PROBLEMS

29. What is the major product obtained from the reaction of each of the following compounds with excess HCl?
a. H3CH2CC CCH2CH3 b. H3C C CCH(CH2CH3)CH2CH2CH2CH3 c. H3C C C H

30. Draw a condensed structure for each of the following:

a. 2-hexyne e. methoxyethyne i. diethylacetylene
b. 5-ethyl-3-octyne f. sec-butyl-tert-butylacetylene j. di-tert-butylacetylene
c. methylacetylene g. 1-bromo-1-pentyne k. cyclopentylacetylene
d. vinylacetylene h. 5-methyl-2-cyclohexenol l. 5,6-dimethyl-2-heptyne

31. A student was given the structural formulas of several compounds and was asked to give them systematic names. How many did she name correctly?
Correct those that are misnamed.
a. 4-ethyl-2-pentyne b. 1-bromo-4-heptyne c. 2-methyl-3-hexyne d. 3-pentyne

32. Identify the electrophile and the nucleophile in each of the following reaction steps. Then draw curved arrows to illustrate the bond-making and
­bond-breaking processes.

+
Br Br
−
CH3CH2C CH + Br CH3CH2C CH
Br
− −
CH3C C H + NH2 CH3C C + NH3
− −
CH3C C + CH3 Br CH3C CCH3 + Br

33. What is each compound’s systematic name?

CH3
a. CH3C CCH2CHCH3 c. CH3C CCH2CCH3 e.
Br CH3
CH3
b. CH3C CCH2CHCH3 d. CH3CHCH2C CCHCH3 f. CH3

CH2CH2CH3 Cl CH3

34. What reagents should be used to carry out the following syntheses?

O
RCH2CH3 RCH CH2
RCH CH2 RCHCH3
Br Br
RCCH3 RC CH O
Br RCCH3
RC CH2 O

Br RCH2CH

35. a. Draw the structures and give the common and systematic names for alkynes with molecular formula C7H12. Ignore stereosiomers. (Hint: There are 14.)
b. How many would there be if stereoisomers are included?

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36. Draw the mechanism for the following reaction:
O
Br2
CH3CH2CH2C CH H2O
CH3CH2CH2CCH2Br

37. How can the following compounds be synthesized, starting with a hydrocarbon that has the same number of carbons as the desired product?
O O
a. CH3CH2CH2CH2CH b. CH3CH2CH2CH2OH c. CH3CH2CH2CCH2CH2CH2CH3

38. What reagents would you use for the following syntheses?
a. (Z)-3-heptene from 3-heptyne b. (E)-3-heptene from 3-heptyne c. hexane from 3-heptyne

39. What is the major product of the reaction of 1 mol of propyne with each of the following reagents?
a. HBr (1 mol) e. aqueous H2SO4, HgSO4 h. H2/Lindlar catalyst
b. HBr (2 mol) f. R2BH in THF followed by i. sodium amide
c. Br2 (1 mol)/CH2Cl2 H2O2/HO - /H2O j. the product of part i followed by
d. Br2 (2 mol)/CH2Cl2 g. excess H2, Pd/C 1-chloropropane

40. Answer Problem 39, parts a–h, using 2-butyne as the starting material instead of propyne.

41. What is each compound’s systematic name?

CH3

a. CH3C CCH2CH2CH2CH CH2 c. CH3CH2C CCH2CH2C CH e.

HOCH2CH2 CH2CH3 NH2

Cl
b. C C d. f.
H H CH3

42. What is the molecular formula of a hydrocarbon that has 1 triple bond, 3 double bonds, 1 ring, and 32 carbons?

43. a.   Starting with 3-methyl-1-butyne, how can you prepare the following alcohols?
1. 2-methyl-2-butanol 2. 3-methyl-1-butanol
b. In each case, a second alcohol would also be obtained. What alcohol would it be?

44. Which of the following names are correct? Correct those that are not correct.
a. 4-heptyne c. 4-chloro-2-pentyne e. 4,4-dimethyl-2-pentyne
b. 2-ethyl-3-hexyne d. 2,3-dimethyl-5-octyne f. 2,5-dimethyl-3-hexyne

45. Which of the following pairs are keto–enol tautomers?

O O
a. CH3CH2CH2CH CHCH2OH and CH3CH2CH2CH3CH3CH d. CH3CH2CH2CH CHCH2CH2CH2OH and CH3CH2CH2CH3CH3CCH3
O O
b. CH3CH2OH and CH3CH e. CH3CH2CH2CH2CH CHCH2CH2CH2OH and CH3CH2CH2CH3CH3CCH2CH3
O
c. CH3CH CHOH and CH3CH2CH

46. How can the following compounds be prepared using ethyne as the starting material?
O O
a. CH3CH b. CH3CH2CHCH2Br c. CH3CCH3 d. e. f.
Br

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47. Do the equilibria of the following acid–base reactions lie to the right or the left? (The pKa of H2O2 is 11.6.)

HOOH + HO− HOO− + H2O

RC CH + HOO− RC C− + HOOH

48. What is each compound’s systematic name?

Br
a. b. c. d.

49. What stereoisomers are obtained when 3-hexyne undergoes each of the following reaction sequences?
a. 1. H2/Lindlar catalyst 2. Br2/CH2Cl2 b. 1. Na/NH3(liq), –78 °C 2. Br2/CH2Cl2 c. 1. Cl2/CH2Cl2 2. Br2/CH2Cl2

50. Show how the following compounds can be synthesized starting with ethyne:
a. cis-2-heptene b. trans-3-hexene

51. Draw the keto tautomer for each of the following:

OH
OH Br
a. b. c. d.
HO OH

52. Show how each of the following compounds can be prepared using the given starting material, any needed inorganic reagents, and any o­ rganic compound
that has no more than four carbons:
O O
a. HC CH CH3CH2CH2CH2CCH3 d. C CH CH2CH

O
b. HC CH CH3CH2CHCH3 e. C CH CCH3
Br
H H
C C

c. HC f. CH3
CH CH3CH2CH2CHCH3 C CCH3
OH

53. A chemist is planning to synthesize 3-octyne by adding 1-bromobutane to the product obtained from the reaction of 1-butyne with sodium amide.
­Unfortunately, however, he forgot to order 1-butyne. How else can he prepare 3-octyne?

1. Na, NH3(liq), −78 °C

54. a. Explain why a single pure product is obtained from hydroboration–oxidation
a. of
H32-butyne,
C C Cwhereas two
CH2CH products
2CH3
are obtained from ­hydroboration–
oxidation of 2-pentyne. 2. D2, Pd/C
b. Name two other internal alkynes that yield only one product upon hydroboration–oxidation.

55. What stereoisomers are obtained from the following reactions?

1. Na, NH3(liq), −78 °C 1. H2/ Lindlar catalyst
a. H3C C C CH2CH2CH3 b. H3C C C CH2CH2CH3
2. D2, Pd/C 2. D2, Pd/C

56. Explain why, in hydroboration–oxidation, HO - and HOOH cannot be added until after the hydroboration reaction is over.

57. Starting with ethyne, describe how the

1. Hfollowing compounds can be synthesized:
2/ Lindlar catalyst
b. (3S,4R)-
a. H3C C4-bromo-3-hexanol
C CH2CH2CH3and (3R,4S)- 4-bromo-3-hexanol
2. D2, Pd/C
b. (3R,4R)- 4-bromo-3-hexanol and (3S,4S)- 4-bromo-3-hexanol

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58. a-Farnesene is a dodecatetraene found in the waxy coating of apple skins. What is its systematic name? Include E and Z where necessary to indicate the
configuration of the double bonds.

a-farnesene

59. Show how the following compound can be prepared from the given starting material. Draw the structure of the compound that is formed in each step of
the synthesis.
O
?
H3C H

60. What are the products of the following reactions?

1. R2BH/THF Na
a. + Cl2 d. + g.
excess CH2Cl2 2. HO−, H2O2, H2O NH3(liq), −78 °C

Pd/C 1. R2BH, THF

b. + Cl2 e. + H2 h.
CH2Cl2 2. HO−, H2O2, H2O

H2SO4 Lindlar
c. + H2O f. + H2 i. + HBr
HgSO4 catalyst excess

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