Chem 210

Practice Exam 3C

Organic Chemistry: Chem 210

Practice Exam 3C There are 30 questions on this exam. Check that you have done all of the problems and filled in the first 30 bubbles on the scantron. Most questions are worth 4 points; there are several two-point questions clearly labeled in the text. The maximum score on this exam is 100 points. Instructions Answer sheet 1) On the scantron, you need to clearly fill: your name and your student number, section number: (it is 001) test form (white = test form A; yellow = test form B). 2) Use a #2 pencil Exam policy 1) No electronic devices of any kind, such as calculators, cell phones, or even more advanced digital watches, are allowed. Possession of such devices during the exam, whether in use or not, is grounds for awarding a zero on the exam. 2) Molecular models are allowed (no instruction pages are permitted, however). 3) There are some blank pages at the end of the test that can be used as scratch paper. 4) Relevant tables, including the periodic table, are attached at the end of this exam. 5) Numerical values given in one question apply only to that question, and should not be used in other questions, unless there is a specific instruction to do so. If necessary, the values from the provided tables should be used, even if they differ from values that you may remember from different sources. 6) The exam results are based strictly on scantrons marks. No extraneous information is used to adjust the scores. Mark your choices with extra care. 7) Feel free to take this copy of the exam with you. The answer key will be posted on the web after the exam (under "News"). Hints 1) As you read the question, underline or circle key words to highlight them for yourself. 2) Questions have only one correct answer, unless indicated otherwise. No partial credit will be given. 3) There is no penalty for guessing.

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Chem 210

Practice Exam 3C

Notes: I. When listing reagents, a slash (/) is used between reagents that are employed simultaneously, and a semicolon (;) is used between reagents that are employed in a stepwise fashion. II. The stereochemistry conventions are illustrated below:
Br

Br

Br

Br

OH
No stereochemistry shown (all stereoisomers possible)

OH
Absolute stereochemistry shown

OH
Relative stereochemistry shown (racemic mixture)

Absolute stereochemistry on one center, unspecified stereochemistry on the other

OH

III. Abbreviations: Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Pe = pentyl, Ph = phenyl (i.e. benzene as a substituent), AcO = acetate (H3CCOO), MCPBA = m-chloroperbenzoic acid., TosO = TsO = tosylate ************************************************************************************* 1. (4 pts) The following transformation is carried out in three steps (I - III). If the second step involves hydrogenation, what are the appropriate reagents for the first (I) step?
Br I II III HO OH OH OH

a) Br2/H2O c) H2SO4/H2O e) NaNH2/THF g) BH3THF; H2O2/NaOH

b) H2/Lindlar d) Hg(OAc)2/H2O; NaBH4 f) O3; Zn/AcOH h) KMnO4/OH

2. (4 pts) How many diols, including stereoisomers, are formed, in the following reaction?

Hg(OAc)2 (excess) H2O

a) 1 b) 2 c) 3 d) 4

NaBH4

e) 6

3. (4 pts) 2-Butyne is allowed to react with Li in NH3(liq). The obtained product is treated with Br2 in CCl4. Which of the following compounds is the end result of this sequence of reactions?

a) H H Br CH3 CH3 H H3C

b) Br H CH3 H3C H

c) Br H CH3 H3C H

d) Br H H Br H3C H3C

e) Br H H Br

Br

Br

Br

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Chem 210

Practice Exam 3C

4 5. Assume that only monochlorides are produced in the following reaction.

Cl2 light
4. (2 pts) Which chloride will be produced in the highest yield? a) b) c) d) 1-chloro-2-methylbutane 2-chloro-2-methylbutane 2-chloro-3-methylbutane 1-chloro-3-methylbutane

5. (2 pts) What fraction of the total would 2o chlorides be? a) 1/6 b) 7/9 c) 5/9 d) 5/21 e) 1/3

6. (4 pts.) Which of the following MO diagrams would best represent planar cyclooctatetraene?

a)

b)

c)

d)

e)

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Chem 210

Practice Exam 3C

7. (4 pts) How many stereoisomers of the product will form in this reaction?

CH3 O excess H2 Pd/C H2C C CH3

a) 1 b) 2 c) 3 d) 4 e) 6

8. (4 pts.) Assuming that all non-hydrogen atoms in the planar molecules shown below are sp2 hybridized, which molecules are antiaromatic?

O N
A

S N N
B

N N O N N
C
c) C d) D

S
D
e) D and E

a) A

b) B

9. (4 pts) Which of the following compounds is among the major products of the following reaction?

CH3 H

1. BH3/THF 2. H2O2, OH

a) CH3 OH OH H

b) CH3 H H OH

c) CH3 OH H H

d) H OH H CH3

e) CH3 H BH2 H

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Chem 210

Practice Exam 3C

10. (4 pts) Which of the following statements about electronic transitions in organic molecules is incorrect? a) Usually, n * transitions are of low intensity because the orbitals involved are perpendicular. b) Electronic transitions occur when incoming photons have energy that matches the energy gap between the orbitals involved. c) Absorption of UV or visible light generates a molecule in its excited electronic state. d) More conjugated systems have shorter max values than less conjugated systems. e) HOMO LUMO transitions are of the lowest energy relative to other electronic transitions in the same molecule. 11. (4 pts) What is the most likely product of the following reaction?
a) HO O KMnO4 H 3O+ O HO O O HO O d) OH H O e) O c) b) O H O O

12. (4 pts) Which set of reagents (in the correct order) would accomplish the following transformation?

CH3CH2CH2

II

CH3CH2CH2 H

CH3 H

I a) b) c) d) e) NaNH2/NH3(l); CH3I, KOH/THF; CH3I H2/Lindlar catalyst BH3-THF; H2O2/NaOH NaNH2/THF; CH3CH2I

II H2/Lindlar catalyst H2/Pd/C NaNH2/THF; CH3I H2SO4 H2/Lindlar

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Chem 210

Practice Exam 3C

13. (4 pts) A reaction of propyne with Hg2+ is run in methanol (CH3OH) in the absence of water, but in the presence of a strong acid (H+) with a non-nucleophilic counterion. If this reaction follows a typical mechanism of electrophilic addition, what would be the expected product?

a) O OCH3

b) OCH3 OCH3 CH3O

c) OCH3

d) OCH3 O

e) OCH3 OCH3

14. (4 pts.) Which of the following reactions would not yield at least one ketone? a) ozonolysis (followed by reductive workup with Zn/H+) of mono-substituted alkene b) oxidative cleavage of a trisubstituted cyclic alkene c) oxymercuration/demercuration of terminal alkyne d) hydroboration of an internal alkyne, followed by H2O2/NaOH e) periodate oxidation of a tertiary 1,2-diol 15. (4 pts) If the molecule shown below is treated with ozone followed by zinc and acetic acid, what are the products formed?

O a) H

O H O O H H H

O O H H O H H O H O H O O O H O H O H CO2

b)

H O O O O

O H H O

c)

H O O H H O O O O O H H O O O H

CO2

d)

e)

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Chem 210

Practice Exam 3C

16. (4 pts) In the vinyl cation the positively-charged carbon is sp hybridized. Which statement about the hybridization type of the negatively-charged carbon in the vinyl carbanion is correct? a) The carbon is sp hybridized to help to stabilize the orbital with the lone pair. b) The carbon is sp hybridized to minimize repulsion between the bonding and nonbonding electrons. c) The carbon is sp2 hybridized to maximize s character in the orbital with the lone pair. d) The carbon is sp2 hybridized to minimize angle strain around the bond. e) The carbon is sp3 hybridized to maximize separation between all electrons. f) The carbon is sp3 hybridized to avoid antiaromaticity that would be present if it were planar. 17. (4 pts) Which of the molecules listed below can be synthesized from propyne using only one of the reactions discussed in Chem 210? Using a reagent in excess is considered as a one-step reaction.

Br Br

Br Br

Br

Br

O H

A
a) A and B b) C and D

C
c) A, B, and D

D
d) B, C, and D e) all

18-19. Radicals listed below are allowed to abstract hydrogen atoms from propane. a) Cl b) H3C c) H d) HO e) H3CS

18. (2 pts) Which radical will generate the largest ratio of 2-propyl to 1-propyl radicals? 19. (2 pts) Which radical will be least selective? 20-21. Fluorocyclohexane undergoes free-radical fluorination with F2. Consider only products containing two fluorine atoms. 20. (2 pts) How many constitutional isomers with two fluorines are present? a) 1 b) 2 c) 3 d) 4 e) 5 f) 6

21. (2 pts) How many meso compounds with two fluorines are present? a) 1 b) 2 c) 3 d) 4 e) 5 f) 6

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Chem 210

Practice Exam 3C

22-25. Some of the possible products of electrophilic addition of HCl to 1-phenyl-1,3butadiene are shown below (Z-isomers have been omitted). A B
Cl Cl HCl Cl Cl

Cl

Cl

D E 22. (2 pts) Which of the above chlorides is not likely to form at all?
a) A b) B c) C d) D e) E f) F

23. (2 pts) Which of the above chlorides is expected to be the major product under thermodynamic control? a) A b) B c) C d) D e) E f) F

24. (2 pts) Which products are 1,4 adducts? a) A and F b) B and E c) B and F d) C and F e) D and E

25. (2 pts) Which 1,2-adduct would be produced in the largest quantities under thermodynamic control? a) A b) B c) C d) D e) E f) F

26. (4 pts) Which of the following is not the product of a radical chain-reaction of 2-pentene with NBS?

Br Br Br a) b) c) d) Br

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Chem 210

Practice Exam 3C

27. (4 pts) Which is the most likely protonation site in the conjugated alkene shown below?
1 2 5 3 4

a) 1

b) 2

c) 3

d) 4

e) 5

28- 30 For questions 28-30 consider the retrosynthetic analysis for the target ketone shown below:

?
O HO OH

28. (4 pts) Based on the reactions covered so far in Chem 210, which of the following structures is not an immediate precursor to the target molecule? a) A b) B c) C d) D e) E

29. (4 pts) Which of the following pairings of a synthetic precursor (see above) with reagents will yield the target compound? a) A reacted with KMnO4/H+ c) C reacted with O3; Zn/AcOH e) E reacted with KMnO4/NaOH b) B reacted with O3 d) D reacted with H2/Lindlar catalyst

30. (4 pts) If the starting materials are limited to building blocks containing no more than 2 carbons, which precursor (see above) will be part of the shortest (fewest steps) synthesis? a) A b) B c) C d) D e) E

=========================================================================== End of the exam

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Chem 210

Practice Exam 3C

Total Strain Energies in Cycloalkanes ring size kJ/mol kcal/mol 115 27.6 3 110 26.4 4 27 6.5 5 0 0 6 26 6.3 7 40 8.6 8

Energy Costs for Interactions in Alkane Conformers Interaction kJ/mole kcal/mole H-H eclipsed 4.0 1.0 H-CH3 eclipsed 6.0 1.4 CH3-CH3 eclipsed 11.0 2.6 CH3-CH3 gauche 3.8 0.9

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Chem 210

Practice Exam 3C

Selectivity of halogen radicals (per H) 3o 2 5 1600 97000 2o 1 3.5 80 1100 1o 1 1 1 1

F Cl Br I

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Chem 210

Practice Exam 3C

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Chem 210

Practice Exam 3C

Answer key: 3C 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. E C C C (2 pts) E (2 pts) A B D D D A A C A E C E E (2 pts) D (2 pts) D (2 pts) B (2 pts) D (2 pts) F (2 pts) B (2 pts) F (2 pts) B A A C B

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