ch12-ques-2013

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Chapter 12 Testbank (Klein)- Draft 3 Chapter 12

Topic: One-Step Syntheses Section: 12.1

Difficulty Level: Easy

1. Predict the major product(s) for the following reaction:

HBr Br Br I II Br III Br IV A) I B) II C) III D) IV E) I and III Ans: E Chapter 12

2. Provide the reagent(s) required to complete the following transformation:

Br

??

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B) Br2/hν C) Br2/ROOR D) HBr/ROOR E) hν /NBS Ans: D Chapter 12

?? Br A) HBr B) Br2/hν C) Br2/ROOR D) HBr/ROOR E) hν /NBS Ans: E Chapter 12

??

Br Br

+ En

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B) Br2/hν C) Br2 D) HBr/ROOR E) hν /NBS Ans: C Chapter 12

Br OH + En ?? A) HBr B) Br2/H2O C) Br2 D) HBr/ROOR E) hν /NBS Ans: B Chapter 12

OH

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A) NaOH B) heat/H2SO4 C) CH3CO2H D) NaOEt E) KOtBu Ans: B Chapter 12

7. Predict the major product(s) for the following transformation:

Br NaSH SH Br HS HS I II III IV A) I B) II C) III D) IV E) I and III Ans: C Chapter 12

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8. Predict the reagent(s) required to complete the following transformation:

Br ?? A) NaOtBu B) HBr C) H2SO4 D) NaOH E) NaSH Ans: D Chapter 12

Br ?? A) NaOtBu B) HBr C) H2SO4 D) NaOH E) NaSH Ans: A

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Chapter 12

10. Predict the major product(s) obtained from the following reaction:

Cl DBU DBU I II III IV A) I B) II C) III D) IV E) II and IV Ans: C Chapter 12

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OH OH _{+ En} ?? A) 1) OsO4; 2) NaHSO3, H2O B) 1) Hg(OAc)2, H2O; 2) NaBH4 C) 1) RCO3H; 2) H3O+ D) H2SO4, H2O E) 1) O3; 2) DMS Ans: C Chapter 12

OH OH + En ?? A) 1) OsO4; 2) NaHSO3, H2O B) 1) Hg(OAc)2, H2O; 2) NaBH4 C) 1) RCO3H; 2) H3O+ D) H2SO4, H2O E) 1) O3; 2) DMS Ans: A Chapter 12

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?? H O O A) 1) OsO4; 2) NaHSO3, H2O B) 1) Hg(OAc)2, H2O; 2) NaBH4 C) 1) RCO3H; 2) H3O+ D) H2SO4, H2O E) 1) O3; 2) DMS Ans: E Chapter 12

OH _{+ En} ?? A) 1) OsO4; 2) NaHSO3, H2O B) 1) Hg(OAc)2, H2O; 2) NaBH4 C) 1) RCO3H; 2) H3O+ D) 1) BH3-THF; 2) H2O2, NaOH E) 1) O3; 2) DMS Ans: B Chapter 12

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Section: 12.1

+ En ?? OH A) 1) OsO4; 2) NaHSO3, H2O B) 1) Hg(OAc)2, H2O; 2) NaBH4 C) 1) RCO3H; 2) H3O+ D) 1) BH3-THF; 2) H2O2, NaOH E) 1) O3; 2) DMS Ans: D Chapter 12

?? + En A) 1) OsO4; 2) NaHSO3, H2O B) 1) Hg(OAc)2, H2O; 2) NaBH4 C) H2, Pt D) 1) BH3-THF; 2) H2O2, NaOH E) 1) O3; 2) DMS Ans: C Chapter 12

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?? A) 1) OsO4; 2) NaHSO3, H2O B) NaNH2 C) H2, Pt D) Na, NH3(l) E) H2, Lindlar’s catalyst Ans: D Chapter 12

?? A) 1) OsO4; 2) NaHSO3, H2O B) NaNH2 C) H2, Pt D) Na, NH3(l) E) H2, Lindlar’s catalyst Ans: E Chapter 12

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Section: 12.1

?? H O A) 1) OsO4; 2) NaHSO3, H2O B) 1) Hg(OAc)2, H2O; 2) NaBH4 C) H2, Pt D) 1) 9-BBN; 2) H2O2, NaOH E) 1) O3; 2) DMS Ans: D Chapter 12

?? O A) 1) OsO4; 2) NaHSO3, H2O B) H2SO4, H2O, HgSO4 C) H2, Pt D) 1) 9-BBN; 2) H2O2, NaOH E) 1) O3; 2) DMS Ans: B Chapter 12

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Br Br ?? Na A) 1) OsO4; 2) NaHSO3, H2O B) H2SO4, H2O, HgSO4 C) NaOH D) xs NaNH2 E) 1) O3; 2) DMS Ans: D Chapter 12

?? O OH + CO₂ A) 1) OsO4; 2) NaHSO3, H2O B) H2SO4, H2O, HgSO4 C) NaOH D) xs NaNH2 E) 1) O3; 2) H2O Ans: E Chapter 12

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Section: 12.1

?? n A) 1) OsO4; 2) NaHSO3, H2O B) ROOR, heat C) NaOH D) xs NaNH2 E) 1) O3; 2) H2O Ans: B Chapter 12

?? Br A) 1) OsO4; 2) NaHSO3, H2O B) HBr, ROOR C) NaBr D) xs NaNH2 E) HBr

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Ans: E Chapter 12

Topic: Functional Group Transformations Section: 12.2

25. Predict the reagent(s) required to convert dimethylhex-2-yne to 4,5-dimethylhex-1-yne. A) 1) OsO4; 2) NaHSO3, H2O B) HBr, ROOR C) NaBr D) 1) xs NaNH2; 2) H3O+ E) HBr Ans: D Chapter 12

Difficulty Level: Medium

26. Predict the reagent(s) required to convert bromo-methylcyclohexane to 1-bromo-2-methylcyclohexane. A) 1) KOtBu; 2) HBr B) 1) NaOEt; 2) HBr C) 1) NaOEt; 2) HBr, ROOR D) 1) KOtBu; 2) HBr, ROOR E) Br2, hν Ans: C Chapter 12

27. Which of the following sequences of reagents will move the alcohol functional group from the tertiary position of 1-methyl-1-cyclohexanol to a secondary position?

A) 1) KOtBu; 2) Hg(OAc)2, H2O; 3) NaBH4

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C) 1) H2SO4, heat; 2) BH3-THF; 3) H2O2, NaOH

D) 1) TsCl, pyr; 2) NaOH; 3) BH3-THF; 4) H2O2, NaOH

E) C and D will both work F) A and B will both work Ans: E

Chapter 12

28. Which sequence of reagents will accomplish the following transformation?

Br ?? Br A) 1) KOtBu; 2) HBr B) 1) NaOEt; 2) HBr, ROOR C) 1) H2SO4, heat; 2) Br2, hν D) 1) NaOEt; 2) HBr E) both A and D work Ans: E

Chapter 12

Topic: Reactions that Change the Carbon Skeleton Section: 12.3

29. Which sequence of reagents will accomplish the following transformation?

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A) 1) KOtBu; 2) 1-bromopropane B) 1) NaNH2; 2) 1-bromopropane C) 1) NaNH2; 2) 2-bromopropane D) 1) O3; 2) DMS E) 1) O3; 2) 1-bromopropane Ans: B Chapter 12

30. Predict the major product(s) for the following reaction:

1) NaNH₂ 2) CH₃I ?? I II III IV A) I B) II C) III D) IV E) II and III Ans: C Chapter 12

31. Predict the major product(s) for the reaction of pent-1-en-4-yne with sodium amide followed by reaction with bromoethane.

A) Hept-1-en-4-yne B) Hept-6-en-3-yne

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C) Hept-3-en-6-yne D) Hept-4-en-1-yne Ans: A

Chapter 12

32. Reaction of compound A (molecular formula = C7H12) with sodium amide

followed by reaction with 1-bromobutane produces

(CH3)2CHCH(CH3)CC(CH2)3CH3. What is the name of compound A?

A) 2,3-dimethylnon-4-yne B) 2,2-dimethylpent-1-yne C) 3,4-dimethylpent-1-yne D) 4,4-dimethylhept-1-yne E) 1-heptyne Ans: C Chapter 12

33. Reaction of compound A (molecular formula = C12H22) with ozone followed by

reaction with DMS produces only (CH3)3CCH2CHO. Which of the following

could be compound A? A) cis-2,3,7,8-tetramethyloct-4-ene B) trans-dodec-6-ene C) 4,4-dimethylpent-1-ene D) cis-2,2,7,7-tetramethyloct-4-ene E) 2,2-dimethyldec-4-ene Ans: D Chapter 12

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O HO O OH ?? A) NaNH2 B) 1) O3; 2) H2O C) KMnO4 D) 1) BH3-THF; 2) H2O2, NaOH E) H2SO4, H2O Ans: B Chapter 12

35. Compound X has molecular formula C8H10. Reaction of Compound X with

excess ozone, followed by reaction with dimethyl sulfide and finally rinsing with water produces only the compounds shown below. Draw a possibility for

Compound X that is consistent with these results.

O O H HO O + OH O Compound X 1) O₃ 2) DMS 3) H₂O (C8H10) _H Ans: Chapter 12

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1) O₃ 2) DMS 3) H₂O H H O O C OHC OH COOH O O O OHC CHO O I II III _IV _V VI A) I, III, and IV B) II, III, and IV C) I, III, and V D) II, IV, and VI E) III and IV Ans: B

Chapter 12

37. One compound is produced when acetylene is treated with the following reagents. What is the IUPAC name of this compound?

1) NaNH₂ 2) 1-bromopropane 3) NaNH₂ 4) 1-bromopropane 5) ozone 6) water ??

Ans: butanoic acid Chapter 12

38. Predict a correct sequence of reactants required to complete the following transformation in which propanal is the only carbon-containing product.

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H O ?? NaNH₂ S H₂O _Br O3 Na/NH3(l) H2/Pt I II III IV V VI VII A) 1) I; 2) III; 3) IV; 4) V; 5) II

B) 1) VI; 2) IV; 3) IV; 4) VII; 5) V; 6) II C) 1) V; 2) II

D) 1) I; 2) IV; 3) VI; 4) V; 5) II E) none of the above are correct Ans: D

Chapter 12

39. Propose an efficient synthesis of propanoic acid from acetylene:

Ans: 1) NaNH₂ 2) CH₃CH₂Br 1) O₃ 2) H₂O CO2H Chapter 12

Topic: How to Approach a Synthesis Problem Section: 12.4

40. Propose an efficient synthesis of cyclopentanone from 1-methylcyclopentane:

O

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Ans: Br₂, hν Br KOtBu 1) ozone 2) DMS O Chapter 12

41. Identify the changes that must occur in transforming cis-2-butene into 2-butanol: A) only the identity of the functional group(s) must change

B) only the carbon skeleton must change

C) only the location of the functional group(s) must change

D) only the identity and location of the functional group(s) must change E) both the carbon skeleton and the identity of the functional group(s)

must change Ans: A

Chapter 12

42. Propose an efficient synthesis of 1-butene from propyne:

Ans: 1) NaNH₂ 2) MeI 1) NaNH₂ 2) H2O 3) H₂/Lindlar Chapter 12

43. The following sequence of reactions transforms acetylene into a compound with an altered carbon skeleton (compound 1), and from that into a compound in which the functional group has been changed (compound 2). Identify compounds 1 and 2:

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1) NaNH2 2) bromoethane 1 1) H2, Ni2B 2) BH₃-THF 3) H2O2, NaOH OH OH OH OH 2 I II III _IV V VI VII VIII

A) Compound 1 = I; Compound 2 = III B) Compound 1 = II; Compound 2 = III C) Compound 1 = VI; Compound 2 = IV D) Compound 1 = II; Compound 2 = IV E) Compound 1 = II; Compound 2 = V F) Compound 1 = VII; Compound 2 = VIII Ans: D

Chapter 12

44. Which of the following sequences efficiently converts 2-methylpropene and sodium acetylide into 3-methylbutanal?

H O 3-methylbutanal ?? A) 1) HBr; 2) NaCCH; 3) O3; 4) H2O B) 1) HBr; 2) NaCCH; 3) O3; 4) DMS C) 1) HBr, ROOR; 2) NaCCH; 3) O3; 4) H2O

D) 1) HBr, ROOR; 2) NaCCH; 3) H2/Ni2B 3) O3; 4) DMS

E) 1) NaCCH; 2) H2/Ni2B; 3) O3; 4) DMS

Ans: D Chapter 12

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Section: 12.4

45. Which of the following sequences most efficiently converts 3-methyl-1-pentene into 3-bromo-3-methylpentane? A) 1) HBr; 2) NaOH; 3) HBr B) 1) Br2, hν; 2) H2, Pt C) 1) H2, Pt; 2) Br2, hν D) 1) NBS, hν; 2) H2, Pt E) 1) HBr, ROOR; 2) NaOH; 3) HBr Ans: C Chapter 12

Difficulty Level: Difficult

46. Propose a strategy to carry out the following transformation:

?? O OH Ans: 1) NBS, hν 2) H2, Pt 3) NaCCH 4) xs O3 5) H₂O Chapter 12

47. Propose an efficient method of converting 3-methyl-2-butanol into 3-methyl-1-butanol.

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Ans: OH _{1) TsCl, pyr} 2) KOtBu 3) BH₃-THF 4) H2O2, NaOH OH Chapter 12

48. Propose an efficient method of converting 3-methyl-1-butanol into 3-methyl-2-butanol. Ans: OH 1) H2SO4, heat 2) Hg(OAc)₂, H₂O 3) NaBH₄ OH Chapter 12

49. Which of the following alkenes cannot be converted into an alkyne by reaction with bromine followed by excess sodium amide and then with water?

I II III IV A) I B) II C) III D) IV E) III and IV Ans: D

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Chapter 12

50. Which of the following provides an efficient method of converting 3-bromo-2-methyl-1-butene into 2-methyl-2-butene?

A) 1) NaOH; 2) H2, Pt B) 1) H2, Pt; 2) NaOEt C) 1) H2, Pt; 2) xs NaNH2 D) 1) H2, Ni2B; 2) KOtBu E) 1) H2, Pt; 2) KOtBu Ans: B Chapter 12

51. Which order of alterations would most effectively transform trans-2-butene into 1-butene?

A) convert to the dibromoalkane, then to the terminal alkyne, then to the terminal alkene

B) convert to an alcohol, then to a terminal alkyne, finally to the terminal alkene

C) convert to the terminal alkene in one step

D) shorten the chain by two carbons, then add a two-carbon alkene to the end

E) convert to an alkane, then to a terminal alkyne, and finally to a terminal alkene

Ans: A Chapter 12

52. What is the minimum number of steps required to convert 2-methylpropane into 2-methylpropene?

A) 1 B) 2

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C) 3 D) 4 E) 5 Ans: B Chapter 12

53. What is the minimum number of steps required to convert 2-methylpropane into 1-bromo-2-methyl-2-propanol? A) 1 B) 2 C) 3 D) 4 E) 5 Ans: C Chapter 12

54. Propose an efficient method of completing the following transformation:

Br ?? HO OH + En Ans: Br 1) NaCCCH₃ 2) Na/NH₃(l) 3) OsO₄ 4) NaHSO3, H2O Chapter 12

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Section: 12.4

?? S Ans: 1) 1 Br₂, hν 2) KOtBu 3) HBr, ROOR 4) NaSMe Chapter 12

Br ?? S Ans: Br _{1) NaOEt} S 2) NBS, hν 3) NaSMe Chapter 12

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OH O ?? Ans: OH O 1) Br₂ 2) xs NaNH₂ 3) H₂O 4) O₃ 5) H₂O Chapter 12

Br CHO ?? Ans: Br CHO 1) NaCCH 2) 9-BBN 3) H₂O₂, NaOH Chapter 12

Topic: Retrosynthetic Analysis Section: 12.5

59. Demonstrate your understanding of retrosynthetic synthesis and determine which compound(s) could lead immediately to the alkene shown below:

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?? Br I II III IV A) I B) II C) III D) IV E) I and IV F) I, III, and IV Ans: E Chapter 12

60. Using retrosynthetic synthesis, determine which compound(s) could lead immediately to the alcohol shown below:

OH ?? I II III IV A) I B) II C) III D) IV E) I and II F) I, II, and IV Ans: E

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Chapter 12

61. Using retrosynthetic synthesis, determine which compound(s) could lead immediately to the alkyne shown below:

??

Br I II III IV Br Br Br Br A) I B) II C) III D) IV E) I and II F) I, II, and IV Ans: D Chapter 12

62. Using the concept of retrosynthetic synthesis, determine which compound(s) could lead immediately to the alkane shown below:

??

I II III IV

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A) II and III B) I and IV C) I D) II E) III F) IV Ans: B Chapter 12

63. Using the concept of retrosynthetic synthesis, determine which compound(s) could lead immediately to the bromoalkene shown below:

Br ?? Br Br OH I II III IV A) I and III B) I and IV C) I D) II E) III F) IV Ans: C Chapter 12

64. Show that you understand the concept of retrosynthetic analysis by working backwards two steps in the synthesis below. Identify possible combinations of A and B that could lead to the alkyl halide (C):

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Br B A C Br I II III IV V VI VII VIII OH Br Cl A) B = I and A = VI B) B = VI and A = I C) B = III and A = VII D) B = IV and A = VII E) B = I and A = III F) B = V and A = VIII Ans: A, D, and E

Chapter 12

65. Show that you understand the concept of retrosynthetic analysis by working backwards two steps in the synthesis below. Identify possible combinations of A and B that can lead to the alkyne (C):

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B A C Br I II III IV V VI VII VIII OH Br Cl Br BrBr A) B = I and A = VI B) B = VI and A = I C) B = III and A = VII D) B = IV and A = VII E) B = I and A = III F) B = VI and A = VIII Ans: B

Chapter 12

66. Show that you understand the concept of retrosynthetic analysis by working backwards two steps in the synthesis below. Identify possible combinations of A and B that can lead to the alcohol (C):

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B A C Br I II III IV V VI VII VIII Br Cl Br BrBr OH Br A) B = I and A = VI B) B = VI and A = I C) B = III and A = VII D) B = IV and A = VII E) B = I and A = III F) B = VIII and A = V Ans: D and F

Chapter 12

67. Show that you understand the concept of retrosynthetic analysis by working backwards two steps in the synthesis below. Identify possible combinations of A and B that can lead to the compound shown (C):

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B A I II III IV V VI VII VIII Cl BrBr OH OH + En OH A) B = I and A = VI B) B = VI and A = I C) B = V and A = II D) B = IV and A = VII E) B = I and A = III F) B = VIII and A = V Ans: C Chapter 12

68. Show that you understand the concept of retrosynthetic analysis by working backwards two steps in the synthesis below. Identify possible combinations of A and B that can lead to the alkene (C):

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B

A

Br I _II III V VI VII Br HO A) B = I and A = V B) B = II and A = VII C) B = III and A = I D) B = I and A = VII E) B = II and A = VI F) B = III and A = II Ans: B and E Chapter 12

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?? 1) Br₂, hν 2) KOtBu 3) BH₃-THF 4) H₂O₂, NaOH 5) H₂SO₄, heat Ans: Chapter 12

70. Devise a method of converting ethylene into PVC (polyvinyl chloride).

Ans: 1) Br₂ 2) xs NaNH₂ 3) H₂O 4) 1 eq HCl 5) ROOR, heat Cl n Chapter 12

71. Devise a method of converting acetylene into the polymer shown below.

Cl n 1) NaNH2 2) CH3Br 3) HCl 4) ROOR, heat Ans:

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Chapter 12

72. Devise a method of converting trans-2-methyl-3-hexene into 5-methylhexanal.

Ans: 1) Br2 2) xs NaNH₂ 3) H₂O 4) disiamylborane 5) H₂O₂, NaOH CHO Chapter 12

73. Devise a method of converting trans-2-methyl-3-hexene into 4-methylpentanoic acid. Ans: 1) Br₂ 2) xs NaNH₂ 3) H₂O 4) ozone 5) H₂O COOH Chapter 12

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A) Br + NaCCCH₃ B) + CH3Br C) Br Br + 2 NaNH₂ D) Br + 1 NaNH₂ Ans: B and C Chapter 12

75. Devise an efficient synthesis of the diol shown below starting with 1,1,3,3-tetramethyl-2-ethylcyclohexane.

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OH OH + En Ans: 1) Br₂, hν 2) KOtBu 3) HBr, ROOR 4) KOtBu 5) Br₂ 6) xs NaNH2 7) CH₃Br 8) H₂, Lindlar 9) OsO₄ 10) NaHSO_3, H₂O Chapter 12

76. Devise an efficient synthesis of the diol shown below starting with 1,1,3,3-tetramethyl-2-ethylcyclohexane.

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OH OH + En Ans: 1) Br₂, hν 2) KOtBu 3) HBr, ROOR 4) KOtBu 5) Br₂ 6) xs NaNH₂ 7) CH₃Br 8) H₂, Lindlar 9) RCO₃H 10) H₃O+ Chapter 12

77. Devise an efficient synthesis of the compound shown below starting with 4-methyl-2-pentanol. O O OH OH Ans: 1) TsCl, pyr 2) KOtBu 3) HBr/ROOR 4) ONa O Chapter 12

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78. To add one carbon directly to the end of a primary alkyl bromide, one could: A) substitute bromide with acetylide, then cleave the triple bond.

B) substitute bromide with acetylide, then reduce the alkyne to an alkene. C) substitute bromide with methoxide.

D) eliminate hydrogen bromide to produce an alkene. Ans: A

Chapter 12

79. To remove one carbon from the end of a primary alkyl bromide, one could: A) substitute bromide with acetylide, then cleave the triple bond.

B) substitute bromide with acetylide, then reduce the alkyne to an alkene. C) substitute bromide with methoxide.

D) eliminate hydrogen bromide to produce an alkene, then cleave the double bond.

Ans: D Chapter 12

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Br OH + OH Br 1) NaOEt 2) BH3-THF 3) H2O2, NaOH OH + OH Ans: ?? Chapter 12

81. Devise a method to complete the following synthesis.

O acetylene 1) NaNH2 2) CH3Br 3) NaNH₂ 4) CH3Br 5) H2, Lindlar's catalyst 6) RCO₃H Ans: Chapter 12

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O acetylene 1) NaNH₂ 2) CH₃Br 3) NaNH₂ 4) CH₃Br 5) Na, NH₃(l) 6) RCO₃H Ans: + En Chapter 12

83. Devise a method to complete the following synthesis.

N N N N 1) NBS, hν 2) HBr, ROOR 3) 2 NaCN Ans: Chapter 12

84. Devise a method to prepare 1,7-heptanediol from propene.

1) NBS, hν 2) HBr, ROOR 3) 2 NaCCH 4) H2, Lindlar 5) BH₃-THF 6) H₂O₂, NaOH Ans: HO OH

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Chapter 12

85. Devise a method to prepare 1,3-dibromopropanol from propene. 1) NBS, hν

2) Br_2, H₂O

Ans: Br Br

OH

Chapter 12

86. Devise a method to prepare 3-bromo-1-propanol from propene. 1) NBS, hν

2) BH3-THF

3) H₂O₂, NaOH

Ans: Br OH

Chapter 12

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1) NBS, hν 2) KCN Ans: N N Chapter 12

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Ans:

1) NBS, hν 2) HBr, ROOR 3) 2 NaCCH 4) H₂, Pt