Organic Chemistry 6th Edition solutions

Organic Chemistry 6
Write the stepwise mechanism for sulfonation of benzene by hot, concentrated sulfuric acid. In this reaction, the electrophile is SO3 formed as shown in the following equation. H2SO4 EF SO3 1 H2O

Organic Chemistry 6
Write a structural formula for the product from Friedel-Crafts alkylation or acylation of benzene with each compound. (a) Cl (b) (c) ClPh Cl O

Organic Chemistry 6
Write a mechanism for the formation of tert -butylbenzene from benzene and tert -butyl alcohol in the presence of phosphoric acid.

Organic Chemistry 6
Draw structural formulas for the product of nitration of each compound. Where you predict ortho-para substitution, show both products. (a) COCH (b) 3 O OCCH3 O

Organic Chemistry 6
In SN2 reactions of alkyl halides, the order of reactivity is RI . RBr . RCl . RF. Alkyl iodides are considerably more reactive than alkyl fl uorides, often by factors as great as 106 . All 1-halo-2,4- dinitrobenzenes, however, react at approximately the same rate in nucleophilic aromatic substitutio

Organic Chemistry 6
Write a stepwise mechanism for each of the following reactions. Use curved arrows to show the fl ow of electrons in each step. Cl FeCl3 1 Cl (a) 2 1 HCl AlCl3 (b) 1 Cl 1 HCl SnCl4 (c) 1 1 HCl O O Cl O O AlCl3 1 CH2Cl2 (d) 1 2HCl

Organic Chemistry 6
Pyridine undergoes electrophilic aromatic substitution preferentially at the 3 position as illustrated by the synthesis of 3-nitropyridine. H2SO4 300C 1 1 HNO3 N Pyridine N 3-Nitropyridine H2O NO2 Under these acidic conditions, the species undergoing nitration is not pyridine but its conjugate acid.

Organic Chemistry 6
Pyrrole undergoes electrophilic aromatic substitution preferentially at the 2 position as illustrated by the synthesis of 2-nitropyrrole. CH3COOH 5C 1 HNO3 1 H2O N NO2 H Pyrrole N H 2-Nitropyrrole .Write resonance contributing structures for the intermediate formed by attack of NO2 1 at the 2 and 3 p

Organic Chemistry 6
Addition of m-xylene to the strongly acidic solvent HF/SbF5 at 245C gives a new species, which shows 1 H-NMR resonances at d 2.88 (3H), 3.00 (3H), 4.67 (2H), 7.93 (1H), 7.83 (1H), and 8.68 (1H). Assign a structure to the species giving this spectrum.

Organic Chemistry 6
Addition of tert -butylbenzene to the strongly acidic solvent HF/SbF5 followed by aqueous work-up gives benzene. Propose a mechanism for this dealkylation reaction. What is the other product of the reaction?

Organic Chemistry 6
What product do you predict from the reaction of SCl2 with benzene in the presence of AlCl3? What product results if diphenyl ether is treated with SCl2 and AlCl3?

Organic Chemistry 6
Other groups besides H1 can act as leaving groups in electrophilic aromatic substitution. One of the best is the trimethylsilyl group, Me3Si!. For example, treatment of Me3SiC6H5 with CF3COOD rapidly forms C6H5D. What are the properties of a siliconcarbon bond that allows you to predict this kind of

Organic Chemistry 6
The following groups are ortho-para directors. (a) !OH (b) !OCCH3 (c) !N(CH3)2 (d) !NHCCH3 (e) ! O O Draw a contributing structure for the resonance-stabilized cation formed during electrophilic aromatic substitution that shows the role of each group in stabilizing the intermediate by further delocal

Organic Chemistry 6
Predict the major product or products from treatment of each compound with HNO3/H2SO4. (a) OCH3 CH3 NO2 (b) (c) (d) NO2 OH NO2 CH3

Organic Chemistry 6
How do you account for the fact that N-phenylacetamide (acetanilide) is less reactive toward electrophilic aromatic substitution than aniline? !NHCCH3 N-Phenylacetamide (Acetanilide) !NH2 Aniline O

Organic Chemistry 6
Propose an explanation for the fact that the trifl uoromethyl group is almost exclusively meta directing. H2SO4 1 HNO3 CF3 1 H2O CF3 NO2

Organic Chemistry 6
Suggest a reason why the nitroso group, !N" O, is ortho-para directing whereas the nitro group, !NO2, is meta directing.

Organic Chemistry 6
Arrange the compounds in each set in order of decreasing reactivity (fastest to slowest) toward electrophilic aromatic substitution. (a) !OCCH3 (A) (B) O O !COCH3 (C) !NO2 (b) (A) !COOH (B) (C) (c) !CH !CH2Cl 3 !Cl (A) (d) (A) !C#N (B) (B) !CHCl2 !OCH2CH3 O !CNHCH3 O (C) (C) !NH2 (e) (A) !NHCCH3 (B)

Organic Chemistry 6
For each compound, indicate which group on the ring is the more strongly activating and then draw a structural formula of the major product formed by nitration of the compound. (a) OCH3 CH3 (b) NHCCH3 CH3 O (c) COOH Cl (d) CH3 SO3H (e) CH3 COOH (f) CCH3 NHCCH3 O O (g) OCH3 Cl (h) NO2

Organic Chemistry 6
The following molecules each contain two aromatic rings. (a) !CNH! O (c) !CO! O (b) O2N! ! Which ring in each undergoes electrophilic aromatic substitution more readily? Draw the major product formed on nitration.

Organic Chemistry 6
Reaction of phenol with acetone in the presence of an acid catalyst gives a compound known as bisphenol A, which is used in the production of epoxy and polycarbonate resins (Section 29.5). Propose a mechanism for the formation of bisphenol A. O H3PO4 OH HO OH 1 1 H2O Phenol Acetone Bisphenol A

Organic Chemistry 6
2,6-Di-tert -butyl-4-methylphenol, alternatively known as butylated hydroxytoluene (BHT), is used as an antioxidant in foods to retard spoilage (Section 8.7). BHT is synthesized industrially from 4- methylphenol by reaction with 2-methylpropene in the presence of phosphoric acid. Propose a mechanism

Organic Chemistry 6
The insecticide DDT is prepared by the following route. Suggest a mechanism for this reaction. The abbreviation DDT is derived from the common name dichlorodiphenyltrichloroethane. CCl3 O CCl 1 39C9H Trichloroacetaldehyde H2SO4 Cl Cl Cl 1 H2O Chlorobenzene DDT

Organic Chemistry 6
Treatment of salicylaldehyde (2-hydroxybenzaldehyde) with bromine in glacial acetic acid at 0C gives a compound with the molecular formula C7H4Br2O2, which is used as a topical fungicide and antibacterial agent. Propose a structural formula for this compound.

Organic Chemistry 6
Propose a synthesis for 3,5-dibromo-2-hydroxybenzoic acid (3,5-dibromosalicylic acid) from phenol.

Organic Chemistry 6
Treatment of benzene with succinic anhydride in the presence of polyphosphoric acid gives the following g -ketoacid. Propose a mechanism for this reaction. COOH O H3PO4 O O Succinic anhydride 4-Oxo-4-phenylbutanoic acid 1 O

Organic Chemistry 6
Following are the fi nal steps in the synthesis of trifl uralin B, a pre-emergent herbicide. N HNO3 H Cl CF3 Cl CF3 O2N NO2 N CF3 Trifluralin B O2N NO2 1 2 (a) Account for the orientation of nitration in Step 1. (b) Propose a mechanism for the substitution reaction in Step 2.

Organic Chemistry 6
A problem in dyeing fabrics is the degree of fastness of the dye to the fabric. Many of the early dyes were surface dyes; that is, they did not bond to the fabric, with the result that they tended to wash off after repeated laundering. Indigo, for example, which gives the blue color to blue jeans, is

Organic Chemistry 6
Use the roadmap you made for problems 20.55 and 21.49 and update it to contain the reactions in the Key Reactions section of this chapter. Because of its highly specifi c nature, do not use reaction 9 on your roadmap. In anticipation of reactions in Chapter 23, on this roadmap you should include the

Organic Chemistry 6
Write the products of the following sequences of reactions. Refer to your roadmaps to see how the combined reactions allow you to navigate between the different functional groups. Note that you will need your old Chapters 611, Chapters 1518 and Chapter 19 roadmaps along with your new Chapters 2022 ro

Organic Chemistry 6
Show how to convert toluene to these compounds. (a) !CH2Br Br! !CH3

Organic Chemistry 6
Show how to prepare each compound from 1-phenyl-1-propanone. Br O O O Br 1-Phenyl-1- propanone (racemic) (a) (

Organic Chemistry 6
Show how to convert toluene to (a) 2,4-dinitrobenzoic acid and (b) 3,5-dinitrobenzoic acid.

Organic Chemistry 6
Show reagents and conditions to bring about the following conversions. CH3 COOH COOH NO2 (a) OH OEt (b) Cl OMe (c) NO2 OCH3 OCH3 CCH3 (d) O O2N CH2CH3 CH"CH2 (e)

Organic Chemistry 6
Propose a synthesis of triphenylmethane from benzene, as the only source of aromatic rings, and any other necessary reagents.

Organic Chemistry 6
Propose a synthesis for each compound from benzene. Cl (a) Cl (b) O H N

Organic Chemistry 6
The fi rst widely used herbicide for the control of weeds was 2,4-dichlorophenoxyacetic acid (2,4-D). Show how this compound might be synthesized from phenol and chloroacetic acid by way of the given chlorinated phenol intermediate. COOH 2,4-Dichlorophenoxyacetic acid (2,4-D) Chloroacetic acid O Cl C

Organic Chemistry 6
Phenol is the starting material for the synthesis of 2,3,4,5,6-pentachlorophenol, known alternatively as pentachlorophenol or more simply as penta. At one time, penta was widely used as a wood preservative for decks, siding, and outdoor wood furniture. Draw the structural formula for pentachloropheno

Organic Chemistry 6
Starting with benzene, toluene, or phenol as the only sources of aromatic rings, show how to synthesize the following. Assume in all syntheses that mixtures of ortho-para products can be separated into the desired isomer. (a) 1-Bromo-3-nitrobenzene (b) 1-Bromo-4-nitrobenzene (c) 2,4,6- Trinitrotoluen

Organic Chemistry 6
3,5-Dibromo-4-hydroxybenzenesulfonic acid is used as a disinfectant. Propose a synthesis of this compound from phenol.

Organic Chemistry 6
Propose a synthesis for 3,5-dichloro-2-methoxybenzoic acid starting from phenol.

Organic Chemistry 6
The following compound used in perfumery has a violet-like scent. Propose a synthesis of this compound from benzene. O 4-Isopropylacetophenone

Organic Chemistry 6
Cancer of the prostate is the second leading cause of cancer deaths among American males, exceeded only by lung cancer. One treatment of prostate cancer is based on the fact that testosterone and androsterone (both androgens) enhance the proliferation of prostate tumors. The drug fl utamide (an antia

Organic Chemistry 6
The compound 4-isobutylacetophenone is needed for the synthesis of ibuprofen (see Chemical Connections: Ibuprofen: the Evolution of an Industrial Synthesis in Chapter 19). Propose a synthesis of 4-isobutylacetophenone from benzene and any other necessary reagents. several steps O 4- Isobutylacetophen

Organic Chemistry 6
Following is the structural formula of musk ambrette, a synthetic musk, essential in perfumes to enhance and retain odor. Propose a synthesis of this compound from m -cresol (3-methylphenol). OCH3 O2N NO2

Organic Chemistry 6
Propose a synthesis of this compound starting from toluene and phenol. O O Br Cl NH2

Organic Chemistry 6
When certain aromatic compounds are treated with formaldehyde, CH2O, and HCl, the CH2Cl group is introduced onto the ring. This reaction is known as chloromethylation. chloromethylation ? 1 CH2O 1 HCl Piperonal CH2Cl CHO O O O O O O (a) Propose a mechanism for this example of chloromethylation. (b) T

Organic Chemistry 6
Following is a retrosynthetic analysis for the acaracide (killing mites and ticks) and fungicide dinocap. Dinocap O2N NO2 O O2N NO2 OH O2N NO2 OH OH O Hexyl Hexyl 1 2 3 (a) Given this analysis, propose a synthesis for dinocap from phenol and l-octene. (b) Is dinocap chiral? If so, which of the possib

Organic Chemistry 6
Following is the structure of miconazole, the active antifungal agent in a number of over-the-counter preparations, including Monistat, which are used to treat vaginal yeast infections. One of the compounds needed for the synthesis of miconazole is the trichloro derivative of toluene shown on its rig

Organic Chemistry 6
Bupropion, the hydrochloride of which was first marketed in 1985 by BurroughsWellcome, now GlaxoSmithKline, is an antidepressant sold under the trade name Wellbutrin. During clinical trials, it was discovered that smokers, after one to two weeks on the drug, reported that their craving for tobacco le

Organic Chemistry 6
Diazepam, better known as Valium, is a central nervous system (CNS) sedative/hypnotic. As a sedative, it diminishes activity and excitement and thereby has a calming effect. In 1976, based on the number of new and refi lled prescriptions processed, diazepam was the most prescribed drug in the United

Organic Chemistry 6
The antidepressant amitriptyline inhibits the re-uptake of norepinephrine and serotonin from the synaptic cleft. Because the re-uptake of these neurotransmitters is inhibited, their effects are potentiated; they remain available to interact with serotonin and norepinephrine receptor sites longer and

Organic Chemistry 6
Show how the antidepressant venlafaxine (Effexor) can be synthesized from these readily available starting materials. Is venlafaxine chiral? If so, how many of the possible stereoisomers are formed in this synthesis? Venlafaxine Cl O Cl O Me2NH MeO Anisole Cyclohexanone Dimethylamine Chloroacetyl chl

Organic Chemistry 6
One potential synthesis of the antiinfl ammatory and analgesic drug nabumetone is chloromethylation (Problem 22.48) of 2-methoxynaphthalene followed by an acetoacetic ester synthesis (Section 19.6). 2-Methoxynaphthalene Nabumetone O Cl MeO MeO MeO 1 8 7 6 2 3 4 5 CH2O HCl acetoacetic ester synthesis

Organic Chemistry 6
The analgesic, soporifi c, and euphoriant properties of the dried juice obtained from unripe seed pods of the opium poppy Papaver somniferum have been known for centuries. By the beginning of the 19th century, the active principle, morphine, had been isolated and its structure determined. Even though

Organic Chemistry 6
Following is the structural formula of the antihypertensive drug labetalol, a nonspecifi c b -adrenergic blocker with vasodilating activity. Members of this class have received enormous clinical attention because of their effectiveness in treating hypertension (high blood pressure), migraine headache

Organic Chemistry 6
Propose a synthesis for the antihistamine p -methyldiphenhydramine, given this retrosynthetic analysis. Is p -methyldiphenhydramine chiral? If so, how many of the possible stereoisomers are formed in this synthesis? O NMe2 p-Methyldiphenhydramine O H Br 1 1 NMe2 HO

Organic Chemistry 6
Meclizine is an antiemetic (it helps prevent or at least lessen the throwing up associated with motion sickness, including seasickness). Among the names of its over-thecounter preparations are Bonine, Sea-Legs, Antivert, and Navicalm. Cl 1 Meclizine 3-Aminomethyltoluene Ethylene oxide Benzoic acid Ch

Organic Chemistry 6
Spasmolytol, as its name suggests, is an antispasmodic. Given this retrosynthetic analysis, propose a synthesis for spasmolytol from salicylic acid, ethylene oxide, and diethylamine. Spasmolytol Salicyclic acid NEt2 Br OCH3 O Br OH OH O

Organic Chemistry 6
Spasmolytol, as its name suggests, is an antispasmodic. Given this retrosynthetic analysis, propose a synthesis for spasmolytol from salicylic acid, ethylene oxide, and diethylamine. Spasmolytol Salicyclic acid NEt2 Br OCH3 O Br OH OH O

Organic Chemistry 6
A newer generation of antipsychotics, among them clozapine, are now used to treat the symptoms of schizophrenia. These drugs are more effective than earlier drugs in improving patient response in the areas of social withdrawal, apathy, memory, comprehension, and judgment. They also produce fewer side

Organic Chemistry 6
Proparacaine is one of a class of -caine local anesthetics. NH2 O O O Proparacaine NH2 O O OH NEt2 NO2 O O O O OH O HO OH OH 1 2 3 4 (a) Given this retrosynthetic analysis, propose a synthesis of proparacaine from 4-hydroxybenzoic acid. (b) Is proparacaine chiral? If so, how many of the possible ster