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    CH CH D D D: Compound K M S ×10 PK

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    panda biru
    This document contains 8 chemistry problems about reaction rates and acidity. Problem 6.4 asks about factors that could account for a smaller exchange rate for bicyclo[2.1.1]hexan-2-one. Problem 6.5 asks to estimate deprotonation extent for hydrocarbon-base combinations using data tables. Problem 6.6 asks how to explain the faster rate of removal of an axial proton over an equatorial proton from 4-t-butylcyclohexanone.

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    CH CH D D D: Compound K M S ×10 PK

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    panda biru
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    This document contains 8 chemistry problems about reaction rates and acidity. Problem 6.4 asks about factors that could account for a smaller exchange rate for bicyclo[2.1.1]hexan-2-one. Problem 6.5 asks to estimate deprotonation extent for hydrocarbon-base combinations using data tables. Problem 6.6 asks how to explain the faster rate of removal of an axial proton over an equatorial proton from 4-t-butylcyclohexanone.

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    This document contains 8 chemistry problems about reaction rates and acidity. Problem 6.4 asks about factors that could account for a smaller exchange rate for bicyclo[2.1.1]hexan-2-one. Problem 6.5 asks to estimate deprotonation extent for hydrocarbon-base combinations using data tables. Problem 6.6 asks how to explain the faster rate of removal of an axial proton over an equatorial proton from 4-t-butylcyclohexanone.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    59 views1 page

    CH CH D D D: Compound K M S ×10 PK

    Uploaded by

    panda biru
    This document contains 8 chemistry problems about reaction rates and acidity. Problem 6.4 asks about factors that could account for a smaller exchange rate for bicyclo[2.1.1]hexan-2-one. Problem 6.5 asks to estimate deprotonation extent for hydrocarbon-base combinations using data tables. Problem 6.6 asks how to explain the faster rate of removal of an axial proton over an equatorial proton from 4-t-butylcyclohexanone.

    Copyright:

    © All Rights Reserved
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    Download as pdf or txt
    of 1

    6.4 a.

    The relative rates of hydroxide ion-catalyzed deuterium exchange at C(3) 621


    have been measured for bicyclo[2.1.1]hexan-2-one, bicyclo[2.2.1]heptan-2-
    PROBLEMS
    one, and bicyclo[2.2.2]octan-2-one. What factor(s) could account for the much
    smaller rate of exchange for bicyclo[2.1.1]hexan-2-one?
    b. Treatment of (+)-camphenilone with K + ·− O-t-Bu in t-BuOD at 185 C results
    in incorporation of D, as indicated below. Racemization occurs at the same
    rate. Suggest a mechanism that could account for these observations.

    CH3
    D
    CH3
    D D O

    6.5. Using data from Tables 6.1 (p. 580) and 6.2 (p. 583), estimate the extent of
    deprotonation for each hydrocarbon-base combination below. Discuss the uncer-
    tainties that could affect the calculation.

    a. indene by 0.01 M NaOCH3 in 1:1 DMSO-C2 H5 OH


    b. fluorene by 0.01 M NaOC2 H5 in 20:1 DMSO-C2 H5 OH
    c. triphenylmethane by 5 M KOCH3 in CH3 OH

    6.6. The rates of removal of axial and equatorial protons from 4-t-butylcyclohexanone
    in NaOD/dioxane have been compared by an NMR technique. The rate of
    removal of an axial proton is 5.5 times faster than for an equatorial proton. How
    do you explain the difference?
    6.7. The following table gives exchange rates in methanolic NaOCH3 and pK values
    for some hydrocarbons. Determine if there is a correlation between the kinetic
    and thermodynamic acidity.

    Compound kexchange pK
    M −1 s−1 ×104 

    9-Phenylfluorene 173 18.5


    Indene 50 19.9
    3,4-Benzofluorene 90.3 19.75
    1,2-Benzofluorene 31.9 20.3
    2,3-Benzofluorene 2.15 23.5
    Fluorene 3.95 22.7

    6.8. The acidity of various substituted acetophenones in DMSO is given below.


    Would you expect the  value to correlate best with
    ,
    + , or
    − ? Explain,
    considering each of the
    parameters explicitly. Do a plot of the pK/pK0 values
    for each
    parameter.

    X CH3

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