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    Alkynes: An Introduction To Organic Synthesis

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    Alkynes are hydrocarbons containing carbon-carbon triple bonds. The simplest alkyne is acetylene. Alkynes undergo addition reactions similar to alkenes, such as addition of HX and X2. The addition of HX and X2 can be stopped at the alkene intermediate stage or proceed to geminal dihalides or tetrahalides. Hydration of alkynes gives Markovnikov addition products with Hg(II) catalysis but gives anti-Markovnikov products with hydroboration-oxidation. Alkynes can be converted to cis-alkenes with Lindlar catalysis or trans-alkenes with reduction in liquid ammonia. Strong oxidizers

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    Alkynes: An Introduction To Organic Synthesis

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    ggwp21
    66 views9 pages
    Alkynes are hydrocarbons containing carbon-carbon triple bonds. The simplest alkyne is acetylene. Alkynes undergo addition reactions similar to alkenes, such as addition of HX and X2. The addition of HX and X2 can be stopped at the alkene intermediate stage or proceed to geminal dihalides or tetrahalides. Hydration of alkynes gives Markovnikov addition products with Hg(II) catalysis but gives anti-Markovnikov products with hydroboration-oxidation. Alkynes can be converted to cis-alkenes with Lindlar catalysis or trans-alkenes with reduction in liquid ammonia. Strong oxidizers

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    Chem 31

    Original Title

    1st - Alkynes

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    Alkynes are hydrocarbons containing carbon-carbon triple bonds. The simplest alkyne is acetylene. Alkynes undergo addition reactions similar to alkenes, such as addition of HX and X2. The addition of HX and X2 can be stopped at the alkene intermediate stage or proceed to geminal dihalides or tetrahalides. Hydration of alkynes gives Markovnikov addition products with Hg(II) catalysis but gives anti-Markovnikov products with hydroboration-oxidation. Alkynes can be converted to cis-alkenes with Lindlar catalysis or trans-alkenes with reduction in liquid ammonia. Strong oxidizers

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
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    66 views9 pages

    Alkynes: An Introduction To Organic Synthesis

    Uploaded by

    ggwp21
    Alkynes are hydrocarbons containing carbon-carbon triple bonds. The simplest alkyne is acetylene. Alkynes undergo addition reactions similar to alkenes, such as addition of HX and X2. The addition of HX and X2 can be stopped at the alkene intermediate stage or proceed to geminal dihalides or tetrahalides. Hydration of alkynes gives Markovnikov addition products with Hg(II) catalysis but gives anti-Markovnikov products with hydroboration-oxidation. Alkynes can be converted to cis-alkenes with Lindlar catalysis or trans-alkenes with reduction in liquid ammonia. Strong oxidizers

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    of 9

    Alkynes

    Alkynes: An Introduction to
    Organic Synthesis
    Based on McMurrys Organic
    Chemistry, 7th edition

    Hydrocarbons that contain carbon-carbon triple


    bonds
    Acetylene, the simplest alkyne is produced
    industrially from methane and steam at high
    temperature

    Naming Alkynes

    General hydrocarbon rules apply with -yne as a suffix


    indicating an alkyne
    Numbering of chain with triple bond is set so that the smallest
    number possible for the first carbon of the triple bond
    Multiple triple bonds are: diynes, triynes, etc
    Double and triple bonds are: enynes
    ! Number nearest a multiple bond (either double or triple)
    ! If you have a choice, double bond lower number than triple

    Electronic Structure of Alkynes


    Carbon-carbon triple bond results from sp
    orbital on each C forming a sigma bond and
    unhybridized pX and py orbitals forming "
    bonds.
    The remaining sp orbitals form bonds to other
    atoms at 180 to C-C triple bond.
    The bond is shorter and stronger than single or
    double
    Breaking a " bond in acetylene (HCCH) requires
    318 kJ/mole (in ethylene it is 268 kJ/mole)

    Reactions of Alkynes: Addition of HX


    and X2
    Addition reactions of alkynes are similar to those
    of alkenes
    Intermediate alkene reacts further with excess
    reagent
    Regiospecificity according to Markovnikov

    Addition of HX
    Initial addition usually gives trans intermediate
    Can often be stopped at this stage if desired (1
    eq. HX)
    Product with excess reagent is a geminal
    dihalide

    Addition of Bromine and Chlorine


    Initial addition usually gives trans intermediate
    Can often be stopped at this stage if desired (1
    eq. Br2)
    Product with excess reagent is tetrahalide

    Addition of HX to Alkynes Involves


    Vinylic Carbocations
    Addition of H-X to alkyne
    should produce a vinylic
    carbocation intermediate
    ! Secondary vinyl
    carbocations are about as
    stable as primary alkyl
    carbocations
    ! Primary vinyl carbocations
    probably do not form at all

    Addition of HX to Alkynes Involves


    Vinylic Carbocations
    H-Br can add to an alkyne to give a vinyl
    bromide if the Br is not on a primary carbon

    Hydration of Alkynes
    Addition of H-OH as in alkenes
    ! Mercury (II) catalyzes Markovnikov oriented
    addition
    ! Hydroboration-oxidation gives the nonMarkovnikov product

    Anti-Markovnikov Addition of HBr


    Addtion of hydrogen bromide to alkynes occurs
    in the presence of peroxides (through freeradical mechanism)

    Keto-enol Tautomerism
    Isomeric compounds that rapidily interconvert
    by the movement of a proton and are called
    tautomers
    ! Enols rearrange to the isomeric ketone by the
    rapid transfer of a proton from the hydroxyl to the
    alkene carbon
    ! The keto form is usually so stable compared to the
    enol

    Mercury(II)-Catalyzed Hydration of
    Alkynes

    Mechanism of Mercury(II)-Catalyzed
    Hydration of Alkynes

    Alkynes do not react with aqueous protic acids


    Mercuric ion (as the sulfate) is a Lewis acid
    catalyst that promotes addition of water in
    Markovnikov orientation

    Mechanism of Mercury(II)-Catalyzed
    Hydration of Alkynes

    Hydration of Unsymmetrical Alkynes


    If the alkyl groups at either end of the C-C triple
    bond are not the same, both products can form
    and this is not normally useful

    Vinylic alcohol

    Hydroboration/Oxidation of Alkynes

    Hydroboration/Oxidation of Alkynes

    BH3 (borane) adds to alkynes to give a vinylic


    borane
    Anti-Markovnikov
    Oxidation with H2O2 produces an enol that
    converts to the ketone or aldehyde

    Comparison of Hydration of Terminal


    Alkynes
    Unhindered terminal alkynes add two boranes
    Hydroboration/oxidation converts terminal
    alkynes to aldehydes because addition of water is
    non-Markovnikov

    Comparison of Hydration of Terminal


    Alkynes
    The product from the mercury(II) catalyzed
    hydration converts terminal alkynes to methyl
    ketones

    Reduction of Alkynes
    Addition of H2 over a metal catalyst (such as
    palladium on carbon, Pd/C) converts alkynes to
    alkanes (complete reduction)
    The addition of the first equivalent of H2
    produces an alkene, which is more reactive than
    the alkyne so the alkene is not observed

    Conversion of Alkynes to cis-Alkenes

    Conversion of Alkynes to cis-Alkenes


    Addition of H2 using chemically deactivated
    palladium on calcium carbonate as a catalyst
    (the Lindlar catalyst) produces a cis alkene
    The two hydrogens add syn (from the same side
    of the triple bond)
    The Lindlar Catalyst will not reduce double
    bonds

    Conversion of Alkynes to trans-Alkenes


    Anhydrous ammonia (NH3) is a liquid below
    -33 C
    ! Alkali metals dissolve in liquid ammonia and
    function as reducing agents

    Alkynes are reduced to trans alkenes with


    sodium or lithium in liquid ammonia
    The reaction involves a radical anion
    intermediate

    26

    Conversion of Alkynes to trans-Alkenes

    The trans stereochemistry is less sterically


    crowded and is formed in this step

    Oxidative Cleavage of Alkynes


    Strong oxidizing reagents (O3 or KMnO4) cleave
    internal alkynes, producing two carboxylic acids
    Terminal alkynes are oxidized to a carboxylic
    acid and carbon dioxide

    Alkyne Acidity: Formation of Acetylide


    Anions
    Terminal alkynes are weak Brnsted acids
    Reaction of strong anhydrous bases with a
    terminal acetylene produces an acetylide ion
    The sp-hydbridization at carbon holds negative
    charge relatively close to the positive nucleus

    Alkylation of Acetylide Anions


    Acetylide ions can react as nucleophiles as well
    as bases
    Reaction with a primary alkyl halide produces a
    hydrocarbon that contains carbons from both
    partners, providing a general route to larger
    alkynes

    Alkylation of Acetylide Anions

    Limitations of Alkyation of Acetylide


    Ions
    Reactions only are efficient with 1 alkyl
    bromides and alkyl iodides
    Acetylide anions can behave as bases as well as
    nucelophiles
    Reactions with 2 and 3 alkyl halides gives
    dehydrohalogenation, converting alkyl halide to
    alkene

    Limitations of Alkyation of Acetylide


    Ions

    Strategies for Synthesis


    Compare the target and the starting material
    Consider reactions that efficiently produce the
    outcome. Look at the product and think of what
    can lead to it
    ! Example:
    ! Prepare octane from 1-pentyne

    Strategy: Use Acetylide Coupling

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