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    Amierson Tilendo
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    Alkyl halides undergo substitution and elimination reactions. In substitution reactions, the halide leaving group is replaced by another group such as OH. There are two mechanisms for substitution reactions - SN1 and SN2. SN1 is a unimolecular reaction that proceeds via a carbocation intermediate. SN2 is a bimolecular reaction that proceeds through a pentacoordinate transition state without formation of a carbocation. The stereochemistry of SN1 reactions results in racemic products while SN2 reactions invert configuration. Factors such as stability of carbocations, nucleophilicity, and solvent influence whether SN1 or SN2 is favored.

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    Lecture . 9,10

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    Alkyl halides undergo substitution and elimination reactions. In substitution reactions, the halide leaving group is replaced by another group such as OH. There are two mechanisms for substitution reactions - SN1 and SN2. SN1 is a unimolecular reaction that proceeds via a carbocation intermediate. SN2 is a bimolecular reaction that proceeds through a pentacoordinate transition state without formation of a carbocation. The stereochemistry of SN1 reactions results in racemic products while SN2 reactions invert configuration. Factors such as stability of carbocations, nucleophilicity, and solvent influence whether SN1 or SN2 is favored.

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    24 views28 pages

    Lecture - 9,10

    Uploaded by

    Amierson Tilendo
    Alkyl halides undergo substitution and elimination reactions. In substitution reactions, the halide leaving group is replaced by another group such as OH. There are two mechanisms for substitution reactions - SN1 and SN2. SN1 is a unimolecular reaction that proceeds via a carbocation intermediate. SN2 is a bimolecular reaction that proceeds through a pentacoordinate transition state without formation of a carbocation. The stereochemistry of SN1 reactions results in racemic products while SN2 reactions invert configuration. Factors such as stability of carbocations, nucleophilicity, and solvent influence whether SN1 or SN2 is favored.

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    REACTIONS OF ALKYL HALIDES

     Alkyl halides (R-X) undergo two types of reactions :


     substitution reactions and elimination reactions.

     In a substitution reaction, the X group in R-X is


     replaced by a different group, e.g. R-X R-OH +XӨ

     In an elimination reaction, the elements of H-X are


     eliminated from R-X; the product is very often an
     alkene.
    ALKYL HALIDES – SUBSTITUTION REACTIONS

    This is a nucleophilic substitution or nucleophilic


    displacement reaction on which OH displaces Br.

    The C-Br bond is polar, and the carbon ( ⊕) is


    susceptible to attack by an anion or any other
    nucleophile.

    ӨOH is the nucleophile (species which ―loves nuclei‖


    or has an affinity for positive charges).

    BrӨ is the leaving group


    ALKYL HALIDES – SUBSTITUTION REACTIONS

     CH3-CH2—Br + ӨOH CH3-CH2—OH + BrӨ

     The general reaction is:


     R-X + NuӨ R-Nu + XӨ
     These are ionic reactions.
     There are two possible ionic mechanisms for nucleophilic
     substitution, SN1 and SN2.

     S – substitution; N – nucleophilic;
     1 – unimolecular (the rate determining, r.d.s., step entails one
    molecule);
     2 – bimolecular (the rate determining step entails two species).
    ALKYL HALIDES
    THE UNIMOLECULAR (SN1) REACTION

     (a)
     In the first step, R-X dissociates, forming a carbocation,
     R⊕, and the leaving group XӨ.
     This is a slow, rate determining step (r.d.s.) and
     entails only one species, R-X.

     (b) R⊕+ NuӨ R-Nu


     In the second step the carbocation and the nucleophile
     combine. This occurs rapidly.

     The overall reaction is R-X + NuӨ R-Nu + XӨ

     The rate of the reaction = k[R-X]


    ALKYL HALIDES: THE BIMOLECULAR (SN2)
    REACTION
     A-NuӨ + R-X ⇋ ӨNu---R---X Ө
     The nucleophile and the alkyl halide combine to form a
     pentacoordinate transition state. This is the slow rate
     determining step (r.d.s); it entails two species, R-X and
     NuӨ . The dotted lines indicate partially formed or
     partially broken covalent bonds.

     B- ӨNu---R---X Ө Nu-R + XӨ
     The pentacoordinate transition state dissociates to form
     the product, Nu-R, and the halide ion (the leaving
     group).
     The rate of the reaction = k[R-X][NuӨ]
     The rate is dependent of the concentration of two species;
     higher concentrations increase the frequency of molecular
     collisions.
    ALKYL HALIDES
    THE UNIMOLECULAR (SN1) REACTION

     (a)
     In the first step, R-X dissociates, forming a carbocation,
     R⊕, and the leaving group XӨ.
     This is a slow, rate determining step (r.d.s.) and
     entails only one species, R-X.

     (b) R⊕+ NuӨ R-Nu


     In the second step the carbocation and the nucleophile
     combine. This occurs rapidly.

     The overall reaction is R-X + NuӨ R-Nu + XӨ

     The rate of the reaction = k[R-X]


    ALKYL HALIDES: SN1 REACTIONS IN MORE
    DETAIL
     A- bromo-2-methylpropane, a 3o alkyl halide
    dissociates, in a slow r.d.s. to a 3o carbocation and
    BrӨ.

     The positively charged carbon in a carbocation is sp2


     hybridized and carbocations have trigonal
    geometry.
     This is a very important point.
     b) A nucleophile, ӨOH, adds to the carbocation to
    give the product, 2-methylpropanol. This is a fast
     process
    THE STEREOCHEMISTRY OF SN1 REACTIONS

     A 3o alkyl halide with three different alkyl


    groups
     attached to the head carbon is chiral.

     There are two enantiomers of such a

     compound, e.g. 3-bromo-3-methylhexane

    .
    THE STEREOCHEMISTRY OF SN1 REACTIONS
    THE STEREOCHEMISTRY OF SN1 REACTIONS
     The initially formed carbocation is planar.

     In the second step, the nucleophile will add from either face
     of the carbocation.

     Both enantiomers of the product are formed in equal amounts.


     The same result is obtained starting with the R enantiomer of the
     alkyl halide, because exactly the same carbocation is formed.
    OTHER ASPECTS OF SN1 REACTIONS

    The most important feature of SN1 reactions is


    the carbocation intermediate.

    A. Alkyl halides which form stable carbocations will undergo SN1 reactions.

    3o alkyl halides form 3o carbocations (stable) and will


    undergo SN1 reactions.
    OTHER ASPECTS OF SN1 REACTIONS

    Alkyl halides which form stable carbocations will undergo


    SN1 reactions.

    2o alkyl halides form 2o carbocations (fairly stable) and


    undergo SN1reactions.

    1o carbocations are unstable, 1o alkyl halides will not undergo


    SN1 reactions.

    Substitution reactions of 1o alkyl halides proceed via the


    SN2 mechanism.
    OTHER ASPECTS OF SN1 REACTIONS
     The RATE of SN1 reactions increases with increasing stability of the
    carbocation.

     The carbocation formed in reaction 1 is more stable than that


     formed in reaction 2, reaction 1 is faster than reaction 2.
    OTHER ASPECTS OF SN1 REACTIONS
     Polar solvents STABILIZE carbocations, and accelerate SN1 reactions.
     The first step of an SN1 reaction is

     If R⊕ is stabilized via interactions with the solvent, the


     equilibrium is pulled to the RIGHT, and the overall process is
    accelerated.

     The DIELECTRIC CONSTANT ( , ―epsilon‖) is an index of
     solvent polarity.

     H2O ( 79) is a polar, protic solvent.


     CH3CH2OH (ethanol, 25) is also protic, but much less polar than
    H2O.
    OTHER ASPECTS OF SN1 REACTIONS
     Polar solvents STABILIZE carbocations, and accelerate SN1 reactions.

     H2O ( 79) interacts with R⊕ and XӨ as shown here.

     The rate of an SN1 reaction of (CH3)3C-Br in pure


     H2O ( 79) is approximately 12,000 times the rate in
     pure CH3CH2OH (ethanol, 25).
    OTHER ASPECTS OF SN1 REACTIONS
     When some 2o alkyl halides undergo the SN1 reaction, products of rearrangement
    are observed.
    ALKYL HALIDES: THE BIMOLECULAR (SN2)
    REACTION
     NuӨ + R-X ⇋ ӨNu---R---X Ө
     The nucleophile and the alkyl halide combine to form a
     pentacoordinate transition state. This is the slow rate
     determining step (r.d.s); it entails two species, R-X and
     NuӨ . The dotted lines indicate partially formed or
     partially broken covalent bonds.

     ӨNu---R---X Ө Nu-R + XӨ
     The pentacoordinate transition state dissociates to form
     the product, Nu-R, and the halide ion (the leaving
     group).
     The rate of the reaction = k[R-X][NuӨ]
     The rate is dependent of the concentration of two species;
     higher concentrations increase the frequency of molecular
     collisions.
    THE STEREOCHEMISTRY OF SN2 REACTIONS

     (a) NuӨ + R-X ⇋ ӨNu---R---X Ө (slow, r.d.s)


     (b) ӨNu---R---X Ө Nu-R + XӨ (fast)

     Let us consider a chiral substrate undergoing


    an
     SN2 reaction.
    THE STEREOCHEMISTRY OF SN2 REACTIONS
    THE STEREOCHEMISTRY OF SN2 REACTIONS
     (a) NuӨ + R-X ⇋ ӨNu---R---X Ө (slow, r.d.s)
     (b) ӨNu---R---X Ө Nu-R + XӨ (fast)

     The pentacoordinate transition state formed at the end of the


     first, slow, rate-determining step is a trigonal bipyramid:
     a three-sided plane perpendicular to the screen;
     the OH and Br groups form apices on either side of the
     pentacoordinate carbon, in the plane of the screen.
    THE STEREOCHEMISTRY OF SN2 REACTIONS
     The nucleophile attacks the substrate from the side
     opposite to the leaving group.
     The stereochemistry of the product is INVERTED,
     relative to that of the starting material.
    THE STEREOCHEMISTRY OF SN2 REACTIONS

     For chiral substrates, reactions proceeding via the


     SN2 mechanism result in inversion of configuration.
     This is a consequence of the ―back side‖ attack by
     the nucleophile.
    OTHER ASPECTS OF SN2 REACTIONS
     SUBSTRATE
     The SN2 reaction involves a transition state with
     pentacoordinate carbon, so sterically hindered alkyl
     halides do not react via this mechanism.
     The RATE of the SN2 reaction for the following
     substrates therefore follow the trend:

     Tertiary alkyl halides do not undergo the SN2 reaction.


    OTHER ASPECTS OF SN2 REACTIONS
     NUCLEOPHILE
     The SN2 reaction is bimolecular, and more
     effective nucleophiles will react faster.
     Order of nucleophilicity: ӨCN > ӨOR > ӨOH.
     Therefore,
     CH3Br + ӨCN CH3CN + Br Ө is a faster
     reaction than
     CH3Br + ӨOR CH3OR + Br Ө , and this in
     turn is faster than
     CH3Br + ӨOH CH3OH+ Br Ө .
    OTHER ASPECTS OF SN2 REACTIONS

     POSSIBILITY OF REARRANGEMENT

     When an alkyl halide undergoes


     substitution via the SN2 mechanism, the

     product has the same carbon skeleton as

     the starting material. No rearrangement

     takes place.
    OTHER ASPECTS OF SN2 REACTIONS

     SOLVENT
     The rate of SN2 reactions (involving
    negatively
     charged nucleophiles) increases when the
     reactions are carried out in polar APROTIC
     solvents.

     Dimethyl sulfoxide (DMSO, 37) is an


    example of
     a polar aprotic solvent.
    OTHER ASPECTS OF SN2 REACTIONS
     SOLVENT: Dimethyl sulfoxide (DMSO, 37) is an
     example of a polar aprotic solvent.

     If, for example, the nucleophile is ӨCN, and the


     source is KCN (potassium cyanide) DMSO will
     solvate the K⊕ ion, thus making ӨCN readily
     available for reaction.

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