Scribd Logo
Upload

Welcome to Scribd!

  • 56 views

    Sn2 Mechanism

    Uploaded by

    Dian Mustikasari
    The SN2 reaction is a nucleophilic substitution reaction where nucleophile and leaving group attack the central carbon simultaneously in a concerted, single-step mechanism. This results in inversion of configuration. Reactivity depends on the nucleophile, with more charged and polarizable nucleophiles like I- being more reactive. It also depends on the leaving group, with weaker bases like I- being better leaving groups. Steric effects are also important, with less substituted and less branched substrates like methyl halides reacting faster than more substituted and branched substrates.

    Copyright:

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

    Sn2 Mechanism

    Uploaded by

    Dian Mustikasari
    56 views18 pages
    The SN2 reaction is a nucleophilic substitution reaction where nucleophile and leaving group attack the central carbon simultaneously in a concerted, single-step mechanism. This results in inversion of configuration. Reactivity depends on the nucleophile, with more charged and polarizable nucleophiles like I- being more reactive. It also depends on the leaving group, with weaker bases like I- being better leaving groups. Steric effects are also important, with less substituted and less branched substrates like methyl halides reacting faster than more substituted and branched substrates.

    Original Description:

    Reaksi mekanisme 2

    Copyright

    © © All Rights Reserved

    Available Formats

    PPT, PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    The SN2 reaction is a nucleophilic substitution reaction where nucleophile and leaving group attack the central carbon simultaneously in a concerted, single-step mechanism. This results in inversion of configuration. Reactivity depends on the nucleophile, with more charged and polarizable nucleophiles like I- being more reactive. It also depends on the leaving group, with weaker bases like I- being better leaving groups. Steric effects are also important, with less substituted and less branched substrates like methyl halides reacting faster than more substituted and branched substrates.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    56 views18 pages

    Sn2 Mechanism

    Uploaded by

    Dian Mustikasari
    The SN2 reaction is a nucleophilic substitution reaction where nucleophile and leaving group attack the central carbon simultaneously in a concerted, single-step mechanism. This results in inversion of configuration. Reactivity depends on the nucleophile, with more charged and polarizable nucleophiles like I- being more reactive. It also depends on the leaving group, with weaker bases like I- being better leaving groups. Steric effects are also important, with less substituted and less branched substrates like methyl halides reacting faster than more substituted and branched substrates.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 18

    Nucleophilic Substitution

    SH S

    1
    I. Nucleophilic Substitution

    R X + Y R Y + X substitution
    substrate nucleophile product leaving reaction
    group

    e.g.,

    H O CH3 Br CH3 OH + Br
    I. Nucleophilic Substitution
    A. Functional group transformation
    R X + HO R OH alcohol
    alkyl
    halide R'O R O R' ether
    (sp3 only)
    O O
    R' C O R' C OR ester

    HS R SH thiol

    R'S R S R' thioether

    CN R C N nitrile

    R' C C R C C R' alkyne

    N3 R N N N azide
    I. Nucleophilic Substitution
    Question 8-1. Give the products. Click on the arrow to check answers.

    CH3Br + NaOH

    Br + CH3S-

    Br + CN-
    I. Nucleophilic Substitution
    Answer 8-1. Give the products. Click on the arrow to check answers.

    CH3Br + NaOH CH3OH

    Br + CH3S- S CH3

    Br + CN- C N
    I. Nucleophilic Substitution
    B. Leaving groups
    weaker base = better leaving group
    reactivity: R-I > R-Br > R-Cl >> R-F
    best L.G. worst L.G.
    most reactive least reactive

    R X + Y R Y + X K>1
    stronger weaker
    base base

    Br + NaF F + NaBr
    SB WB
    precipitate
    drives rxn
    acetone
    + NaI + NaBr (s) (Le Châtelier)
    Br I
    WB SB
    I. Nucleophilic Substitution
    C. Two mechanisms

    general: Rate = k1[RX] + k2[RX][Y–]

    k1 increases
    RX = CH3X 1º 2º 3º

    k2 increases

    k1 ~ 0 k2 ~ 0
    Rate = k2[RX][Y–] Rate = k1[RX]
    (bimolecular) (unimolecular)
    SN2 SN1
    II. SN2 Mechanism
    A. Kinetics
    e.g., CH3I + OH–  CH3OH + I–

    find: Rate = k[CH3I][OH–], i.e., bimolecular

     both CH3I and OH– involved in RLS

    and recall, reactivity: R-I > R-Br > R-Cl >> R-F

     C-X bond breaking involved in RLS

     concerted, single-step mechanism:


    [HO---CH3---I]–

    CH3I + OH–

    CH3OH + I–
    II. SN2 Mechanism
    B. Stereochemistry: inversion of configuration

    Stereospecific reaction:

    H Br HO H
    NaOH

    (R)-(–)-2-bromooctane (S)-(+)-2-octanol

    Reaction proceeds with


    inversion of configuration.
    II. SN2 Mechanism
    C. Mechanism

    Back-side attack: inversion of configuration

    H + - H H

    HO C I HO C I HO C + I
    H H
    H HH H

    HO C I HO C I HO C I

    sp3 sp2 sp3


    high energy TS
    II. SN2 Mechanism
    D. Steric effects
    e.g., R–Br + I–  R–I + Br–

    1. branching at the  carbon ( X–C–C–C.... )


    

    Compound Rel. Rate


    methyl CH3Br 150
    1º RX CH3CH2Br 1 increasing
    2º RX (CH3)2CHBr 0.008 steric hindrance

    3º RX (CH3)3CBr ~0
    II. SN2 Mechanism
    D. Steric effects
    1. branching at the  carbon

    H
    I C Br minimal steric hindrance
    H
    H
    H H
    H C
    H
    I C Br maximum steric hindrance
    H C
    H C
    H H
    H
    II. SN2 Mechanism
    D. Steric effects
    1. branching at the  carbon

    Reactivity toward SN2:

    CH3X > 1º RX > 2º RX >> 3º RX

    react more does not


    readily difficult react by
    by SN2 S N2
    (k2 large) (k2 ~ 0)
    II. SN2 Mechanism
    D. Steric effects
    2. branching at the  carbon

    Rel. Rate
     
    CH3 CH2 CH2 Br 1
    CH3
    increasing
    CH3 CH CH2 Br 0.003 steric
    hindrance
    CH3
    CH3 C CH2 Br 0.00001
    CH3

    ~ no SN2 with neopentyl substrates


    II. SN2 Mechanism
    E. Nucleophiles and nucleophilicity
    1. anions

    R X + OH R OH + X

    R X + CN R CN + X

    2. neutral species

    R X + H2O R O H + X ROH + HX
    solvolysis H hydrolysis
    reactions
    R X + R'OH R O R' + X ROR' + HX
    H alcoholysis
    II. SN2 Mechanism
    E. Nucleophiles and nucleophilicity
    3. nucleophilicity
    a. charged species are more nucleophilic than neutral species
    HO– > H2O
    RO– > ROH
    HS– > H2S
    b. when nucleophilic atoms are in the same row, nucleophilicity
    follows basicity
    H2N– > HO– > F–
    H3N > H2O
    RO– > RCO2–
    c. when nucleophilic atoms are in the same column, nucleophilicity
    follows ionic radius (polarizability)
    I– > Br– > Cl– > F–
    HS– > HO–
    PH3 > NH3
    II. SN2 Mechanism
    E. Nucleophiles and nucleophilicity

    Summary:
    very good Nu: I–, HS–, RS–, H2N–
    good Nu: Br–, HO–, RO–, CN–, N3–
    fair Nu: NH3, Cl–, F–, RCO2–
    poor Nu: H2O, ROH
    very poor Nu: RCO2H
    II. SN2 Mechanism
    Question 8-2. Which reaction will proceed faster in each of the following pairs?
    What will be the product?

    NaN3 NaOH
    Cl I
    NaN3 NaOH
    I I

    Br NaCN NaSH
    Br

    NaCN NaOH
    Br Br

    You might also like