Qoi0809 Oh Rx

QOI 0809 OH #2

Name___________________________________

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

1) Classify the reaction below as an oxidation, a reduction, or neither.

(CH3)2CHCH2OH → (CH3)2CHCHO

A) oxidation B) reduction C) neither

1)


PhCO2H → PhCH2OH


2)


cis-pent-2-ene → pentane


3)

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

4) Provide the structure of the major organic product in the reaction below. 4)



7) Provide the structure of the major organic product in the reaction below.

(CH3)3CCH2CH2OH Na2Cr2O7

H2SO4→

7)


1



10) In the chromic acid oxidation of alcohols, the chromium is:

A) oxidized from Cr+3 to Cr+6.

B) oxidized from Cr+6 to Cr+3.

C) reduced from Cr+3 to Cr+6.

D) reduced from Cr+6 to Cr+3.

E) none of the above

10)


11) Chromic acid oxidations are believed to proceed through a chromate ester intermediate. In

the oxidation of propran-1-ol, provide the structure of this ester and give the mechanism

for its conversion to the intermediate aldehyde.

11)


(CH3)2CHCH2OH Na

12)


14) Show the most efficient use of the Williamson ether synthesis to prepare

CH3CH2CH2OCH(CH3)2.

14)


15) The Williamson ether synthesis proceeds via an __________ mechanism.

A) E1

B) SN1

C) SN2

D) E2


15)


16) The enzyme, alcohol dehydrogenase, which is produced by the liver, converts ethanol to

__________, a normal body metabolite.

16)

2

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

17) Poisonings by methanol and ethylene glycol are relatively common. How are these poisonings treated

clinically?


CH3CH2CH(CH3)CH2CO2CH3 1. LiAlH4

2. H3O+→


19) Which of the following reagents can be used to convert cyclopentanol to cyclopentane?

A) TsCl, pyridine followed by LiAlH4

B) Na2Cr2O7, H2SO4

C) NaBH4 followed by H3O+

D) H2SO4, heat followed by H2, Pt

E) both A and D

19)


20) Draw the tosylate ion and explain why it is a particularly good leaving group.


21) Which of the following alcohols will give a positive chromic acid test?

A) tert-butanol

B) cyclohexanol

C) pentan-3-ol

D) both A and B

E) both B and C

21)


22) Why are alcohols unreactive toward nucleophilic substitution reactions?

23) How can the electrophilicity of alcohols be increased? Suggest several specific ways.


PhCH2CH2OH 1. TsC1, pyridine

2. NaCN, acetone→


3


26) When (R)-butan-2-ol is treated with TsCl in pyridine, the product formed is:

A) an achial compound.

B) a single enantiomer.

C) a racemic mixture.

D) a mixture of diastereomers.

E) none of the above.

26)


27) Predict the major product of the reaction below and provide a stepwise mechanism which

accounts for its formation.

(CH3)3CCH2OH + HBr →

27)


28) Predict the major product of the reaction below and provide a stepwise mechanism which accounts for its

formation.

CH3(CH2)6CH2OH + HBr →

29) It is necessary to add ZnCl2 to promote the reaction of HCl with some alcohols while these same alcohols react

with HBr quite readily. Explain.


30) Which of the following alcohols will react most rapidly with the Lucas reagent (HCl, ZnCl2)?

A) CH3CH2CH2CH2OH B) (CH3)3COH

C) CH3CH(OH)CH2CH3 D) (CH3)2CHCH2OH

30)




4



(CH3)2CHCH2OH PBr3

34)


PhCH2(OH)CH3 SOCl2

35)


36) Which set of reagents will best convert 2,2-dimethylpropan-1-ol (neopentyl alcohol) to

4,4-dimethylpentan-2-ol?

A) 1. SOCl2

2. Mg

3. CH3CHO

4. H3O+

B) 1. HCl, ZnCl2

2. Mg

3. CH3CHO

4. H3O+

C) 1. HCl, ZnCl2

2. Mg

3. CH2O

4. H3O+

D) 1. HCl

2. Mg

3. CH3CHO

4. H3O+

36)


37) Which undergoes dehydration using concentrated H2SO4 faster, cyclopentanol or 1-methylcyclopentanol?

Explain briefly.


38) Which of the following alcohols undergoes dehydration upon heating with concentrated H2SO4

without carbocation rearrangement?

A) 3-methylpentan-3-ol

B) 2-methyl-2-phenylpropan-1-ol

C) 3,3-dimethylpentan-2-ol

D) 2-methylhexan-3-ol

E) both A and B

38)




40) What is Zaitsev's rule?

5




42) Dimethyl ether (CH3OCH3) can be prepared by heating methanol in concentrated H2SO4. Provide a detailed,

stepwise mechanism for this process.

43) When an alcohol is heated in concentrated H2SO4, dehydration to produce both alkenes and ethers is possible.

Which process is more favored by higher reaction temperatures and why?

44) Provide a detailed, stepwise mechanism for the reaction below.

45) What alkene, which contains no oxygen atoms and a single CC, will give CH3CO(CH2)4CHO upon treatment

with OsO4 followed by cleavage with periodic acid?


46) The reaction of CH3CH2MgBr with CH3COCH2CH3 gives:

A) an achiral product.

B) the racemate of a chiral product.

C) a single enantiomer.

D) a mixture of diastereomers.


46)


47) Draw the products formed in the Fischer esterification reaction between acetic acid

(CH3CO2H) and cyclohexanol.

47)


48) Draw the structure of dimethyl sulfate, and provide a mechanism for the reaction of this compound with

sodium benzoate (PhCO2Na).

49) Nitroglycerine is formed by the reaction of glycerine (propane-1,2,3-triol) and nitric acid. Provide the structure

of nitroglycerine.

50) What series of synthetic steps could be used to prepare 1-bromopentane from 1-bromopropane?

6

51) What series of synthetic steps could be used to prepare 1-methylcyclohexanol from cyclohexene?

52) What series of synthetic steps could be used to prepare hexan-3-ol from propan-1-ol?

53) What series of synthetic steps could be used to prepare (CH3)2CHCHO from (CH3)3CH?

54) What series of synthetic steps could be used to prepare PhCH(OH)CH2CH3 from PhCH2OH?

55) What series of synthetic steps could be used to carry out the transformation shown below?







61) Which of the following reagents is not typically viewed as an oxidizing agent?

A) Cl2 B) O2 C) KMnO4 D) H2O2 E) KCl

61)

7

62) Which of the following reagents is the best choice for oxidizing a primary alcohol to an aldehyde?

A) Na2Cr2O7, H2SO4

B) H2CrO4

C) KMnO4

D) pyridinium chlorochromate

E) LiAlH4

62)


63) Name the product which results when 1-methylcyclohexanol is treated with PCC.

64) Describe the composition of the Jones reagent.


65) Which of the following catalysts is commonly used in industry to dehydrogenate alcohols?

A) CuO B) NaBH4 C) (CH3)2S D) Na E) Zn

65)

66) What compound is produced when (R)-pentan-2-ol is treated with TsCl followed by NaI?

A) sodium (R)-pent-3-oxide

B) (S)-2-iodopentane

C) sodium (S)-pent-2-oxide

D) (R)-2-iodopentane


66)


67) Provide the structure of the major organic product which results when ethyl tosylate is

reacted with potassium t-butoxide.

67)


68) Through what basic mechanism is 1-methylcyclohexanol converted to

1-bromo-1-methylcyclohexane upon treatment with HBr?

A) SN2

B) E2

C) SN1

D) E1

E) radical chain

68)

69) What compound results when 1-butanol is treated with P/I2?

A) CH3CH2CH2CH2I

B) CH3CH2CH2CH2PI2

C) CH3CH2CH2CH2OP(OH)2

D) racemic CH3CH2CHICH3

E) Primary alcohols don't react with P/I2.

69)

8

70) What class of organic compound is the major product of the acid catalyzed reaction of an alcohol

with a carboxylic acid?

A) nitrile

B) sulfonate ester

C) ester

D) thiol

E) ether

70)


71) Provide the major organic product of the following reaction. 71)




75) Provide the reagents necessary to carry out the multistep synthesis shown below. 75)

9





80) What type of linkage bonds the individual nucleotides together in DNA? 80)

81) Provide the structure of the major organic product that results when 3-hexanol is treated

with sodium dichromate.

81)

82) Provide the structure of the major organic product that results when 1-octanol is treated

with pyridinium chlorochromate.

82)

83) Provide the name of the major organic product that results when cyclopentanol is

subjected to the following sequence of reactions: 1. TsCl, pyridine; 2. LiAlH4.

83)

84) Provide the structure of the major organic product that results when 4-methyl-1-pentanol

is treated with PBr3.

84)

85) Provide the name of the major organic product that results when

(R)-2-methyl-3-pentanol is heated with conc. H2SO4..

85)

10

86) Provide the name of the major organic product that results when cyclopentanol is treated

with acetyl chloride.

86)

87) Provide the name of the major organic product that results when cyclopentanol is

subjected to the following sequence of reactions: 1. NaH; 2. CH3CH2Br.

87)


trans-4-methylcyclohexanol is treated with thinoyl chloride.

88)


trans-4-methylcyclohexanol is treated with Lucas reagent.

89)

90) Provide the name of the major organic product that results when (R)-2-butyl tosylate is

treated with sodium iodide.

90)


91) Which of the following compounds has carbon in the highest oxidation state?

A) CH3CH2OH B) CH3C(OCH2CH3)3

C) CO2 D) CH3C(O)CH3

91)

92) Which of the following oxidants will convert a primary alcohol to an aldehyde?

1) sodium dichromate /sulfuric acid 3) pyridinium chlorochromate

2) copper oxide 4) dimethylsulfoxide, oxalyl chloride

A) 2, 3, and 4

B) 1, 2, 3, and 4

C) 3

D) 3 and 4


92)

93) Which alcohol reacts most rapidly with the Lucas reagent?

A) isobutanol B) benzyl alcohol C) methanol D) 2-propanol

93)

94) Identify the sequence of reactions that successfully completes the following transformation.

A) 1) BH3 2) H2O2 / NaOH 3) P, I2

B) HI / hν

C) 1) HBr / hν 2) NaI, acetone

D) A and C

E) all of the above

94)

11


95) With close attention to stereochemistry, provide the major organic product for the reaction

shown below.

95)

96) Provide the necessary reagents for the following conversion. 96)

97) Predict the outcome of the following reaction. 97)

98) What reagents are necessary for the following conversion? 98)


99) Which energetic material is a nitrate ester?

A) TNT B) nitroglycerin C) nitromethane D) RDX

99)


100) Predict the outcome of the following sequence of reactions. 100)

12

Answer KeyTestname: UNTITLED4

1) AID: oc6w 11-1Diff: 1

2) BID: oc6w 11-2Diff: 1

3) BID: oc6w 11-3Diff: 1

4)

ID: oc6w 11-4Diff: 2

5)


6) No reaction. Tertiary alcohols are not oxidized by PCC.ID: oc6w 11-6Diff: 2

7) (CH3)3CCH2CO2H


8)


9)


10) DID: oc6w 11-10Diff: 1

13


11)


12) (CH3)2CHCH2O- Na+


13)


14) (CH3)2CHO-Na+ + CH3CH2CH2Br


15) CID: oc6w 11-15Diff: 1

16) acetic acidID: oc6w 11-16Diff: 2

17) The enzyme alcohol dehydrogenase converts these compounds to toxic substances in the body. If the patient receives

intravenous infusions of ethanol, then the ethanol swamps the enzyme and the potentially deadly alcohols pass from

the body unoxidized.ID: oc6w 11-17Diff: 3

18) CH3CH2CH(CH3)CH2CH2OH


19) EID: oc6w 11-19Diff: 2

20) Extensive resonance stabilization of this ion makes it a particularly good leaving group.


21) EID: oc6w 11-21Diff: 2

14


22) The hydroxide ion, a relatively strong base, is a very poor leaving group.ID: oc6w 11-22Diff: 2

23) The key is to convert the hydroxyl group into a better leaving group. Methods to do this include protonation,

conversion to the tosylate ester, and conversion to the halide.ID: oc6w 11-23Diff: 2

24) PhCH2CH2CN


25)


26) BID: oc6w 11-26Diff: 2

27)


28)


29) Cl- is a weaker nucleophile than is Br-. The Lewis acid ZnCl2 coordinates with the oxygen of the alcohol to increase its

electrophilicity and make it a better leaving group.ID: oc6w 11-29Diff: 2

30) BID: oc6w 11-30Diff: 2

15


31)


32)


33)


34) (CH3)2CHCH2Br


35) PhCH2CHClCH3ID: oc6w 11-35Diff: 1

36) AID: oc6w 11-36Diff: 2

37) 1-methylcyclopentanol; goes via the more stable 3° carbocationID: oc6w 11-37Diff: 2

38) AID: oc6w 11-38Diff: 2

39)


40) When the product distribution of a series of isomeric alkenes is governed by their thermodynamic stabilities, the most

substituted isomer will predominate.ID: oc6w 11-40Diff: 2

41)


16


42)


43) Elimination to produce alkenes is favored by higher temperatures. The △S for this process is more positive than is the

case for the ether formation. This results in a more favorable -T△S term, making △G for the elimination reaction more

negative.ID: oc6w 11-43Diff: 3

44)


45) 1-methylcyclohexeneID: oc6w 11-45Diff: 2

46) AID: oc6w 11-46Diff: 2

47)


17


48)


49)


50) 1. Mg, ether

2. ethylene oxide

3. HBr or PBr3ID: oc6w 11-50Diff: 2

51) 1. H2O, H+ or BH3; H2O2, -OH or Hg(OAc)2, H2O; NaBH4

2. Na2Cr2O7, H+ or PCC or KMnO4

3. CH3MgI

4. H3O+


52) 1. PCC

2. CH3CH2CH2MgBr

3. H3O+

or

1. HBr or PBr3

2. Mg, Et2O

3. CH3CH2CHO


53) 1. Br2, hν

2. NaOEt, heat

3. BH3

4. H2O2, -OH

5. PCCID: oc6w 11-53Diff: 3

54) 1. PCC

2. CH3CH2MgBr

3. H3O+


18


55) 1. PBr3 or HBr

2. Mg, ether

3. CH3CH2CHO

4. H3O+

5. PCC or Na2Cr2O7 or KMnO4ID: oc6w 11-55Diff: 2

56) 1. Hg(OAc)2, CH3CH2OH

2. NaBH4

or

1. BH3

2. H2O2, -OH

3. Na

4. CH3CH2I

Note: The hydration in the second option could be accomplished with H+, H2O or Hg(OAc)2, H2O as well.


57) 1. HBr, ROOR

2. NaCN

or

1. BH3

2. H2O2, -OH

3. HBr or PBr3

4. NaCNID: oc6w 11-57Diff: 2

58) 1. BH3

2. H2O2, -OH


59) 1. Cl2, hν

2. NaOEt, heat

3. BH3

4. H2O2, -OH

5. PCC

6. CH3MgBr

7. H2SO4, heat


60) 1. HBr

2. Mg, Et2O

3. D2O


19


61) EID: oc6w 11-61Diff: 2

62) DID: oc6w 11-62Diff: 2

63) No reaction occurs; Tertiary alcohols are resistant to mild oxidation conditions.ID: oc6w 11-63Diff: 2

64) Jones reagent is a dilute solution of chromic acid in acetone.ID: oc6w 11-64Diff: 2

65) AID: oc6w 11-65Diff: 2

66) BID: oc6w 11-66Diff: 2

67) CH3CH2OC(CH3)3ID: oc6w 11-67Diff: 2

68) CID: oc6w 11-68Diff: 2

69) AID: oc6w 11-69Diff: 1

70) CID: oc6w 11-70Diff: 1

71)


72)


20


73)


74)


75) 1. H2SO4, Δ

2. BH3·THF

3. H2O2, NaOH


76)


77)


78)


21


79)


80) phosphate esterID: oc6w 11-80Diff: 1

81) CH3CH2COCH2CH2CH3ID: oc6w 11-81Diff: 2

82) CH3(CH2)6CHO


83) cyclopentaneID: oc6w 11-83Diff: 2

84) (CH3)2CHCH2CH2CH2Br


85) 2-methyl-2-penteneID: oc6w 11-85Diff: 3

86) cyclopentyl acetateID: oc6w 11-86Diff: 3

87) ethoxycyclopentaneID: oc6w 11-87Diff: 2

88) cis-1-chloro-4-methylcyclohexaneID: oc6w 11-88Diff: 2

89) a mixture of trans- and cis-1-chloro-4-methylcyclohexanesID: oc6w 11-89Diff: 2

90) (S)-2-iodobutaneID: oc6w 11-90Diff: 2

91) CID: oc6w 11-91Diff: 2

22


92) AID: oc6w 11-92Diff: 3

93) BID: oc6w 11-93Diff: 2

94) DID: oc6w 11-94Diff: 3

95)


96) 1) TsCl, pyridine 2) LiAlD4ID: oc6w 11-96Diff: 3

97)


98) 1) Na2Cr2O7 / H2SO4 2) EtOH / acid catalyst


99) BID: oc6w 11-99Diff: 2

100)


23

Documents

Qoi0809 Oh Rx