Describe how naphthalene could be prepared from the given

Draw the structure for each of the following: a. phenol b. benzyl phenyl ether c. benzonitrile d. benzaldehyde e. anisole f. styrene g. toluene h. tert -butylbenzene i. benzyl chloride

Name the following:

Provide the necessary reagents next to the arrows.

Draw the structure for each of the following: a. m -ethylphenol b. p -nitrobenzenesulfonic acid c. ( E )- 2-phenyl-2-pentene d. o -bromoaniline e. 4-bromo-1-chloro-2-methylbenzene f. m -chlorostyrene g. o -nitroanisole h. 2,4-dichloromethylbenzene i. m -chlorobenzoic acid

For each of the statements in Column I, choose a substituent from Column II that i ts the description for the compound on the right:

What product would be obtained from the reaction of excess benzene with each of the following reagents? a. isobutyl chloride + AlCl 3 b. 1-chloro-2,2-dimethylpropane + AlCl 3 c. dichloromethane + AlCl 3

Draw the product(s) of each of the following reactions: a. benzoic acid + HNO 3 /H 2 SO 4 b. isopropylbenzene + Cl 2 + FeCl 3 c. p -xylene + acetyl chloride + AlCl 3 followed by H 2 O d. o -methylaniline + benzenediazonium chloride e. cyclohexyl phenyl ether + Br 2 f. phenol + H 2 SO 4 + g. ethylbenzene + Br 2 /FeBr 3 h. m -xylene + Na 2 Cr 2 O 7 + HCl +

Rank the following substituted anilines in order from most basic to least basic:

For each horizontal row of substituted benzenes, indicate a. the one that would be the most reactive in an electrophilic aromatic substitution reaction. b. the one that would be the least reactive in an electrophilic aromatic substitution reaction. c. the one that would yield the highest percentage of meta product in an electrophilic aromatic substitution reaction.

The compound with the 1 H NMR spectrum shown here is known to be highly reactive toward electrophilic aromatic substitution. Identify the compound.

Draw the product of each of the following reactions:

Show how the following compounds could be synthesized from benzene: a. m -chlorobenzenesulfonic acid b. m -chloroethylbenzene c. m -bromobenzonitrile d. 1-phenylpentane e. m -bromobenzoic acid f. m -hydroxybenzoic acid g. p -cresol h. benzyl alcohol i. benzylamine

How many electrophilic aromatic substitution products are obtained from the chlorination of a. o -xylene? b. p -xylene? c. m -xylene?

Arrange the following groups of compounds in order from most reactive to least reactive toward electrophilic aromatic substitution: a. benzene, ethylbenzene, chlorobenzene, nitrobenzene, anisole b. 1-chloro-2,4-dinitrobenzene, 2,4-dinitrophenol, 1-methyl-2,4-dinitrobenzene c. toluene, p -cresol, benzene, p -xylene d. benzene, benzoic acid, phenol, propylbenzene e. p -methylnitrobenzene, 2- chloro-1-methyl-4-nitrobenzene, 1-methyl-2,4-dinitrobenzene, p -chloromethylbenzene f. bromobenzene, chlorobenzene, l uorobenzene, iodobenzene

What are the products of the following reactions?

Describe two ways to prepare anisole from benzene.

For each of the following compounds, indicate the ring carbon that would be nitrated if the compound is treated with HNO 3 /H 2 SO

Show two ways that the following compound could be synthesized:

Why is anisole nitrated more rapidly than thioanisole under the same conditions?

If anisole is allowed to sit in D 2 O that contains a small amount of D 2 SO 4 , what products will be formed?

Which of the following compounds will react with HBr more rapidly?

An aromatic hydrocarbon with a molecular formula of C 13 H 20 has an 1 H NMR spectrum with a signal at ~7 ppm that integrates to 5H. It also has two singlets; one of the singlets has 1.5 times the area of the second. What is the structure of the aromatic hydrocarbon?

The following tertiary alkyl bromides undergo an S N 1 reaction in aqueous acetone to form the corresponding tertiary alcohols. List the alkyl bromides in order from most reactive to least reactive.

The following tertiary alkyl bromides undergo an S N 1 reaction in aqueous acetone to form the corresponding tertiary alcohols. List the alkyl bromides in order from most reactive to least reactive.

Use the four compounds shown here to answer the following questions: a. Why are the ortho-halo-substituted benzoic acids stronger acids than benzoic acid? b. Why is o-fluorobenzoic acid the weakest of the ortho -halo-substituted benzoic acids? c. Why do o-chlorobenzoic acid and o-bromobenzoic acid have similar \(pK_a\) values?

. a. List the following esters in order from most reactive to least reactive in the i rst slow step of a nucleophilic additionelimination reaction (formation of the tetrahedral intermediate): CH3 Cl AB C D O CH3 O C O CH3 O C O CH3 O C O CH3 O C b. List the same esters in order from most reactive to least reactive in the second slow step of a nucleophilic additionelimination reaction (collapse of the tetrahedral intermediate).

A mixture of 0.10 mol benzene and 0.10 mol p -xylene was allowed to react with 0.10 mol nitronium ion until all the nitronium ion was gone. Two products were obtained: 0.002 mol of one and 0.098 mol of the other. a. What was the major product? b. Why was more of one product obtained than of the other?

What are the products of the following reactions?

Benzene underwent a FriedelCrafts acylation followed by a Clemmensen reduction. The product gave the following 1 H NMR spectrum. What acyl chloride was used in the FriedelCrafts acylation?

Would m -xylene or p -xylene react more rapidly with Cl 2+ FeCl 3 ? Explain your answer.

What products would be obtained from the reaction of the following compounds with H 2 CrO 4 + ?

Which set of underlined hydrogens will have its \(^{1}H NMR\) signal at a higher frequency?

FriedelCrafts alkylations can be carried out with carbocations formed from reactions other than the reaction of an alkyl halide with AlCl 3 . Propose a mechanism for the following reaction:

Show how the following compounds could be prepared from the given starting materials. You can use any necessary organic or inorganic reagents.

A chemist isolated an aromatic compound with molecular formula C 6 H 4 Br 2 . He treated this compound with nitric acid and sulfuric acid and isolated three different isomers with molecular formula C 6 H 3 Br 2 NO 2 . What was the structure of the original compound?

List the following compounds in order from largest Keq to smallest Keq for hydrate formation:

a. Describe four ways the following reaction could be carried out. O b. Describe three ways the following reaction could be carried out.

Propose a mechanism for each of the following reactions:

How could you prepare the following compounds with benzene as one of the starting materials?

Describe how naphthalene could be prepared from the given starting material.

Identify AJ:

Using resonance contributors for the intermediate carbocation, explain why a phenyl group is an orthopara director.

The p Ka values of a few ortho-, meta-, and para-substituted benzoic acids are shown here:

When heated with chromic acid, compound A forms benzoic acid. Identify compound A from its 1 H NMR spectrum.

Describe two synthetic routes for the preparation of p -methoxyaniline from benzene.

Which is a more stable intermediate in each pair?

What reagents would be required to carry out the following transformations?

Show how the following compounds could be prepared from benzene:

An unknown compound reacts with ethyl chloride and aluminum trichloride to form a compound that has the following 1 H NMR spectrum. What is the structure of the compound?

How could you distinguish the following compounds, using a. their infrared spectra? b. their 1 H NMR spectra?

p -Fluoronitrobenzene is more reactive toward hydroxide ion than is p -chloronitrobenzene. What does this tell you about the ratedetermining step for nucleophilic aromatic substitution?

a. Explain why the following reaction leads to the products shown: NaNO2 HCl CH3CHCH2NH2 CH3CCH3 + CH3C CH2 CH3 CH3 OH CH3 b. What product would be obtained from the following reaction?

Describe how mescaline could be synthesized from benzene. The structure of mescaline is given on page 908.

Propose a mechanism for the following reaction that explains why the coni guration of the asymmetric center in the reactant is retained in the product:

Explain why hydroxide ion catalyzes the reaction of piperidine with 2,4-dinitroanisole but has no effect on the reaction of piperidine with 1-chloro-2,4-dinitrobenzene.

Propose a reasonable mechanism for each of the following reactions:

What are the products of the following reactions?

Tyramine is an alkaloid found in mistletoe and ripe cheese. Dopamine is a neurotransmitter involved in the regulation of the central nervous system.

Describe how 3-methyl-1-phenyl-3-pentanol can be prepared from benzene. You can use any inorganic reagents and solvents, and any organic reagents provided they contain no more than two carbons.

a. How could aspirin be synthesized from benzene? b. Ibuprofen is the active ingredient in pain relievers such as Advil, Motrin, and Nuprin. How could ibuprofen be synthesized from benzene? c. Acetaminophen is the active ingredient in Tylenol. How could acetominophen be synthesized from benzene?

a. Ketoprofen, like ibuprofen, is an anti-inl ammatory analgesic. How could ketoprofen be synthesized from the given starting material? O O CH CH3 CH3 ketoprofen O OH C b. Ketoprofen and ibuprofen both have a propanoic acid substituent (see Problem 105 ). Explain why the identical subunits are synthesized in different ways.

Show how Novocain, a painkiller used frequently by dentists, can be prepared from benzene and compounds containing no more than four carbons.

Show how lidocaine, one of the most widely used injectable anesthetics, can be prepared from benzene and compounds containing no more than four carbons.

Saccharin, an artii cial sweetener, is about 300 times sweeter than sucrose. Describe how saccharin could be prepared from benzene

Problem 1P Draw the structure for each of the following: a. 2-phenylhexane c. 3-benzylpentane b. benzyl alcohol d. bromomethylbenzene

Problem 2P If electrophilic addition to benzene is overall an endergonic reaction, how can electrophilic addition to an alkene be overall an exergonic reaction?

Problem 3P Why does hydration inactivate FeBr3?

Propose a mechanism for the following reaction:

Problem 5P The reaction coordinate diagram in Figure 19.3 shows that the rate-determining step for sulfonation is the slower of the two steps in the mechanism, whereas the rate-determining step for desulfonation is the faster of the two steps. Explain how the faster step can be the rate determining step.

Problem 6P Show the mechanism for the generation of the acylium ion if an acid anhydride is used instead of an acyl chloride for the source of the acylium ion.

Problem 7P What would be the major product of a Friedel–Crafts alkylation using the following alkyl chlorides? a. CH3CH2Cl b. CH3CH2CH2Cl c. CH3CH2CH(Cl)CH3 d. (CH3)3CCl e. (CH3)2CHCH2Cl f. CH2=CHCH2Cl

Describe two ways to prepare each of the following compounds from benzene.

What are the products of the following reactions?

Show how the following compounds could be prepared from benzene: a. benzaldehyde b. styrene c. 1-bromo-2-phenylethane d. 2-phenylethanol e. aniline f. benzoic acid

Name the following compounds:

Problem 12P Draw a structure for each of the following compounds: a. para-toluidine b. meta-cresol c. para-xylene d. ortho-chlorobenzenesulfonic acid

Problem 13P Draw the structure for each of the following: a. m-chloromethylbenzene b. p-bromophenol c. o-nitroaniline d. m-chlorobenzonitrile e. 2-bromo-4-iodophenol f. m-dichlorobenzene g. 2,5-dinitrobenzaldehyde h. 4-bromo-3-chloroaniline i. o-xylene

Problem 14P Correct the following incorrect names: a. 2,4,6-tribromobenzene b. 3-hydroxynitrobcnzene c. para-methylbromobenzene d. 1,6-dichlorobenzene

For each of the following substituents, indicate whether it withdraws electrons inductively, donates electrons by hyperconjugation, withdraws electrons by resonance, or donates electrons by resonance. (Effects should be compared with that of a hydrogen; remember that many substituents can be characterized in more than one way.)

List the compounds in each set from most reactive to least reactive toward electrophilic aromatic substitution: a. benzene, phenol, toluene, nitrobenzene, bromobenzene b. dichloromethylbenzene, dil uoromethylbenzene, toluene, chloromethylbenzene

Problem 18P a. Draw the resonance contributors for benzaldehyde. b. Draw the resonance contributors for chlorobenzene.

Problem 19P What product(s) would result from nitration of each of the following? a. Propylbenzene c. benzaldehyde e. benzenesulfonic acid b. Bromobenzene d. Benzonitrile f. cyclohexylbenzene

Are the following substituents ortho–para directors or meta directors? a. \(\mathrm{CH}=\mathrm{CHC} \equiv \mathrm{N}\) b. \(\mathrm{NO}_{2}\) c. \(\mathrm{CH}_{2} \mathrm{OH}\) d. \(\mathrm{COOH}\) e. \(\mathrm{CF}_{3}\) f. \(\mathrm{N}=\mathrm{O}\) Equation Transcription: NO2 CH2OH CF3 Text Transcription: CH?CHCN NO_2 CH_2OH COOH CF_3 N?O

What product(s) would be obtained from the reaction of each of the following compounds with one equivalent of \(\mathrm{Br}_{2}\) , using \(\mathrm{FeBr}_{3}\) as a catalyst? Equation Transcription: Br2 FeBr3 Text Transcription: Br_2 FeBr_3

Which species in each of the following pairs is more acidic?

a. Which is the strongest acid, benzoic acid, o -l uorobenzoic acid, or o -chlorobenzoic acid? ( Hint : see Problem \(17\) .) b. Which of these compounds is the weakest acid? Equation Transcription: Text Transcription: 17

Problem 23P Explain why the pKa of p-nitrophenol is 7.14, whereas the pKa of m-nitrophenol is 8.39.

Problem 26P Give the products, if any, of each of the following reactions: a. benzonitrile + methyl chloride + AlCl3 c. benzoic acid + CH3CH2Cl + AlCl3 b. aniline + Br2 d. benzene + 2 CH3Cl + AlCl3

Show how the following compounds could be synthesized from benzene:

Problem 27P a. Does a coupling reaction have to be used to synthesize p-dipropylbenzene? b. Can a coupling reaction be used to synthesize p-dipropylbenzene?

Problem 28P Show how each of the following compounds can be synthesized from benzene: a. p-chloroaniline b. m-chloroaniline c. m-xylene d. 2-phenylpropene e. m-nitrobenzoic acid f. p-nitrobenzoic acid g. m-bromopropylbenzene h. o-bromopropylbenzene i. 1-phenyl-2-propanol

Problem 29P What is the major product(s) of each of the following reactions? a. bromination of p-methylbenzoic acid b. chlorination of o-benzenedicarboxylic acid c. bromination of p-chlorobenzoic acid d. nitration of p-fluoroanisole e. nitration of p-methoxybenzaldehyde f. nitration of p-tert-butylmethylbenzene

Problem 30P A student had prepared three ethyl-substituted benzaldehydes, but neglected to label them. The student at the next bench said they could be identified by brominating a sample of each and determining how many bromo-substituted products were formed. Is the student’s advice sound?

Problem 32P Why isn’t FeBr3 used as a catalyst in the first step of the synthesis of 1,3,5-tribromobenzene?

Explain why a diazonium group on a benzene ring cannot be used to direct an incoming substituent to the meta position.

Problem 34P Write the sequence of steps required for the conversion of benzene into benzenediazonium chloride.

Problem 35P Show how the following compounds could be synthesized from benzene: a. m-nitrobenzoic acid b. m-bromophenol c. o-chlorophenol d. m-methylnitrobenzene e. p-methylbenzonitrile f. m-chlorobenzaldehyde

What product is formed from the reaction of p-methylphenol with benzenediazonium chloride?

Problem 37P In the mechanism for electrophilic aromatic substitution with a diazonium ion as the electrophile, why does nucleophilic attack occur on the terminal nitrogen of the diazonium ion ratherthan on the nitrogen that has the formal positive charge?

Draw the structure of the activated benzene ring and the diazonium ion used in the synthesis of each of the following compounds , whose structures can be found on page \(635\). a. butter yellow b. methyl orange Equation Transcription: Text Transcription: 635

Problem 39P Which amide bond is hydrolyzed in the first step of the conversion of temozolomide tomethyldiazonium?

Explain why a secondary amine forms a nitrosamine rather than a diazonium ion when it reacts with a nitrosonium ion.

Diazomethane can be used to convert a carboxylic acid into a methyl ester. Propose a mechanism for this reaction.

Problem 42P Draw resonance contributors for the carbanion that would be formed if meta-chloronitrobenzenewere to react with hydroxide ion. Why doesn’t the reaction occur?

Problem 43P a. List the following compounds in order from greatest tendency to least tendency to undergonucleophilic aromatic substitution: chlorobenzene 1-chloro-2,4-dinitrobenzene p-chloronitrobenzene b. List the same compounds in order from greatest tendency to least tendency to undergoelectrophilic aromatic substitution.

Problem 44P Show how each of the following compounds could be synthesized from benzene: a. o-nitrophenol b. p-nitroaniline c. p-bromoanisole d. anisole

Problem 46P Draw the structure for each of the following: a. phenol b. benzyl phenyl ether c. benzonitrile d. benzaldehyde e. anisole f. styrene g. toluene h. tert-butylbenzene i. benzyl chloride

Design a synthesis for each of the following, using an intramolecular reaction:

Name the following:

Provide the necessary reagents next to the arrows.

Draw the structure for each of the following: a. m -ethylphenol b. p -nitrobenzenesulfonic acid c. ( E )-2-phenyl-2-pentene d. o -bromoaniline e. 4-bromo-1-chloro-2-methylbenzene f. m -chlorostyrene g. o -nitroanisole h. 2,4-dichloromethylbenzene i. m -chlorobenzoic acid

For each of the statements in Column I, choose a substituent from Column II that i ts the description for the compound on the right: Column I Column II a. Z donates electrons by hyperconjugation and does not donate or withdraw electrons by resonance. \(O H\) b. Z withdraws electrons inductively and withdraws electrons by resonance. \(Br\) c. Z deactivates the ring and directs ortho-para. \({ }^{+} \mathrm{NH}_{3}\) d. Z withdraws electrons inductively, donates electrons by resonance, and activates the ring. \(\mathrm{CH}_{2} \mathrm{CH}_{3}\) e. withdraws electrons inductively and does not donate or withdraw electrons by resonance. \(\mathrm{NO}_{2}\) Equation Transcription: Text Transcription: OH Br ^+NH_3 CH_2CH_3 NO_2

Problem 51P What product would be obtained from the reaction of excess benzene with each of the following reagents? a. isobutyl chloride + AlCl3 b. 1-chloro-2,2-dimethylpropane + AlCl3 c. dichloromethane + AlCl3

Problem 52P Draw the product(s) of each of the following reactions: a. benzoic acid + HNO3/H2SO4 b. isopropylbenzene + Cl2 + FeCl3 c. p-xylene + acetyl chloride + AlCl3 followed by H2O d. o-methylaniline + benzenediazonium chloride e. cyclohexyl phenyl ether + Br2 f. phenol + H2SO4 + ? g. ethylbenzene + Br2/FeBr3 h. m-xylene + Na2Cr2O7 + HCl + ?

Rank the following substituted anilines in order from most basic to least basic:

For each horizontal row of substituted benzenes, indicate a. the one that would be the most reactive in an electrophilic aromatic substitution reaction. b. the one that would be the least reactive in an electrophilic aromatic substitution reaction. c. the one that would yield the highest percentage of meta product in an electrophilic aromatic substitution reaction.

The compound with the \({ }^{1} \mathrm{H}\) NMR spectrum shown here is known to be highly reactive toward electrophilic aromatic substitution. Identify the compound. Equation Transcription: 1H Text Transcription: ^1 H

Draw the product of each of the following reactions:

Problem 57P Show how the following compounds could be synthesized from benzene: a. m-chlorobenzenesulfonic acid b. m-chloroethylbenzene c. m-bromobenzonitrile d. 1-phenylpentane e. m-bromobenzoic acid f. m-hydroxybenzoic acid g. p-cresol h. benzyl alcohol i. benzylamine

Problem 58P How many electrophilic aromatic substitution products are obtained from the chlorination of a. o-xylene? b. p-xylene? c. m-xylene?

Problem 59P Arrange the following groups of compounds in order from most reactive to least reactive toward electrophilic aromatic substitution: a. benzene, ethylbenzene, chlorobenzene, nitrobenzene, anisole b. 1-chloro-2,4-dinitrobenzene, 2,4-dinitrophenol, 1-methyl-2,4-dinitrobenzene c. toluene, p-cresol, benzene, p-xylene d. benzene, benzoic acid, phenol, propylbenzene e. p-methylnitrobenzene, 2-chloro-1-methyl-4-nitrobenzene, 1-methyl-2,4-dinitrobenzene, p-chloromethylbenzene f. bromobenzene, chlorobenzene, fluorobenzene, iodobenzene

What are the products of the following reactions?

Problem 61P Describe two ways to prepare anisole from benzene.

For each of the following compounds, indicate the ring carbon that would be nitrated if the compound is treated with \(\mathrm{HNO}_{3} / \mathrm{H}_{2} \mathrm{SO}_{4}\): Equation Transcription: HNO3/H2SO4 Text Transcription: HNO_3/H_2SO_4

Show two ways that the following compound could be synthesized:

Why is anisole nitrated more rapidly than thioanisole under the same conditions?

Problem 65P If anisole is allowed to sit in D2O that contains a small amount of D2SO4, what products will be formed?

The following tertiary alkyl bromides undergo an \(\mathrm{S}_{\mathrm{N}} 1\) reaction in aqueous acetone to form the corresponding tertiary alcohols. List the alkyl bromides in order from most reactive to least reactive. Equation Transcription: SN1 Text Transcription: S_N 1

Problem 67P An aromatic hydrocarbon with a molecular formula of C13H20 has an 1H NMR spectrum with a signal at ~7 ppm that integrates to 5H. It also has two singlets; one of the singlets has 1.5 times the area of the second. What is the structure of the aromatic hydrocarbon?

Problem 69P Show how the following compounds could be synthesized from benzene: a. N,N,N-trimethylanilinium iodide b. 2-methyl-4-nitrophenol c. p-benzylchlorobenzene d. benzyl methyl ether e. p-nitroaniline f. m-bromoiodobenzene g. p-dideuteriobenzene h. p-nitro-N-methylaniline i. 1-bromo-3-nitrobenzene

Show how the following compounds could be synthesized from benzene: a. \(N, N, N\) -trimethylanilinium iodide b. 2-methyl-4-nitrophenol c. \(p\)-benzylchlorobenzene d. benzyl methyl ether e. \(p\)-nitroaniline f. \(m\)-bromoiodobenzene g. \(p\)-dideuteriobenzene h. \(p\)-nitro- N -methylaniline i. 1-bromo-3-nitrobenzene Equation Transcription: Text Transcription: N,N,N p m

Use the four compounds shown here to answer the following questions:

a. List the following esters in order from most reactive to least reactive in the i rst slow step of a nucleophilic addition–elimination reaction (formation of the tetrahedral intermediate): b. List the same esters in order from most reactive to least reactive in the second slow step of a nucleophilic addition–elimination reaction (collapse of the tetrahedral intermediate).

Problem 72P A mixture of 0.10 mol benzene and 0.10 mol p-xylene was allowed to react with 0.10 mol nitronium ion until all the nitronium ion was gone. Two products were obtained: 0.002 mol of one and 0.098 mol of the other. a. What was the major product? b. Why was more of one product obtained than of the other?

What are the products of the following reactions?

Benzene underwent a Friedel–Crafts acylation followed by a Clemmensen reduction. The product gave the following \({ }^{1} \mathrm{H}\) NMR spectrum. What acyl chloride was used in the Friedel–Crafts acylation? Equation Transcription: 1H Text Transcription: ^1 H

Problem 75P Would m-xylene or p-xylene react more rapidly with Cl2+ FeCl3? Explain your answer.

What products would be obtained from the reaction of the following compounds with \(\mathrm{H}_{2} \mathrm{CrO}_{4}+\Delta\)? Equation Transcription: H2CrO4+? Text Transcription: H_2CrO_4+ Delta

Problem 77P Which set of underlined hydrogens will have its 1H NMR signal at a higher frequency? a. CH3CH2CH3 or CH3OCH2CH3 b. CH3CH=CH2 or CH3OCH=CH2

Friedel–Crafts alkylations can be carried out with carbocations formed from reactions other than the reaction of an alkyl halide with \(\mathrm{AlCl}_{3}\). Propose a mechanism for the following reaction: Equation Transcription: Text Transcription: AlCl_3

Show how the following compounds could be prepared from the given starting materials. You can use any necessary organic or inorganic reagents.

Problem 80P A chemist isolated an aromatic compound with molecular formula C6H4Br2. He treated this compound with nitric acid and sulfuric acid and isolated three different isomers with molecular formula C6H3Br2NO2. What was the structure of the original compound?

List the following compounds in order from largest \(K_{e q}\) to smallest \(K_{e q}\) for hydrate formation: Equation Transcription: Text Transcription: K_eq

a. Describe four ways the following reaction could be carried out. b. Describe three ways the following reaction could be carried out.

Propose a mechanism for each of the following reactions:

How could you prepare the following compounds with benzene as one of the starting materials?

Describe how naphthalene could be prepared from the given starting material.

Using resonance contributors for the intermediate carbocation, explain why a phenyl group is an ortho–para director.

Identify A–J:

The \(\mathrm{pK}_{a}\) values of a few ortho-, meta-, and para-substituted benzoic acids are shown here: The \(\mathrm{pK}_{a}\) values depend on the substituent. For chloro-substituted benzoic acids, the ortho isomer is the most acidic and the para isomer is the least acidic; for nitro-substituted benzoic acids, the ortho isomer is the most acidic and the meta isomer is the least acidic; and for amino-substituted benzoic acids, the meta isomer is the most acidic and the ortho isomer is the least acidic. Explain these relative acidities. a. Cl: ortho > meta > para b. \(\mathrm{NO}_{2}\) : ortho > para > meta c. \(\mathrm{NH}_{2}\): meta > para > ortho Equation Transcription: pKa NO2 NH2 Text Transcription: pK_a NO_2 NH_2

When heated with chromic acid, compound A forms benzoic acid. Identify compound A from its \({ }^{1} \mathrm{H}\) NMR spectrum. Equation Transcription: 1H Text Transcription: ^1 H

Problem 90P Describe two synthetic routes for the preparation of p-methoxyaniline from benzene.

Which is a more stable intermediate in each pair?

What reagents would be required to carry out the following transformations?

Show how the following compounds could be prepared from benzene:

An unknown compound reacts with ethyl chloride and aluminum trichloride to form a compound that has the following \({ }^{1} \mathrm{H}\) NMR spectrum. What is the structure of the compound? Equation Transcription: 1H Text Transcription: ^1 H

How could you distinguish the following compounds, using a. their infrared spectra? b. Their \({ }^{1} \mathrm{H}\) NMR spectra? Equation Transcription: 1H Text Transcription: ^1 H

Problem 96P p-Fluoronitrobenzene is more reactive toward hydroxide ion than is p-chloronitrobenzene. What does this tell you about the rate determining step for nucleophilic aromatic substitution?

a. Explain why the following reaction leads to the products shown: b. What product would be obtained from the following reaction?

Describe how mescaline could be synthesized from benzene. The structure of mescaline is given on page \(908\). Equation Transcription: Text Transcription: 908

Propose a mechanism for the following reaction that explains why the configuration of the asymmetric center in the reactant is retained in the product:

Explain why hydroxide ion catalyzes the reaction of piperidine with \(2,4\)-dinitroanisole but has no effect on the reaction of piperidine with \(1\)-chloro-\(2,4\)-dinitrobenzene. Equation Transcription: Text Transcription: 2,4 1

Propose a reasonable mechanism for each of the following reactions:

What are the products of the following reactions?

Tyramine is an alkaloid found in mistletoe and ripe cheese. Dopamine is a neurotransmitter involved in the regulation of the central nervous system. a. How can tyramine be prepared from \(\beta\)-phenylethylamine? b. How can dopamine be prepared from tyramine? c. Give two ways to prepare \(\beta\)-phenylethylamine from \(\beta\)-phenylethyl chloride. d. How can \(\beta\)-phenylethylamine be prepared from benzyl chloride? e. How can \(\beta\)-phenylethylamine be prepared from benzaldehyde? Equation Transcription: Text Transcription: beta

Problem 104P Describe how 3-methyl-1-phenyl-3-pentanol can be prepared from benzene. You can use any inorganic reagents and solvents, and any organic reagents provided they contain no more than two carbons.

a. How could aspirin be synthesized from benzene? b. Ibuprofen is the active ingredient in pain relievers such as Advil, Motrin, and Nuprin. How could ibuprofen be synthesized from benzene? c. Acetaminophen is the active ingredient in Tylenol. How could acetominophen be synthesized from benzene?

a. Ketoprofen, like ibuprofen, is an anti-inl ammatory analgesic. How could ketoprofen be synthesized from the given starting material? b. Ketoprofen and ibuprofen both have a propanoic acid substituent (see Problem 105 ). Explain why the identical subunits are synthesized in different ways.

Show how Novocain, a painkiller used frequently by dentists, can be prepared from benzene and compounds containing no more than four carbons.

Show how lidocaine, one of the most widely used injectable anesthetics, can be prepared from benzene and compounds containing no more than four carbons.

Problem 109P Saccharin, an artificial sweetener, is about 300 times sweeter than sucrose. Describe how saccharin could be prepared from benzene.