Scribd Logo
Upload

Welcome to Scribd!

  • 122 views

    Bayer Villager Oxidation

    Uploaded by

    Sabitry Yadav
    Oxidation is a process where oxygen is added, hydrogen is removed, electrons are lost, or the oxidation number increases. Ethanol can be oxidized to ethanal by removing hydrogen using an oxidizing agent like potassium dichromate. The Baeyer-Villiger oxidation rearranges ketones into esters and cyclic ketones into lactones or hydroxy acids using peroxy acids as oxidizing agents. The reaction proceeds through initial protonation followed by addition and rearrangement, retaining stereochemistry and favoring migration of groups that stabilize positive charge.

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd

    Bayer Villager Oxidation

    Uploaded by

    Sabitry Yadav
    122 views11 pages
    Oxidation is a process where oxygen is added, hydrogen is removed, electrons are lost, or the oxidation number increases. Ethanol can be oxidized to ethanal by removing hydrogen using an oxidizing agent like potassium dichromate. The Baeyer-Villiger oxidation rearranges ketones into esters and cyclic ketones into lactones or hydroxy acids using peroxy acids as oxidizing agents. The reaction proceeds through initial protonation followed by addition and rearrangement, retaining stereochemistry and favoring migration of groups that stabilize positive charge.

    Original Title

    Bayer villager oxidation

    Copyright

    © © All Rights Reserved

    Available Formats

    PPTX, PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Oxidation is a process where oxygen is added, hydrogen is removed, electrons are lost, or the oxidation number increases. Ethanol can be oxidized to ethanal by removing hydrogen using an oxidizing agent like potassium dichromate. The Baeyer-Villiger oxidation rearranges ketones into esters and cyclic ketones into lactones or hydroxy acids using peroxy acids as oxidizing agents. The reaction proceeds through initial protonation followed by addition and rearrangement, retaining stereochemistry and favoring migration of groups that stabilize positive charge.

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    122 views11 pages

    Bayer Villager Oxidation

    Uploaded by

    Sabitry Yadav
    Oxidation is a process where oxygen is added, hydrogen is removed, electrons are lost, or the oxidation number increases. Ethanol can be oxidized to ethanal by removing hydrogen using an oxidizing agent like potassium dichromate. The Baeyer-Villiger oxidation rearranges ketones into esters and cyclic ketones into lactones or hydroxy acids using peroxy acids as oxidizing agents. The reaction proceeds through initial protonation followed by addition and rearrangement, retaining stereochemistry and favoring migration of groups that stabilize positive charge.

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    of 11

    What is oxidation?

    Oxidation is nothing but a process in which either;


    ⚫ Addition of oxygen.
    ⚫ Removal of hydrogen.
    ⚫ Loss of an electron.
    ⚫ Increase in oxidation number takes place.
    ⚫ Ethanol can be oxidized to ethanal:

    CH3CH2OH CH3CH O 2

    Oxidation by loss of hydrogen

    • We would need to use an oxidizing agent to remove the


    hydrogen
    from ethanol.

    • The commonly used oxidizing agent is Potassium Dichromate(VI)


    Solution acified with dil.H2SO4.
    ⚫ The transformation for ketones into esters and
    cyclic ketones into lactones or hydroxy acid
    by peroxy acid was discovered as early as
    1899 by A.Baeyer and Villiger.
    ⚫ A wide range of oxidizing agents can be used to
    perform the Baeyer-Villiger oxidations.
    ⚫ Reagents typically used to carryout this
    rearrangement is peroxy acid.
    ⚫ The mechanism of Baeyer-Villiger rearrangement is
    not clear, however it is believed the reaction
    proceed as follows:
    ⚫ Initial protonation of the carbonyl oxygen is
    followed by addition of peracid to yield an adduct
    which undergoes rearrangement where the R group
    migrates to the electron deficient oxygen. This is
    followed by deprotonation.
    ⚫ Salient points are retention of stereochemistry by
    the migrating group, migration concerted with
    departure of leaving group and increased migratory
    aptitude of groups possessing greater electron
    donating power.
    ⚫ Retention of stereochemistry by the migrating group.
    ⚫ Migration is concerted with the departure of
    the leaving group. The concerted step is rate
    determining.
    ⚫Migrating groups with greater electron donating
    power have correspondingly greater migratory
    aptitude because of the increased ability to stabilize
    a positive charge in the transition state. This renders
    stereoselectivity to the oxidation of unsymmetrical
    ketones.
    ⚫ Migration is favored when the migrating group is
    antiperiplanar to the O-O bond of the leaving group;
    this is known as the primary stereoelectronic
    effect.
    ⚫ The order of preference for migration among alkyl
    group is, Tertiary > Secondary > Primary >
    Methyl.

    ⚫ Aryl group migrates in preference to methyl and


    primary alkyl groups.

    ⚫ In aryl series, migration is facilitated by


    electron
    para position.
    ⚫ Baeyer-Villiger oxidation has great synthesis utility
    as it permits the transformation of ketones into
    esters. An oxygen atom is inserted next to the
    carbonyl group. This reaction is applicable to both
    acyclic ketones and cyclic ketones. Oxidation of
    cyclic ketones occurs with ring expansion and form
    lactones as illustrated in the conversion of
    Cyclohexanone to lactone by this method.
    ⚫ Baeyer-Villiger oxidation is also possible by the
    action of enzymes. For eg. Cyclohexanone is
    converted into lactone by using purified
    cyclohexanone oxygenase enzyme.

    ⚫ Aldehydes also undergo Baeyer-Villiger oxidation to


    usually give carboxylic acids. The reaction involves
    either migration of hydrogen of fragmentation of the
    intermediate.

    You might also like