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    Oxidaciones_alcoholes

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    albertiiyo19

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    Oxidaciones_alcoholes

    Uploaded by

    albertiiyo19
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    Oxidaciones_alcoholes

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    albertiiyo19

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    Oxidation of a primary alcohol gives an

    aldehyde or a carboxylic acid, depending on the


    experimental conditions
    OH O O
    [O] [O]
    CH3 -C H CH3 -C- H CH3 -C- OH
    H
    A primary An aldehyde A carboxylic
    alcohol acid

    to an aldehyde is a two-electron oxidation


    to a carboxylic acid is a four-electron oxidation
    A common oxidizing agent for this purpose is
    chromic acid, prepared by dissolving
    chromium(VI) oxide or potassium dichromate in
    aqueous sulfuric acid
    H2 SO4
    CrO3 + H2 O H2 CrO 4
    Chromium(VI) Chromic acid
    oxide

    H2 SO4 H2 O
    K2 Cr 2 O7 H2 Cr 2 O7 2 H2 CrO 4
    Potassium Chromic acid
    dichromate
    Oxidation of 1-octanol gives octanoic acid
    the aldehyde intermediate is not isolated
    O
    H2 CrO4
    OH H
    H 2O, aceton e
    1-Hexan ol Hexan al
    (not isolated)
    O
    OH
    Hexan oic acid
    2°alcohols are oxidized to ketones by chromic
    acid
    OH O 3+
    + H2 CrO4 + Cr
    aceton e

    2-Isoprop yl-5-methyl- 2-Is op ropyl-5-methyl-


    cycloh exanol cycloh exanone
    (Men thol) (Men thone)
    Step 1: formation of a chromate ester
    O
    O fas t and
    OH revers ible O-Cr-OH
    + HO-Cr-OH + H2 O
    O
    H H
    Cycloh exanol O
    An alkyl chromate

    Step 2: reaction of the chromate ester with a base,


    here shown as H2O
    chromiu m(V I) chromiu m(IV)
    O
    slow , rate -
    H O
    O Cr-OH determining
    O + O+ H + Cr-OH
    O
    H H O
    Cyclohexan on e
    O
    H H
    chromic acid oxidizes a 1°alcohol first to an
    aldehyde and then to a carboxylic acid
    in the second step, it is not the aldehyde per se that
    is oxidized but rather the aldehyde hydrate

    fas t and
    O OH O-CrO3 H
    revers ible H2 CrO4
    R-C-H + H2 O R-C-OH R-C-OH
    H H
    An ald ehyde An ald ehyde H2 O
    hydrate
    O
    R-C-OH + HCrO3 - + H3 O+
    A carb oxylic
    acid
    Pyridinium chlorochromate (PCC): a form of
    Cr(VI) prepared by dissolving CrO3 in aqueous
    HCl and adding pyridine to precipitate PCC as a
    solid
    pyrid inium ion
    chlorochromate ion

    CrO3 + HCl + ClCrO3 -


    N N
    H
    Pyrid ine Pyrid inium ch lorochromate
    (PCC)

    PCC is selective for the oxidation of 1°alcohols to


    aldehydes; it does not oxidize aldehydes further to
    carboxylic acids
    PCC oxidizes a 1°alcohol to an aldehyde
    O
    PCC
    OH H
    Geraniol Geranial

    PCC also oxidizes a 2°alcohol to a ketone

    OH PCC O

    Men thol Men thone


    Glycols are cleaved by oxidation with periodic
    acid, HIO4
    OH
    CHO
    + HIO 4 + HIO 3
    CHO
    OH
    cis- 1,2-Cyclo- Periodic Hexanedial Iodic
    hexanediol acid acid
    The mechanism of periodic acid oxidation of a
    glycol is divided into two steps
    Step 1: formation of a cyclic periodate
    O O
    C OH C O
    + O I OH I OH + H2 O
    C OH C O
    O O
    A cyclic period ate

    Step 2: redistribution of electrons within the five-


    membered ring
    O O
    C O C O
    I OH + I OH
    C O C O
    O O
    this mechanism is consistent with the fact that HIO4
    oxidations are restricted to glycols that can form a
    five-membered cyclic periodate glycols that cannot
    form a cyclic periodate are not oxidized by HIO4

    OH OH
    O
    HIO4
    HO

    OH O
    The t rans is omer is Th e cis is omer forms
    un reactive tow ard a cyclic periodate and
    periodic acid is cleaved

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