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Seat No. ___________________________ Name ____________________________________ (please print and circle your last name)

CHEMISTRY 332

FINAL EXAM

December 14, 2005

I. (18 points)

II. (48 points)

III. (50 points)

IV. (40 points)

V. (26 points)

VI. (18 points)

TOTAL (200 points)

Total of best 5 quiz scores

Total of best 4 midterm scores

Total course points

Course grade

HAPPY HOLIDAYS!

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I. (18 pts) Nomenclature. Provide a correct name for 6 out of 7 of the following compounds (3 ptseach). Clearly cross out the one problem you do not wish to have graded.

A. H2C CHCOH

O

B. NHCCH3

O

C. CH

O

CH3O

D.S

(CH3)2CH

E. CC

O

CCH2CH3

F.O

H

H H

OCH3

CH2OH

HH

HOHO

HO

G. O

O

O

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II. (48 pts) Predict all major carbon-containing products of 12 out of 15 of the following reactions.Make certain to indicate stereochemistry where it is pertinent. “No reaction” is a possible answer.Clearly cross out the three problems you do not wish to have graded (4 pts each).

A. CH2COEtH2C

O1. NaOEt, EtOH

2. H3O+CHCCH3

O

cat. NaOEt, EtOH

B.

CH

OCH3

O

CH3CH2NH2NaBH3CN

H2C CHCH2Br

C. C C

H

CH2BrCH3

CH3 NaCN 1. LiAlH4

2. H2O

D. CH3 OCH(CH3)2

HNO3

H2SO4

1. HCl, Fe

2. NaOH

E.

O2N NH2NaNO2HCl

OHCH3

F.1. LiAlH4

2. H2OCH3CH2COEt

O1. LiN(i-Pr)2

2.H2C CHCH2Br

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G.

O

O OH

CH2OH

HHOCH2

HO

H

HIO4

(list all products and their ratio)

H.NaBH4

O OOO CH3

CH3

N

I.

N

1. NaNH22. H2O

CH3

CClO

J. COHSOCl2

OO2N

AlCl3

CH3

CH3

K.H2C CHCCH3

O

Ph3P C(CH3)2

L. ONaOH

1. Me2CuLi

2. H2O

CHO

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M.cat. H2SO4

Br1. Mg2. CO23. H3O+

EtOH

N.

OHPCC t-BuNH2

O.1. NaH H3O+

OCOEt

O

2. CH2Br

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III. (50 pts) Provide detailed step-by-step mechanisms for 5 out of 7 of the following reactions (10points each). Provide resonance structures for all intermediates and indicate equilibria where theyexist. Clearly cross out the two problems you do not wish to have graded.

A. (CH3)3C + BrCH2AlCl3 (CH3)3C CH2 + HBr

B.

N NBr OC(CH3)3

+ KBr+ KOC(CH3)3

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C. COEt COMecat. HCl+ MeOH + EtOH

O O

D.

O N-t-Bu

+ H2Ocat. HOAc+ t-BuNH2

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E.

O OCOEt

+ EtOH

O

1. NaOEt

2. mild H3O++ EtOCOEt

O

F.

OH

+ HBr

Br

+ H2O

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G. CNH2CH3

OBr2

NaOHNH2CH3 + CO2

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IV. (40 pts) Synthesis. Using as starting materials only benzene, organic compounds containing 4 orfewer carbons, and any necessary inorganic reagents, indicate how 4 out of 6 of the followingcompounds might be synthesized in the laboratory. Use only reactions expected to go in goodyield. Clearly cross out the two problems you do not wish to have graded.

A. CCH3

OO

B. CH C

CH3

CH3CH3O

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C. NHCH3CH2CH2 C

O

CH3

D. CH3O CCH2CH

O

CH2

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E. CH3 N N OH

F. CH3CCHCH2CH2C

O

CO2Et

O

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V. (26 pts) Miscellaneous.

A. (4 pts) Circle the most acidic compound and underline the least acidic compound.

CH2OHCOCH3

O

CH3CH2CH2COH

O

CH3OCCH2COCH3

O O

B. (4 pts) Circle the most basic compound and underline the least basic compound.

C NH2N 2NHN

C. (4 pts) Circle all compounds that will readily undergo cationic chain growth polymerization.

H2C CHCO2Me H2C CHOEt H2C CHPh H2C CHCH CH2

D. (4 pts) Circle all compounds that will react with NaBH4 to give an alcohol.

COEt

O

O

H2C CHCH2CH

O

MeO OMe

E. (4 pts) Circle all compounds that are readily reduced by LiAlH4.

CN CO O

OO

F. (6 pts) Identify the type of orbital symmetry controlled reaction given below usingappropriate TERMS AND NUMBERS. (Examples: electrocyclic ring closure, 4+2cycloaddition, 3,3-sigmatropic rearrangement, etc.). You do NOT need to identify anyadditional terms.

1. H2C CHOCH2CH CH2 H2C CHCH2CH2CH

O

2.

Me Me Me

H

Me

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VI. (18 pts) Carbohydrates

A. (8 pts)

1. Draw all possible 2-ketopentoses. Incorrect or duplicate structures cancel out correctstructures. (4 pts)

2. Circle all of the above 2-ketopentoses that are D sugars. (2 pts)

3. Draw the osazone that you expect to form from any one of the above 2-ketopentoses whenallowed to react with excess PhNHNH2. Show both the starting 2-ketopentose and theosazone product. (2 pts)

B. (5 pts)

1. Draw all possible 3-ketopentoses. Incorrect or duplicate structures cancel out correctstructures. (3 pts)

2. Circle all optically active 3-ketopentoses drawn above. (2 pts)

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C. (5 pts) Circle all of the following terms that correctly describe the following compound (NOTE:wrong answers will be subtracted from correct answers).

O

H H

O

H

HOOCH3

HO

HH

HCH2OH

optically inactive

aldose

ketose

pyranoside

reducing sugar

reactive towards Fehlings solution

furanoside

a monosaccharide

a D sugar

forms an optically inactive product upon reaction with H3O+

reactive towards Tollens reagent

an epimer of ß-methyl glucoside