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1 Million+ Step-by-step solutionsmath books Q:Predict the major product(s) and mechanism(s) for reaction between 2-bromobutanePredict the major product(s) and mechanism(s) for reaction between 2-bromobutane (sec-butyl bromide) and each of the reagents in Problem 42.
(a) KCl in DMF
(b) KI in DMF
(c) KC1 in CH3NO2
(d) NH3 in CH3CH2OH
(e) NaOCH2CH3 in CH3CH2OH
(f) CH3CH2OH
(g) KOC(CH3)3 in (CH3)3COH
(h) (CH3)3P in CH3OH
(i) CH3C02H
Q:Predict the major product(s) and mechanism(s) for reaction between 2-bromo-2-methylpropanePredict the major product(s) and mechanism(s) for reaction between 2-bromo-2-methylpropane (tert-butyl bromide) and each of the reagents in Problem 42.
(a) KCl in DMF
(b) KI in DMF
(c) KC1 in CH3NO2
(d) NH3 in CH3CH2OH
(e) NaOCH2CH3 in CH3CH2OH
(f) CH3CH2OH
(g) KOC(CH3)3 in (CH3)3COH
(h) (CH3)3P in CH3OH
Q:Three reactions of 2-chloro-2-methylpropane are shown here, (a) Write the majorThree reactions of 2-chloro-2-methylpropane are shown here,
(a) Write the major product of each transformation
(b) Compare the rates of the three reactions. Assume identical solution polarities and reactant concentrations. Explain mechanistically.
Three reactions of 2-chloro-2-methylpropane are shown here, 
(a) Write the majorQ:Fill in the blanks in the following table with theFill in the blanks in the following table with the major product(s) of the reaction of each haloalkane with the reagents shown.
Fill in the blanks in the following table with theQ:Indicate the major mechanism(s) (simply specify SN2, SN1, E2, orIndicate the major mechanism(s) (simply specify SN2, SN1, E2, or El) required for the formation of each product that you wrote in Problem 47.
Indicate the major mechanism(s) (simply specify SN2, SN1, E2, orQ:For each of the following reactions, indicate whether the reactionFor each of the following reactions, indicate whether the reaction would work well, poorly, or not at all. Formulate alternative products, if appropriate.
(a)
For each of the following reactions, indicate whether the reaction

(b)

For each of the following reactions, indicate whether the reaction

(c)

For each of the following reactions, indicate whether the reaction

(d)

For each of the following reactions, indicate whether the reaction

(e)

For each of the following reactions, indicate whether the reaction

(f)

For each of the following reactions, indicate whether the reaction

(g)

For each of the following reactions, indicate whether the reaction

(h)

For each of the following reactions, indicate whether the reaction

(i)

For each of the following reactions, indicate whether the reaction

(j)

For each of the following reactions, indicate whether the reaction

(k)

For each of the following reactions, indicate whether the reaction

(l)

For each of the following reactions, indicate whether the reactionQ:Unimolecular elimination to form an alkene accompanies substitution in secondaryUnimolecular elimination to form an alkene accompanies substitution in secondary and tertiary systems.
Q:Propose syntheses of the following molecules from the indicated startingPropose syntheses of the following molecules from the indicated starting materials. Make use of any other reagents or solvents that you need. In some cases, there may be no alternative but to employ a reaction that results in a mixture of products. If so, use reagents and conditions that will maximize the yield of the desired material.
(a) CH3CH2CHICH3 from butane
(b) CH3CH2CH2CH2I, from butane
(c) (CH3)3COCH3, from methane and 2-methylpropane
(d) Cyclohexene, from cyclohexane
(e) Cyclohexanol, from cyclohexane
Q:[(l-Bromo-l-methyl)ethyl]benzene, shown in the margin, undergoes solvohsis in a unimolecular,[(l-Bromo-l-methyl)ethyl]benzene, shown in the margin, undergoes solvohsis in a unimolecular, strictly first-order process. The reaction rate for [RBr] = 0.1 M RBr in 9:1 acetone: water is measured to be 2 × 10-4 mol L-1s-1.
(a) Calculate the rate constant k from these data. What is the product of this reaction?
(b) In the presence of 0.1 M LiCl, the rate is found to increase to 4 × 10-4 mol L-1s-1, although the reaction still remains strictly first order. Calculate the new rate constant kLiCI and suggest an explanation
(c) When 0.1 M LiBr is pas ent instead of LiCl, the measured rale drops to 1.6 × 10-4 mol L-1s-1. Explain this observation, and write the appropriate chemical equations to describe the reactions.
Q:In this chapter we have encountered many examples of SN1In this chapter we have encountered many examples of SN1 solvolysis reactions, all of which proceed according to the following scheme:
In this chapter we have encountered many examples of SN1

Upon mixing the colorless substrate and solvent, a reddish-orange color is observed immediately, signaling the formation of an intermediate carbocation. This color fades over a period of about a minute, and analysis of the solution reveals the presence of the final product in 100% yield
(a) There are two reasons for the buildup of a detectable concentration of carbocation in this case. One is that the carbocation derived from dissociation of this particular substrate is unusually stable. The other is that the solvent (2.2.2-trifluoroethanol) is an unusually poor nucleophile, even compared with ordinary alcohols such as ethanol. Suggest an explanation for the poor nucleophilicity of the solvent
(b) What can you say about the relative rates of the two steps (rate, and rate2), and how do they compare to those in the usual SN1 reaction mechanism?
(c) How might increasing carbocation stability and decreasing solvent nucleophilicity affect the relative magnitudes of rate1 and rate2 in an SN1 process?
(d) Write the complete mechanism for the reaction above.

Q:Match each of the following transformations to the correct reactionMatch each of the following transformations to the correct reaction profile shown here, and draw the structures of the species present at all points on the energy curves marked by capital letters.
(i)
Match each of the following transformations to the correct reaction

(ii)

Match each of the following transformations to the correct reaction

(iii)

Match each of the following transformations to the correct reaction

(iv)

Match each of the following transformations to the correct reaction

(a) (CH3)3CCl + (C6H5)3P →
(b) (CH3)2CHI + KBr →
(c) (CH3)3CBr + HOCH2CH3 →
(d) CH3CH2Br + NaOCH2CH3 →

Q:Formulate the structure of the most likely product of theFormulate the structure of the most likely product of the following reaction of 4-chloro-4-methyl-1-pentanol in neutral polar solution.
Formulate the structure of the most likely product of theQ:The following reaction can proceed through both El and E2The following reaction can proceed through both El and E2 mechanisms.
The following reaction can proceed through both El and E2

The El rate constant kEI = 1.4 × 10-4s-1 and the E2 rate constant kE2 = 1.9 × 10-4 L mol-1 s-1; 0.02 M haloalkane.
(a) What is the predominant elimination mechanism with 0.5 M NaOCH3?
(b) What is the predominant elimination mechanism with 2.0 M NaOCH3?
(c) At what concentration of base does exactly 50% of the starting material react by an El route and 50% by an E2 pathway?

Q:The compound below is an example of a methyl ester.The compound below is an example of a methyl ester. Methyl esters react with lithium iodide to give lithium carboxylate salts. The solvent in this example is pyridine (margin).
The compound below is an example of a methyl ester.

Suggest several experiments that would allow you to determine the likely mechanism of this process.

Q:Ethers containing the 1,1-dimethylethyl (tert-butyl) group are readily cleaved withEthers containing the 1,1-dimethylethyl (tert-butyl) group are readily cleaved with dilute, strong acid, as shown in the example below.
Ethers containing the 1,1-dimethylethyl (tert-butyl) group are readily cleaved with

Suggest a plausible mechanism for this process. What role might the strong acid play?

Q:Give the mechanism and major product for the reaction ofGive the mechanism and major product for the reaction of a secondary haloalkane in a polar aprotic solvent with the following nucleophiles. The pKa value of the conjugate acid of the nucleophile is given in parentheses.
(a) N3- (4.6)
(b) H2N- (35)
(c) NH3 (9.5)
(d) HSe- (3.7)
(e) F- (3.2)
(f) C6H5O- (9.9)
(g) PH3 (-12)
(h) NH2OH (6.0)
(i) NCS- (-0.7)
Q:Cortisone is an important steroidal anti-inflammatory agent. Cortisone can beCortisone is an important steroidal anti-inflammatory agent. Cortisone can be synthesized efficiently from the alkene shown here.
Cortisone is an important steroidal anti-inflammatory agent. Cortisone can be

Of the following three chlorinated compounds, two give reasonable yields of the alkene shown above by E2 elimination with base, but one does not. Which one does not work well, and why? What does it give during attempted E2 elimination?

Cortisone is an important steroidal anti-inflammatory agent. Cortisone can beQ:The chemistry of derivatives of trans-decalin is of interest becauseThe chemistry of derivatives of trans-decalin is of interest because this ring system is part of the structure of steroids. Make models of the brominated systems (i and ii) to help you answer the following questions.
The chemistry of derivatives of trans-decalin is of interest because

(a) One of the molecules undergoes E2 reaction with NaOCH2CH3 in CH3CH2OH considerably faster than does the other. Which molecule is which? Explain
(b) The following deuterated analogs of systems i and ii react with base to give the products shown.

The chemistry of derivatives of trans-decalin is of interest becauseThe chemistry of derivatives of trans-decalin is of interest because

Specify whether anti or syn eliminations have taken place. Draw the conformations that the molecules must adopt for elimination to occur. Does your answer to (b) help you in solving (a)?

Q:Which of the following haloalkanes will undergo hydrolysis most rapidly? (a)Which of the following haloalkanes will undergo hydrolysis most rapidly?
(a) (CH3)3CF
(b) (CH3)3CCl
(c) (CH3)3CBr
(d) (CH3)3CI
Q:The reaction is an example of which of the following processes? (a)The reaction
The reaction 
is an example of which of the following processes? 
(a)

is an example of which of the following processes?
(a) El
(b) E2
(c) SN1
(d) SN2

Q:Which reaction intermediate is involved in the following reaction? (a) AWhich reaction intermediate is involved in the following reaction?
Which reaction intermediate is involved in the following reaction? 
(a) A

(a) A secondary radical
(b) A tertiary radical
(c) A secondary carbocation
(d) A tertiary carbocation

Q:Substitution is favored by unhindered substrates and small, less basicSubstitution is favored by unhindered substrates and small, less basic nucleophiles.
Q:Draw the structures of the following alcohols, (a) 2-(Trimethylsilyl) ethanol; (b) 1-methylcycloprDraw the structures of the following alcohols,
(a) 2-(Trimethylsilyl) ethanol;
(b) 1-methylcyclopropanol:
(c) 3-( l-methylethyl)-2-hexanol;
(d) (R)-2-pentanol;
(e) 3,3-dibromocyclohexanol.
Q:Rank each group of compounds in order of increasing boilingRank each group of compounds in order of increasing boiling point,
(a) Cyclohexane, cyclohexanol, chlorocyclohexane;
(b) 2,3-dimethyl-2-pentanol, 2-methyl-2-hexanol, 2-heptanol.
Q:Explain the order of water solubilities for the compounds inExplain the order of water solubilities for the compounds in each of the following groups,
(a) Ethanol > chloroethane > ethane;
(b) Methanol > ethanol > 1-propanol.
Q:1, 2-Ethanediol exists to a much greater extent in the1, 2-Ethanediol exists to a much greater extent in the gauche conformation than does 1, 2-dichloroethane. Explain. Would you expect the gauche: anti conformational ratio of 2-chloroethanol to be similar to that of 1,2-dichloroethane or more like that of 1,2-ethanediol?
Q:The most stable conformation of trqans-l,2-cyclohexanediol is the chair inThe most stable conformation of trqans-l,2-cyclohexanediol is the chair in which both hydroxy groups are equatorial,
(a) Draw the structure or, better yet, make a model of the compound in this conformation,
(b) Reaction of this diol with the chlorosilane R3SiCl, R = (CH3)2CH (iso-propyl), gives the corresponding disilyl ether shown in the margin. Remarkably, this transformation causes the chair to flip, giving a conformation where both silyl ether groups are in axial positions. Explain this observation by means of either structural drawings or models.
The most stable conformation of trqans-l,2-cyclohexanediol is the chair inQ:Rank the compounds in each group in order of decreasingRank the compounds in each group in order of decreasing acidity.
(a) CH3CHCICH20H, CH3CHBrCH2OH, BrCH2CH2CH2OH
(b) CH3CH2CH2OH, CCI3CH2OH, (CH3)2CC1CH2OH
(c) (CH3)2CHOH, (CF3)2CHOH, (CC13)2CHOH
Q:Write an appropriate equation to show how each of theWrite an appropriate equation to show how each of the following alcohols acts as, first, a base, and, second, an acid in solution. How do the base and acid strengths of each compare with those of methanol?
(a) (CH3)2CHOH;
(b) CH3CHFCH2OH;
(c) CCl3CH2OH.
Q:Given the pKa values of -2.2 for CH3+OH2 and 15.5Given the pKa values of -2.2 for CH3+OH2 and 15.5 for CH3OH, calculate the pH at which
(a) methanol will contain exactly equal amounts of CH3+OH2 and CH3O-;
(b) 50% CH3+OH and 50% CH3+OH2 will be present;
(c) 50% CH3OH and 50% CH3O- will be present.
Q:Do you expect hyperconjugation to be important in the stabilizationDo you expect hyperconjugation to be important in the stabilization of alkyloxonium ions (e.g., R+OH2, R2+OH)? Explain your answer.
Q:Evaluate each of the following possible alcohol syntheses as beingEvaluate each of the following possible alcohol syntheses as being good (the desired alcohol is the major or only product), not so good (the desired alcohol is a minor product), or worthless.
(a)
Evaluate each of the following possible alcohol syntheses as being

(b)

Evaluate each of the following possible alcohol syntheses as being

(c)

Evaluate each of the following possible alcohol syntheses as being

(d)

Evaluate each of the following possible alcohol syntheses as being

(e)

Evaluate each of the following possible alcohol syntheses as being

(f)

Evaluate each of the following possible alcohol syntheses as being

(g)

Evaluate each of the following possible alcohol syntheses as being

(h)

Evaluate each of the following possible alcohol syntheses as beingQ:For every process in Problem 34 that gives the designatedFor every process in Problem 34 that gives the designated product in poor yield, suggest a superior method if possible.
In problem
(a)
For every process in Problem 34 that gives the designated

(b)

For every process in Problem 34 that gives the designated

(c)

For every process in Problem 34 that gives the designated

(d)

For every process in Problem 34 that gives the designated

(e)

For every process in Problem 34 that gives the designated

(f)

For every process in Problem 34 that gives the designated

(g)

For every process in Problem 34 that gives the designated

(h)

For every process in Problem 34 that gives the designatedQ:Give the major products of each of the following reactions.Give the major products of each of the following reactions. Aqueous work-up steps (when necessary) have been omitted.
(a)
Give the major products of each of the following reactions.

(b)

Give the major products of each of the following reactions.

(c)

Give the major products of each of the following reactions.

(d)

Give the major products of each of the following reactions.

(e)

Give the major products of each of the following reactions.

(f)

Give the major products of each of the following reactions.Q:What is the direction of the following equilibrium? H- + H2OWhat is the direction of the following equilibrium?
H- + H2O ⇋ H2 + HO-
Q:Formulate the product of each of the following reactions. TheFormulate the product of each of the following reactions. The solvent in each case is (CH3CH2)2O.
(a)
Formulate the product of each of the following reactions. The

(b)

Formulate the product of each of the following reactions. The

(c)

Formulate the product of each of the following reactions. TheQ:Write out a mechanism for every reaction depicted in ProblemWrite out a mechanism for every reaction depicted in Problem 38.
(a)
Write out a mechanism for every reaction depicted in Problem

(b)

Write out a mechanism for every reaction depicted in Problem

(c)

Write out a mechanism for every reaction depicted in ProblemQ:Give the major products of each of the following reactionsGive the major products of each of the following reactions [after work-up with aqueous acid in (d), (f), and (h)].
(a)
Give the major products of each of the following reactions

(b)

Give the major products of each of the following reactions

(c)

Give the major products of each of the following reactions

(d)

Give the major products of each of the following reactions

(e)

Give the major products of each of the following reactions

(f)

Give the major products of each of the following reactions

(g)

Give the major products of each of the following reactions

(h)

Give the major products of each of the following reactionsQ:The common practice of washing laboratory glassware with acetone canThe common practice of washing laboratory glassware with acetone can lead to unintended consequences. For example, a student plans to carry out the preparation of methylmagnesium iodide, CH3MgI, which he will add to benzaldehyde, C6H5CHO. What compound is he intending to synthesize after aqueous work-up? Using his freshly washed glassware, he carries out the procedure arid finds that he has produced an unexpected tertiary alcohol as a product. What substance did he make? How did it form?
Q:Which of the following halogenated compounds can be used successfullyWhich of the following halogenated compounds can be used successfully to prepare a Grignard reagent for alcohol synthesis by subsequent reaction with an aldehyde or ketone? Which ones cannot and why?
(a)
Which of the following halogenated compounds can be used successfully

(b)

Which of the following halogenated compounds can be used successfully

(c)

Which of the following halogenated compounds can be used successfully

(d)

Which of the following halogenated compounds can be used successfully

(e)

Which of the following halogenated compounds can be used successfullyQ:Give the major products of each of the following reactionsGive the major products of each of the following reactions (after aqueous work-up). The solvent in each case is ethoxyethane (diethyl ether).
(a)
Give the major products of each of the following reactions

(b)

Give the major products of each of the following reactions

(c)

Give the major products of each of the following reactions

(d)

Give the major products of each of the following reactions

(e)

Give the major products of each of the following reactionsQ:For each reaction presented in Problem 43. write out theFor each reaction presented in Problem 43. write out the complete, step-by-step mechanism using curved-arrow notation. Include the aqueous acid work-up.
(a)
For each reaction presented in Problem 43. write out the

(b)

For each reaction presented in Problem 43. write out the

(c)

For each reaction presented in Problem 43. write out the

(d)

For each reaction presented in Problem 43. write out the

(e)

For each reaction presented in Problem 43. write out theQ:Write the structures of the products of reaction of ethylmagnesiumWrite the structures of the products of reaction of ethylmagnesium bromide, CH3CH2MgBr, with each of the following carbonyl compounds. Identify any reaction that gives more than one stereoisomeric product, and indicate whether you would expect the products to form in identical or in differing amounts.
(a)
Write the structures of the products of reaction of ethylmagnesium

(b)

Write the structures of the products of reaction of ethylmagnesium

(c)

Write the structures of the products of reaction of ethylmagnesium

(d)

Write the structures of the products of reaction of ethylmagnesium

(e)

Write the structures of the products of reaction of ethylmagnesium

(f)

Write the structures of the products of reaction of ethylmagnesium

(g)

Write the structures of the products of reaction of ethylmagnesium

(h)

Write the structures of the products of reaction of ethylmagnesium

(i)

Write the structures of the products of reaction of ethylmagnesium

(j)

Write the structures of the products of reaction of ethylmagnesiumQ:Give the expected major product of each of the followingGive the expected major product of each of the following reactions. PCC is the abbreviation for pyridinium chlorochromate (Section 8-6).
(a)
Give the expected major product of each of the following

(b)

Give the expected major product of each of the following

(c)

Give the expected major product of each of the following

(d)

Give the expected major product of each of the following

(e)

Give the expected major product of each of the followingQ:Write out a mechanism for every reaction depicted in ProblemWrite out a mechanism for every reaction depicted in Problem 46.
(a)
Write out a mechanism for every reaction depicted in Problem

(b)

Write out a mechanism for every reaction depicted in Problem

(c)

Write out a mechanism for every reaction depicted in Problem

(d)

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