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QOI 0809 C=C Name___________________________________ ESSAY. Write your answer in the space provided or on a separate sheet of paper. 1) Draw the major organic product generated in the reaction below. Pay particular attention to regio - and stereochemical detail. 2) Draw the major organic product generated in the reaction below. Pay particular attention to regio - and stereochemical detail. 3) Draw the major organic product generated in the reaction below. Pay particular attention to regio - and stereochemical detail. 4) Draw the major organic product generated in the reaction below. Pay particular attention to regio - and stereochemical detail. 5) Draw the major organic product generated in the reaction below. Pay particular attention to regio - and stereochemical detail. 6) Draw the major organic product generated in the reaction below. Pay particular attention to regio - and stereochemical detail. 1

QOI 0809 C C - UAlgw3.ualg.pt/~abrigas/qoi0809_alkenes.pdf · QOI 0809 C=C Name_____ ESSAY. Write your answer in the space provided or on a separate sheet of paper. 1)Draw the major

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QOI 0809 C=C

Name___________________________________

ESSAY. Write your answer in the space provided or on a separate sheet of paper.

1) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

2) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

3) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

4) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

5) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

6) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

1

7) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

8) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

9) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

10) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

11) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

12) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

13) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

2

14) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

15) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

16) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

17) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

(Z)-3-hexene 1. BH3·THF

2. H2O2, -OH→

18) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

19) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

20) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

3

21) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

22) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

23) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

24) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

25) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

26) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

27) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

4

28) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

29) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

30) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

31) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

32) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and

stereochemical detail.

33) Humulene is a monocyclic terpene constituent of carnations. When 0.25 mol of humulene is hydrogenated in

the presence of platinum catalyst, 0.75 mol of H2 reacts with the humulene to produce a monocyclic

hydrocarbon of formula C15H30. What is the molecular formula of humulene?

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

34) Treatment of cyclopentene with peroxybenzoic acid __________.

A) gives the same product as treatment of cyclopentene with OsO4

B) results in oxidative cleavage of the ring to produce an acyclic compound

C) yields an equimolar mixture of enantiomeric epoxides

D) yields a meso epoxide

E) none of the above

34)

5

ESSAY. Write your answer in the space provided or on a separate sheet of paper.

35) Complete the following reaction and provide a detailed, step-by-step mechanism for the process.

36) Complete the following reaction and provide a detailed, step-by-step mechanism for the process.

37) Complete the following reaction and provide a detailed, step-by-step mechanism for the process.

38) Provide a detailed, step-by-step mechanism for the reaction shown below.

39) Provide a detailed, step-by-step mechanism for the reaction shown below.

40) When isobutylene [CH2C(CH3)2] is treated with BF3, polyisobutylene is formed. Provide a step-by-step

mechanism for this polymerization reaction.

41) Provide the reagents necessary to complete the following transformation.

42) Provide the reagents necessary to complete the following transformation.

6

43) Provide the reagents necessary to complete the following transformation.

44) Provide the reagents necessary to complete the following transformation.

45) Provide the reagents necessary to convert 3-methyl-2-butanol to 2-methyl-2-butanol.

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

46) Both (E)- and (Z)-hex-3-ene can be subjected to a hydroboration-oxidation sequence. How are the

products from these two reactions related to each other?

A) The products of the two isomers are not structurally related.

B) The products of the two isomers are related as constitutional isomers.

C) The (E)- and (Z)-isomers generate the same products in exactly the same amounts.

D) The products of the two isomers are related as diastereomers.

E) The (E)- and (Z)-isomers generate the same products but in differing amounts.

46)

47) Both (E)- and (Z)-hex-3-ene can be treated with D2 in the presence of a platinum catalyst. How

are the products from these two reactions related to each other?

A) The (E)- and (Z)-isomers generate the same products but in differing amounts.

B) The (E)- and (Z)-isomers generate the same products in exactly the same amounts.

C) The products of the two isomers are related as enantiomers.

D) The products of the two isomers are related as constitutional isomers.

E) The products of the two isomers are related as diastereomers.

47)

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.

48) Give the structure of the alkene which would yield the following products upon

ozonolysis-reduction.

CH3CH2CH2CH2CHO + CH2O

48)

49) Give the structure of the alkene which would yield the following products upon

ozonolysis-reduction.

CH3COCH3 + CH3CH2CHO

49)

7

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

50) Addition of Br2 to (E)-hex-3-ene produces __________.

A) a mixture of enantiomeric dibromides which is optically inactive

B) a meso dibromide

C) (E)-3,4-dibromo-3-hexene

D) (Z)-3,4-dibromo-3-hexene

E) a mixture of enantiomeric dibromides which is optically active

50)

ESSAY. Write your answer in the space provided or on a separate sheet of paper.

51) The following reaction is known to proceed by a free radical chain mechanism. Suggest a reasonable,

step-by-step mechanism for this reaction.

CH3CHCH2 + CHCl3 ROOR

CH3CH2CH2CCl3

52) Consider how the ICl bond is polarized and predict the product which results when this mixed halogen adds

to 1-methylcyclohexene.

53) β-Ocimene is a natural product with a pleasant odor. Based on the information below, deduce the structure of

β-ocimene.

54) Based on the relative stabilities of the intermediates involved, explain the basis for Markovinkov's rule in the

addition of hydrogen halides to alkenes.

55) Explain the regioselectivity observed in the radical addition of HBr to 2-methylpropene.

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.

56) The mechanism for the acid-catalyzed hydration of alkenes is simply the reverse of the

mechanism by which alcohols are dehydrated using concentrated acid. This is an

illustration of the principle of __________.

56)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

57) Which of the following is the best reaction sequence to use if one wants to accomplish a

Markovnikov addition of water to an alkene with minimal skeletal rearrangement?

A) water + dilute acid

B) oxymercuration-demercuration

C) hydroboration-oxidation

D) water + concentrated acid

E) none of the above

57)

8

ESSAY. Write your answer in the space provided or on a separate sheet of paper.

58) Draw the Lewis structure of dibromocarbene.

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

59) Which of the following additions to alkenes occur(s) specifically in an anti fashion?

A) addition of H2

B) addition of H2O in dilute acid

C) addition of Br2

D) hydroboration-oxidation

E) both A and B

59)

60) Which of the following additions to alkenes occur(s) specifically in an syn fashion?

A) addition of H2

B) dihydroxylation using OsO4, H2O2

C) hydroboration

D) addition of HCl

E) A, B, and C

60)

61) HBr can be added to an alkene in the presence of peroxides (ROOR). What function does the

peroxide serve in this reaction?

A) electrophile

B) acid catalyst

C) radical chain initiator

D) nucleophile

E) solvent

61)

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.

62) Name the major product which results when HBr is added to 3-ethyl-3-hexene. 62)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

63) Which of the following intermediates is thought to occur in the mechanism by which alkenes are

hydrated in the presence of acid?

A) free radical

B) carbene

C) carbocation

D) alkyne

E) carbanion

63)

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.

64) Name the major alcohol product which results when 3,3-dimethylbut-1-ene is treated

with dilute acid.

64)

9

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

65) What synthetic goal is achieved by subjecting an alkene to an oxymercuration-demercuration

sequence?

A) anti-Markovnikov addition of H2O wherein skeletal rearrangement is prevented

B) Markovnikov addition of H2O wherein skeletal rearrangement is promoted

C) anti-Markovnikov addition of H2O wherein skeletal rearrangement is promoted

D) syn-hydroxylation

E) Markovnikov addition of H2O wherein skeletal rearrangement is prevented

65)

66) When an alkene is subjected to treatment with Hg(OAc)2 in alcohol followed by reaction with

NaBH4, what new class of compound is formed?

A) syn diol B) alkane C) epoxide D) ether E) alkyne

66)

67) Which of the following compounds is (are) appropriate to promote the cationic polymerization of

isobutylene?

A) BF3

B) NaOH

C) H2SO4

D) ROOR

E) both H2SO4 and BF3

67)

ESSAY. Write your answer in the space provided or on a separate sheet of paper.

68) Why can methyl acrylate (H2CCHCO2CH3) be polymerized through anionic polymerization?

69) Name the compound PhCO3H and give its most common use as a reagent.

70) Provide the structure of the product which results when the alkene below is treated with O3 followed by

(CH3)2S.

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.

71) Provide the structure of the major organic product of the reaction below. 71)

10

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

73) Provide the structure of the major organic product of the reaction below. 73)

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

75) Provide the structure of the major organic product of the reaction below. 75)

76) Provide the structure of the major organic product of the reaction below. 76)

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

11

78) Provide the structure of the major organic product of the reaction below. 78)

79) Provide the structure of the major organic product of the reaction below. 79)

80) Provide the structure of the major organic product of the reaction below. 80)

81) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

81)

82) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

82)

83) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

83)

12

84) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

84)

85) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

85)

86) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

86)

87) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

87)

88) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

88)

89) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

89)

13

90) Draw the major organic product generated in the reaction below. Pay particular attention

to regio- and stereochemical detail.

90)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

91) Which of the following alkenes will yield a meso dihalide when reacted with Br2/CCl4 at room

temperature?

A)

B)

C)

D)

E) both Band D

91)

92) Acid catalyzed hydration (H2SO4/water/△) of an unknown compound (A)with a chemical formula

C6H12, yielded a racemic mixture of product C6H13OH. Which, if any, of the following

compounds is/are possible structures for the initial compound (A)?

A) compounds 2 and 3

B) compound 2 only

C) compound 1 only

D) compounds 1 and 3

E) none of the above

92)

14

93) A reaction of an unknown alkene with MCPBA in dichloromethane followed by work-up with

H2O/H+ yielded, as the major product, a racemic mixture of (2S, 3S) and (2R,

3R)-3-methylpentan-2,3-diol. What is the specific structure of the alkene used in the reaction?

A) (E)-3-methylpent- 2-ene

B) 2-methylpent-2-ene

C) (Z)-3-methylpent-2-ene

D) 2,3-dimethylbut-2-ene

E) none of the above

93)

SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.

94) When 3,6-dimethylcyclohexene is reacted with dry gaseous HBr, one of the products is

1-bromo-1,4-dimethylcyclohexane. Provide a detailed step-by-step mechanism to

explain the formation of this product

94)

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

95) Treatment of 2-methylpropene with which of the following reaction conditions results in an

anti-Markovnikov addition product?

A) dry gaseous HBr with peroxides present

B) BH3-THF, followed by alkaline H2O2

C) aqueous Hg(OAc)2, followed by alkaline NaBH4

D) dilute H2SO4 and heat

E) both A and B

95)

15

96) An unknown compound with empirical formula C3H5 was treated with Br2/CCl4. The bromine

solution went from orangish/red to clear immediately at room temperature. Upon treatment with

O3 followed by work-up with dimethylsulfide the following products were identified. From the

information provided what is/are the most likely structure(s) for this unknown compound.

A)

B)

C)

D)

E) both A and D

96)

16

Answer KeyTestname: UNTITLED1

1)

ID: oc6w 8-1Diff: 3

2)

ID: oc6w 8-2Diff: 1

3)

ID: oc6w 8-3Diff: 1

4)

ID: oc6w 8-4Diff: 3

5)

ID: oc6w 8-5Diff: 2

6)

ID: oc6w 8-6Diff: 3

7)

ID: oc6w 8-7Diff: 2

17

Answer KeyTestname: UNTITLED1

8)

ID: oc6w 8-8Diff: 2

9)

ID: oc6w 8-9Diff: 2

10)

ID: oc6w 8-10Diff: 1

11)

ID: oc6w 8-11Diff: 3

12)

ID: oc6w 8-12Diff: 2

13)

ID: oc6w 8-13Diff: 2

14)

ID: oc6w 8-14Diff: 2

18

Answer KeyTestname: UNTITLED1

15)

ID: oc6w 8-15Diff: 3

16)

ID: oc6w 8-16Diff: 3

17)

ID: oc6w 8-17Diff: 3

18)

ID: oc6w 8-18Diff: 2

19)

ID: oc6w 8-19Diff: 1

20)

ID: oc6w 8-20Diff: 3

21)

ID: oc6w 8-21Diff: 3

22)

ID: oc6w 8-22Diff: 1

19

Answer KeyTestname: UNTITLED1

23)

ID: oc6w 8-23Diff: 3

24)

ID: oc6w 8-24Diff: 3

25)

ID: oc6w 8-25Diff: 3

26)

ID: oc6w 8-26Diff: 3

27)

ID: oc6w 8-27Diff: 2

28)

ID: oc6w 8-28Diff: 2

29)

ID: oc6w 8-29Diff: 3

20

Answer KeyTestname: UNTITLED1

30)

ID: oc6w 8-30Diff: 3

31)

ID: oc6w 8-31Diff: 2

32)

ID: oc6w 8-32Diff: 2

33) C15H24ID: oc6w 8-33Diff: 2

34) DID: oc6w 8-34Diff: 3

35)

ID: oc6w 8-35Diff: 1

36)

ID: oc6w 8-36Diff: 2

37)

ID: oc6w 8-37Diff: 2

21

Answer KeyTestname: UNTITLED1

38)

ID: oc6w 8-38Diff: 2

39)

ID: oc6w 8-39Diff: 3

40)

ID: oc6w 8-40Diff: 2

41) 1. Br2, hν

2. H2O, Δ

or

1. Br2, hν

2. NaOCH3, CH3OH

3. H3O+ or Hg(OAc)2, H2O; NaBH4ID: oc6w 8-41Diff: 3

42) 1. NaOCH3, CH3OH

2. OsO4, H2O2 or cold, dilute KMnO4, -OH

ID: oc6w 8-42Diff: 2

43) 1. NaOCH3, CH3OH

2. MCPBA or CH3CO3H

3. H3O+ or -OH

ID: oc6w 8-43Diff: 3

22

Answer KeyTestname: UNTITLED1

44) 1. Br2, hν

2. NaOCH3, CH3OH

3. CH2I2, Zn(Cu)

ID: oc6w 8-44Diff: 3

45) 1. conc. H2SO4

2. H3O+ or Hg(OAc)2, H2O

or

1. PBr3

2. NaOCH3, CH3OH

3. NaBH4ID: oc6w 8-45Diff: 2

46) CID: oc6w 8-46Diff: 2

47) EID: oc6w 8-47Diff: 2

48) CH3CH2CH2CH2CHCH2ID: oc6w 8-48Diff: 1

49) (CH3)2CCHCH2CH3ID: oc6w 8-49Diff: 1

50) BID: oc6w 8-50Diff: 2

51) ROOR → 2 RO·

RO· + HCCl3 → ROH + ·CCl3

Cl3C· + CH2CHCH3 → Cl3CCH2 CH·

CH3

Cl3CCH2 CH·

CH3 + HCCl3 → Cl3CCH2CH2CH3 + ·CCl3

ID: oc6w 8-51Diff: 3

52)

ID: oc6w 8-52Diff: 3

23

Answer KeyTestname: UNTITLED1

53)

ID: oc6w 8-53Diff: 2

54) The rate-determining step in this reaction is the production of a carbocation intermediate. Since this step is

endothermic, Hammond's postulate allows one to gauge the relative stabilites of the transition states by comparing the

relative stabilities of the carbocation intermediates. The reaction pathway which produces the more substituted

carbocation will thus occur more rapidly.ID: oc6w 8-54Diff: 2

55) The reaction proceeds via the addition of Br· to the alkene. Two competing pathways are possible, but the transition

state leading to the more substituted alkyl radical is lower in energy. This process ultimately makes the addition

anti-Markovnikov in nature.ID: oc6w 8-55Diff: 3

56) microscopic reversibilityID: oc6w 8-56Diff: 1

57) BID: oc6w 8-57Diff: 1

58)

ID: oc6w 8-58Diff: 3

59) CID: oc6w 8-59Diff: 1

60) EID: oc6w 8-60Diff: 1

61) CID: oc6w 8-61Diff: 2

62) 3-bromo-3-ethylhexaneID: oc6w 8-62Diff: 2

63) CID: oc6w 8-63Diff: 2

64) 2,3-dimethyl-2-butanolID: oc6w 8-64Diff: 2

65) EID: oc6w 8-65Diff: 2

24

Answer KeyTestname: UNTITLED1

66) DID: oc6w 8-66Diff: 2

67) EID: oc6w 8-67Diff: 2

68) The intermediate carbanion and the transition state leading to it are stabilized by the electron-withdrawing capacity of

the carbonyl group.ID: oc6w 8-68Diff: 2

69) peroxybenzoic acid; an oxidizing agent which converts alkenes to epoxidesID: oc6w 8-69Diff: 1

70)

ID: oc6w 8-70Diff: 3

71)

ID: oc6w 8-71Diff: 1

72)

ID: oc6w 8-72Diff: 2

25

Answer KeyTestname: UNTITLED1

73)

ID: oc6w 8-73Diff: 3

74)

ID: oc6w 8-74Diff: 3

75)

ID: oc6w 8-75Diff: 2

76)

ID: oc6w 8-76Diff: 2

77)

ID: oc6w 8-77Diff: 2

26

Answer KeyTestname: UNTITLED1

78)

ID: oc6w 8-78Diff: 3

79)

ID: oc6w 8-79Diff: 2

80)

ID: oc6w 8-80Diff: 3

81)

ID: oc6w 8-81Diff: 3

82)

ID: oc6w 8-82Diff: 3

27

Answer KeyTestname: UNTITLED1

83)

ID: oc6w 8-83Diff: 3

84)

ID: oc6w 8-84Diff: 3

85)

ID: oc6w 8-85Diff: 3

86)

ID: oc6w 8-86Diff: 3

87)

ID: oc6w 8-87Diff: 3

28

Answer KeyTestname: UNTITLED1

88)

ID: oc6w 8-88Diff: 3

89)

ID: oc6w 8-89Diff: 3

90)

ID: oc6w 8-90Diff: 3

91) BID: oc6w 8-91Diff: 2

92) EID: oc6w 8-92Diff: 2

93) CID: oc6w 8-93Diff: 3

94)

ID: oc6w 8-94Diff: 3

29

Answer KeyTestname: UNTITLED1

95) EID: oc6w 8-95Diff: 1

96) AID: oc6w 8-96Diff: 2

30