Scribd Logo
Upload

Welcome to Scribd!

  • 16 views

    R CCHR' O H R CCHR' R R CCHR' + R R' R C C: 5.10.5. Eliminations Reactions Not Involving C

    Uploaded by

    panda biru
    This document discusses elimination reactions, specifically E1 elimination reactions. It notes that E1 eliminations favor the more substituted alkene due to the carbocation intermediate. Tertiary alcohols undergo E1 elimination most readily, followed by secondary then primary alcohols. Rearranged products can also occur if the carbocation intermediate is capable of rearranging. Eliminations can occur on compounds with substituents other than hydrogen atoms on beta carbons, as long as the substituent can provide electrons to the elimination process. Vicinal dibromides can undergo elimination through debromination by reducing agents like iodide ion, and the stereochemistry of the reaction has been determined using labeled compounds.

    Copyright:

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

    R CCHR' O H R CCHR' R R CCHR' + R R' R C C: 5.10.5. Eliminations Reactions Not Involving C

    Uploaded by

    panda biru
    16 views1 page
    This document discusses elimination reactions, specifically E1 elimination reactions. It notes that E1 eliminations favor the more substituted alkene due to the carbocation intermediate. Tertiary alcohols undergo E1 elimination most readily, followed by secondary then primary alcohols. Rearranged products can also occur if the carbocation intermediate is capable of rearranging. Eliminations can occur on compounds with substituents other than hydrogen atoms on beta carbons, as long as the substituent can provide electrons to the elimination process. Vicinal dibromides can undergo elimination through debromination by reducing agents like iodide ion, and the stereochemistry of the reaction has been determined using labeled compounds.

    Original Description:

    kol

    Original Title

    page_583

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    This document discusses elimination reactions, specifically E1 elimination reactions. It notes that E1 eliminations favor the more substituted alkene due to the carbocation intermediate. Tertiary alcohols undergo E1 elimination most readily, followed by secondary then primary alcohols. Rearranged products can also occur if the carbocation intermediate is capable of rearranging. Eliminations can occur on compounds with substituents other than hydrogen atoms on beta carbons, as long as the substituent can provide electrons to the elimination process. Vicinal dibromides can undergo elimination through debromination by reducing agents like iodide ion, and the stereochemistry of the reaction has been determined using labeled compounds.

    Copyright:

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

    R CCHR' O H R CCHR' R R CCHR' + R R' R C C: 5.10.5. Eliminations Reactions Not Involving C

    Uploaded by

    panda biru
    This document discusses elimination reactions, specifically E1 elimination reactions. It notes that E1 eliminations favor the more substituted alkene due to the carbocation intermediate. Tertiary alcohols undergo E1 elimination most readily, followed by secondary then primary alcohols. Rearranged products can also occur if the carbocation intermediate is capable of rearranging. Eliminations can occur on compounds with substituents other than hydrogen atoms on beta carbons, as long as the substituent can provide electrons to the elimination process. Vicinal dibromides can undergo elimination through debromination by reducing agents like iodide ion, and the stereochemistry of the reaction has been determined using labeled compounds.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 1

    564 This elimination reaction is the reverse of acid-catalyzed hydration, which was

    discussed in Section 5.2. Since a carbocation or closely related species is the inter-
    CHAPTER 5 mediate, the elimination step is expected to favor the more-substituted alkene. The
    Polar Addition E1 mechanism also explains the trends in relative reactivity. Tertiary alcohols are the
    and Elimination
    Reactions most reactive, and reactivity decreases going to secondary and primary alcohols. Also
    in accord with the E1 mechanism is the fact that rearranged products are found in
    cases where a carbocation intermediate would be expected to rearrange.

    R
    R3CCHR' R3CCHR' R
    + H+ R3CCHR' R2CCHR' R2C C
    OH O+H2 + + R'

    For some alcohols, exchange of the hydroxyl group with solvent competes with
    dehydration.301 This exchange indicates that the carbocation can undergo SN 1 capture
    in competition with elimination. Under conditions where proton removal is rate deter-
    mining, it would be expected that a significant isotope effect would be seen, which is,
    in fact, observed.

    H*
    H2SO4
    PhCHCHPh PhCH CHPh
    H2O
    OH kH/kD = 1.8

    Ref. 302

    5.10.5. Eliminations Reactions Not Involving C−H Bonds

    The discussion of elimination processes thus far has focused on reactions that
    involve removal of a proton bound to a ß-carbon, but it is the electrons in the C−H

    bond that are essential to the elimination process. Compounds bearing other substituents
    that can release electrons undergo -eliminations. Many such reactions are known,
    and they are frequently stereospecific.
    Vicinal dibromides can be debrominated by certain reducing agents, including
    iodide ion. The stereochemical course in the case of 1,1,2-tribromocyclohexane was
    determined using a 82 Br-labeled sample prepared by anti addition of 82 Br 2 to bromo-
    cyclohexene. Exclusive anti elimination gave unlabeled bromocyclohexene, whereas
    82
    Br-labeled product resulted from syn elimination. Debromination with sodium iodide
    was found to be cleanly an anti elimination.303

    82Br

    NaI
    82Br
    Br
    Br
    anti elimination
    product

    301
    C. A. Bunton and D. R. Llewellyn, J. Chem. Soc., 3402 (1957); J. Manassen and F. S. Klein, J. Chem.
    Soc., 4203 (1960).
    302
    D. S. Noyce, D. R. Hartter, and R. M. Pollack, J. Am. Chem. Soc., 90, 3791 (1968).
    303
    C. L. Stevens and J. A. Valicenti, J. Am. Chem. Soc., 87, 838 (1965).

    You might also like