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22.E: Arenes, Electrophilic Aromatic Substitution (Exercises)

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    Exercise 22-1 How many structurally different monomethyl derivatives are possible for each of the following compounds? Name each.

    a. naphthalene
    b. anthracene
    c. phenanthrene

    Exercise 22-2 How many isomeric products could each of the dimethylbenzenes give on introduction of a third substituent? Name each isomer, using chlorine as the third substituent.

    Exercise 22-3 Name each of the following compounds by the IUPAC system:

    a. \(\ce{(C_6H_5)_2CHCl}\)
    b. \(\ce{C_6H_5CHCl_2}\)
    c. \(\ce{C_6H_5CCl_3}\)
    d. Roberts and Caserio Screenshot 22-E-1.png
    e. Roberts and Caserio Screenshot 22-E-2.png

    f. Roberts and Caserio Screenshot 22-E-3.png

    Exercise 22-4 Identify the two compounds with molecular formula \(\ce{C_7H_7Cl}\) from the infrared spectra shown in Figure 22-2.

    Roberts and Caserio Screenshot 22-E-4.png

    Figure 22-2: Infrared spectra of two isomeric compounds of formula \(\ce{C_7H_7Cl}\) (see Exercise 22-4)

    Exercise 22-5 Predict the effect on the ultraviolet spectrum of a water solution of benzenamine when hydrochloric acid is added. Explain why a solution of sodium benzenoxide absorbs at longer wavelengths than a solution of benzenol (see Table 22-3).

    Exercise 22-6* Estimate the chemical shifts of the protons of (a) the separate \(\ce{CH_2}\) of "1,4-hexamethylenebenzene" as compared with "1,2-hexamethylenebenzene"; and (b) cyclooctatetraene (see Section 21-9A).

    Roberts and Caserio Screenshot 22-E-5.png

    Exercise 22-7 Establish the structures of the following benzene derivatives on the basis of their empirical formulas and NMR spectra shown in Figure 22-6. Remember that equivalent protons normally do not split each other's resonances.

    a. \(\ce{C_8H_{10}}\)
    b. \(\ce{C_8H_7OCl}\)
    c. \(\ce{C_9H_{10}O_2}\)
    d. \(\ce{C_9H_{12}}\)

    Roberts and Caserio Screenshot 22-E-6.png

    Figure 22-6: Proton NMR spectra of some benzene derivatives at \(60 \: \text{MHz}\) with reference to TMS at \(0 \: \text{ppm}\) (see Exercise 22-7).

    Exercise 22-8 Calculate from appropriate bond-energy and stabilization-energy tables (4-3 and 21-1) the heats of chlorine with benzene to give (a) chlorobenzene and (b) 5,6-dichloro-1,3-cyclohexadiene. Your answer should indicate that substitution is energetically more favorable than addition.

    Exercise 22-9 Devise an experimental test to determine whether the following addition-elimination mechanism for bromination of benzene actually takes place.

    Roberts and Caserio Screenshot 22-E-7.png

    Exercise 22-10 Why is nitration with ethanoyl nitrate accelerated by added fluoroboric acid, \(\ce{HBF_4}\), but retarded by added hydrochloric acid?

    Exercise 22-11 Why do fairly reactive arenes, such as benzene, methylbenzene, and ethylbenzene, react with excess nitric acid in nitromethane solution at a rate that is independent of the concentration of the arene (i.e., zero order in arene concentration)? Does this lack of dependencies on arene concentration mean that nitration of an equimolar mixture of benzene and methylbenzene would necessarily give an equimolar mixture of nitrobenzene and nitromethylbenzenes? Why or why not?

    Exercise 22-12 Reagents, besides the molecular halogens, that effect halogen substitution include hypochlorous and hypobromous acids. They are most effective when a strong acid is present and care is taken to exclude formation of halide ions. Account for the catalytic effect of acid and the anticatalytic effect of halide ions.

    Exercise 22-13 Arrange the following bromine-containing species in order of their expected reactivity in achieving electrophilic aromatic bromination: \(\ce{HOBr}\), \(\ce{Br_2}\), \(\ce{Br}^\oplus\), \(\ce{Br}^\ominus\), \(\ce{HBr}\), \(\ce{H_2OBr}^\oplus\), \(\ce{BrCl}\).

    Exercise 22-14 Aluminum chloride is a much more powerful catalyst than ferric bromide for bromination of benzene. Would you expect the combination of aluminum chloride and bromine to give much chlorobenzene in reaction with benzene? Explain.

    Exercise 22-15

    a. The bromination of benzene is catalyzed by small amounts of iodine. Devise a possible explanation for this catalytic effect.

    b. The kinetic expression for the bromination of naphthalene in ethanoic acid involves a term that is first order in naphthalene and second order in bromine. How can two molecules of bromine and one of naphthalene be involved in the rate-determining step of bromination? Explain why the kinetic expression simplifies to first order in naphthalene and first order in bromine in \(50\%\) aqueous ethanoic acid.

    Exercise 22-16 Write a mechanism for the alkylation of benzene with 2-propanol catalyzed by boron trifluoride.

    Exercise 22-17 Explain how it is possible that the ratio of products isolated from equilibration of 1,2-, 1,3-, and 1,4-dimethylbenzenes is 18:58:24 if the presence of a small amount of \(\ce{HF-BF_3}\), but is essentially 0:100:0 in the presence of excess \(\ce{HF-BF_3}\). Notice that \(\ce{HBF_4}\) is an extremely strong acid.

    Exercise 22-18 Account for the following observations:

    a. 3-Methyl-2-butanol alkylates benzene in \(\ce{HF}\) to give (1,1-dimethylpropyl)benzene.

    b. 1-Chloronorbornane will not alkylate in the presence of \(\ce{AlCl_3}\).

    Roberts and Caserio Screenshot 22-E-8.png

    c. 1-Methylcyclopentyl cation is formed from each of the compounds shown below under the indicated conditions at low temperatures \(\left( -70^\text{o} \right)\).

    chlorocyclohexane \(\overset{\ce{SbF_5-SO_2}}{\longrightarrow}\)

    cyclohexene \(\overset{\ce{HF-SbF_5-SO_2}}{\longrightarrow}\)

    cyclohexanol \(\overset{\ce{FSO_3H-SbF_5}}{\longrightarrow}\)

    Exercise 22-19 Anthraquinone can be synthesized from phthalic anhydride and benzene in two steps. The first step is catalyzed by \(\ce{AlCl_3}\), the second by fuming sulfuric acid. Write mechanisms for both reactions and suggest why fuming sulfuric is required in the second step but not in the first.

    Roberts and Caserio Screenshot 22-E-9.png

    Exercise 22-20 Suggest possible routes for the synthesis of the following compounds:

    a. diphenylmethane from benzoic acid and benzene
    b. 1-ethyl-4-methylbenzene from methylbenzene

    Exercise 22-21

    a. Substitution of a chloromethyl group, \(\ce{-CH_2Cl}\), on an aromatic ring is chloromethylation and is accomplished using methanal, \(\ce{HCl}\), and a metal-halide catalyst \(\left( \ce{ZnCl_2} \right)\). Write reasonable mechanistic steps that could be involved in this reaction:

    \[\ce{C_6H_6} + \ce{CH_2O} + \ce{HCl} \overset{\ce{ZnCl_2}}{\longrightarrow} \ce{C_6H_5CH_2Cl} + \ce{CH_2O}\]

    b. Phenylmethyl chloride can be formed from benzene and chloromethyl methyl ether, \(\ce{ClCH_2OCH_3}\), in the presence of stannic chloride, \(\ce{SnCl_4}\). Write reasonable mechanistic steps, again supported by analogy, for this reaction. Notice that \(\ce{SnCl_4}\) is a Lewis acid.

    Exercise 22-22 The Gattermann reaction (not to be confused with the Gattermann-Koch aldehyde synthesis) introduces the \(\ce{H-C=O}\) function into reactive aromatic compounds such as 2-naphthalenol. The necessary reagents are \(\ce{HCN}\), \(\ce{HCl}\), and a metal-halide catalyst (\(\ce{ZnCl_2}\) or \(\ce{AlCl_3}\)), and the initial product must be treated with water. Write a mechanism for this reaction that is supported by analogy to other reactions discussed in this chapter.

    Roberts and Caserio Screenshot 22-E-10.png

    Exercise 22-23 Show explicitly how an alkyl side chain of alkylbenzenesulfonates could be formed with a quaternary carbon, if the \(\ce{C_{12}}\) alkane used at the start of the synthesis contained any branched-chain \(\ce{C_{12}}\) isomers.

    Exercise 22-24 Draw the structures of the intermediate cations for nitration of nitrobenzene in the 2, 3, and 4 positions. Use the structures to explain why the nitro group is meta-orienting with deactivation. Use the same kind of arguments to explain the orientation observed with \(\ce{-CF_3}\), \(\ce{-CHO}\), \(\ce{-CH_2Cl}\), and \(\ce{-NH_2}\) groups in electrophilic aromatic substitution (Table 22-6).

    Exercise 22-25* The product distribution in the bromination of methylbenzene (toluene) depends on the nature of the brominating agent. Pertinent information follows:

    Roberts and Caserio Screenshot 22-E-11.png

    Explain why the distribution varies with the nature of the substituting agent. Predict the product distribution of isomeric ions if \(\ce{Br}^\oplus\) were to add to methylbenzene in the gas phase.

    Exercise 22-26 Construct an energy diagram, similar to Figure 22-8, for nitration of phenyltrimethylammonium ion in the meta and para positions.

    Exercise 22-27 Using the rationale developed in Section 22-5, predict the major products of nitration of the following compounds. It will help to work out the Lewis structures of the substituent groups.

    a. phenylnitromethane, \(\ce{C_6H_5CH_2NO_2}\)
    b. methylthiobenzene, \(\ce{C_6H_5SCH_3}\)
    c. nitrosobenzene, \(\ce{C_6H_5NO}\)
    d. phenyldimethylphosphine oxide, \(\ce{C_6H_5PO(CH_3)_2}\)

    Exercise 22-28 The energy diagram in Figure 22-8 represents a two-step reaction in which the first step is slower than the second. This circumstance is found in nitration and halogenation reactions. Show how this diagram would change when (a) the rate-determining step is loss of a proton from the intermediate ion, (b) the reactants rapidly form a \(\pi\) complex prior to the slow step of the electrophilic attack at carbon, and (c) the rate-determining step is \(\pi\)-complex formation.

    Exercise 22-29 Predict the favored position(s) of substitution in the nitration of the following compounds:

    a. 4-nitro-1-phenylbenzene
    b. 4-methylbenzenecarboxylic acid
    c. 3-methylbenzenecarboxylic acid
    d. 1,3-dibromobenzene
    e. 1-fluoro-3-methoxybenzene
    f. 1,3-dimethylbenzene

    Exercise 22-30*

    a. In the nitration of para-cymene by ethanoyl nitrate in ethanoic anhydride, the observed product composition at \(0^\text{o}\) is \(41\%\) \(5\) and \(6\), \(41\%\) \(3\), \(8\%\) \(4\), and \(10\%\) of 4-nitromethylbenzene. Use these results to determine the relative reactivities of the para-cymene ring carbons towards \(\ce{NO_2^+}\). Give your answer relative to \(\ce{C_3}\) as unity (\(\ce{C_3}\) is the carbon next to the isopropyl group). determine the relative reactivities based on the data obtained in Equation 22-1. How does neglect of ipso substitution affect calculation of relative reactivities of the ring carbons?

    b. Write a mechanism for the solvolytic conversion of \(5\) and \(6\) to \(3\).

    Exercise 22-31 Draw the Kekulé-type valence-bond structures for napthalene, anthracene, and phenanthrene. Estimate the percentage of double-bond character for the 9,10 bond of phenanthrene, assuming that each of the valence-bond structures contributes equally to the hybrid structure.

    Exercise 22-32 Devise an experiment that would establish whether the acylation of naphthalene in the 2 position in nitrobenzene solution is the result of thermodynamic control of the orientation.

    Exercise 22-33 Predict the orientation in the following reactions:

    a. 1-methylnaphthalene \(+ \ce{Br_2}\)
    b. 2-methylnaphthalene \(+ \ce{HNO_3}\)
    c. 2-napthalenecarboxylic acid \(+ \ce{HNO_3}\)

    Exercise 22-34 Show how one can predict qualitatively the character of the 1,2 bond in acenapthylene.

    Roberts and Caserio Screenshot 22-E-12.png

    Exercise 22-35* Explain why sodium in liquid ammonia reduces methoxybenzene (anisole) to 1-methoxy-1,4-cyclohexadiene, whereas it reduces sodium benzoate to sodium 2,5-cyclohexadienecarboxylate:

    Roberts and Caserio Screenshot 22-E-13.png

    Exercise 22-36 Predict the Birch reduction products of the following reactions:

    a. anthracene \(\underset{\ce{C_2H_5OH}}{\overset{\ce{Na}}{\longrightarrow}}\)

    b. naphthalene \(\underset{\ce{NH_3} \left( l \right)}{\overset{\ce{Na}}{\longrightarrow}}\)

    c.* methylbenzene \(\underset{\ce{NH_3} \left( l \right)}{\overset{\ce{Na}, \: \ce{C_2H_5OH}}{\longrightarrow}}\)

    Exercise 22-37* A side reaction when reducing benzene derivatives to 1,4-cyclohexadienes with lithium or sodium in liquid ammonia is over-reduction to give cyclohexenes. Addition of ethanol greatly reduces the importance of this side reaction. Explain what role ethanol plays in preventing over-reduction.

    Exercise 22-38 Neglecting steric-hindrance effects use the stabilization energies in Table 21-1 to explain why cis-butenedioic anhydride adds more readily to anthracene than to benzene and adds across the 9,10 positions but not the 1,4 positions of anthracene.

    Exercise 22-39 What products would you expect to be formed in the ozonization of the following substances? Consider carefully which bonds are likely to be most reactive.

    a. 1,2-dimethylbenzene
    b. naphthalene
    c. acenaphthylene (see Exercise 22-34)

    Exercise 22-40* The rate of the Diels-Alder addition between cyclooctatetraene and tetracyanoethene is proportional to the tetracyanoethene concentration, \(\ce{[C_2(CN)_4]}\), at low concentrations of the addends but becomes independent of \(\ce{[C_2(CN)_4]}\) at high concentrations. Write a mechanism that accounts for this behavior.

    Exercise 22-41* Write reasonable mechanisms for the different oxidation reactions of cyclooctatetraene with mercuric ethanoate in ethanoic acid, methanol, and water solutions. Notice that compounds of the type \(\ce{Hg(OR)_2}\) appear to act in some cases as \(^\oplus \ce{OR}\)-donating agents and also that the oxide produced from cyclooctatetraene and peroxyacids (Section 15-11C) rearranges readily in the presence of acids to phenylethanal.

    Exercise 22-42* The dianion \(\ce{C_8H_6^{2-}}\), which corresponds to pentalene, has been prepared and appears to be reasonably stable. Why may the dianon be more stable than pentalene itself? (See Section 21-9B.)

    Exercise 22-43* Predict which of the following compounds may have some aromatic character. Give your reasons.

    Roberts and Caserio Screenshot 22-E-14.png

    Exercise 22-44 Write structural formulas for all of the possible isomers of \(\ce{C_8H_{10}}\) that contain one benzene ring. Show how many different mononitration products each could give if no carbon skeleton rearrangements occur but nitration is possible either in the ring or side chain. Name all of the mononitration products by an accepted system.

    Exercise 22-45 Write structural formulas (more than one may be possible) for aromatic substances that fit the following descriptions:

    a. \(\ce{C_8H_{10}}\), which can give only one theoretically possible ring nitration product
    b. \(\ce{C_6H_3Br3}\), which can give three theoretically possible nitration products.
    c. \(\ce{C_6H_3Br_2Cl}\), which can give two theoretically possible nitration products.
    d. \(\ce{C_8H_8(NO_2)_2}\), which can give only two theoretically possible different ring monobromosubstitution products.

    Exercise 22-46 Predict the most favorable position for mononitration for each of the following substances. Indicate whether the rate is greater, or less, than for the nitration of benzene. Give your reasoning in each case.

    a. fluorobenzene
    b. trifluoromethylbenzene
    c. phenylethanone
    d. phenylmethyldimethylamine oxide, \(\ce{C_6H_5CH_2} \overset{\oplus}{\ce{N}} \ce{(CH_3)_2} \overset{\ominus}{\ce{O}}\)
    e. diphenylmethane
    f. 4-bromo-1-methoxybenzene
    g. phenylsulfinylbenzene, \(\ce{C_6H_5SOC_6H_5}\)
    h. 1-tert-butyl-4-methylbenzene
    i. diphenyliodonium nitrate, \(\ce{(C_6H_5)_2} \overset{\oplus}{\ce{I}} \overset{\ominus}{\ce{N}}\) \ce{O_3}\)
    j. 1,3-diphenylbenzene (meta-terphenyl)
    k. \(\ce{N}\)-(4-phenylphenyl)ethanamide

    Exercise 22-47 Explain why the bromination of benzenamine (aniline) gives 2,4,6-tribromobenzenamine (2,4,6-tribromoaniline), whereas the nitration with mixed acids gives 3-nitrobenzenamine (meta-nitroaniline).

    Exercise 22-48 Explain how comparison of the following resonance structures for para substitution with the corresponding ones for meta substitution may (or may not) lead to the expectation that ortho-para orientation would be favored for the nitro, cyano, and \(\ce{-CH=CHNO_2}\) groups.

    Roberts and Caserio Screenshot 22-E-15.png

    Exercise 22-49 Starting with benzene, show how the following compounds could be prepared. Specify the required reagents and catalysts.

    a. 1-bromo-4-nitrobenzene
    b. 4-isopropyl-3-nitrobenzenesulfonic acid
    c. 4-tert-butylbenzenecarbaldehyde
    d. \(\ce{C_6H_5COCH_2CH_2CO_2H}\)
    e. 1,2,4,5-tetrachlorocyclohexane

    Exercise 22-50 Offer a suitable explanation of each of the following facts:

    a. Nitration of arenes in concentrated nitric acid is retarded by added nitrate ions and strongly accelerated by small amounts of sulfuric acid.

    b. Nitrobenzene is a suitable solvent to use in Friedel-Crafts acylation of benzene derivatives.

    c. Benzene and other arenes usually do not react with nucleophiles by either addition or substitution.

    d. Pyridine is almost inert to nitration with mixed nitric and sulfuric acids, a reaction the proceeds readily with benzene.

    Exercise 22-51 Indicate the structures of the major product(s) expected in the following reactions:

    a. Roberts and Caserio Screenshot 22-E-16.png

    b. Roberts and Caserio Screenshot 22-E-17.png

    c. Roberts and Caserio Screenshot 22-E-18.png

    d. Roberts and Caserio Screenshot 22-E-19.png (\(\ce{T}\) is \(\ce{^3H}\), or tritium)

    e. Roberts and Caserio Screenshot 22-E-20.png

    f. Roberts and Caserio Screenshot 22-E-21.png

    g. Roberts and Caserio Screenshot 22-E-22.png

    h. Roberts and Caserio Screenshot 22-E-23.png

    i. Roberts and Caserio Screenshot 22-E-24.png

    Exercise 22-52 Draw the structures of the products A, B, C, and D in the stepwise reaction sequences shown.

    a. Roberts and Caserio Screenshot 22-E-25.png

    b. Roberts and Caserio Screenshot 22-E-26.png

    Exercise 22-53 The pesticide DDT is made commercially by the reaction of chlorobenzene with trichloroethanal (chloral) in the presence of an acid catalyst \(\left( \ce{H_2SO_4} \right)\). Show the steps that are likely to be involved in this reaction:

    Roberts and Caserio Screenshot 22-E-27.png

    Exercise 22-54 Hexachlorophene, the controversial germicide, is prepared from 2,4,5-trichlorobenzenol (2 moles) and methanal (1 mole) in the presence of concentrated sulfuric acid. Show the steps involved and the expected orientation of the substituents in the final product.

    Exercise 22-55 Trifluoroperoxyethanoic acid, \(\ce{CF_3C(O)O-OH}\) reacts with methoxybenzene to give 2- and 4-methoxybenzenols:

    Roberts and Caserio Screenshot 22-E-28.png

    Explain the nature of this reaction. What is likely to be the substituting agent? What products would you expect from trifluoroperoxyethanoic acid and fluorobenzene? Would fluorobenzene be more, or less, reactive than methoxybenzene?

    Exercise 22-56 Ethanoic anhydride reacts with concentrated nitric acid to yield the rather unstable ethanoyl nitrate (acetyl nitrate), which is a useful nitrating agent. With mixtures of benzene and methylbenzene, ethanoyl nitrate products a mixture of nitrobenzene and 2- and 4-nitromethylbenzenes. When nitrated separately, each compound reacts at the same overall rate, but when mixed together, 25 times more nitromethylbenzene is formed than nitrobenzene.

    a. Write equations for the formation of ethanoyl nitrate and its use in nitration of benzene derivatives.

    b. Consider possible mechanisms for nitrations with ethanoyl nitrate and show how the above observations with benzene and methylbenzene alone or in mixtures can be rationalized by proper choice of the rate-determining step.

    Exercise 22-57 4-Nitromethylbenzene-2,6-\(\ce{D_2}\) is nitrated by a mixture of nitric and sulfuric acids at the same rate as ordinary 4-nitromethylbenzene under conditions in which the rate of nitration \(v\) is given by \(v = k \left[ \text{nitromethylbenzene} \right] \left[ \ce{NO_2^+} \right]\). (Review Section 15-6B.)

    a. Explain what conclusion may be drawn from this result as to the mechanism of nitration under these conditions.

    b. What would you expect the nitration rate of \(\ce{C_6D_6}\) to be as compared with \(\ce{C_6H_6}\) in the ethanoyl nitrate nitration in Exercise 22-56?

    Exercise 22-58

    a. From the data of Table 21-1 estimate the overall loss in stabilization energy for the addition of chlorine to the 1,4-positions of naphthalene and to the 9,10 positions of phenanthrene. Which is likely to be the more favorable reaction?

    b. Predict whether anthracene is more likely to undergo electrophilic substitution at the 1,2 or 9 position. Show your reasoning.

    Exercise 22-59 Phenanthrene is oxidized more easily than benzene or naphthalene. Chromic acid oxidation of phenanthrene forms a substance known as phenanthraquinone. Which structure, A, B, or C, would you expect to be formed most readily by oxidation of phenanthrene? Explain.

    Roberts and Caserio Screenshot 22-E-29.png

    Exercise 22-60 Explain why the nitration and halogenation of biphenyl (phenylbenzene) goes with activation at the ortho and para positions but with deactivation at the meta position. Suggest a reason why biphenyl is more reactive than 2,2'-dimethylbiphenyl in nitration.

    Roberts and Caserio Screenshot 22-E-30.png


    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."