QOI 0809 alkynes

Name___________________________________

ESSAY. Write your answer in the space provided or on a separate sheet of paper. 1) Give the IUPAC name for (CH3)2 C(CH2 CH3 )C CCH(CH3 )2. 2) Give the IUPAC name for HC CCH2 CH2 CH3 . 3) Give the IUPAC name for CH3CH2 C CCH(OH)CH3 . 4) Give the IUPAC name for CH3CH CHCH CHC CCH3 . 5) Give the IUPAC name for BrCH2 CH2C CCH2 CH3 . 6) Draw an acceptable structure for acetylene. 7) Draw an acceptable structure for 3-sec-butylhept-1-yne. 8) Draw an acceptable structure for (S)-5-phenyloct-2-yne. 9) Draw an acceptable structure for hepta-3,6-dien-1-yne. 10) Draw an acceptable structure for hex- 2-yne. MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 11) How many distinct terminal alkynes exist with a molecular formula of C5 H8 ? A) 1 B) 2 C) 3 D) 4 12) How many distinct internal alkynes exist with a molecular formula of C6 H10? A) 1 B) 2 C) 3 D) 4 11) E) 5 12) E) 5 13)

13) The carbon-carbon triple bond of an alkyne is composed of __________. A) three bonds B) one bond and two bonds C) two bonds and one bond D) three bonds 14) In trans-hept-4-en-2-yne the shortest carbon-carbon bond is between carbons __________. A) 1 and 2 B) 2 and 3 C) 3 and 4 D) 4 and 5 E) 6 and 7 15) Which of the following improperly describes the physical properties of an alkyne? A) insoluble in most organic solvents B) nearly insoluble in water C) boiling point nearly the same as an alkane with similar carbon skeleton D) less dense than water E) relatively nonpolar

14)

15)

ESSAY. Write your answer in the space provided or on a separate sheet of paper. 16) How many moles of water are produced when one mole of propyne undergoes complete combustion? 17) Why are terminal alkynes more acidic then other hydrocarbons? 18) Provide the structure of the major organic product(s) in the reaction below.

19) Provide the structure of the major organic product(s) in the reaction sequence below. CH3 CH2C CH 1. NaNH2 2. PhCH2 Br

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 20) Which of the species below is less basic than acetylide? A) CH3 ONa B) CH3 Li C) CH3 MgBr D) both A and C E) all of the above ESSAY. Write your answer in the space provided or on a separate sheet of paper. 21) Describe a qualitative, nonspectroscopic means for distinguishing terminal alkynes from internal ones. 22) 2-Methylhex-3-yne can be prepared by the reaction of an alkynide with an alkyl halide. Does the better synthesis involve alkynide attack on bromoethane or on 2-bromopropane? Explain your reasoning. 23) Provide the structure of the major organic product(s) in the reaction below. 20)

24) Provide the structure of the major organic product(s) in the reaction below.

25) Provide the structure of the major organic product(s) in the reaction sequence below.

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 26) When 2,2-dibromobutane is heated at 200C in the presence of molten KOH, what is the major organic product? A) but-1-yne B) 1-bromobut-2-yne C) 1-bromobut-1-yne D) but-1-ene E) but-2-yne 27) A mixture of hept-1-yne, hept-2-yne, and hept-3-yne was hydrogenated in the presence of a platinum catalyst until hydrogen uptake ceased. If one assumes that the hydrogenation went to completion, how many different seven-carbon hydrocarbons were produced? A) 2 B) 1 C) 3 D) 8 E) 6 ESSAY. Write your answer in the space provided or on a separate sheet of paper. 28) Provide the structure of the major organic product(s) in the reaction below. 26)

27)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 29) In the reduction of alkynes using sodium in liquid ammonia, which of the species below is not thought to be an intermediate in the commonly accepted mechanism? A) vinyl radical B) vinyl anion C) vinyl cation D) radical anion ESSAY. Write your answer in the space provided or on a separate sheet of paper. 30) Provide the structure of the major organic product(s) in the reaction below. 29)

31) Provide the structure of the major organic product(s) in the reaction below.

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 32) In the addition of hydrogen bromide to alkynes in the absence of peroxides, which of the following species is thought to be an intermediate? A) vinyl radical B) vinyl anion C) vinyl cation D) carbene E) none of the above ESSAY. Write your answer in the space provided or on a separate sheet of paper. 33) Provide the structure of the major organic product(s) in the reaction below. 32)

34) Provide the structure of the major organic product(s) in the reaction sequence below.

35) Treatment of hex-2-yne with mercuric sulfate in dilute sulfuric acid yields a mixture of two ketones. Similar treatment of hex-3-yne produces a single ketone instead of a mixture. Explain. 36) Provide the structure of the major organic product(s) in the reaction below.

37) Provide the structure of the major organic product(s) in the reaction below. CH3 CH2CH2 CH2 CH2 C C CH2CH3 1. O3 2. H2 O

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 38) Among the compounds water, but-1-yne, but-2-yne, and ethane, which are stronger acids than ammonia? A) water and but-1-yne B) water and ethane C) but-1-yne and but-2-yne D) but-1-yne and ethane 38)

39) To a solution of propyne in diethyl ether, one molar equivalent of CH3 Li was added and the resulting mixture was stirred for 0.5 hour. After this time, an excess of D2 O was added. Describe the major organic product(s) of this reaction. A) CH3 C CD + CH4 B) CH3 C CCD3 C) CH3 C CCH3 D) CD3C CD3 E) CH3 C CD + CH3 D ESSAY. Write your answer in the space provided or on a separate sheet of paper. 40) Provide the structure of the major organic product(s) in the reaction below. Ph C C Ph D2 Pd/BaSO4 , quinoline

39)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 41) __________ is produced when 1 equivalent of HBr is added to hex-1-yne in the presence of peroxides. A) Z-1-Bromohex-1-ene B) E-2-Bromohex-2-ene C) A mixture of E and Z isomers of 1-bromohex-1-ene D) E-1-Bromohex-1-ene E) 2-Bromohex-1-ene 42) Which of the alkyne addition reactions below involve(s) an enol intermediate? A) hydroboration/oxidation B) treatment with HgSO4 in dilute H2 SO4 C) hydrogenation D) both A and B E) none of the above ESSAY. Write your answer in the space provided or on a separate sheet of paper. 43) Draw the products which result when oct-3-yne is heated in basic potassium permanganate solution. 44) Describe a sequence of reactions by which racemic 2,3-dibromobutane can be straightforwardly prepared from propyne. 45) Describe a sequence of reactions by which hexan-2-ol can be straightforwardly prepared from hex-1-yne. 46) Describe a sequence of reactions by which hept-3-yne can be straightforwardly prepared from acetylene. 47) Describe a sequence of reactions by which meso-2,3-dibromobutane can be straightforwardly prepared from propyne. 48) Describe a sequence of reactions by which hept-1-yne can be straightforwardly prepared from hept-1-ene. 41)

42)

49) Describe a sequence of reactions by which butylbenzene can be straightforwardly prepared from phenylacetylene. 50) Describe a sequence of reactions by which (E)-5-bromopent-2-ene can be straightforwardly prepared from propyne. 51) Describe a sequence of reactions by which CH3 CH2CH2 COCH2 CH3 can be straightforwardly prepared from but-1-yne. 52) Describe a sequence of reactions by which trans-pent-2-ene can be straightforwardly prepared from propyne. 53) Describe a sequence of reactions by which meso-hexane-3,4-diol can be straightforwardly prepared from hex-3-yne. 54) Describe a sequence of reactions by which (Z)-hex-3-en-1-ol can be straightforwardly prepared from but-1-yne. 55) Describe a sequence of reactions by which 1-propylcyclohexan-1-ol can be straightforwardly prepared from propyne. 56) Describe a sequence of reactions by which the compound shown below can be straightforwardly prepared from acetylene.

57) Describe a sequence of reactions by which the compound shown below can be straightforwardly prepared from acetylene.

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 58) How many moles of oxygen are required in the complete combustion of 1 mole of acetylene? A) 1.5 B) 2 C) 3 D) 2.5 E) 1 SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question. 59) Give the IUPAC name for Cl3 CCH2 CH2CH2 CCH. 59) 58)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 60) How many distinct alkynes exist with a molecular formula of C4 H6 ? A) 0 B) 1 C) 2 D) 3 6 60) E) 4

61) How many distinct alkynes exist with a molecular formula of C4 H8 ? A) 0 B) 1 C) 2 D) 3

61) E) 4

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question. 62) Name the compound which results when pent-2-yne is subjected to catalytic hydrogenation using a platinum catalyst. 62)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 63) Which of the following reagents should be used to convert hex-3-yne to (E)-hex-3-ene? A) HgSO4, H2O B) H2, Pt C) H2, Lindlar's catalyst D) H2SO4, H2O E) Na, NH3 64) Which of the following reagents should be used to convert hex-3-yne to (Z)-hex-3-ene? A) HgSO4, H2O B) H2, Lindlar's catalyst C) H2SO4, H2O D) Na, NH3 E) H2, Pt SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question. 65) Name the product which results when CH3C CLi reacts with CH3CH2 COCH2 CH3 followed by addition of water. 65) 63)

64)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 66) Which of the following reagents should be used to convert an internal alkyne to an -diketone? A) KMnO 4 , H2 O, neutral B) Na, NH3 C) O3 then H2 O D) HgSO4, H2SO4 E) Sia2 BH then H2 O2 SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question. 67) Name the compound which results when pent-1-yne is treated with sodium in liquid ammonia. 67) 66)

68) Provide the IUPAC name for the compound below.

68)

69) What products result when calcium carbide is combined with water? 70) Circle the shortest bond in the compound below.

69) 70)

71) Explain why the synthetic route shown below would be unsuccessful. 1. CH3 CH2Br H C C:- Na+ 2. NaNH2 3. (CH3 )3 CBr (H3 C)3 C C C CH2 CH3

71)

72) Provide the major organic product of the reaction shown below.

72)

73) Explain why the synthetic route shown below would be unsuccessful. 1. CH3 CH2Br H C C:- Na+ 2. NaOCH3 3. CH3 CH2I H3 CH2C C C CH2CH3

73)

74) Provide the major organic product of the reaction shown below.

74)

75) What conditions could be used to isomerize hept-2-yne to hept-1-yne? 76) Provide the major organic product of the reaction shown below.

75) 76)

77) Provide the major organic product of the reaction shown below.

77)

78) Provide the IUPAC name for Cl3 C(CH2 )3 CCH. 79) Provide the IUPAC name for (CH3 )2 CHCH2CH(OH)CH2CCCH3.

78) 79)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 80) What is the major organic product that results when 3-heptyne is hydrogenated in the presence of Lindlar's catalyst? A) heptane B) 2-heptyne C) (Z)-2-heptene D) (Z)-3-heptene E) (E)-3-heptene 81) What is the major organic product that results when 3-heptyne is subjected to excess hydrogen and a platinum catalyst? A) (E)-3-heptene B) (Z)-3-heptene C) (Z)-2-heptene D) heptane E) 2-heptyne 80)

81)

82) What is the major organic product that results when 3-heptyne is treated with sodium metal in ammonia? A) (Z)-3-heptene B) (Z)-2-heptene C) heptane D) (E)-3-heptene E) 2-heptyne 83) What is the major organic product that results when 1-heptyne is treated with 2 equivalents of HBr? A) 1,1-dibromoheptane B) 2,3-dibromo-2-heptene C) 2,2-dibromoheptane D) 2,3-dibromo-1-heptene E) 1,2-dibromoheptane 84) What class of organic product results when 1-heptyne is treated with a mixture of mercuric acetate in aqueous sulfuric acid? A) ketone B) diol C) ether D) aldehyde E) carboxylic acid 85) What class of organic product results when 1-heptyne is reacted with disiamylborane followed by treatment with basic hydrogen peroxide? A) aldehyde B) diol C) ketone D) carboxylic acid E) ether SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question. 86) What two organic compounds result when 3-heptyne is heated in basic aqueous KMnO4 ? 87) What two organic compounds result when 3-heptyne is treated with ozone followed by hydrolysis? 86) 87)

82)

83)

84)

85)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 88) The correct IUPAC name for the following structure is __________. 88)

A) (Z) 4-isopropyl-3-hepten-5-yne C) (E) 4-isopropyl-3-hepten-5-yne

B) (Z) 4-isopropyl-4-hepten-2-yne D) (E) 4-isopropyl-4-hepten-2-yne

10

89) What is the correct IUPAC name for the following compound?

89)

A) 4-(1-bromopropyl)-1-hexen-5-yne C) 4-allyl-5-bromo-1-hexyne

B) 5-bromo-4-ethynyl-1-heptene D) 3-(1-bromopropyl)-5-hexen-1-yne 90)

90) Which of the following bases are sufficiently strong to deprotonate a terminal alkyne with an equilibrium constant greater than 1? 1) 2) sodium methoxide lithium diisopropyl amide A) 1, 2, 3 and 4 B) 3 and 4 C) 2, 3 and 4 D) 2 and 3 E) 1, 2, and 3 3) 4) n-butyl lithium phenylmagnesium bromide

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question. 91) Complete the synthesis below by providing all necessary reagents and show all intermediate structures. 91)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 92) Complete the transformation below by indicating the necessary sequence of reagents. 92)

A) 1) Na / ND3 B) 1) Br2 / H2O C) 1) D2 / Pd, BaSO4, quinoline D) 1) Na / ND3 E) 1) DBr

2) Br2 / H2O 2) D2 / Pd, BaSO4 , quinoline 2) Br2 / H2O 2) Br2 2) BD3 3) H2 O 3) H2 O2 / NaOH

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question. 93) Predict the necessary starting material for the reaction below. 93)

11

94) Complete the short synthesis below by providing the necessary reagents.

94)

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Answer Key Testname: UNTITLED2

1) 2,5,5-trimethylhept-3-yne
ID: oc6w 9-1 Diff: 2

2) pent-1-yne
ID: oc6w 9-2 Diff: 1

3) hex-3-yn-2-ol
ID: oc6w 9-3 Diff: 2

4) octa-2,4-dien-6-yne
ID: oc6w 9-4 Diff: 3

5) 1-bromohex-3-yne
ID: oc6w 9-5 Diff: 2

6) H C C H
ID: oc6w 9-6 Diff: 1

7)

ID: oc6w 9-7 Diff: 2

8)

ID: oc6w 9-8 Diff: 2

9) HC CCH CHCH2 CH CH2

10)

ID: oc6w 9-10 Diff: 1

11) B
ID: oc6w 9-11 Diff: 2

12) C
ID: oc6w 9-12 Diff: 2

13) B
ID: oc6w 9-13 Diff: 1

13

Answer Key Testname: UNTITLED2

14) B
ID: oc6w 9-14 Diff: 1

15) A
ID: oc6w 9-15 Diff: 2

16) two
ID: oc6w 9-16 Diff: 2

17) The carbanion which results upon deprotonation of a terminal alkyne has the lone pair of electrons in an sp hybrid orbital. The greater % s character of this orbital gives this orbital a significantly lower energy.
ID: oc6w 9-17 Diff: 2

18)

ID: oc6w 9-18 Diff: 2

19) CH3 CH2C CCH2 Ph

20) A
ID: oc6w 9-20 Diff: 2

21) Add a solution of Cu+ or Ag+. Terminal alkynes react to form insoluble metal acetylides which precipate.
ID: oc6w 9-21 Diff: 2

22) Attack on the primary bromide (bromoethane) is much more favorable. Reaction of an alkynide with the secondary bromide would result mostly in elimination instead of substitution.
ID: oc6w 9-22 Diff: 2

23)

ID: oc6w 9-23 Diff: 2

24)

ID: oc6w 9-24 Diff: 2

14

Answer Key Testname: UNTITLED2

25)

ID: oc6w 9-25 Diff: 2

26) E
ID: oc6w 9-26 Diff: 3

27) B
ID: oc6w 9-27 Diff: 2

28)

ID: oc6w 9-28 Diff: 2

29) C
ID: oc6w 9-29 Diff: 3

30)

ID: oc6w 9-30 Diff: 2

31)

ID: oc6w 9-31 Diff: 2

32) C
ID: oc6w 9-32 Diff: 3

33)

ID: oc6w 9-33 Diff: 3

15

Answer Key Testname: UNTITLED2

34)

ID: oc6w 9-34 Diff: 3

35) The two carbons of the triple bond in hex-3-yne are equivalent, and only 3-hexanone results. In the case of hex-2-yne, the two carbons of the triple bond are not equivalent, and a mixture of 2- and 3-hexanone results.
ID: oc6w 9-35 Diff: 1

36)

ID: oc6w 9-36 Diff: 3

37) CH3 CH2CH2 CH2 CH2 CO2 H + CH3CH2 CO2 H

38) A
ID: oc6w 9-38 Diff: 2

39) A
ID: oc6w 9-39 Diff: 2

40)

ID: oc6w 9-40 Diff: 2

41) C
ID: oc6w 9-41 Diff: 2

42) D
ID: oc6w 9-42 Diff: 2

43) CH3 CH2CO2 - K+ + CH3 CH2CH2 CH2 CO2- K+

44) 1. 2. 3. 4.

NaNH2 CH3 I H2, Lindlar's catalyst Br2 , CCl4

ID: oc6w 9-44 Diff: 2

16

Answer Key Testname: UNTITLED2

45) 1. HgSO4, H2O, H2 SO4 2. NaBH4

46) 1. 2. 3. 4.

NaNH2 CH3 CH2Br NaNH2 CH3 CH2CH2 Br

ID: oc6w 9-46 Diff: 1

47) 1. 2. 3. 4.

NaNH2 CH3 Br Na, NH3 Br2 , CCl4

ID: oc6w 9-47 Diff: 3

48) 1. Br2 2. NaNH2, heat

49) 1. NaNH2 2. CH3 CH2Br 3. H2, Pt

50) 1. NaNH2 2. ethylene oxide (oxirane) 3. H+, H2O 4. Na, NH3 5. PBr3
ID: oc6w 9-50 Diff: 3

51) 1. NaNH2 2. CH3 CH2Br 3. HgSO4, H2O, H2 SO4

52) 1. NaNH2 2. CH3 CH2Br 3. Na, NH3

17

Answer Key Testname: UNTITLED2

53) 1. H2, Lindlar's catalyst 2. OsO4 , H2 O2 or cold, dilute KMnO4 , -OH or 1. Na, NH3 2. PhCO3H 3. H3O+ or - OH
ID: oc6w 9-53 Diff: 3

54) 1. NaNH2 2. ethylene oxide (oxirane) 3. H+, H2O 4. H2, Lindlar's catalyst
ID: oc6w 9-54 Diff: 3

55) 1. NaNH2 2. cyclohexanone 3. H+, H2O 4. H2, Pt

56) 1. 2. 3. 4.

NaNH2 CH3 CH2Br NaNH2 cyclopentanone 5. H+, H2O

ID: oc6w 9-56 Diff: 2

57) 1. 2. 3. 4. 5. 6.

NaNH2 CH3 I NaNH2 CH3 I Na, NH3 PhCO3H

ID: oc6w 9-57 Diff: 3

58) D
ID: oc6w 9-58 Diff: 2

59) 6,6,6-trichlorohex-1-yne
ID: oc6w 9-59 Diff: 2

60) C
ID: oc6w 9-60 Diff: 1

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Answer Key Testname: UNTITLED2

61) A
ID: oc6w 9-61 Diff: 1

62) pentane
ID: oc6w 9-62 Diff: 1

63) E
ID: oc6w 9-63 Diff: 2

64) B
ID: oc6w 9-64 Diff: 2

65) 3-ethylhex-4-yn-3-ol
ID: oc6w 9-65 Diff: 3

66) A
ID: oc6w 9-66 Diff: 2

67) pent-1-ene
ID: oc6w 9-67 Diff: 2

68) 3-ethylhex-4-yn-3-ol
ID: oc6w 9-68 Diff: 2

69) acetylene and calcium hydroxide

70)

ID: oc6w 9-70 Diff: 2

71) The tert-butyl bromide would not undergo SN2 when treated with the intermediate alkynide because the steric hinderance in the halide is too great. Instead, the alkynide would deprotonate the tertiary bromide via an E2 mechanism.
ID: oc6w 9-71 Diff: 2

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Answer Key Testname: UNTITLED2

72)

ID: oc6w 9-72 Diff: 2

73) Sodium methoxide is not a sufficiently strong base to deprotonate the intermediate terminal alkyne.
ID: oc6w 9-73 Diff: 2

74)

ID: oc6w 9-74 Diff: 2

75) 1. NaNH2, 150C 2. H2O

76)

ID: oc6w 9-76 Diff: 2

77)

ID: oc6w 9-77 Diff: 2

20

Answer Key Testname: UNTITLED2

78) 6,6,6-trichloro-1-hexyne or 6,6,6-trichlorohex-1-yne

79) 2-methyl-6-octyn-4-ol or 2-methyloct-6-yn-4-ol

80) D
ID: oc6w 9-80 Diff: 2

81) D
ID: oc6w 9-81 Diff: 2

82) D
ID: oc6w 9-82 Diff: 2

83) C
ID: oc6w 9-83 Diff: 2

84) A
ID: oc6w 9-84 Diff: 2

85) A
ID: oc6w 9-85 Diff: 2

86) CH3 CH2CO2 - and CH3CH2 CH2 CO2ID: oc6w 9-86 Diff: 2

87) CH3 CH2CO2 H and CH3CH2 CH2 CO2H

88) D
ID: oc6w 9-88 Diff: 3

89) D
ID: oc6w 9-89 Diff: 3

90) C
ID: oc6w 9-90 Diff: 3

91) 1) NaNH2 , 2) bromoethane, 3) Na / NH3

92) C
ID: oc6w 9-92 Diff: 3

93) 3-methyl-2-hepten-5-yne
ID: oc6w 9-93 Diff: 3

21

Answer Key Testname: UNTITLED2

94) 1) Br2

2) CH3 CCNa

3) Na / NH3

ID: oc6w 9-94 Diff: 3

22