Organic Chemistry 6th Edition solutions

Organic Chemistry 6
Determine whether the statement is true or false. If it is true, explain why. If it is false, explain why or give an example that disproves the statement. \(\int_{0}^{4} \frac{x}{x^{2}-1} d x=\frac{1}{2} \ln 15\) Equation Transcription:

Organic Chemistry 6
Show how to bring about each conversion in good yield. (a) PhCOOH (b) CH2"CHCl O O Ph

Organic Chemistry 6
Show how to convert hexanoic acid to each amine. (a) NMe2 (b) H N

Organic Chemistry 6
Show how to convert (R)-2-phenylpropanoic acid to each compound. Ph (R)-2-Phenyl-1-propanol (a) OH Ph (R)-2-Phenyl-1-propanamine (b) NH2

Organic Chemistry 6
Draw a structural formulas for each compound. (a) Dimethyl carbonate (b) Benzonitrile (c) Isopropyl 3- methylhexanoate (d) Diethyl oxalate (e) Ethyl (Z)-2-pentenoate (f ) Butanoic anhydride (g) Dodecanamide (h) Ethyl 3-hydroxybutanoate ( i ) Octanoyl chloride ( j) Diethyl cis-1,2- cyclohexanedicarbox

Organic Chemistry 6
Write the IUPAC name for each compound. O O Ph OCH3 Ph O O O Ph O O (a) NHCH3 O (b) Ph9S9NH (c) 2 O O (d) (g) Cl O Cl O (h) (i) CH3(CH2)5CN EtO OEt O O NH2 O (e) (f) CH3OSOCH

Organic Chemistry 6
Both the melting point and boiling point of acetamide are higher than those of its N,N-dimethyl derivative. How do you account for these differences? O CH3CNH2 Acetamide mp 82.3C, bp 221.2C O CH3CN(CH3)2 N,N-Dimethylacetamide mp 220C, bp 165C

Organic Chemistry 6
Each hydrogen of a primary amide typically has a separate 1 H-NMR resonance, as illustrated by the separate signals for the two amide hydrogens of propanamide, which fall at d 6.22 and d 6.58. Furthermore, each methyl group of N,N-dimethylformamide has a separate resonance (d 3.88 and d 3.98). How do

Organic Chemistry 6
Propose a structural formula for compound A, C7H14O2, consistent with its 1 H-NMR and IR spectra. 10 9 8 7 6 5 4 3 2 1 0 ppm C7H14O2 Compound A 1H 2H 3H 6H 2H 0 100 10 20 30 40 50 90 60 70 80 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400 2.5 3 4 5 6 7 8 109 11 12 1413 15 20 Trans

Organic Chemistry 6
Propose a structural formula for compound B, C6H13NO, consistent with its 1 H-NMR and IR spectra. 10 9 8 7 6 5 4 3 2 1 0 ppm Chemical Shift ( ) . Problems 729 0 100 10 20 30 40 50 90 60 70 80 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400 2.5 3 4 5 6 7 8 109 11 12 1413 15 20 Trans

Organic Chemistry 6
Propose a structural formula for each compound consistent with its 1 H-NMR and 13C-NMR spectra. (a) C5H10O2 1 H-NMR 13C-NMR 0.96 (d, 6H) 161.11 1.96 (m, 1H) 70.01 3.95 (d, 2H) 27.71 8.08 (s, 1H) 19.00 (b) C7H14O2 1 H-NMR 13C-NMR 0.92 (d, 6H) 171.15 1.52 (m, 2H) 63.12 1.70 (m, 1H) 37.31 2.09 (s, 3H) 2

Organic Chemistry 6
Draw a structural formula for the principal product formed when benzoyl chloride is treated with each reagent. O2Na1 O (e) OH, pyridine (a) (b) SH, pyridine (c) NH2 (two equivalents) (d) (f) (CH3)2CuLi, then H3O1 (g) CH3O NH2, pyridine (h) C6H5MgBr (two equivalents), then H3O1 OH

Organic Chemistry 6
Draw a structural formula of the principal product formed when ethyl benzoate is treated with each reagent. (a) H2O, NaOH, heat (b) H2O, H2SO4, heat (c) CH3CH2CH2CH2NH2 (d) DIBALH (278C), then H2O (e) LiA1H4, then H2O (f) C6H5MgBr (two equivalents), then HCl/H2O

Organic Chemistry 6
The mechanism for hydrolysis of an ester in aqueous acid involves formation of a tetrahedral carbonyl addition intermediate. Evidence in support of this mechanism comes from an experiment designed by Myron Bender. He fi rst prepared ethyl benzoate enriched with oxygen-18 in the carbonyl oxygen and th

Organic Chemistry 6
Predict the distribution of oxygen-18 in the products obtained from hydrolysis of ethyl benzoate labeled in the ethoxy oxygen under the following conditions. O C!O!CH2CH3 oxygen-18 (a) In aqueous NaOH (b) In aqueous HCl (c) What distribution would you predict if the reaction were done with the tert-b

Organic Chemistry 6
Draw a structural formula for the principal product formed when benzamide is treated with each reagent. (a) H2O, HCl, heat (b) NaOH, H2O, heat (c) LiAlH4, then H2O

Organic Chemistry 6
Draw a structural formula of the principal product formed when benzonitrile is treated with each reagent. (a) H2O (one equivalent), H2SO4, heat (b) H2O (excess), H2SO4, heat (c) NaOH, H2O, heat (d) LiAlH4, then H2O

Organic Chemistry 6
Show the product expected when the following unsaturated d-ketoester is treated with each reagent. OEt O O (a) (b) (c) (d) 9999999999: 1. DIBALH, 2788 9 2. H2O 9999999: 1. LiAlH4, THF 9 2. H2O 999: NaBH4 9 CH3OH 9999: H2 (1 mol) Pd, EtOH

Organic Chemistry 6
The reagent diisobutylaluminum hydride (DIBALH) reduces esters to aldehydes. When nitriles are treated with DIBALH, followed by mild acid hydrolysis, the product is also an aldehyde. Propose a mechanism for this reduction.

Organic Chemistry 6
Show the product of treating this anhydride with each reagent. O O O H H (a) (b) (c) (d) (e) 9999999: NH3 (2 mol) 9999: CH3OH 99999: 1. LiAlH4 9 2. H2O 999999: H2O, NaOH 9 heat 9999: H2O, HCl hea

Organic Chemistry 6
The analgesic acetaminophen is synthesized by treating 4-aminophenol with one equivalent of acetic anhydride. Draw a structural formula for acetaminophen

Organic Chemistry 6
Treating choline with acetic anhydride gives acetylcholine, a neurotransmitter. Write an equation for the formation of acetylcholine. (CH3)3 CH2CH2OH Choline N 1

Organic Chemistry 6
Nicotinic acid, more commonly named niacin, is one of the B vitamins. Show how nicotinic acid can be converted to (a) ethyl nicotinate and then to (b) nicotinamide. O COH N Nicotinic acid (Niacin) ? O COEt N Ethyl nicotinate ? O CNH2 N Nicotinamide

Organic Chemistry 6
Complete each reaction. (a) NH2 1 CH3COCCH3 O (d) NH2 CH3(CH2) 1 5CH O O CH3O (b) 1 O CH3CCl 2HN (c) 1 O CH3COCH3 HN

Organic Chemistry 6
Show the product of treating g-butyrolactone with each reagent. O O (a) NH3 9: (b) (c) (d) NaOH (e) (f) 9999999999999999: 1. DIBALH, ether, 278C 9 2. H2O, HCl 99999999: 1. 2 CH3Li, ether 9 2. H2O, HCl 9:H2O heat 99999999999: 1. 2 PhMgBr, ether 9 2. H2O, HCl 9999: 1. LiAlH4 2. H2O

Organic Chemistry 6
Show the product of treating the following g-lactam with each reagent. O NCH3 (a) (b) (c) 99999: 1. LiAlH4 9 2. H2O 999999: H2O, NaOH 9 heat 9999: H2O, HCl heat

Organic Chemistry 6
Draw structural formulas for the products of complete hydrolysis of meprobamate, phenobarbital, and pentobarbital in hot aqueous acid. (a) H (b) (c) 2N NH2 O O O O Meprobamate (racemic) Phenobarbital (racemic) O NH O O H N Pentobarbital (racemic) O NH O O H N Meprobamate is a tranquilizer prescribed

Organic Chemistry 6
N,N-Diethyl-m-toluamide (DEET) is the active ingredient in several common insect repellents. Propose a synthesis for DEET from 3-methylbenzoic acid. 3-Methylbenzoic acid (m-Toluic acid) N,N- Diethyl-m-toluamide (DEET) OH O NEt2 H3C O H3C

Organic Chemistry 6
Isoniazid, a drug used to treat tuberculosis, is prepared from pyridine-4-carboxylic acid. How might this synthesis be carried out? ? N COH Pyridine-4- carboxylic acid Pyridine-4- carboxylic acid hydrazide (Isoniazid) O N CNHNH2 O

Organic Chemistry 6
Show how to convert phenylacetylene to allyl phenylacetate. C#CH Phenylacetylene O CH2COCH2CH"CH2 Allyl phenylacetate

Organic Chemistry 6
A step in a synthesis of PGE1 (prostaglandin E1, alprostadil) is the reaction of a trisubstituted cyclohexene with bromine to form a bromolactone. Propose a mechanism for formation of this bromolactone and account for the observed stereochemistry of each substituent on the cyclohexane ring. many step

Organic Chemistry 6
Barbiturates are prepared by treating a derivative of diethyl malonate with urea in the presence of sodium ethoxide as a catalyst. Following is an equation for the preparation of barbital, a long-duration hypnotic and sedative, from diethyl diethylmalonate and urea. 1. EtO2Na1 2. H2O Urea 5,5- Diethy

Organic Chemistry 6
The following compound is one of a group of b-chloroamines, many of which have antitumor activity. Describe a synthesis of this compound from anthranilic acid and ethylene oxide. O A -chloramine NH2 COOH 2-Aminobenzoic acid (Anthranilic acid) several steps 1 2 O N O Cl

Organic Chemistry 6
Show how to synthesize 5-nonanone from 1-bromobutane as the only organic starting material.

Organic Chemistry 6
Procaine (its hydrochloride is marketed as Novocain) was one of the fi rst local anesthetics for infi ltration and regional anesthesia. See Chemical Connections: From Cocaine to Procaine and Beyond. According to the following retrosynthetic scheme, procaine can be synthesized from 4-aminobenzoic acid

Organic Chemistry 6
The following sequence of steps converts (R)-2-octanol to (S)-2-octanol. A B (R)-2-Octanol OH OH (S)-2-Octanol p -TsCl pyridine CH3COO2Na1 DMSO 2. H2O 1. LiAIH4 Propose structural formulas for intermediates A and B, specify the confi guration of each, and account for the inversion of confi guration i

Organic Chemistry 6
Reaction of a primary or secondary amine with diethyl carbonate under controlled conditions gives a carbamic ester. 1 1 H2N EtOH Diethyl carbonate Butylamine Ethyl N-butylcarbamate O EtO OEt O N H EtO Propose a mechanism for this reaction.

Organic Chemistry 6
Several sulfonylureas, a class of compounds containing RSO2NHCONHR, are useful drugs as orally active replacements for injected insulin in patients with adult-onset diabetes. These drugs decrease blood glucose concentrations by stimulating b cells of the pancreas to release insulin and by increasing

Organic Chemistry 6
Following are structural formulas for two more widely used sulfonylurea hypo glycemic agents. S O O Tolazamide (Tolinase) N N H N H O (a) S O O Gliclazide (Diamicron) N N H N H H H O (b) Show how each might be synthesized by converting an appropriate amine to a carbamic ester and then treating the ca

Organic Chemistry 6
Amantadine is effective in preventing infections caused by the infl uenza A virus and in treating established illnesses. It is thought to block a late stage in the assembly of the virus. Amantadine is synthesized by treating 1-bromoadamantane with acetonitrile in sulfuric acid to give N- adamantylace

Organic Chemistry 6
In a series of seven steps, (S)-malic acid is converted to the bromoepoxide shown on the right in 50% overall yield. This synthesis is enantioselectiveof the stereoisomers possible for the bromoepoxide, only one is formed. OH HOOC COOH A (C8H14O5) C (C9H18O4 B ) F (C4H8OBr2) O D E Br 1.CH3CH2OH, H1 4

Organic Chemistry 6
Following is a retrosynthetic analysis for the synthesis of the herbicide (S)-Metolachlor from 2-ethyl-6- methylaniline, chloroacetic acid, acetone, and methanol. O OH Cl O O (S)-Metolachlor Cl OMe N 2- Ethyl-6-methylaniline NH2 O OMe HN OMe Cl N 1 1 O OMe 1 Acetone MeOH Methanol Chloroacetic acid 1

Organic Chemistry 6
Following is a retrosynthetic analysis for the anthelmintic (against worms) diethylcarbamazine. Me N NEt N 2 O MeNH2 1 1 O (A) Me N N OEt Me N N H O Me Ethylene (C) oxide (B) Ethyl chloroformate Methylamine N Cl OEt OH OH O 1 2 4 3 Diethylcarbamazine is used chiefl y against nematodes, small cylindri

Organic Chemistry 6
Given this retrosynthetic analysis, propose a synthesis for the antidepressant moclobemide. Moclobemide Morpholine Ethylene oxide p-Chlorobenzoic acid N O N O O H N O Cl HO O Cl H 1 1

Organic Chemistry 6
Propose a synthesis for diphenhydramine starting from benzene, benzoic acid, and 2-(N,N- dimethylamino)ethanol. O NMe2 NMe2 Diphenhydramine O Benzophenone 2-(N,N-Dimethylamino)- ethanol 1 HO The hydrochloride salt of diphenhydramine, best known by its trade name of Benadryl, is an antihistamine.

Organic Chemistry 6
Propose a synthesis of the topical anesthetic cyclomethycaine from 4-hydroxybenzoic acid and 2- methylpiperidine and any other necessary reagents. O O O N HN Cyclomethycaine 1 HO OH O 4- Hydroxybenzoic acid 2-Methylpiperidine

Organic Chemistry 6
Following is an outline of a synthesis of bombykol, the sex attractant of the male silkworm moth. Of the four stereoisomers possible for this conjugated diene, the 10- trans-12-cis isomer shown here is over 106 times more potent as a sex attractant than any of the other three possible stereoisomers.

Organic Chemistry 6
In Problem 7.28, we saw this step in Johnsons synthesis of the steroid hormone progesterone. O O O Me 2. H2O, CH3OH Me B C Me Me 1 H H H O Me Me Me Me H H H Propose a mechanism for this step in the synthesis.

Organic Chemistry 6
Using the principles for writing mechanisms and the four steps in the How to Write Mechanisms for Interconversions of Carboxylic Acid Derivatives box of this chapter, write mechanisms showing all electron fl ow arrows for the following reactions: (a) Hydrolysis of N,N-dimethylacetamide in acidic wate

Organic Chemistry 6
The following statements are true experimental observations. Explain the reason behind each observation. (a) The reaction of acetic acid with ammonia in water does not give any amide products. (b) The reaction of acetyl chloride with water causes the pH to decrease. (c) The hydrolysis of an amide at

Organic Chemistry 6
We have seen two methods for converting a carboxylic acid and an amine into an amide. Suppose that you start instead with a dicarboxylic acid such as hexanedioic acid and a diamine such as 1,6- hexanediamine. Show how amide formation in this case can lead to a polymer (a macromolecule of molecular we

Organic Chemistry 6
Using the same reasoning as in Problem 18.58, show how amide formation between this combination of dicarboxylic acid and diamine will also lead to a polymer, in this case Kevlar. HOOC9 9COOH 1 1,4-Benezenedicarboxylic acid (Terephthalic acid) H2N9 9NH2 Kevlar 1,4-Benezenediamine

Organic Chemistry 6
A urethane is a molecule in which a carbonyl group is part of an ester and an amide (it is an amide in one direction, an ester in the other direction). Propose a mechanism for the reaction of an isocyanate with an alcohol to form a urethane. O 9N"C"O 1 EtOH Phenylisocyanate Ethanol 9NH9C9OEt A uretha

Organic Chemistry 6
Suppose that you start with a diisocyanate and a diol. Show how their reaction can lead to a polymer called a polyurethane (Section 29.5D). OH A polyurethane HO 1 O"C"N N"C"O A diisocyanate Ethylene glycol

Organic Chemistry 6
Use the roadmap you made for problems 15.19, 16.72, and 17.45 and update it to contain the reactions in the Key Reactions section of this chapter. Because of their highly specifi c nature, do not use reactions 1, 2, and 10 on your roadmap.

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 both your old Chapters 611 roadmap and your new Chapters 1518 roadmap for these. (a) 1. BH3 2. H2

Organic Chemistry 6
Using your roadmaps as a guide, show how to convert (E)-3-hexene into propyl propionate. You must use (E)-3-hexene as the source of all carbon atoms in the target molecule. Show all reagents and all molecules synthesized along the way. ? (E)-3-Hexene Propyl propanoate O O

Organic Chemistry 6
Using your roadmaps as a guide, show how to convert 1-bromopentane and sodium cyanide into N- hexylhexanamide. You must use 1-bromopentane and sodium cyanide as the source of all carbon atoms in the target molecule. Show all reagents and all molecules synthesized along the way. ? 1- Bromopentane N-He

Organic Chemistry 6
Using your roadmaps as a guide, show how to convert 1-bromopropane and carbon dioxide into 4- propyl-4-heptanol. You must use 1-bromopropane and carbon dioxide as the source of all carbon atoms in the target molecule. Show all reagents and all molecules synthesized along the way. ? 1- Bromopropane 4-

Organic Chemistry 6
Using your roadmaps as a guide, show how to convert 1-bromopropane and carbon dioxide into 4- heptanone. You must use 1-bromopropane and carbon dioxide as the source of all carbon atoms in the target molecule. Show all reagents and all molecules synthesized along the way. ? 1- Bromopropane 4-Heptanon

Organic Chemistry 6
Minoxidil is a molecule that causes hair growth in some people. It was originally synthesized as a vasodilator for the treatment of hypertension (high blood pressure). Most of the patients taking the drug for hypertension were seen to grow body hair. Due to other side effects, its oral use was stoppe

Organic Chemistry 6
Chloroformates have the functional group O R O Cl, in which R is often a tertbutyl or benzyl group. A chloroformate is used in the following synthesis of the antibacterial drug, linezolid (Zyvox). Linezolid (Zyvox) O N O O F O N H N Based on your knowledge of carboxylic acid derivatives, predict the

Organic Chemistry 6
Acid anhydrides are often used in place of acid chlorides because a less acidic carboxylic acid, not the much stronger acid HCl, is the byproduct of the reaction. In the following reaction of a carbohydrate derivative, acetic anhydride is used to obtain the product in 99% yield as a single stereoisom

Organic Chemistry 6
The benzyl ether group (!OBn) is often used as a protecting group for OH groups during the synthesis of complex molecules. The following structure has a number of benzyl ether groups used for this purpose. Draw the product of the following transformation. What role does the diisopropylethylamine play