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11.5 Characteristics of the \(S_{N}1\) Reaction

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  • Page ID
    67266
  • Objectives

    After completing this section, you should be able to

    1. discuss how the structure of the substrate affects the rate of a reaction occurring by the SN1 mechanism.
    2. arrange a given list of carbocations (including benzyl and allyl) in order of increasing or decreasing stability.
    3. explain the high stability of the allyl and benzyl carbocations.
    4. arrange a given series of compounds in order of increasing or decreasing reactivity in SN1 reactions, and discuss this order in terms of the Hammond postulate.
    5. discuss how the nature of the leaving group affects the rate of an SN1 reaction, and in particular, explain why SN1 reactions involving alcohols are carried out under acidic conditions.
    6. explain why the nature of the nucleophile does not affect the rate of an SN1 reaction.
    7. discuss the role played by the solvent in an SN1 reaction, and hence determine whether a given solvent will promote reaction by this mechanism.
    8. compare the roles played by the solvent in SN1 and in SN2 reactions.
    9. determine which of two SN1 reactions will occur faster, by taking into account factors such as the structure of the substrate and the polarity of the solvent.
    10. determine whether a given reaction is most likely to occur by an SN1 or SN2 mechanism, based on factors such as the structure of the substrate, the solvent used, etc.

    Key Terms

    Make certain that you can define, and use in context, the key terms below.

    • benzylic
    • dielectric constant
    • polarity

    Content

    SN1 Mechanism

     

    The first order kinetics of SN1 reactions suggests a two-step mechanism in which the rate-determining step consists of the ionization of the alkyl halide, as shown in the diagram below. In this mechanism, a carbocation is formed as a high-energy intermediate, and this species bonds immediately to nearby nucleophiles. If the nucleophile is a neutral molecule, the initial product is an "onium" cation, as drawn above for t-butyl chloride, and presumed in the energy diagram. In evaluating this mechanism, we may infer several outcomes from its function.

     

     

     

     

     

     

     

     

    The only reactant that is undergoing change in the first (rate-determining) step is the alkyl halide, so we expect such reactions would be unimolecular and follow a first-order rate equation. Hence the name SN1 is applied to this mechanism.

    1. Since nucleophiles only participate in the fast second step, their relative molar concentrations rather than their nucleophilicities should be the primary product-determining factor. If a nucleophilic solvent such as water is used, its high concentration will assure that alcohols are the major product. Recombination of the halide anion with the carbocation intermediate simply reforms the starting compound. Note that SN1 reactions in which the nucleophile is also the solvent are commonly called solvolysis reactions. The hydrolysis of t-butyl chloride is an example.
    2. The Hammond postulate suggests that the activation energy of the rate-determining first step will be inversely proportional to the stability of the carbocation intermediate. The stability of carbocations was discussed earlier, and a qualitative relationship is given below.

     

    image058.png

    Benzyl Carbocation

    image060.png

     

    Carbocation
    Stability
    CH3(+) < CH3CH2(+) < (CH3)2CH(+) CH2=CH-CH2(+) < C6H5CH2(+) (CH3)3C(+)

    Consequently, we expect that 3º-alkyl halides will be more reactive than their 2º and 1º-counterparts in reactions that follow an SN1 mechanism. This is opposite to the reactivity order observed for the SN2 mechanism. Allylic and benzylic halides are exceptionally reactive by either mechanism.

    Fourth, in order to facilitate the charge separation of an ionization reaction, as required by the first step, a good ionizing solvent will be needed. Two solvent characteristics will be particularly important in this respect. The first is the ability of solvent molecules to orient themselves between ions so as to attenuate the electrostatic force one ion exerts on the other. This characteristic is related to the dielectric constant, ε, of the solvent. Solvents having high dielectric constants, such as water (ε=81), formic acid (ε=58), dimethyl sulfoxide (ε=45) & acetonitrile (ε=39) are generally considered better ionizing solvents than are some common organic solvents such as ethanol (ε=25), acetone (ε=21), methylene chloride (ε=9) & ether (ε=4). The second factor is solvation, which refers to the solvent's ability to stabilize ions by encasing them in a sheath of weakly bonded solvent molecules. Anions are solvated by hydrogen-bonding solvents, as noted earlier. Cations are often best solvated by nucleophilic sites on a solvent molecule (e.g. oxygen & nitrogen atoms), but in the case of carbocations these nucleophiles may form strong covalent bonds to carbon, thus converting the intermediate to a substitution product. This is what happens in the hydrolysis reactions described above.

    Fifth, the stereospecificity of these reactions may vary. The positively-charged carbon atom of a carbocation has a trigonal (flat) configuration (it prefers to be sp2 hybridized), and can bond to a nucleophile equally well from either face. If the intermediate from a chiral alkyl halide survives long enough to encounter a random environment, the products are expected to be racemic (a 50:50 mixture of enantiomers). On the other hand, if the departing halide anion temporarily blocks the front side, or if a nucleophile is oriented selectively at one or the other face, then the substitution might occur with predominant inversion or even retention of configuration.

    Just as with SN2 reactions, the nucleophile, solvent and leaving group also affect SN1 (Unimolecular Nucleophilic Substitution) reactions. Polar protic solvents have a hydrogen atom attached to an electronegative atom so the hydrogen is highly polarized. Polar aprotic solvents have a dipole moment, but their hydrogen is not highly polarized. Polar aprotic solvents are not used in SN1 reactions because some of them can react with the carbocation intermediate and give you an unwanted product. Rather, polar protic solvents are preferred.

    Solvent Effects on the SN1 Reaction

     

    Since the hydrogen atom in a polar protic solvent is highly positively charged, it can interact with the anionic nucleophile which would negatively affect an SN2, but it does not affect an SN1 reaction because the nucleophile is not a part of the rate-determining step (See SN2 Nucleophile). Polar protic solvents actually speed up the rate of the unimolecular substitution reaction because the large dipole moment of the solvent helps to stabilize the transition state. The highly positive and highly negative parts interact with the substrate to lower the energy of the transition state. Since the carbocation is unstable, anything that can stabilize this even a little will speed up the reaction.

     
    Sometimes in an SN1 reaction the solvent acts as the nucleophile. This is called a solvolysis reaction (see example below). The polarity and the ability of the solvent to stabilize the intermediate carbocation is very important as shown by the relative rate data for the solvolysis (see table below). The dielectric constant of a solvent roughly provides a measure of the solvent's polarity. A dielectric constant below 15 is usually considered non-polar. Basically, the dielectric constant can be thought of as the solvent's ability to reduce the internal charge of the solvent. So for our purposes, the higher the dielectric constant the more polar the substance and in the case of SN1 reactions, the faster the rate.
    Table.jpg
    Below is the same reaction conducted in two different solvents and the relative rate that corresponds with it.
    Rel Rate.gif
    The figure below shows the mechanism of an SN1 reaction of an alkyl halide with water. Since water is also the solvent, this is an example of a solvolysis reaction. 
    Solvolysis.gif
    Examples of polar protic solvents are: acetic acid, isopropanol, ethanol, methanol, formic acid, water, etc.

    Effects of Nucleophile

     

    The strength of the nucleophile does not affect the reaction rate of SN1 because, as stated above, the nucleophile is not involved in the rate-determining step. However, if you have more than one nucleophile competing to bond to the carbocation, the strengths and concentrations of those nucleophiles affects the distribution of products that you will get. For example, if you have (CH3)3CCl reacting in water and formic acid where the water and formic acid are competing nucleophiles, you will get two different products: (CH3)3COH and (CH3)3COCOH. The relative yields of these products depend on the concentrations and relative reactivities of the nucleophiles.
     Nucleophile.gif

    Effects of Leaving Group

    Leaving groups.jpg

    An SN1 reaction speeds up with a good leaving group. This is because the leaving group is involved in the rate-determining step. A good leaving group wants to leave so it breaks the C-Leaving Group bond faster. Once the bond breaks, the carbocation is formed and the faster the carbocation is formed, the faster the nucleophile can come in and the faster the reaction will be completed.

    A good leaving group is a weak base because weak bases can hold the charge. They're happy to leave with both electrons and in order for the leaving group to leave, it needs to be able to accept electrons. Strong bases, on the other hand, donate electrons which is why they can't be good leaving groups. As you go from left to right on the periodic table, electron donating ability decreases and thus ability to be a good leaving group increases. Halides are an example of a good leaving group whos leaving-group ability increases as you go down the column.

    Leaving group ability (1).jpg

    The two reactions below is the same reaction done with two different leaving groups. One is significantly faster than the other. This is because the better leaving group leaves faster and thus the reaction can proceed faster.

    Leaving group rxns.gif

    Other examples of good leaving groups are sulfur derivatives such as methyl sulfate ion and other sulfonate ions (See Figure below)

    Methyl Sulfate Ion.jpg     Mesylate Ion.jpg     Triflate Ion.jpg     Tosylate Ion.jpg

                     Methyl Sulfate Ion                       Mesylate Ion                                          Triflate Ion                                     Tosylate Ion

    Predicting SN1 vs. SN2 mechanisms; competition between nucleophilic substitution and elimination reactions

    When considering whether a nucleophilic substitution is likely to occur via an SN1 or SN2 mechanism, we really need to consider three factors:

    1) The electrophile: when the leaving group is attached to a methyl group or a primary carbon, an SN2 mechanism is favored (here the electrophile is unhindered by surrounded groups, and any carbocation intermediate would be high-energy and thus unlikely). When the leaving group is attached to a tertiary, allylic, or benzylic carbon, a carbocation intermediate will be relatively stable and thus an SN1 mechanism is favored.

    2) The nucleophile: powerful nucleophiles, especially those with negative charges, favor the SN2 mechanism. Weaker nucleophiles such as water or alcohols favor the SN1 mechanism.

    3) The solvent:  Polar aprotic solvents favor the SN2 mechanism by enhancing the reactivity of the nucleophile. Polar protic solvents favor the SN1 mechanism by stabilizing the carbocation intermediate. SN1 reactions are frequently solvolysis reactions.

    For example, the reaction below has a tertiary alkyl bromide as the electrophile, a weak nucleophile, and a polar protic solvent (we’ll assume that methanol is the solvent).  Thus we’d confidently predict an SN1 reaction mechanism.  Because substitution occurs at a chiral carbon, we can also predict that the reaction will proceed with racemization.

    image106.png

    In the reaction below, on the other hand, the electrophile is a secondary alkyl bromide – with these, both SN1 and SN2 mechanisms are possible, depending on the nucleophile and the solvent.  In this example, the nucleophile (a thiolate anion) is strong, and a polar protic solvent is used – so the SN2 mechanism is heavily favored.  The reaction is expected to proceed with inversion of configuration.

    image108.png

    Template:ExampleStart

    Exercise 8.15: Determine whether each substitution reaction shown below is likely to proceed by an SN1 or SN2 mechanism.

    image108a.png

    Solution

    Template:ExampleEnd

    Problems

    1. Put the following leaving groups in order of decreasing leaving group ability

     Leaving groups ques.gif

    2. Which solvent would an SN1 reaction occur faster in? H2O or CH3CN

    3. What kind of conditions disfavor SN1 reactions?

    4. What are the products of the following reaction and does it proceed via SN1 or SN2?

    Rxn2.gif

    5. How could you change the reactants in the problem 4 to favor the other substitution reaction?

    6. Indicate the expected product and list why it occurs through SN1 instead of SN2?

    Rxn1 revised (1).gif

    Answers

    1.  Leaving groups (1).gif

    2. An SN1 reaction would occur faster in H2O because it's polar protic and would stailize the carbocation and CH3CN is polar aprotic.

    3. Polar aprotic solvents, a weak leaving group and primary substrates disfavor SN1 reactions.

    4. Rxn product 1.gif

    Reaction proceeds via SN1 because a tertiary carbocation was formed, the solvent is polar protic and Br- is a good leaving group.

    5. You could change the solvent to something polar aprotic like CH3CN or DMSO and you could use a better base for a nucleophile such as NH2- or OH-. 

    6. Rxn product 2.gif

    This reaction occurs via SN1 because Cl- is a good leaving group and the solvent is polar protic. This is an example of a solvolysis reaction because the nucleophile is also the solvent.

    Exercises

    Questions

    Q11.5.1

    Rank the following by increasing reactivity in an SN1 reaction.

    Q11.5.2

    3-bromo-1-pentene and 1-bromo-2-pentene undergo SN1 reaction at almost the same rate, but one is a secondary halide while the other is a primary halide. Explain why this is.

    Q11.5.3

    Label the following reactions as most likely occuring by an SN1 or SN2 mechanism. Suggest why.

    Solutions

    S11.5.1

    Consider the stability of the intermediate, the carbocation.

    A < D < B < C (most reactive)

    S11.5.2

    They have the same intermediates when you look at the resonance forms.

     

    S11.5.3

    A – SN1  *poor leaving group, protic solvent, secondary cation intermediate

    B – SN2  *good leaving group, polar solvent, primary position.

    Contributors