Organic Chemistry 9th Edition solutions

Organic Chemistry 9
One problem with elimination reactions is that mixtures of products are often formed. For example, treatment of 2-bromo-2-methylbutane with KOH in ethanol yields a mixture of two alkene products. What are their likely structures?

Organic Chemistry 9
How many alkene products, including E,Z isomers, might be obtained by dehydration of 3-methyl-3-hexanol with aqueous sulfuric acid? ________________ Equation Transcription: Text Transcription: CH_3CH_2CH_2CCH_2CH_3 CH_3 H_2SO_4

Organic Chemistry 9
What product would you expect to obtain from addition of \(\mathrm {Cl_2}\) to 1,2-dimethylcyclohexene? Show the stereochemistry of the product. ________________ Equation Transcription: Text Transcription: Cl_2

Organic Chemistry 9
Addition of HCl to 1,2-dimethylcyclohexene yields a mixture of two products. Show the stereochemistry of each, and explain why a mixture is formed.

Organic Chemistry 9
What product would you expect from the reaction of cyclopentene with NBS and water? Show the stereochemistry.

Organic Chemistry 9
When an unsymmetrical alkene such as propene is treated with N-bromosuccinimide in aqueous dimethyl sulfoxide, the major product has the bromine atom bonded to the less highly substituted carbon atom. Is this Markovnikov or non-Markovnikov orientation? Explain. _____

Organic Chemistry 9
What products would you expect from oxymercurationdemercuration of the following alkenes? (a) \(\mathrm {CH_3CH_2CH_2CH=CH_2}\) (b) ________________ Equation Transcription: Text Transcription: CH_3CH_2CH_2CH=CH_2 CH_3 CH_3C=CHCH_2CH_3

Organic Chemistry 9
From what alkenes might the following alcohols have been prepared? ________________ Equation Transcription: Text Transcription: CH_3CCH_2CH_2CH_2CH_3 CH_3

Organic Chemistry 9
What products would you obtain from reaction of 2-methyl-2-pentene with: (a) \(\mathrm{BH_3}\), followed by \(\mathrm{H_2O_2, OH^-}\) (b) \(\mathrm{Hg(OAc)_2}\), followed by \(\mathrm{NaBH_4}\) ________________ Equation Transcription: Text Transcription: BH

Organic Chemistry 9
How might you prepare the following alcohol? ________________ Equation Transcription: Text Transcription: CH_3 CH_3CH_2CHCHCH_2CH_3

Organic Chemistry 9
Show the structures of the products you would obtain by hydroborationoxidation of the following alkenes: ________________ Equation Transcription: Text Transcription: CH_3 CH_3C=CHCH_2CH_3 CH_3

Organic Chemistry 9
What alkenes might be used to prepare the following alcohols by hydroborationoxidation? ________________ Equation Transcription: Text Transcription: CH_3 CH_3CHCH_2CH_2OH H_3C CH_3CHCHCH_3 CH_2OH

Organic Chemistry 9
The following cycloalkene gives a mixture of two alcohols on hydroboration followed by oxidation. Draw the structures of both, and explain the result.

Organic Chemistry 9
What product would you obtain from catalytic hydrogenation of the following alkenes? ________________ Equation Transcription: Text Transcription: CH_3 CH_3C=CHCH_2CH_3 CH_3 CH_3 H_3C CH_3 CH_3 CH_3 CH_3 CH_3

Organic Chemistry 9
What product would you expect from reaction of cis-2-butene with meta-chloroperoxybenzoic acid? Show the stereochemistry.

Organic Chemistry 9
Starting with an alkene, how would you prepare each of the following compounds? ________________ Equation Transcription: Text Transcription: CH CH_3 CH_3CH_2CHCCH_3 CH_3 HOCH_2CHCHCH_2OH

Organic Chemistry 9
What alkene would yield a mixture of cyclopentanone and propanal on treatment with ozone followed by reduction with zinc? ________________ Equation Transcription: Text Transcription: O_3 CH_3CH_2CH

Organic Chemistry 9
What products would you expect from reaction of 1-methylcyclohexene with the following reagents? (a) Aqueous acidic \(\mathrm{KMnO_4}\) (b) \(O_3\), followed by Zn, \(\mathrm{CH_3CO_2H}\) ________________ Equation Transcription: Text Transcription: KMnO_4 O_

Organic Chemistry 9
Propose structures for alkenes that yield the following products on reaction with ozone followed by treatment with Zn: (a) \(\mathrm{(CH_3)_2C=O+H_2C=O}\) (b) 2 equiv \(\mathrm{CH_3CH_2CH=O}\) ________________ Equation Transcription: Text Transcriptio

Organic Chemistry 9
What products would you expect from the following reactions? ________________ Equation Transcription: Text Transcription: CH_2 CHCl_3 CH_3 CH_3CHCH_2CH=CHCH_3+CH_2I_2

Organic Chemistry 9
Show the structure of poly(vinyl chloride), a polymer made from \(\mathrm{H_2C=CHCl}\), by drawing several repeating units. ________________ Equation Transcription: Text Transcription: H_2C=CHCl

Organic Chemistry 9
Show the monomer units you would use to prepare the following polymers: ________________ Equation Transcription: Text Transcription: OCH_3 OCH_3 OCH_3 CH_2-CH-CH_2-CH-CH_2-CH

Organic Chemistry 9
One of the chain-termination steps that sometimes occurs to interrupt polymerization is the following reaction between two radicals. Propose a mechanism for the reaction, using fishhook arrows to indicate electron flow. ________________ Equation Transcription:

Organic Chemistry 9
What products are formed from acid-catalyzed hydration of racemic \((\pm)\)-4-methyl-1-hexene? What can you say about the relative amounts of the products? Is the product mixture optically active? ________________ Equation Transcription: Text Transcription: +/-

Organic Chemistry 9
What products are formed from hydration of 4-methylcyclopentene? What can you say about the relative amounts of the products?

Organic Chemistry 9
Name the following alkenes, and predict the products of their reaction with (1) meta-chloroperoxybenzoic acid, (2) \(\mathrm{KMnO_4}\) in aqueous acid, and (3) \(\mathrm{O_3}\), followed by Zn in acetic acid: Equation Transcription: Text Transcription: KMnO

Organic Chemistry 9
Draw the structures of alkenes that would yield the following alcohols on hydration (red = O). Tell in each case whether you would use hydroborationoxidation or oxymercurationdemercuration.

Organic Chemistry 9
The following alkene undergoes hydroborationoxidation to yield a single product rather than a mixture. Explain the result, and draw the product showing its stereochemistry.

Organic Chemistry 9
From what alkene was the following 1,2-diol made, and what method was used, epoxide hydrolysis or \(\mathrm{OsO_4}\)? ________________ Equation Transcription: Text Transcription: OsO_4

Organic Chemistry 9
Predict the products for the following reactions, showing the complete mechanism and appropriate stereochemistry: ________________ Equation Transcription: Text Transcription: Br_2 Cl_2 Cl_2

Organic Chemistry 9
Predict the products for the reactions in Problem 8-26 if each were run in DMSO with water. Show the complete mechanism including appropriate regiochemistry and stereochemistry.

Organic Chemistry 9
Draw the structures of the organoboranes formed when borane reacts with each alkene below, including the regiochemistry and stereochemistry as appropriate. Propose a mechanism for each reaction.

Organic Chemistry 9
m-CPBA is not the only peroxyacid capable of epoxide formation. For each reaction below, predict the products and show the mechanism. ________________ Equation Transcription: Text Transcription: CF_3CO_3H CO_3H

Organic Chemistry 9
Provide the mechanism and products for the acid-catalyzed epoxide opening reactions below, including appropriate stereochemistry. Equation Transcription: Text Transcription: H_3O^+ H_3C CH_3 H_3O^+ H_3C H_3O^+

Organic Chemistry 9
Propose a curved-arrow mechanism to show how ozone \(\mathrm{(O_3)}\) reacts with a carboncarbon double bond to form a molozonide, the first intermediate in ozonolysis. ________________ Equation Transcription: Text Transcription: (O_3)

Organic Chemistry 9
Which of the reactions below would result in a product mixture that would rotate plane-polarized light? ________________ Equation Transcription: Text Transcription: CH_2 CH_3 H_2 H_3C CH_3 H_3O^+ H_3C O_3 H_3O^+

Organic Chemistry 9
Reaction of 2-methylpropene with \(\mathrm{CH_3OH}\) in the presence of \(\mathrm{H_2SO_4}\) catalyst yields methyl tert-butyl ether, \(\mathrm{CH_3OC(CH_3)_3}\), by a mechanism analogous to that of acid-catalyzed alkene hydration. Write the mechanism, using curved arrows for each step.

Organic Chemistry 9
Iodine azide, \(\mathrm{IN_3}\), adds to alkenes by an electrophilic mechanism similar to that of bromine. If a monosubstituted alkene such as 1-butene is used, only one product results: (a) Add lone-pair electrons to the structure shown for \(\mathrm{IN_3}\), and draw a second resonance form

Organic Chemistry 9
10-Bromo-\(\alpha\)-chamigrene, a compound isolated from marine algae, is thought to be biosynthesized from \(\gamma\)-bisabolene by the following route: Draw the structures of the intermediate bromonium and cyclic carbocation, and propose mechanisms for all three steps.

Organic Chemistry 9
Isolated from marine algae, prelaureatin is thought to be biosynthesized from laurediol by the following route. Propose a mechanism. ________________ Equation Transcription: Text Transcription: Br^+

Organic Chemistry 9
Dichlorocarbene can be generated by heating sodium trichloroacetate. Propose a mechanism for the reaction, and use curved arrows to indicate the movement of electrons in each step. What relationship does your mechanism bear to the base-induced elimination of HCl from chloroform?

Organic Chemistry 9
Reaction of cyclohexene with mercury(II) acetate in \(\mathrm {CH_3OH}\) rather than \(\mathrm {H_2O}\), followed by treatment with \(\mathrm {NaBH_4}\), yields cyclohexyl methyl ether rather than cyclohexanol. Suggest a mechanism. ________________ Equation Transcr

Organic Chemistry 9
Use your general knowledge of alkene chemistry to suggest a mechanism for the following reaction. ________________ Equation Transcription: Text Transcription: CO_2CH_3 Hg(OAc)_2 CO_2CH_3 AcO-Hg

Organic Chemistry 9
Treatment of 4-penten-1-ol with aqueous \(\mathrm{Br_2}\) yields a cyclic bromo ether rather than the expected bromohydrin. Suggest a mechanism, using curved arrows to show electron movement. ________________ Equation Transcription: Text Transcription:

Organic Chemistry 9
Hydroboration of 2-methyl-2-pentene at \(\mathrm{25\ ^\circ C}\), followed by oxidation with alkaline \(\mathrm {H_2O_2}\), yields 2-methyl-3-pentanol, but hydroboration at \(\mathrm{160\ ^\circ C}\) followed by oxidation yields 4-methyl-1-pentanol. Suggest a mechanism.

Organic Chemistry 9
Predict the products of the following reactions (the aromatic ring is unreactive in all cases). Indicate regiochemistry when relevant. ________________ Equation Transcription: Text Transcription: H_2/Pd Br_2 OsO_4 Cl_2,H_2O CH_2I_2,Zn/cu

Organic Chemistry 9
Suggest structures for alkenes that give the following reaction products. There may be more than one answer for some cases. ________________ Equation Transcription: Text Transcription: H_2/Pd CH_3 CH_3CHCH_2CH_2CH2CH_3 Br_2 CH_3 CH_2CHC

Organic Chemistry 9
Predict the products of the following reactions, showing both regiochemistry and stereochemistry where appropriate: ________________ Equation Transcription: Text Transcription: CH_3 O_3 Zn,H_3O^+ KMnO_4 H_3O^+ CH_3 BH_3 H_2O_2,^-OH CH_3 Hg(OAc)_2

Organic Chemistry 9
Which reaction would you expect to be faster, addition of HBr to cyclohexene or to 1-methylcyclohexene? Explain.

Organic Chemistry 9
What product will result from hydroborationoxidation of 1-methylcyclo pentene with deuterated borane, \(\mathrm {BD_3}\)? Show both the stereochemistry (spatial arrangement) and the regiochemistry (orientation) of the product. Equation Transcription: Text Transcri

Organic Chemistry 9
The cis and trans isomers of 2-butene give different cyclopropane products in the SimmonsSmith reaction. Show the structures of both, and explain the difference. Equation Transcription: Text Transcription: cis-CH_3CH=CHCH_3 CH_2I,ZN(Cu) trans-CH_3CH=CHCH_

Organic Chemistry 9
Predict the products of the following reactions. Dont worry about the size of the molecule; concentrate on the functional groups. ________________ Equation Transcription: Text Transcription: CH_3 CH_3 Br_2 OSO_4 NaHSO_3 BH_3,THF H_2O_2^,-O

Organic Chemistry 9
Addition of HCl to 1-methoxycyclohexene yields 1-chloro-1-methoxycyclohexane as a sole product. Use resonance structures of the carbocation intermediate to explain why none of the alternate regioisomer is formed. Equation Transcription: Text Transcripti

Organic Chemistry 9
How would you carry out the following transformations? Tell what reagents you would use in each case. Equation Transcription: Text Transcription: CH_3 CH_3 CH_3CH=CHCHCH_3 CH_3 CH_3CH CH_3CHCH H_3C CH_3 CH_3C=CH_2 CH_3 CH_3CHCH_2OH

Organic Chemistry 9
Draw the structure of an alkene that yields only acetone, \(\mathrm {(CH_3)=O}\), on ozonolysis followed by treatment with \(\mathrm {Zn}\). Equation Transcription: Text Transcription: (CH_3)=O Zn

Organic Chemistry 9
Show the structures of alkenes that give the following products on oxidative cleavage with \(\mathrm {KMnO_4}\) in acidic solution: Equation Transcription: Text Transcription: KMnO_4 CH_3CH_2CO_2H+CO_2 (CH_3)_2C=O+CH_3CH_2CH_2CO_2H (CH_3)_2C=O CH_3CH_2

Organic Chemistry 9
In planning the synthesis of one compound from another, its just as important to know what not to do as to know what to do. The following reactions all have serious drawbacks to them. Explain the potential problems of each. Equation Transcription:

Organic Chemistry 9
Which of the following alcohols could not be made selectively by hydroborationoxidation of an alkene? Explain. Equation Transcription: Text Transcription: CH_3CH_2CH_2CHCH_3 (CH_3)_2CHC(CH_3)_2 CH_3 CH_3

Organic Chemistry 9
Plexiglas, a clear plastic used to make many molded articles, is made by polymerization of methyl methacrylate. Draw a representative segment of Plexiglas. ________________ Equation Transcription: Text Transcription: H_2C CH_3 OCH_3

Organic Chemistry 9
Poly(vinyl pyrrolidone), prepared from N-vinylpyrrolidone, is used both in cosmetics and as a synthetic substitute for blood. Draw a representative segment of the polymer. Equation Transcription: Text Transcription: N-CH=CH_2

Organic Chemistry 9
When a single alkene monomer, such as ethylene, is polymerized, the product is a homopolymer. If a mixture of two alkene monomers is polymerized, however, a copolymer often results. The following structure represents a segment of a copolymer called Saran. What two monomers were copolymerized to make

Organic Chemistry 9
Compound A has the formula \(\mathrm{C_{10}H_{16}}\). On catalytic hydrogenation over palladium, it reacts with only 1 molar equivalent of \(\mathrm{H_2}\). Compound A also undergoes reaction with ozone, followed by zinc treatment, to yield a symmetrical diketone, B \(\mathrm{(C_{10}H_{16}O_2)}\).

Organic Chemistry 9
An unknown hydrocarbon A with the formula \(\mathrm {C_6H_{12}}\) reacts with 1 molar equivalent of \(\mathrm {H_2}\) over a palladium catalyst. Hydrocarbon A also reacts with \(\mathrm {OsO_4}\) to give diol B. When oxidized with \(\mathrm {KMnO_4}\) in acidic solution, A gives two fragments. One fr

Organic Chemistry 9
Using an oxidative cleavage reaction, explain how you would distinguish between the following two isomeric dienes:

Organic Chemistry 9
Compound A, \(\mathrm {C_{10}H_{18}O}\), undergoes reaction with dilute \(\mathrm {H_2SO_4}\) at \(\mathrm {50\ ^\circ C}\) to yield a mixture of two alkenes, \(\mathrm {C_{10}H_{16}}\). The major alkene product, B, gives only cyclopentanone after ozone treatment followed by reduction with zinc in ac

Organic Chemistry 9
Draw the structure of a hydrocarbon that absorbs 2 molar equivalents of \(\mathrm {H_2}\) on catalytic hydrogenation and gives only butanedial on ozonolysis. Equation Transcription: Text Transcription: H_2 HCCH_2CH_2CH

Organic Chemistry 9
SimmonsSmith reaction of cyclohexene with diiodomethane gives a single cyclopropane product, but the analogous reaction of cyclohexene with 1,1-diiodoethane gives (in low yield) a mixture of two isomeric methylcyclopropane products. What are the two products, and how do they differ?

Organic Chemistry 9
The sex attractant of the common housely is a hydrocarbon with the formula \(\mathrm {C_{23}H_{46}}\). On treatment with aqueous acidic \(\mathrm {KMnO_{4}}\), two products are obtained, \(\mathrm {CH_3(CH_2)_{12}CO_2H}\) and \(\mathrm {CH_3(CH_2)_{7}CO_2H}\). Propose a structure.

Organic Chemistry 9
Compound A has the formula \(\mathrm {C_8H_8}\). It reacts rapidly with \(\mathrm {KMnO_4}\) to give \(\mathrm {CO_2}\) and a carboxylic acid, B \(\mathrm {(C_7H_6O_2)}\), but reacts with only 1 molar equivalent of \(\mathrm {H_2}\) on catalytic hydrogenation over a palladium catalyst. On hydrogenati

Organic Chemistry 9
How would you distinguish between the following pairs of compounds using simple chemical tests? Tell what you would do and what you would see. (a) Cyclopentene and cyclopentane (b) 2-Hexene and benzene

Organic Chemistry 9
\(\alpha\)-Terpinene, \(\mathrm {C_{10}H_{16}}\), is a pleasant-smelling hydrocarbon that has been isolated from oil of marjoram. On hydrogenation over a palladium catalyst, a-terpinene reacts with 2 molar equivalents of \(\mathrm {H_2}\) to yield a hydrocarbon, \(\mathrm {C_{10}H_{20}}\). On ozonoly

Organic Chemistry 9
Evidence that cleavage of 1,2-diols by \(\mathrm {HIO_4}\) occurs through a five membered cyclic periodate intermediate is based on kinetic datathe measurement of reaction rates. When diols A and B were prepared and the rates of their reaction with \(\mathrm {HIO_4}\) were measured, it was found that

Organic Chemistry 9
Reaction of HBr with 3-methylcyclohexene yields a mixture of four products: cis- and trans-1-bromo-3-methylcyclohexane and cis- and trans-1-bromo-2-methylcyclohexane. The analogous reaction of HBr with 3-bromocyclo hexene yields trans-1,2-dibromocyclohexane as the sole product. Draw structures of the

Organic Chemistry 9
Well see in the next chapter that alkynes undergo many of the same reactions that alkenes do. What product might you expect from each of the following reactions? Equation Transcription: Text Transcription: CH_3 CH_3CHCH_2CH_2CCH Br_2 H_2,Pd/C

Organic Chemistry 9
Hydroxylation of cis-2-butene with \(\mathrm {OsO_4}\) yields a different product than hydroxylation of trans-2-butene. Draw the structure, show the stereochemistry of each product, and explain the difference between them. Equation Transcription: Text Transcrip

Organic Chemistry 9
Compound A, \(\mathrm {C_{11}H_{16}O}\), was found to be an optically active alcohol. Despite its apparent unsaturation, no hydrogen was absorbed on catalytic reduction over a palladium catalyst. On treatment of A with dilute sulfuric acid, dehydration occurred and an optically inactive alkene B, \(\