Chem 210

Practice Exam 4C

Organic Chemistry: Chem 210

Practice Exam 4C
There are 34 questions on this exam. Check that you have done all of the problems and filled in the first 34 bubbles on the scantron. Most questions are worth 4 points; there are several 1 and 2-point questions clearly labeled in the text. Instructions
Answer sheet 1) On the scantron, you need to clearly fill: your name and your student number, section number Section 001, 12:20 pm lecture Section 002, 3:35 pm lecture test form (white = test form A; yellow = test form B; blue = test form C, green = test form D). 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) You may not take the exam with you. You may copy your answers on the provided page and compare them with the answer key. 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. No partial credit will be given. 3) There is no penalty for guessing.

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Chem 210

Practice Exam 4C

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)

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

III. Abbreviations: Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Pe = pentyl, Ph = phenyl (i.e. benzene as a substituent), AcO = acetate (H3CCOO), MCPBA = mchloroperbenzoic acid., TosO = TsO = tosylate

1.

(4 pts) One can exchange 127I with 128I in some iodo compounds. When the reaction is run on optically active (S)-2-iodobutane, the rate of racemization (i.e. the rate of loss of optical activity) is found to be exactly twice the initial rate of exchange (128I for 127I). Which reaction mechanism is most consistent with this observation? NOTE: Optical rotation does not depend on the isotope present, i.e. (S)-2iodobutane with 127I has the same rotation as (S)-2-iodobutane with 128I.
127 128

CH3CH2CHCH3 S-2-Iodobutane

a) SN1 (free ions) 2.

b) SN2

c) E1

e) E2

(4 pts) Addition of Br2 to cis-2-hexene gives racemic products, even though attack of the bromide ion on the unsymmetrical bromonium ion intermediate is not equally likely at both carbons. The reasons for the racemic products are: a) b) c) d) e) f) The reaction is reversible, after a while both enantiomers are produced in equal amounts The product is a meso compound The bromonium ion formed has a plane of symmetry Two enantiomeric bromonium ions are formed in equal amounts The Br attack is equally likely from both sides of the bromonium ion Four different stereoisomers are formed, but all in equal amounts

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Chem 210

Practice Exam 4C

3.

(4 pts) Reaction of HBr with 3-bromocyclohexene (A) yields only trans-1,2dibromo-cyclohexane. Reaction of 3-methylcyclohexene (B) with HBr gives a mixture of cis- and trans-1-bromo-3-methylcyclohexane and cis- and trans-1bromo-2-methylcyclohexane. Which statement explains the reactivity differences between A and B? a) b) c) d) e) There is no difference in reactivity. In the case of A the 1,2 and 1,3 dibromo products cannot be distinguished. The reactions of A and B have totally different mechanisms: one is radical the other ionic. A bromonium ion formed in the case of A can be attacked only in the anti manner A has a chiral center and B has a plane of symmetry In the case of B, there is a hydride shift following the protonation

4.

(4 pts) What is the structure of the species formed by removing hydride from methane? a) pyramidal, carbon is sp3 hybridized b) planar, carbon is sp2 hybridized c) tetrahedral d) T-shaped, with angles between C-H bonds of 90 degrees (4 pts) Two samples, A and B, are isomers and have identical physical properties except for optical rotation. Sample A has []D = - 17 o. Sample B has []D = + 17o What must be true about A and B? a) b) c) d) e) f) A and B are diastereoisomers A and B have at least one chiral center each A and B are enantiomers A has R and B has S absolute configuration A and B are structurally unrelated A can be converted to B by an SN2 process

5.

6.

(4 pts) The best way to accomplish the following transformation

Br O CH2CH3

is to use the following conditions: a) b) c) d) CH3CH2O Na+ in ethanol CH3CH2OH and heat CH3CH2OH in water CH3CH2O Na+ in DMSO

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Chem 210

Practice Exam 4C

7.

(4 pts) For the following series of reactions, what is the absolute configuration of the chiral centers produced?
H3C C C CH3 H2 Lindlar's catalyst Br2 CCl4 Product(s)

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

2S, 3S 2R, 3R 2S, 3R 2R, 3S 50% (a) and 50% (b) 50% (c) and 50% (d) 25% (a), 25% (b), 25% (c) and 25% (d) a meso form and 50% (a) and (b) a meso form and 50% (c) and (d) only a meso form is produced

8.

(2 pts) Which series of reactions will achieve the following transformation? Br 1. 2. Cl a) b) c) d) e) f) g) h) i) 1. HBr Cl2 Cl2 HBr Cl2 NBS/h HCl HBr Br2 @ -40 o C 2. Cl2 HBr Br2 Cl2 NBS/h Cl2 HBr HCl HCl Cl

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Chem 210

Practice Exam 4C

9-12. The seven lowest energy molecular orbitals for ethylene (on the left) and formaldehyde (on the right) are shown below.

9. 10. 11. 12.

What is the HOMO for ethylene ? (2 pts) What is the LUMO for ethylene ? (2 pts) What is the HOMO for formaldehyde ? (2 pts) What is the LUMO for formaldehyde ? (2 pts)

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Chem 210

Practice Exam 4C

13.

(2 pts) Which of the following will show optical activity?

H H 3C H C CH3 A H 3C B CH 3 C H H Cl H3 C H Br D Br H CH 3

a) A and B

b) A and C

c) B and C

d) B and D

e) C and D

14. (4 pts) (1S, 2S)-1-Bromo-1-deutero-2-methylbutane is converted to 1,2-dibromo-1deutero-2-methylbutane in a two step process. What is the stereochemistry of the major product(s)? Note: D = 2H.
Br H D tBuOK tBuOH Br2 CCl4 Br D Br H

a. b. c. d. 15

(1S, 2R) (1R, 2S) (1S, 2S) (1R, 2R)

e. (1S, 2R) and (1R, 2S) f. (1S, 2R) and (1R, 2R) g. (1S, 2R) and (1S, 2S) h. (1S, 2S) and (1R, 2R)

(4 pts) Which of the listed molecules is the product of the following reaction?
1) O3

2) Zn/H3O+

H (a) OH OH (b) O (c) O O

O (d) O O O (e) HO OH (f) H O

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Chem 210

Practice Exam 4C

What reagents are necessary to carry out reaction 16-19 (2 pts each)? (a) OsO4/NaHSO3 (b) BH3/THF; H2O2/OH (e) NBS/CCl4/h (d) KMnO4/H3O+ (g) HBr/ether (h) O3; Zn/HOAc (j) BH3/THF; H2O2/OHPBr3
O

(c) Br2/H2O (f) Hg(OAc)2/H2O; NaBH4 (i) KMnO4/OH

16
O

OH

17
Br

Br

18
OH

19 20. (4 pts) What is the correct mechanism of reaction between formaldehyde and boron trifluoride?
O (a) H C + H BF3 H O C H BF3 BF3 H

O (b) H C + H BF3 H

O C

O (c) H C + H BF3 H

O C

BF3 H

O (d) H C + H BF3 H

O C H BF3

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Chem 210

Practice Exam 4C

21.

(4 pts) The major product of the following sequence of reactions is:

NBS, H2O DMSO NaOH CH3CH2OH

O (a) CH3 H OH (c) H H3C Br (b) H H3C OH (d) H H3C CH3 H CH3 H OH (e) H H3C (f) H3C

O H CH3 C C CH3

22.

(4 pts) The lowest energy conformation of (1S)(2R)-1-bromo-2methylcyclohexane is best represented by:

Br Br (a) (d)

Br Br (b) (e)

Br Br (c) (f)

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Chem 210

Practice Exam 4C

23.

(4 pts) Which of the following compounds is likely to form during the NBS bromination of 4-methylcyclopentene?

NBS h, CCl4 a) Br

b)

c) Br

Br d) Br e) f) Br Br

Br

24.

(4 pts) The major product of the following reaction is:

OH Br2 H2O ?

OH (a) Br OH (b) Br

OH OH (c) HO

Br OH

Br (d) HO OH (e)

H CH2Br (f)

CH2Br H

(g) (a) and (b)

(h) (c) and (d)

(i) (e) and (f)

(j) none of the above

25.

(2 pts) Which of the following compounds is (are) not aromatic:

a)
N

b)

c)
H H

d)

e)
Na

f) a and b

g) c and d

h) b and c

i) b and d
Page 9 of 17

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Chem 210

Practice Exam 4C

26.

(4 pts) For the following reaction given below: (R and S) OTos CH3CO2H OCH3 OCH3 O OCCH3

(A) I. What type of mechanism is most likely to be involved? II. What happens to the rate of the reaction if the concentration of (A) is doubled?
I. SN1 SN1 SN1 SN2 SN2 E1 E1 E2 E2 II. no change doubles quadruples doubles quadruples no change doubles no change doubles

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

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Chem 210

Practice Exam 4C

27.

(4 pts) What is the most plausible mechanism for the following reaction ?
Br CH3C C Na
+

CH3CHCH3

Br (a) CH3C C Na +
+

H CH2CHCH3

H2C CH CH3 + CH3C

+ NaBr CH

Br (b) CH3C C Na
+

+ CH3CHCH3

CH3C

CCH(CH3)2

+ NaBr

Br (c) CH3C C Na
+

+ CH3CHCH3

- NaBr

CH3CHCH3

CH3C CCH(CH3)2

(d) CH3C

Na

H H H

CH3 H Br

H2C CHCH3 + NaBr

+ CH3C CH

Br (e) CH3C C Na
+

CH3CHCH3

CH3C

CH

+ CH3CH CH2 + NaBr

Br (f) CH3C C Na
+

CH3CHCH3

Br CH3C CH Na CH3CHCH3
+

Br CH3CCH2 H3C CH CH3

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Chem 210

Practice Exam 4C

NOTE: The following statement corresponds to questions 28, 29, and 30.

Hydrocarbon A (C7H12) was treated with BH3 followed by H2O2/NaOH to provide B (C7H14O) as the only product. Reaction of B with TsCl/pyridine followed by KOH gives C (isomeric with A) in addition to other olefin(s). Treatment of C with ozone, followed by Zn/AcOH produces only the compound shown below:

H3C CHO
28.

CHO

What is the correct structure for A ? (4 pts)

(a)

(b)

(c)

(d)

(e)

(f)

(g)

29.

What is the correct structure for B ? (2 pts)

HO

OH (d)

(a)

OH (b) OH

(c)

(e)

HO

(f) OH

(g)

OH

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Chem 210

Practice Exam 4C

30.

What is the correct structure for C ? (2 pts)

(a)

(b)

(c)

(d)

(e)

(f)

(g)

31-34. (1 pts each) Questions 31-34 involve reactions of an alkyl bromide and two possible reagents. Which reaction in each pair will show the faster rate of disappearance (consumption) of the alkyl bromide?
a. (CH3)3B

31.

Br

b. (CH3)3N c. The reaction rates would be the same.

-

a. CH3O (assume protic solvent)

32.

H3C

Br

b. CH3S (assume protic solvent) c. The reaction rates would be the same.

a. EtOH in H2O

33.

Br

b. EtOH c. The reaction rates would be the same.

34.

CH3 Br CH3 +

a. CN b. HS

c. The reaction rates would be the same.

end of the exam

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Chem 210

Practice Exam 4C

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 4C

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 4C

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Chem 210

Practice Exam 4C

Key 4C 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 31 32 33 34

Answers B 4p D 4p C 4p B 4p C 4p B 4p E 2p F 4p B 4p A 2p B 2p A 2p B 4p E 4p; F 2p D 2p J 2p E 2p B 4p B 4p E 4p C 4p B 4p I 4p H 2p B 4p D 4p A 4p E 2p G 2p B 1p B 1p A 1p C 1p

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