acetals are stable when isolated and purified
    Acetal formation is reversible
    An excess of water in the presence of an acid catalyst will hydrolyze an acetal to
    the corresponding aldehyde (or ketone)

    Chapter 16 8
    Dissolving aldehydes (or ketones) in water causes formation of an
    equilibrium between the carbonyl compound and its hydrate
    The hydrate is also called a gem-diol (gem i.e. geminal, indicates the presence of
    two identical substituents on the same carbon)
    The equilibrum favors a ketone over its hydrate because the tetrahedral ketone
    hydrate is sterically crowded

    Chapter 16 9
    ⚫ Acetals as Protecting Groups
    Acetal protecting groups are stable to most reagents except
    aqueous acid
    Example: An ester can be reduced in the presence of a ketone
    protected as an acetal

    Chapter 16 10
    Acetal formation from ketones and simple alcohols is less
    favorable than formation from aldehydes
    Formation of cyclic 5- and 6- membered ring acetals from ketones is, however,
    favorable
    Such cyclic acetals are often used as protecting groups for aldehydes and
    ketones
    These protecting groups can be removed using dilute aqueous acid

    Chapter 16 11
    ⧫ The Addition of Primary and Secondary Amines
    Aldehydes and ketones react with primary amines (and ammonia)
    to yield imines
    They react with secondary amines to yield enamines

    Chapter 16 12
    ⚫ Imines
    These reactions occur fastest at pH 4-5
    Mild acid facilitates departure of the hydroxyl group from the aminoalcohol
    intermediate without also protonating the nitrogen of the amine starting
    compound

    Chapter 16 13
    ⚫ Enamines
    Secondary amines cannot form a neutral imine by loss of a
    second proton on nitrogen
    An enamine is formed instead

    Chapter 16 14
    ⧫ The Addition of Hydrogen Cyanide
    Aldehydes and ketone react with HCN to form a cyanohydrin
    A catalytic amount of cyanide helps to speed the reaction

    The cyano group can be hydrolyzed or reduced


    Hydrolysis of a cyanohydrin produces an a-hydroxycarboxylic acid (Sec. 18.8H)
    Reduction of a cyanohydrin produces a b-aminoalcohol

    Chapter 16 15

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