Location via proxy:   [ UP ]  
[Report a bug]   [Manage cookies]                
Scribd Logo
Upload

Welcome to Scribd!

  • 43 views

    Phase-Transfer Catalysis

    Uploaded by

    SIMARAN JAISWAL 41 M3S
    The document describes phase-transfer catalysis (PTC), which involves reactions between reagents dissolved in immiscible organic and aqueous solutions. PTC uses a catalyst that is soluble in both solutions to transfer reagents between the phases. Common catalysts include quaternary ammonium and phosphonium salts. The catalyst forms ion pairs with inorganic reagents, keeping them soluble in the organic phase where they can react with organic substrates. This "naked" or "bikini" state of the inorganic reagents enhances their reactivity. Examples of PTC reactions and mechanisms are provided.

    Copyright:

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

    Phase-Transfer Catalysis

    Uploaded by

    SIMARAN JAISWAL 41 M3S
    43 views16 pages
    The document describes phase-transfer catalysis (PTC), which involves reactions between reagents dissolved in immiscible organic and aqueous solutions. PTC uses a catalyst that is soluble in both solutions to transfer reagents between the phases. Common catalysts include quaternary ammonium and phosphonium salts. The catalyst forms ion pairs with inorganic reagents, keeping them soluble in the organic phase where they can react with organic substrates. This "naked" or "bikini" state of the inorganic reagents enhances their reactivity. Examples of PTC reactions and mechanisms are provided.

    Original Title

    ptc

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    The document describes phase-transfer catalysis (PTC), which involves reactions between reagents dissolved in immiscible organic and aqueous solutions. PTC uses a catalyst that is soluble in both solutions to transfer reagents between the phases. Common catalysts include quaternary ammonium and phosphonium salts. The catalyst forms ion pairs with inorganic reagents, keeping them soluble in the organic phase where they can react with organic substrates. This "naked" or "bikini" state of the inorganic reagents enhances their reactivity. Examples of PTC reactions and mechanisms are provided.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    43 views16 pages

    Phase-Transfer Catalysis

    Uploaded by

    SIMARAN JAISWAL 41 M3S
    The document describes phase-transfer catalysis (PTC), which involves reactions between reagents dissolved in immiscible organic and aqueous solutions. PTC uses a catalyst that is soluble in both solutions to transfer reagents between the phases. Common catalysts include quaternary ammonium and phosphonium salts. The catalyst forms ion pairs with inorganic reagents, keeping them soluble in the organic phase where they can react with organic substrates. This "naked" or "bikini" state of the inorganic reagents enhances their reactivity. Examples of PTC reactions and mechanisms are provided.

    Copyright:

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

    Phase-transfer catalysis

    • An aqueous solution
    • An organic solution (chloroform, hydrocarbons)
    • An organic reagent soluble in the organic solvent only
    • An inorganic reagent (NaOH, NaI or NaCN) soluble in
    water only
    • A catalyst soluble in both phases. The catalyst is able to
    complex the inorganic reagent
    Phase-transfer catalysis (PTC)

    Examples of polar aprotic solvents. Good


    solvents for both organic compounds and
    polar inorganic salts
    O O O O
    S S
    Me Me Me Me H NMe2 H NMe2

    dimethyl sulfoxide (DMSO) N,N-dimethylformamide (DMF)

    O O
    N N
    Me Me

    N-methylpyrrolidone (NMP)
    SN2 reaction of octyl chloride with sodium
    cyanide
    +
    P
    Br-

    tetrabutylphosphonium bromide no reaction


    (n-Bu)4P+ Br-

    Cl NaCN
    n-Bu P Br
    4
    water/decane

    CN
    The principle of phase-transfer catalysis
    developed by Makosza
    • The catalyst (Bu4P+ Cl-) contains highly lipophilic butyl
    groups, which makes the compound soluble in an
    organic solvent. It is also a polar phosphonium salt,
    which makes the compound soluble in water as well.

    Bu4P CN R-Cl R-CN Bu4P Cl Organic


    phase
    Phase
    boundary

    NaCl NaCN Bu4P Cl Aqueous


    Bu4P CN
    phase
    Typical phase-transfer catalysts
    ammonium salts 1-4 and phosphonium salts 5,6

    n Bu R Et Me
    nBu
    N Me N Cl N OH
    n Bu N R Cl Et Me
    X R Et Me
    n Bu
    1 2 3 4
    X=
    a Br (TBAB) a R = n-C8H17 (TEBA) (Triton B)
    bF (TBAF) (Aliquat 336)
    c OH (TBAH) b R = n-C8-C10
    d HSO4 (Adogen)
    e BH3CN
    f ClCrO3
    n Bu nBu P Br
    n Bu P Br
    n Bu

    5 6
    Typical phase-transfer catalysts
    crown ethers 7-9 and a cryptand 10
    Complexes with potassium cation are shown for 7 and 10

    O O
    O
    O O O O
    O + O
    K
    O O O O
    O O
    O O
    O

    7 8 9
    18-crown-6
    with potassium cation O O

    N K N

    O O
    O O

    10
    Naked (bikini) anions

    • The high reactivity of nucleophiles under phase-transfer


    catalysis is attributed to their poor solvation in the
    organic phase or at the phase boundry. The poorly
    solvated anions are sometimes called ‘naked’. Makosza
    suggested ‘bikini’ because each loose ion pair in an
    organic solvent is associated with a few molecules of
    water extracted from an aqueous solution.

    + Et
    N - Triethylbenzylammonium chloride
    Et Cl
    Et (TEBA)
    Note 13 carbon atoms in the molecule for high lipophilicity
    Synthesis of TEBA

    .. Et Et
    Et
    N N+ -
    + Et-Cl Cl
    Et Et
    “Purple benzene”
    a strong oxidant in an organic phase

    O O
    O O O O
    K MnO4 K MnO4
    O O O O
    O O
    Synthesis of 7,7-dichloronorcarane under
    PTC conditions

    + -
    HCX3 + NaOH Na CX3 + H2O (1)
    + - + - + -
    Na CX3 + R4N X R4N CX3 + NaX (2)
    + - + -
    R4N CX3 :CX2 + R4N X (3)
    Cl
    :CX2 + (4)
    Cl
    7,7-dichloronorcarane
    (7,7-dichlorobicyclo[4.1.0]heptane)
    The mechanism of the norcarane synthesis

    Organic Phase
    CHX3
    X X

    CHX3 OH :CX2 H2O R4N+ X-


    Phase Boundary

    R4N+ OH-

    R4N+ X- =
    Aqueous Phase
    NaOH N
    H2O
    Cl
    Graduate Studies in Chemistry • Competitive stipends and fellowships;
    waived tuition; and assisted health
    MS and PhD Programs offered in: insurance (PhD’s supported: 82)

    • Analytical • Ranked top 10 of 178 by National


    • Biological / Biochemical Research Council in “Student support
    and Outcomes” and “Faculty Diversity”
    • Biophysical / Computational http://www.nap.edu/rdp/
    • Organic / Medicinal
    • Masters program ranked number 9 in
    the United States (number one in the
    For more information: Southeast) by the American Chemical
    www.chemistry.gsu.edu Society for MS degrees conferred in
    chegsc@langate.gsu.edu 2008-2009
    http://pubs.acs.org/cen/email/html/8834acsnews1.html
    13
    Center for Diagnostics and
    Therapeutics

    14
    15
    16

    You might also like