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19.10: Benzyne

Last updated

Jun 5, 2019
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- 19.9: Nucleophilic Aromatic Substitution
- 19.11: Elimination-Addition

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Objectives

After completing this section, you should be able to

identify the reagents and conditions required to produce phenol from chlorobenzene on an industrial scale.
write the mechanism for the conversion of an alkyl halide to a phenol through a benzyne intermediate.
discuss the experimental evidence which supports the existence of benzyne intermediates.
discuss the bonding in benzyne, and hence account for its high reactivity.

Key Terms

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

benzyne
elimination-addition mechanism

Study Notes

An elimination-addition mechanism involves the elimination of the elements of a small molecule from a substrate to produce a highly reactive intermediate, which then undergoes an addition reaction.

The elimination-addition mechanism of nucleophilic aromatic substitution involves the remarkable intermediate called benzyne or arynes.

14-6C Elimination-Addition Mechanism of Nucleophilic Aromatic Substitution. Arynes

The reactivities of aryl halides, such as the halobenzenes, are exceedingly low toward nucleophilic reagents that normally effect displacements with alkyl halides and activated aryl halides. Substitutions do occur under forcing conditions of either high temperatures or very strong bases. For example, chlorobenzene reacts with sodium hydroxide solution at temperatures around $340^\text{o}$ and this reaction was once an important commercial process for the production of benzenol (phenol):

Roberts and Caserio Screenshot 14-6-4.png

In addition, aryl chlorides, bromides, and iodides can be converted to areneamines $\ce{ArNH_2}$ by the conjugate bases of amines. In fact, the reaction of potassium amide with bromobenzene is extremely rapid, even at temperatures as low as $-33^\text{o}$ with liquid ammonia as solvent:

Roberts and Caserio Screenshot 14-6-5.png

However, displacement reactions of this type differ from the previously discussed displacements of activated aryl halides in that rearrangement often occurs. That is, the entering group does not always occupy the same position on the ring as that vacated by the halogen substituent. For example, the hydrolysis of 4-chloromethylbenzene at $340^\text{o}$ gives an equimolar mixture of 3- and 4-methylbenzenols:

Roberts and Caserio Screenshot 14-6-6.png

Even more striking is the exclusive formation of 3-methoxybenzenamine in the amination of 2-chloromethoxybenzene. Notice that this result is a violation of the principle of least structural change (Section 1-1H):

Roberts and Caserio Screenshot 14-6-7.png

The mechanism of this type of reaction has been studied extensively, and much evidence has accumulated in support of a stepwise process, which proceeds first by base-catalyzed elimination of hydrogen halide $\left( \ce{HX} \right)$ from the aryl halide - as illustrated below for the amination of bromobenzene:

Elimination

Roberts and Caserio Screenshot 14-6-8.png

The product of the elimination reaction is a highly reactive intermediate $9$ called benzyne, or dehydrobenzene, which differs from benzene in having two less hydrogen and an extra bond between two ortho carbons. Benzyne reacts rapidly with any available nucleophile, in this case the solvent, ammonia, to give an addition product:

Addition

Roberts and Caserio Screenshot 14-6-9.png

The rearrangements in these reactions result from the attack of the nucleophile at one or the other of the carbons of the extra bond in the intermediate. With benzyne the symmetry is such that no rearrangement would be detected. With substituted benzynes isomeric products may result. Thus 4-methylbenzyne, $10$ , from the reaction of hydroxide ion with 4-chloro-1-methylbenzene gives both 3- and 4-methylbenzenols:

Roberts and Caserio Screenshot 14-6-10.png

In the foregoing benzyne reactions the base that produces the benzyne in the elimination step is derived from the nucleophile that adds in the addition step. This need not always be so, depending on the reaction conditions. In fact, the synthetic utility of aryne reactions depends in large part of the success with which the aryne can be generated by one reagent but captured by another. One such method will be discussed in Section 14-10C and involves organometallic compounds derived from aryl halides. Another method is to generate the aryne by thermal decomposition of a 1,2-disubstituted arene compound such as $11$ , in which both substituents are leaving groups - one leaving with an electron pair, the other leaving without:

Roberts and Caserio Screenshot 14-6-11.png

When $11$ decomposes in the presence of an added nucleophile, the benzyne intermediate is trapped by the nucleophile as it is formed. Or, if a conjugated diene is present, benzyne will react with it by a [4 + 2] cycloaddition. In the absence of other compounds with which it can react, benzyne will undergo [2 + 2] cycloaddition to itself:

Roberts and Caserio Screenshot 14-6-12.png

Exercises

Contributors

Dr. Dietmar Kennepohl FCIC (Professor of Chemistry, Athabasca University)
Prof. Steven Farmer (Sonoma State University)

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."

14-6C Elimination-Addition Mechanism of Nucleophilic Aromatic Substitution. Arynes

Exercises

Contributors

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