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11.6: Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides

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  • Objectives

    After completing this section, you should be able to

    1. explain the term “electrophilic addition reaction,” using the reaction of a protic acid, HX, with an alkene as an example.
    2. write the mechanism for the reaction of a protic acid, HX, with an alkene.
    3. sketch a reaction energy diagram for the electrophilic addition of an acid, HX, to an alkene.

    Key Terms

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

    • carbocation (carbonium ion)
    • electrophilic addition reaction

    Study Notes

    An electrophilic addition reaction is a reaction in which a substrate is initially attacked by an electrophile, and the overall result is the addition of one or more relatively simple molecules across a multiple bond.

    The mechanism for the addition of hydrogen halide to propene shown in the reading is quite detailed. Normally, an organic chemist would write this mechanism as follows:

    hydrogen halide addition to propeneHowever, the more detailed mechanism shown in the reading does allow you to see the exact fate of all the electrons involved in the reaction.

    In your previous chemistry course, you were probably taught the importance of balancing chemical equations. It may come as a surprise to you that organic chemists usually do not balance their equations, and often represent reactions using a format which is quite different from the carefully written, balanced equations encountered in general chemistry courses. In fact, organic chemists are rarely interested in the inorganic products of their reactions; furthermore, most organic reactions are non-quantitative in nature.

    In many of the reactions in this course, the percentage yield is indicated beneath the products: you are not expected to memorize these figures. The question of yield is very important in organic chemistry, where two, five, ten or even twenty reactions may be needed to synthesize a desired product. For example, if a chemist wishes to prepare compound D by the following reaction sequence:

    \[A → B → C → D\]

    and each of the individual steps gives only a 50% yield, one mole of A would give only

    1 mol × 50% 100% × 50% 100% × 50% 100% = 0.125 mol of D

    You will gain first-hand experience of such situations in the laboratory component of this course.

    This page looks at the reaction of the carbon-carbon double bond in alkenes such as ethene with hydrogen halides such as hydrogen chloride and hydrogen bromide. Symmetrical alkenes (like ethene or but-2-ene) are dealt with first. These are alkenes where identical groups are attached to each end of the carbon-carbon double bond.

    Addition to symmetrical alkenes

    What happens?

    All alkenes undergo addition reactions with the hydrogen halides. A hydrogen atom joins to one of the carbon atoms originally in the double bond, and a halogen atom to the other.

    For example, with ethene and hydrogen chloride, you get chloroethane:

    Figure 7.7.1 Electrophilic addition of HCl to ethene.

    With but-2-ene you get 2-chlorobutane:

    Figure 7.7.2 Electrophilic addition of HCl to but-2-ene.

    What happens if you add the hydrogen to the carbon atom at the right-hand end of the double bond, and the chlorine to the left-hand end? You would still have the same product. The chlorine would be on a carbon atom next to the end of the chain - you would simply have drawn the molecule flipped over in space. That would be different of the alkene was unsymmetrical - that's why we have to look at them separately.


    The addition of hydrogen halides is one of the easiest electrophilic addition reactions because it uses the simplest electrophile: the proton. Hydrogen halides provide both a electrophile (proton) and a nucleophile (halide). First, the electrophile will attack the double bond and take up a set of π electrons, attaching it to the molecule (1). This is basically the reverse of the last step in the E1 reaction (deprotonation step). The resulting molecule will have a single carbon- carbon bond with a positive charge on one of them (carbocation). The next step is when the nucleophile (halide) bonds to the carbocation, producing a new molecule with both the original hydrogen and halide attached to the organic reactant (2). The second step will only occur if a good nucleophile is used.

    general rxn.gif

    Figure 7.7.3 Mechanism of Electrophilic Addition of Hydrogen Halide to Ethene


    Figure 7.7.4 Mechanism of Electrophilic Addition of Hydrogen Halide to Propene

    All of the halides (HBr, HCl, HI, HF) can participate in this reaction and add on in the same manner. Although different halides do have different rates of reaction, due to the H-X bond getting weaker as X gets larger (poor overlap of orbitals)s.

    Reaction rates

    Variation of rates when you change the halogen

    Reaction rates increase in the order HF - HCl - HBr - HI. Hydrogen fluoride reacts much more slowly than the other three, and is normally ignored in talking about these reactions.

    When the hydrogen halides react with alkenes, the hydrogen-halogen bond has to be broken. The bond strength falls as you go from HF to HI, and the hydrogen-fluorine bond is particularly strong. Because it is difficult to break the bond between the hydrogen and the fluorine, the addition of HF is bound to be slow.

    Variation of rates when you change the alkene

    This applies to unsymmetrical alkenes as well as to symmetrical ones. For simplicity the examples given below are all symmetrical ones- but they don't have to be.

    Reaction rates increase as the alkene gets more complicated - in the sense of the number of alkyl groups (such as methyl groups) attached to the carbon atoms at either end of the double bond. For example:

    There are two ways of looking at the reasons for this - both of which need you to know about the mechanism for the reactions.

    Alkenes react because the electrons in the pi bond attract things with any degree of positive charge. Anything which increases the electron density around the double bond will help this.

    Alkyl groups have a tendency to "push" electrons away from themselves towards the double bond. The more alkyl groups you have, the more negative the area around the double bonds becomes.

    The more negatively charged that region becomes, the more it will attract molecules like hydrogen chloride.

    The more important reason, though, lies in the stability of the intermediate ion formed during the reaction. The three examples given above produce these carbocations (carbonium ions) at the half-way stage of the reaction:

    The stability of the intermediate ions governs the activation energy for the reaction. As you go towards the more complicated alkenes, the activation energy for the reaction falls. That means that the reactions become faster.

    Contributors and Attributions

    • John D. Robert and Marjorie C. Caserio (1977) Basic Principles of Organic Chemistry, second edition. W. A. Benjamin, Inc. , Menlo Park, CA. ISBN 0-8053-8329-8. This content is copyrighted under the following conditions, "You are granted permission for individual, educational, research and non-commercial reproduction, distribution, display and performance of this work in any format."

    very important regarding electrophilic addition reactions is that if the starting alkene is asymmetrical, there are two possible courses that could be followed, depending on which of the two alkene carbons forms the new sigma bond in the first step.


    Of course, the two reaction courses involve two different carbocation intermediates, which may have different energy levels. Two different products are possible, and in general the product which predominates will be the one that is derived from the lower-energy carbocation intermediate.

    This important regiochemical principle is nicely illustrated by a simple electrophilic addition that is commonly carried out in the organic laboratory: the conversion of an alkene to an alkyl bromide by electrophilic addition of HBr to the double bond. Let's look at a hypothetical addition of HBr to 2-methyl-2-butene, pictured below. Two different regiochemical outcomes are possible:


    The initial protonation step could follow two different pathways, resulting in two different carbocation intermediates: pathway 'a' gives a tertiary carbocation intermediate (Ia), while pathway 'b' gives a secondary carbocation intermediate (Ib) We know already that the tertiary carbocation is more stable (in other words, lower in energy). According to the Hammond postulate, this implies that the activation energy for pathway a is lower than in pathway b, meaning in turn that Ia forms faster.


    Because the protonation step is the rate determining step for the reaction, the tertiary alkyl bromide A will form much faster than the secondary alkyl halide B, and thus A will be the predominant product observed in this reaction. This is a good example of a non-enzymatic organic reaction that is highly regiospecific.

    In the example above, the difference in carbocation stability can be accounted for by the electron-donating effects of the extra methyl group on one side of the double bond. It is generally observed that, in electrophilic addition of acids (including water) to asymmetrical alkenes, the more substituted carbon is the one that ends up bonded to the heteroatom of the acid, while the less substituted carbon is protonated.


    This rule of thumb is known as Markovnikov's rule, after the Russian chemist Vladimir Markovnikov who proposed it in 1869.

    While it is useful in many cases, Markovikov's rule does not apply to all possible electrophilic additions. It is more accurate to use the more general principle that has already been stated above:

    When an asymmetrical alkene undergoes electrophilic addition, the product that predominates is the one that results from the more stable of the two possible carbocation intermediates.

    How is this different from Markovnikov's original rule? Consider the following hypothetical reaction, which is similar to the HBr addition shown above except that the six methyl hydrogens on the left side of the double bond have been replaced by highly electron-withdrawing fluorines.


    Now when HBr is added, it is the less substituted carbocation that forms faster in the rate-determining protonation step, because in this intermediate the carbon bearing the positive charge is located further away from the electron-withdrawing, cation-destabilizing fluorines. As a result, the predominant product is the secondary rather than the tertiary bromoalkane. This would be referred to as an 'anti-Markovnikov' addition product, because it 'breaks' Markovnikov's rule.


    Predict the product of the following reaction:


    Organic Chemistry With a Biological Emphasis by Tim Soderberg (University of Minnesota, Morris)

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