Chem 210

Practice Exam 4B

Organic Chemistry: Chem 210

Practice Exam 4B
There are 28 questions on this exam including one spectral problem. Check that you have done all of the problems and filled in the first 28 bubbles on the scantron. The number of points per question are clearly labeled in the text. The maximum score on the exam is 100 points.

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 4B

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) The first transition state in the overall exergonic addition of HBr to propene resembles the intermediate (carbocation). Chose the best phrase to complete the following statement: The second transition state (for addition of Br to the carbocation) ....... a) b) c) d) e) f) resembles the final product resembles the 2-propyl cation resembles propene has all carbons almost entirely sp3 hybridized has much higher energy than the first transition state has both carbons of the former system sp2 hybridized

2. (4 pts) The alternative reaction pathways for radical chain reactions of Br2 with ethane may be represented as follows: (1) (2) CH3 CH3 CH3 CH3 + + Br2 Br2 CH3 CH2 Br + HBr 2 CH3 Br

Which statement is correct? a) b) c) d) e) f) reaction (1) is more likely because it is more endothermic reaction (2) is more likely because it is more endothermic reaction (1) is more likely because it is more exothermic reaction (2) is more likely because it is more exothermic reactions (1) and (2) are equally likely because they have almost identical Hrxn both reactions are unlikely, because they are too much uphill in energy
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Chem 210

Practice Exam 4B

3. (4 pts) What is the product of the following reaction?

CH3CH2CH2C

CCH3

H2O, H2SO4 HgSO4 OH

a)

CH3CH2CH2CHCH2CH3 CH3CH2CH2CH2CH2CH2OH O CH3CH2CH2CCH2CH3 O CH3CH2CH2CH2CCH3 c and d

b) c) d) e)

4. (4 pts) The main reasons for the following rearrangement are: Cl HCl CH3

a) the initially formed carbocation is secondary, and it rearranges to the more stable tertiary one by shift of an alkyl group b) the reaction converts one tertiary carbocation into another to relieve torsional strain c) the tertiary chloride is much more stable than a secondary one, because of hyperconjugation d) this is a radical chain reaction, controlled by relative bond strengths

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Chem 210

Practice Exam 4B

5. (4 pts) What is the main product of the following reaction?

OCH2CH3 1) O3 2) Zn/HOAc ?

OCH2CH3 a) O

CH3CH2O OH OH b) c) H

O H O

O d) H O OCH2CH3 (e) HO

O OH O

6. (4 pts) Rank the following in order of stability (lowest to highest):

A a) b) c) d) D<B<C<A D<C<B<A A<C<B<D D<B=C<A

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Chem 210

Practice Exam 4B

7. (4 pts) The mechanism for the following transformation is best presented by:
H H2O
+

H a)

H2O H

H b)

H2O H H

c)

H2O H

H d) H
+

H H2O

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Chem 210

Practice Exam 4B

8. (4 pts) Which one of the following mechanisms is the most likely for HBr addition to propene?
Br a) CH3CH CH2 H Br CH3CHCH3 + Br CH3CHCH3

b) CH3CH CH2

Br H Br CH3CHCH3 + Br CH3CHCH3

c)

Br CH3CH CH2 Br H CH3CHCH2 + H

+

Br CH3CHCH3

d)

Br CH3CH CH2 H Br CH3CH2CH2 + Br CH3CHCH3

e)

CH3CH CH2

H Br

CH3CHCH3

Br Br CH3CHCH3

9. (4 pts) For the following multistep synthesis, which set of reagents would be more likely to give the desired product?

CH3CH2CH2C

CH

(i)

(ii)

(iii)

OH OH CH3CH2CH2CH CHCH2CH3

a) (i) HBr, (ii) O3 followed by Zn/H+, (iii) Li/NH3 b) (i) NaNH2/NH3 followed by CH3CH2I (ii) Lindlars catalyst/H2 (iii) OsO4 followed by NaHSO3 c) (i) H2/Pd/C (1 equivalent), (ii) NaNH2/NH3 followed by CH3CH2Br, (iii) KMnO4/ OH/H2O d) (i) HgSO4/H2O/H2SO4, (ii) Lindlars catalyst/H2, (iii) OsO4 followed by NaHSO3

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Chem 210

Practice Exam 4B

10. (4 pts) For the cyclononatetraenyl system, which has the largest resonance stabilization?

a) the radical b) the cation c) the anion d) the radical anion

e) the dication f) the dianion g) the diradical h) the radical cation

11. (2 pts) A solution of compound A showed [] = 17o. Which of the following conclusions must be correct:

a) b) c) d) e) f)

Compound A contains at least one chiral center. Compound A cannot be a mixture of enantiomers. Compound A has S absolute configuration. Compound A is a diasteromer. A and its mirror image are not superimposable. A is a mixture of unequal amounts of two stereoisomers.

12. (4 pts) The radical chain chlorination of 2,4-dimethylpentane with Cl2 produces these monchlorinated compounds:

Cl

Cl Cl A B C

The ratio of A : B : C is:

a) 3 : 2 : 1 b) 6 : 1 : 1 c) 2 : 6 : 10

d) 10 : 4 : 7 e) 12 : 7 : 10 f) 6 : 5 : 3

g) 6 : 7 : 5 h) 2 : 7 : 10

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Chem 210

Practice Exam 4B

13 - 15. (4 pts each) Questions 13 15 refer to structures a d below:

H3 C H Cl (a) OH H CH 3 H 3C Cl H (b) H HO CH3 HO CH 3 CH 3 H H Cl (c) H 3C H HO (d) Cl H CH 3

13. (4 pts) Which of the above structures (a d) corresponds to (2S)(3R)-3chlorobutan-2-ol?

14. (4 pts) Which of the structures (a d) is identical to the structure below?:

Cl H3 C H CH 3 H OH

15. (4 pts) Which of the following statements about compounds a d is correct: a) b) c) d) a and c are enantiomers a and d are enantiomers a and d are diastereomers b and c are diastereomers

16 17. (4 pts each) Questions refer to C7H16 which has 9 constitutional isomers (not counting the stereoisomers). 16. (4 pts) How many isomers (total) of C7H16 have no secondary hydrogens? a) none d) three b) one e) four c) two f) five

17. (4 pts) How many constitutional isomers of C7H16 have stereoisomers? a) none d) three b) one e) four c) two f) five

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Chem 210

Practice Exam 4B

18. (4 pts) Give mechanistic symbols (SN1, SN2, E1, E2) that are the most consistent with the following statements: i) ii) iii) iv) v) These reaction mechanisms represent concerted processes. Methyl halides react with sodium ethoxide in ethanol only by this mechanism. These reaction mechanisms involve carbocation intermediates. The principal substitution product obtained by solvolysis of tert-butyl bromide in ethanol arises from this mechanism. These reaction mechanisms are most likely involved when the products have different carbon skeleton than starting material.

i a) b) c) d) e) f) g) h) SN2, E2 SN1, SN2 SN1, SN2 SN1, E1 all SN1, SN2 SN2, E2 SN2, E2

ii SN2 SN2 E2 E2 E2 SN2 SN2 E2

iii SN1, E2 SN1, E1 SN2, E2 SN1, E2 E1, E2 SN1, E1 SN1, E1 SN1, E1

iv SN1 SN1 E1 E1 SN2 E2 SN1 SN1

v SN1, E1 SN1, SN2 E1, E2 SN1, E1 E1, E2 E1, E2 SN1, E1 SN1, SN2

19. (2 pts) Order the following steroid structures according to theirmax values in hexane, from the lowest to the highest.
C 9H 19 C 8H 17 C 8H 17 C 9H19

AcO

AcO

AcO

AcO

a) A < B < C < D c) C < A < D < B e) D < A < B < C g) B < D < C < A

b) D < C < B < A d) B < D < A < C f) C < B < A < D h) A < C < D < B

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Chem 210

Practice Exam 4B

20. (4 pts) Selected bond angles for five hydrocarbons are shown below. Arrange these hydrocarbons according to their pKa values, from the lowest to the highest.
128o H 115o H H 117o H H H 108o H 180o H H H 120o

H H

109.5o

H H H

a) E<A<F<B<C<D b) D<A<B<C<E<F c) B<D<A<F<E<C d) F<D<C<B<A<E e) A<E<D<C<B<F

f) D<C<B<F<A<E g) F<E<C<B<A<D h)C<E<F<A<D<B i) E<A<B<C<D<F j) F<B<C<D<E<A

21 24. (2 pts each) Questions 21 - 24 should be answered based on the following information about naphthalene (A) and 2-methoxynaphthalene (B). The HOMOs and LUMOs of these two systems are shown below, where the size of the circle represents the size of the lobe of the corresponding atomic p orbital. The shadings represents signs of the wavefunction on a given atom (white = positive, gray = negative). The energies of the orbitals are given in eV (1 eV = 23.06 kcal/mol).
1 2 3 4 9 8 12 5 7 6 3 4 5 7 6 11 1 9 O 2 10

10

-0.40 eV

-0.45 eV

-8.84 eV

-8.60 eV

continued on the next page

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Chem 210

Practice Exam 4B

21. (2 pts) In nitration of A, what is the most likely position for the incoming nitro group? a) 1 d) 1 and 6 g) 1, 4, 6, and 9 b) 2 e) 2 and 7 h) 2, 3, 7, and 8 c) 5 f) 5 and 10

22. (2 pts) In a Friedel-Crafts reaction of B, what is the most likely position for the incoming acyl group? a) 1 f) 6 b) 2 g) 7 c) 3 h) 8 d) 4 i) 9 e) 5 j) 11

23. (2 pts) In the reaction with Br2/FeBr3 which of the substrates will be more reactive? a) b) c) d) A B A and B are equally reactive It cannot be determined based on the given data

24. (2 pts) Which of the two compounds will lose an electron more easily to yield the corresponding radical cation? a) b) c) d) A B A and B will equally lose electrons It cannot be determined based on the given data

25. (4 pts) Under the specified conditions, substrate X undergoes substitution and elimination reactions to give products A - D. A and B are stereoisomers, but not enantiomers. C and D are enantiomers. A is not an isomer of C. Which of the following could be the starting material X?
X H2O A+B+C+D

Br

Br

CH3

Br

CH3 Br CH3

H3C H I

H3C

H II III

CH3

H IV

H3C

a) I

b) II

c) III

d) IV
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Chem 210

Practice Exam 4B

26. (4 pts) Which of the two stereoisomers of 4-t-butylcyclohexyl iodide (127I) will undergo SN2 substitution with 128I faster, and why? H H I127 H H A B a. A will react faster because it is the more stable of the two isomers. b. A will react faster because it will yield a more stable product, and the transition state for both reactions is of the same energy. c. A will react faster because the 127I can depart unhindered. d. A will react faster because the approach of 128I from the bottom face in B is hindered by the axial hydrogens shown. e. B will react faster because it is the more stable of the two isomers. f. B will react faster because it is less stable than A, and the transition state for both reactions is of the same energy. g. B will react faster because it will yield the more stable product. h. B will react faster because the approach of 128I from the top face in A is hindered by the two 1,3-diaxial hydrogens shown. i. A and B will react with equal rates because the transition state for both reactions is the same. j. The relative rates of A and B cannot be determined, since one iodide replaces another iodide, and the chair flip will convert the stereoisomers. H I127 H

27. (4 pts) (Z)-2-Butene reacts with Br2/H2O. The resulting bromohydrin when treated with methoxide in methanol undergoes an intramolecular SN2 reaction. Taking into consideration the stereochemical consequences of the reaction mechanisms involved, chose the final product(s) of these transformations. O H H3C A a. b. c. d. e. A only B only C only Equal amounts of A and B Equal amounts of B and C CH3 H H3C H B f. g. h. i. j. O H CH3 H H3C C Equal amounts of A and C A major, B minor C major, A minor B major, C minor Equal amounts of A, B, and C O H CH3

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Chem 210

Practice Exam 4B

28. (4 pts) The following bimolecular elimination reaction (E2) is carried out with different halogen leaving groups. The percent yield of the two products (2-hexene and 1-hexene) for each leaving group is listed below.

X + CH3O-

Leaving group X=I X=Br X=Cl X=F

Conj. Acid pKa -10 -9 -7 3.2

%-Yield of 2-hexene 81% 72% 67% 30%

%-Yield of 1-hexene 19% 28% 33% 70%

Which of the following statements is (are) true concerning this series of E2 reactions? a. Based on the pKas of the conjugate acid, I is the best leaving group and F is the poorest leaving group. b. Based on these data, leaving groups are not important for E2 reactions. c. When I , Br , and Cl are used as leaving groups, Zaitsevs rule is followed. d. F is the strongest base (and therefore the poorest leaving group) and the transition state for reaction with fluoride as the leaving group has the least double bond character. e. Both a and b are true. f. Both a and c are true. g. Both c and d are true. h. Both a and d are true. i. a, c, and d are true.

end of the exam

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Chem 210

Practice Exam 4B

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 4B

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 4B

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Chem 210

Practice Exam 4B

Answer Key: 4B

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)

B C E B D A B E B C E E C B D B C G F E G A B B C F C I

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