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    2013 - KOF Isotop Effect and Carbocation

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    Ardhito Setiawan
    1. Kinetic isotope effects measure the rate change that occurs due to isotopic substitution, either at the site of bond breaking/making (primary effect) or elsewhere (secondary effect). Typical primary kinetic isotope effect values are provided for several light/heavy isotope pairs. 2. Two examples of kinetic isotope effect measurements are shown for dehydrohalogenation reactions, with a primary kinetic isotope effect of 6.7 for C-H/C-D bond breaking and 1.4 for no bond breaking. 3. Further examples demonstrate using kinetic isotope effects to determine if a C-H bond is broken in the rate determining step of electrophilic aromatic nitration, and the inertness of vinyl and phenyl

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    2013 - KOF Isotop Effect and Carbocation

    Uploaded by

    Ardhito Setiawan
    5 views6 pages
    1. Kinetic isotope effects measure the rate change that occurs due to isotopic substitution, either at the site of bond breaking/making (primary effect) or elsewhere (secondary effect). Typical primary kinetic isotope effect values are provided for several light/heavy isotope pairs. 2. Two examples of kinetic isotope effect measurements are shown for dehydrohalogenation reactions, with a primary kinetic isotope effect of 6.7 for C-H/C-D bond breaking and 1.4 for no bond breaking. 3. Further examples demonstrate using kinetic isotope effects to determine if a C-H bond is broken in the rate determining step of electrophilic aromatic nitration, and the inertness of vinyl and phenyl

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    2013- KOF Isotop Effect and Carbocation

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    1. Kinetic isotope effects measure the rate change that occurs due to isotopic substitution, either at the site of bond breaking/making (primary effect) or elsewhere (secondary effect). Typical primary kinetic isotope effect values are provided for several light/heavy isotope pairs. 2. Two examples of kinetic isotope effect measurements are shown for dehydrohalogenation reactions, with a primary kinetic isotope effect of 6.7 for C-H/C-D bond breaking and 1.4 for no bond breaking. 3. Further examples demonstrate using kinetic isotope effects to determine if a C-H bond is broken in the rate determining step of electrophilic aromatic nitration, and the inertness of vinyl and phenyl

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    5 views6 pages

    2013 - KOF Isotop Effect and Carbocation

    Uploaded by

    Ardhito Setiawan
    1. Kinetic isotope effects measure the rate change that occurs due to isotopic substitution, either at the site of bond breaking/making (primary effect) or elsewhere (secondary effect). Typical primary kinetic isotope effect values are provided for several light/heavy isotope pairs. 2. Two examples of kinetic isotope effect measurements are shown for dehydrohalogenation reactions, with a primary kinetic isotope effect of 6.7 for C-H/C-D bond breaking and 1.4 for no bond breaking. 3. Further examples demonstrate using kinetic isotope effects to determine if a C-H bond is broken in the rate determining step of electrophilic aromatic nitration, and the inertness of vinyl and phenyl

    Copyright:

    © All Rights Reserved
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    1

    TestingaMechanism: TestingaMechanism:
    KineticIsotopeEffects KineticIsotopeEffects
    i ff i ff Primary Isotope Effect Primary Isotope Effect - - rate change due to rate change due to
    isotopic substitution at a site of bond breaking isotopic substitution at a site of bond breaking
    or bond making in the rate determining step of or bond making in the rate determining step of
    a mechanism. a mechanism.
    Secondary Isotope Effect Secondary Isotope Effect -- rate change due to rate change due to
    i t i b tit ti t th th it f b d i t i b tit ti t th th it f b d isotopic substitution at other than a site of bond isotopic substitution at other than a site of bond
    breaking or bond making in the rate breaking or bond making in the rate
    determining step of a mechanism. determining step of a mechanism.
    PrimaryKineticIsotope
    Effect:Typical Values
    Nuclide k
    light heavy
    k
    (at 25
    o
    C)
    C H/C D 6 8 C-H/C-D 6 - 8
    C-H/C-T 15 - 16
    C
    12
    /
    13
    C 1.04
    C
    12
    /
    C
    14
    1.07
    14 15
    N/ N 103 N/ N 1.03
    16
    O/
    18
    O 1.02
    32
    S/
    34
    S
    1.01
    35
    Cl/
    37
    Cl 1.01
    2
    EXAMPLES OF
    KINETIC ISOTOPE EFFECTS
    Consider thefollowing dehydrohalogenation reactions:
    CaseI:
    CH
    3
    CH
    2
    CH
    2
    Br
    NaOC
    2
    H
    5
    C
    2
    H
    5
    OH
    C CH
    2
    H
    3
    C
    H
    H C
    k k
    H D
    / k k
    H D
    /
    = 6.7
    1
    o
    KIE f C H/C D
    CH
    3
    CD
    2
    CH
    2
    Br
    NaOC
    2
    H
    5
    C
    2
    H
    5
    OH
    C CH
    2
    H
    3
    C
    D
    CaseII:
    CH
    3
    CH
    2
    C
    CH
    3
    CH
    3
    Br
    H
    2
    O
    C C
    CH
    3
    CH
    3
    H
    3
    C
    H
    H
    2
    O
    C C
    CH
    3
    CH
    3
    H
    3
    C
    D
    C
    CH
    3
    CH
    3
    Br CH
    3
    CD
    2
    k k
    H D
    / k k
    H D
    / = 1.4
    1
    o
    KIE for C-H/C-D
    o
    KIE for C-H/C-D 2
    3
    Rationale:
    Transition Statefor CaseI (E-2)
    H (D)
    (D)

    C
    2
    H
    5
    O
    H
    H
    Br
    H
    3
    C
    H
    C
    C

    -
    -
    Transition Statefor CaseII (E-1)
    H (D)
    (D)

    -
    Br
    H
    3
    C
    H
    C
    C
    CH
    3
    CH
    3
    rds

    +
    H (D)
    (D)
    H
    3
    C
    H
    C
    C
    CH
    3
    CH
    3
    +
    Br
    -
    MoreExamplesofKineticIsotope MoreExamplesofKineticIsotope
    Effects Effects
    Consider the following decomposition of an azo compound:
    R N N R R N N R 2 R + N
    2
    k k
    N N
    14 15 = 1.02
    Rationale: Although the above rate enhancement is small in absolute terms,
    for the nitrogen nuclides indicated, the enhancement is indicative
    of a primary kinetic isotope effect.
    Consider the nitration of benzene shown below:
    C
    6
    H
    6
    HNO
    3
    /H
    2
    SO
    4
    C
    6
    H
    5
    NO
    2
    rate
    H
    HNO /H SO
    C
    6
    D
    6
    HNO
    3
    /H
    2
    SO
    4
    C
    6
    D
    5
    NO
    2
    rate
    D
    Observation: rate
    H
    rate
    D
    =
    ~
    Conclusion to be drawn: A C-H (C-D) bond is not being broken in the
    rate determining step of electrophilic aromatic
    nitration.
    3
    INTERMEDIETKARBOKATION
    StrukturC
    +
    :hibridisasi
    6
    =>
    4
    CONTOHC
    +
    :
    1. Metil karbokation
    2 t b til k b k ti 2. t-butil karbokation
    3. Benzil kation
    4. Alil kation
    Contoh lain : tulis struktur resonansinya
    7
    =>
    1. CH
    3
    O C
    +
    (CH
    3
    )
    2
    1. Ph
    2
    N C
    +
    - (Ph)
    2
    CH
    2 CH
    2
    etc
    +
    +
    BENZYL
    BENZYL AND ALLYL CARBOCATIONS BENZYL AND ALLYL CARBOCATIONS
    RESONANCE
    STABILIZATION
    CH
    2 CH
    2
    etc
    +
    +
    etc
    CH
    2 CH
    2
    ALLYL
    + +
    O H
    3
    C CH
    2
    +
    (benzylic) (allylic)
    Systems that are similar in form to benzyl and allyl are called benzylic and allylic.
    isoelectronic
    with allylic
    5
    SenyawaVinilandFenil
    Vinyl and Phenyl compounds are completely inert in both y y y
    S
    N
    1 and S
    N
    2 reactions!!
    C
    CH
    2
    H
    Cl
    vinyl
    phenyl
    Cl
    Pembentukan C
    +
    :dr sistem tdk jenuh
    Tulislah persamaan reaksi :
    1. Sikloheksena dan HCl
    2. 2-metilpropena dan H
    2
    O/H
    +
    10
    =>
    2
    3. 2-metilpropena dan HOCl
    4. 2-metil2-butena dan HBr
    5. Styrena dan HBr
    6. Me
    2
    N
    +
    --CH=CH
    2
    +HI ?
    6
    tgl 25senin :jam12.3014.10
    Rabu tgl 27:12.3014.10
    atau atau
    kamis tgl 28:12.3014.10
    1. Di danTri-arilmetil kation
    2. Aromatik kation
    11
    =>
    3. 2-metilpropena dan HOCl
    4. 2-metil2-butena dan HBr
    5. Styrena dan HBr
    6. Me
    2
    N
    +
    --CH=CH
    2
    +HI ?

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