Chem 210

Training Set II

Organic Chemistry: Chem 210

Training Set II
The questions are arranged approximately in the order of the coverage of material in the lecture. This set covers the material of the second exam.

Notes: I. 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)

OH
Absolute stereochemistry on one center, unspecified stereochemistry on the other

II. Abbreviations: Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Pe = pentyl, Ph = phenyl (i.e. benzene as a substituent), AcO = acetate (H3CCOO).

1. The following molecule is fluorometholone, a steroidal anti-inflammatory agent. How many stereogenic centers does it contain?
O HO H 3C F O CH3 H 3C H fluorometholone H CH3 OH

a) 5

b) 6

c) 7

d) 8

e) 9

f) 10

g) 11

2. How many chiral carbons are there in reserpine (an antipsychotic drug)?
N O N H O O O O O O O O reserpine

a) 9

b) 8

c) 7

d) 6

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Chem 210

Training Set II

3. Which structure is different from the others?

a) H NC Br CH 3 H3 C NC b) Br H H H 3C c) CN Br Br NC d) CH 3 H Br H3 C e) H CN

4-7. Designate the absolute configuration (R/S) for each of the compounds below:
O F 3C H NHCH3

4.
(prozac)
O HC C Br CH2 CH3

a) R

b) S

5.

a) R

b) S

6.

OH NH2

a) R

b) S

CH3
2

7.
H H 3C

a) 2R, 4S c) 2S, 4S

b) 2S, 4R d) 2R, 4R

CH3

8. What is the absolute stereochemistry designation for the following compound?

O HO 1 OH OH

a) 2S, 3S

b) 2S, 3R

c) 2R, 3S

d) 2R, 3R
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Chem 210

Training Set II

9. What is the absolute configuration of the following molecules? (NS = the molecule has no stereogenic center) Note: For the purpose of this question only, the order of stereocenters is not specified; i.e. R, S = S, R.
Cl Cl HO I O II H2C N O O III Cl IV CH NH O Br F F Br

a) b) c) d) e) f) g) h) i) j)

I R R R R R S S S S S

II R, S R, R S, S R, S R, S R, S R, R S, S R, S R, S

III R S R R NS S S R R NS

IV NS R, R S, S R, S NS R, S R, R S, S R, S NS

10. Which of the structures below are chiral?

H O H CH 2OH CH 3 O O CH 3 O A Cl Cl H CH2 OH B H H H CH 2OH CH 2OH CH 3 CH3 C H 3C O D CH 3

a) A, B

b) B, C c) B, D

d) A, C

e) A, D

f) C, D

11. At least one of the compounds in question 10 is a meso compound. Choose one which meets this definition. a) A b) B c) C d) D e) E

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Chem 210

Training Set II

12. Which of the following molecules is (are) chiral?

Cl C H I H Br II CH(CH3)2 III H3C H O H IV O V O VI O H H

H3C H

a) b) c) d) e)

I II III I and II III and V

f) III and VI g) II, IV, and VI h) I, III, and VI i) I, III, V, and VI j) I, II, III, and VI

13-15. What is the relationship between the molecules in the following pairs? (E = enantiomers, D = diastereomers, I = identical) 13. a) E b) D c) I
OH H O OH OH OH OH and HO OH OH OH OH O H

14. a) E

b) D

c) I
CO 2H H Cl H CHO Cl and Cl Cl H CO2 H CHO H

15. a) E

b) D
Br

c) I
Br and O O Br O O Br

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Chem 210

Training Set II

16. What is the relationship between the molecules in the following pairs? (E = enantiomers, D = diastereomers, I = identical)
OH COOH Cl Cl H H CH 3 OH CH 3 and OH H H3 C Cl CH3 H and Cl COOH OH

a) b) c) d) e)

A E E D I I

B E D E D I

f) g) h) i)

A D I D E

B D E I I

17. How are the following compounds related?

a) diastereomers

b) enantiomers

c) meso compounds

d) identical

18. The following compounds differ by

a) their chemical and physical properties. b) nothing. c) the direction in which they rotate plane of polarized light. d) their interactions with achiral molecules.

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Chem 210

Training Set II

19-22. For each of the pairs of molecules shown below, decide whether they are: a) non-superimposable mirror images b) diastereomers c) identical molecules. 19.
H3C H H3C H

20. H3C H H3C H

21. H3C C C C H H H CH3 H3C C C C CH3 H

22. Frozen (non-rotating) gauche butane and its mirror image.

23. Transition state 2 is structurally most like

a) intermediate 1 b) transition state 3 c) intermediate 2 d) product

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Chem 210

Training Set II

24. Consider the following energy diagram for a unimolecular reaction. Which of the following statements is correct? G TS1 B TS2

C reaction progress

a) The overall reaction is endergonic, and the first step (AB) is slower than the second step. b) The overall reaction is exergonic and the intermediate is more stable than the second transition state (TS2). c) According to the Hammond postulate both transition states (TS1 and TS2) resemble the intermediate, and the intermediate is equally likely to go forward (BC) and backward (BA). d) The reaction is endergonic and the second step (BC) is the rate-limiting step. e) The first step (AB) is endergonic, and therefore, TS1 must resemble A. f) The second step (BC) is exergonic, and therefore, TS2 must resemble C. 25. For the following two reactions, which is true?

a) Reaction A is faster and less exergonic than B. b) Reaction B is faster and more exergonic than A. c) Reaction A is faster and less endergonic than B. d) Reaction B is faster and more endergonic than A.

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Chem 210

Training Set II

26. Consider the following four addition reactions of H-X to ethylene. Assume that the homolytic bond strength of the bond is 62 kcal/mol, and that S for all reactions is 40 cal/(Kmol). Which of these reactions will be the least exergonic at 300 K? (You may assume that all tabulated data can be used at 300 K, and that the C-H bond strength is unaffected by a substituent on the adjacent carbon.) a) b) c) d) H2C=CH2 H2C=CH2 H2C=CH2 H2C=CH2 + H-Cl H3C-CH2-Cl + H-Br H3C-CH2-Br + H-OH H3C-CH2-OH + H-I H3C-CH2-I

27. In a radical chain reaction, the following reaction would be best described as a

a) termination step b) initiation step c) propagation step d) substitution step 28. Calculate H of the following substitution reaction:

a) -5 kcal/mol

b) -14 kcal/mol

c) 14 kcal/mol

d) 19 kcal/mol

29. Using bond dissociation energies, which of the following products would result from this reaction? Assume that the bond dissociation energy of a C-H bond in chloromethane is the same as in methane.

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Chem 210

Training Set II

30. Which one of the following is the worst nucleophile? a) 2,3-dimethyl-2-butene b) CH3OH c) CH3 d) BF3

31. Consider the following reaction. What is the critical LUMO in the reactants?

a) a nonbonding lone pair on nitrogen b) a C-H antibonding orbital (*) c) a N-H bonding orbital () d) a C-I antibonding orbital (*) 32. The following reaction is an example of

a) nucleophile/electrophile combination. b) a homolytic bond cleavage. c) a two step reaction. d) an exergonic reaction. 33. How many degrees of unsaturation are in the following compound?
OH O OH

a) 6

b) 7

c) 10

d) 11

34. What is the correct IUPAC name for the following compound?

a) (2E, 4Z) 2,5-dichloro-4-isopropyl-2,4-heptadiene b) (2Z, 4E) 2,5-dichloro-4-isopropyl-2,4-heptadiene c) (2E, 4E) 2,5-dichloro-4-isopropyl-2,4-heptadiene d) (2Z, 4Z) 2,5-dichloro-4-isopropyl-2,4-heptadiene
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Chem 210

Training Set II

35. Assign double bond configurations to the following alkene:

COOH NC H2N H2C CN CH2OH

a) E

b) Z

c) E,Z

d) E,E

e) Z,Z

36. What are the correct stereochemical designations for the structure below? a) b) c) d) E, E Z, Z E, Z No stereoisomers are possible

Cl CO2H

37. Which of the following alkenes has the most negative heat of hydrogenation?

38. Select the best definition of hyperconjugation: a) transfer of hydrogen from a C-H bond to the system b) participation of an H atom on a terminal carbon in the electron sharing c) delocalization of electron density from a properly oriented bonds into the system d) sharing of electron density in a carbocation with properly oriented single and double bonds e) transfer of electron density from the HOMO to a * orbital f) interaction between a properly aligned lone electron pair with the empty system.

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Chem 210

Training Set II

39-41. The heats of combustion (to CO2 and H2O) of some C5 compounds are given below. Z-2-pentene 3369 kJ/mol E-2-pentene 3365 kJ/mol 1-pentene 3376 kJ/mol pentane 3536 kJ/mol The heat of formation of CO2 is 393 kJ/mol and that of H2O is 285 kJ/mol. Based on these data (under the standard conditions) answer the following questions: 39. What is the heat of hydrogenation of 1-pentene (in kJ/mol)? a) 160 b) 125 c) 98 d) +98

40. What is the steric strain energy of Z-2-pentene (in kJ/mol)? a) 167 b) 7 c) 4 d) 0

41. What is Hrx for the following equilibrium (in kJ/mol)? 1-pentene E-2-pentene a) 11 b) 7 c) 4 d) +11

42. Which of the following is not a possible product of HBr addition?

43. Which of the following is the most likely to undergo a favorable hydride shift?

a)

b)

c)

d)

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Chem 210

Training Set II

44. Which energy diagram best represents the given reaction?

45. Which reaction will be the fastest?

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Chem 210

Training Set II

46. Consider the following reaction which proceeds without carbocation rearrangement. Which statement(s) is (are) true concerning the mechanism of the reaction?
Br + HBr Br A B
+

Compound 2-methyl-2-butene HBr 2-bromo-2-methylbutane 2-bromo-3-methylbutane

Hfo (kcal/mol) -10.1 -8.7 -34.0 -30.5

a) The reaction proceeds without a discernible intermediate for either pathway. b) The first transition state for the path leading to A is lower in energy than the first transition state for the path leading to product B. c) The reaction energy profiles for the formation of products A and B are superimposable. d) The products are more stable than the starting materials. e) The first transition states reflect the intermediate stabilities, whereas the second transition states reflect the product stabilities. f) The second transition state for the path leading to product A is lower in energy than the second transition state for the path leading to product B. g) Both a and d are true. h) Both b and e are true. i) Both e and f are true. j) Statements b, d, and f are true. 47. Consider the following rearrangement. Select the structure of the intermediate that has correct mechanistic arrows accounting properly for the transformation.
H+ H2O

-H3O+

H a) b)

H2O c)

H2O H

H d) H H2O e) f)

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Chem 210

Training Set II

48. Which of the following mechanisms is most applicable to the reaction shown?

49. List the following carbocations in order of decreasing stabilization energies (starting with the most stabilized).

a) II, III, I, IV

b) III, IV, II, I

c) III, IV, I, II

d) I, II, IV, III

50. Protonation of 1,2-butadiene gives carbocation A, and protonation of 2-butyne yields carbocation B. In both cases the most stable carbocation possible is produced, but no carbocation rearrangements take place (no hydride or alkyl shifts). Which of the two carbocations (A or B) is more stable and why? a) A is more stable because it is a terminal carbocation, according to Markovnikovs rule. b) A is more stable because it is stabilized by resonance and hyperconjugation. c) A is more stable because the cationic carbon is sp hybridized. d) B is more stable because it has two methyl groups that can provide extra stabilization by hyperconjugation and inductive effects. e) B is more stable because it is a secondary vinyl cation. f) B is more stable because the carbon utilizes its s atomic orbitals to form bonding hybrids, leaving the empty p orbital. g) A and B are equally stable, but they have different structures. h) A and B are equally stable because they have identical structures.
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Chem 210

Training Set II

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

Training Set II

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Chem 210

Training Set II

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Chem 210

Training Set II

Answer key: Set 2

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. D D B B A B C C D C A or C H C C A C A C C B A A C B A 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. C A A D D D D D D D A A C B C A D A D D J D A C B

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