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    Alkynes

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    Augustine Franzcoust Papontz
    The document summarizes reactions of alkynes, which are hydrocarbons containing a carbon-carbon triple bond. It discusses various addition reactions alkynes undergo, including: 1) Addition of hydrogen halides like HBr, which can form either primary or secondary carbocations depending on conditions. 2) Addition of water, which involves keto-enol tautomerism. 3) Hydroboration-oxidation reactions of internal and terminal alkynes, which form alcohols. It also explains the relative acidities of hydrogens bonded to sp, sp2, and sp3 hybridized carbons, and how this affects reaction selectivity and product formation.

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    © All Rights Reserved
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    Alkynes

    Uploaded by

    Augustine Franzcoust Papontz
    14 views37 pages
    The document summarizes reactions of alkynes, which are hydrocarbons containing a carbon-carbon triple bond. It discusses various addition reactions alkynes undergo, including: 1) Addition of hydrogen halides like HBr, which can form either primary or secondary carbocations depending on conditions. 2) Addition of water, which involves keto-enol tautomerism. 3) Hydroboration-oxidation reactions of internal and terminal alkynes, which form alcohols. It also explains the relative acidities of hydrogens bonded to sp, sp2, and sp3 hybridized carbons, and how this affects reaction selectivity and product formation.

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    5. Alkynes

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    The document summarizes reactions of alkynes, which are hydrocarbons containing a carbon-carbon triple bond. It discusses various addition reactions alkynes undergo, including: 1) Addition of hydrogen halides like HBr, which can form either primary or secondary carbocations depending on conditions. 2) Addition of water, which involves keto-enol tautomerism. 3) Hydroboration-oxidation reactions of internal and terminal alkynes, which form alcohols. It also explains the relative acidities of hydrogens bonded to sp, sp2, and sp3 hybridized carbons, and how this affects reaction selectivity and product formation.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    14 views37 pages

    Alkynes

    Uploaded by

    Augustine Franzcoust Papontz
    The document summarizes reactions of alkynes, which are hydrocarbons containing a carbon-carbon triple bond. It discusses various addition reactions alkynes undergo, including: 1) Addition of hydrogen halides like HBr, which can form either primary or secondary carbocations depending on conditions. 2) Addition of water, which involves keto-enol tautomerism. 3) Hydroboration-oxidation reactions of internal and terminal alkynes, which form alcohols. It also explains the relative acidities of hydrogens bonded to sp, sp2, and sp3 hybridized carbons, and how this affects reaction selectivity and product formation.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 37

    Reactions

    of
    Alkynes

    Organic Chemistry. 4th Edition.Paula Yurkanis Bruice


    Irene Lee. Case Western Reserve University. Cleveland, OH ©2004, Prentice Hall
    Alkynes are hydrocarbons that contain a carbon–carbon
    triple bond
    General formula: CnH2n–2 (acyclic); CnH2n–4 (cyclic)
    Nomenclature
    In common nomenclature, alkynes are named as
    substituted acetylenes
    A substituent receives the lowest number if there is no
    functional group suffix,

    Cl Br
    3-bromo-2-chloro-4-octyne
    CH3CHCHC CCH2CH2CH3 not 6-bromo-7-chloro-4-octyne
    because 2 < 6
    1 2 3 4 5 6 7 8

    or if the same number for the functional group suffix is


    obtained in both directions

    CH3 1-bromo-5-methyl-3-hexyne
    CH3CHC CCH2CH2Br not 6-bromo-2-methyl-3-hexyne
    because 1 < 2
    6 5 4 3 2 1
    The Structure of Alkynes

    A triple bond is composed of a  bond and two  bonds


    Addition Reactions of Alkynes
    Sequential Addition of HCl
    An alkyne is less reactive than an alkene
    Relative Stabilities of Carbocations
    1. Addition of Hydrogen Halides

    In the presence of 1 mole equivalent of HBr


    H Br H
    CH3CH2C CH CH3CH2C CH CH3CH2C CH

    Br-

    H
    CH3CH2C CH CH3CH2CH CH

    The secondary vinylic cation


    is more stable
    In the presence of excess HBr,
    a carbocation is formed by adding the electrophile to the
    sp2 carbon bonded to the greater number of hydrogen
    Br Br
    HBr
    CH3CH2C CH2 CH3CH2CCH3
    Br

    Br Br
    CH3CH2C CH3 CH3CH2C CH3
    A secondary vinylic cation is about as stable as a primary
    cation,
    therefore a pi-complex may be the actual reaction
    intermediate

    - Cl

    + H
    HC CH

    Many (but not all) alkyne addition reactions are


    stereoselective
    2. Addition of HBr in the presence of peroxide
    peroxide
    CH3CH2C CH + HBr CH3CH2CH CHBr
    3. Addition of Halogens to Alkynes

    Cl Cl Cl
    Cl2 Cl2
    CH3CH2C CCH3 CH3CH2C CCH3 CH3CH2C CCH3
    CH2Cl2 CH2Cl2
    Cl Cl Cl

    Br Br Br
    Br2 Br2
    CH3C CH CH3C CH CH3C CCH3
    CH2Cl2 CH2Cl2
    Br Br Br
    4. Addition of Water

    O tautomerization OH
    RCH2 C R RCH C R
    keto tautomer enol tautomer
    Examples of Water Addition
    Hg2+ is added to increase the rate of water addition to
    terminal alkynes
    Hydroboration–Oxidation of Internal
    Alkynes
    Hydroboration–Oxidation of Terminal
    Alkynes

    CH3 CH3
    CH3 CH3
    CH3CH CH B H
    CH3CH2C CH + CH3CH CH BH 2
    2
    C C
    H CH2CH3

    CH2CH3 O
    -
    HO , H2O2 H
    C C CH3CH2CH2CH
    H 2O HO H
    Formation of Ketone versus Aldehyde
    5. Addition of Hydrogen
    Formation of Cis Alkene
    Conversion of Internal Alkynes to Trans
    Alkenes
    Reason for trans addition:
    Acidity of a Hydrogen Bonded to an sp
    Hybridized Carbon

    HC CH H2C CH2 CH3CH3


    pKa = 25 pKa = 44 pKa = 50
    Electronegativities versus Acid
    Strengths

    relative base strength


    CH3CH2- > H2C CH- > H2N- > HC C- > HO- > F-

    strongest weakest
    base base
    The stronger the acid, the weaker its conjugate base

    top 252
    Synthesis Using Acetylide Ions:
    Formation of C–C Bond
    Designing a Synthesis

    Example 1

    O
    ?
    CH3CH2C CH CH3CH2CCH2CH2CH3
    Example 2
    Example 3
    Commercial Use of Ethyne

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