Chem 210

Practice Exam 2C

Organic Chemistry: Chem 210

Practice Exam 2C There are 26 questions on this exam. Check that you have done all of the problems and filled in the first 26 bubbles on the scantron. Most questions are worth 4 points; there are a few 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 2C

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. (4 pts) During the early stages of chlorination of propane, the reaction mixture is composed mainly of equal molar amounts of propane and Cl2 (the products are still very minor components). The irradiation of the mixture constantly produces a small concentration of Cl radicals. Based on thermodynamic considerations (and neglecting statistical factors) which of the following reactions is most likely to occur under these conditions? a) Cl + CH3CH2CH3 HCl + (CH3)2HC b) Cl + CH3CH2CH3 HCl + CH3CH2H2C c) Cl + CH3CH2CH3 CH3CH2CH2Cl + H d) Cl + CH3CH2CH3 (CH3)2CHCl + e) Cl + Cl2 Cl2 + Cl H

2.

(4 pts) Which carbocation is the most stabilized?

a)

b)

c)

d)

e)

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Chem 210

Practice Exam 2C

3.

(4 pts) A racemic mixture of two enantiomers is allowed to react with a non-chiral reagent in such a way that a new stereogenic center is created in the product in the position adjacent to the existing stereogenic center. The new stereogenic center does not match any of the existing stereogenic centers in the starting enantiomers. From the stereochemical point of view, what is the most likely composition of the mixture of isomeric products of this transformation? a) b) c) d) e) two enantiomers in equal amounts two diastereomers in equal amounts two diastereomers in non-equal amounts four stereoisomers, in different amount each four stereoisomers, with enantiomeric pairs in equal amounts, but diastereomeric pairs in non-equal amounts f) four stereoisomers with diastereomeric pairs in equal amounts (4 pts) Which of the following structures represents the lowest-energy form of (1S, 2S, 4R)trimethyl-cyclohexane?

4.

a)

b)

c)

d)

e)

5.

(4 pts) Consider a positively charged C2H3 species in which the positively charged carbon is sp hybridized, the uncharged carbon is sp2 hybridized and an empty p orbital is perpendicular to the system. What it the best description of this cation? a) vinyl b) allenyl c) alkyl d) allyl e) hyperconjugated

6.

(4 pts) There are five isomers of hexane. How many different meso compounds exist for dibromohexanes (C6H12Br2)? a) 1 b) 2 c) 3 d) 4 e) 5 f) 6

7.

(4 pts) E-2-pentene reacts with one equivalent of HBr. If there are no carbocation rearrangements, how many different isomeric products (including stereoisomers) will form? a) 1 b) 2 c) 3 d) 4 e) 5 f) 6

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Chem 210

Practice Exam 2C

8.

(4 pts) The structural formula of cocaine is shown below. How many stereogenic carbon atoms are there in this molecule?
CH3 N O OCH3

O O

a) 1

b) 2

c) 3

d) 4

e) 5

f) 6

9.

(4 pts) Consider the addition of HBr to 3,3-dimethylbut-1-ene, shown below. What is the best mechanistic explanation for the formation of the observed product?

CH3 CH3 C CH CH2 CH3

HBr

H H3C C H3C C

CH3 CH3 Br

a) protonation of the alkene, followed by the trapping of the carbocation with bromide ion b) protonation of the alkene followed by a hydride shift and addition of bromide to the carbocation c) double bond shift in the alkene followed by the protonation and addition of bromide to the carbocation d) addition of bromide to the alkene followed by a double bond shift and protonation e) protonation of the alkene followed by a methyl shift and addition of bromide to the carbocation (4 pts) Taking into account the stability of various cycloalkanes and carbocations, as well as the rules governing mechanisms of carbocation rearrangements, what is the most likely product of this reaction?

10.

?
I I I

a)

b)

c)

d)

e)

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Chem 210

Practice Exam 2C

11.

(4 pts) What is the name the following compound according to the IUPAC rules?

Cl

Cl
a) b) c) d) e) (3Z, 6E, 2S, 5R)-3-ethyl-7-methyl-2,5-dichloro-3,6-nonadiene (3E, 6Z, 2S, 5R)-3-ethyl-7-methyl-2,5-dichloro-3,6-nonadiene (3E, 6Z, 5R, 8S)-3-methyl-7-ethyl-5,8-dichloro-3,6-nonadiene (3Z, 6Z, 5S, 8R)-3-methyl-7-ethyl-5,8-dichloro-3,6-nonadiene (3E, 6Z, 2S, 5S)-3-ethyl-7-methyl-2,5-dichloro3,6-nonadiene

12.

(4 pts) Which of the following statements best describes the stereochemical relationships of compounds A, B and C shown below?
O H O A H H O B O H H O C O H

a) b) c) d) e)

All compounds are chiral. None of the compounds is chiral. A and B are meso compounds. A and B are diastereomers, and C is a meso compound. A and B are chiral.

13.

(4 pts) An aqueous solution containing only one constitutional isomer of compound A shows optical activity. Which one of the following possibilities cannot be correct? a) b) c) d) e) f) A has a chiral center A does not have stereogenic centers A is a mixture of isomers A is a mixture of E/Z isomers A is a 50/50 mixture of diastereomers A is planar molecule

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Chem 210

Practice Exam 2C

14.

(4 pts) Which compound is identical to 1?

H Cl H 1

H Cl H

Cl

Cl

Cl

Cl

Cl (a) (b)

Cl (c)

Cl (d)

Cl

15.

(4 pts) Which of the following is the product of the "back-side" substitution by the hydroxide ion (HO) on (R)-CH3CHDI? D = 2H (deuterium)

a) D H OH D

b) H I H

c) D OH I

d) H OH

e) D H I

H3C

H3C

H3C

H3C

OH

16.

(4 pts) Based on your knowledge of the electronic structures of the reactant, what are the critical HOMO and LUMOs of this polar reaction?

H H N H
HOMO s orbital of BF3 lone-pair orbital of NH3 lone-pair orbital of NH3 p orbital of BF3 p orbital of NH3
+

F B F F H

H H

F F

N B

a) b) c) d) e)

LUMO orbital of NH3 p orbital of BF3 * orbital of BF3 orbital of NH3 * orbital of BF3

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Chem 210

Practice Exam 2C

17.

(4 pts) For which of the following compounds does radical chlorination yield a single isomer of the mono-chlorinated product?
E (CH3)3CCH2CH3 F CH3C

B C2H6

C C3H8

CCH3

a) A and C

b) C and E

c) A, B, and F

d) B, D, and E

e) C, D, and E

18.

(4 pts) The heats of formation (Hf) and the heats of hydrogenation (Hh) of two isomeric pentenes are given below. What is the heat of hydrogenation of Z-2-pentene (in kcal/mol)?

Hf (kcal/mol) Hh (kcal/mol)
a) 34.0

7.5 27.5
c) 26.5 d) 21.0

6.5 ?
e) 20.0 f) 1

b) 28.5

19.

(4 pts) Which of the following statements about hyperconjugation is not correct? a) hyperconjugation requires proper alignment of the participating bond with the system (or a p orbital) b) hyperconjugation in propene leads to an increase in the electron density on the terminal carbon of the double bond (as compared to ethene) c) hyperconjugation results in delocalization of electron density from a single bond into a system (or a p orbital) d) hyperconjugation provides a mechanism of stabilization in alkyl-substituted carbocations e) the strength of hyperconjugation increases with the increased electronegativity of the atom forming the participating bond

20.

(4 pts) Which of the following reactions is not exothermic? a) b) c) d) CH3Cl CH3Cl CH3Cl CH3Cl + CH3CH3 + (CH3)3CH + CH2=CHCH3 + CH2=CH2 CH4 CH4 CH4 CH4 + + + + CH3CH2Cl (CH3)3CCl CH2=CHCH2Cl CH2=CHCl

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Chem 210

Practice Exam 2C

21.

(4 pts) Consider the second mechanistic step of the electrophilic addition of HBr to (R)-3methylpentene, leading to the formation of a secondary alkyl bromide, under conditions where no rearrangements are observed. What is the relationship between the two transition states giving the final bromides? a) b) c) d) e) f) they are regioisomers of equal stability they are regioisomers of different stability they are enantiomers of equal stability they are enatiomers of different stability they are diastereomers of equal stability they are diastereomers of different stability

22-23. Taking into account that So of the following reaction is 0.033 kcal/(molK) answer questions 22 and 23. C2H4 + HCl CH3CH2Cl

22. (2 pts) What is the heat of the reaction, in kcal/mol? a) +74 b) +14 c) 0 d) 14 e) 74

23. (2 pts) Which statement about G for this reaction at 300 K is correct? a) G > 0 b) G < 0 c) G = 0

24.

(4 pts) Which of the following molecules are chiral?

HO HO

CH 3 CH3 H H

Cl

Cl F

Cl Cl

Cl Cl Br Cl

Cl C

a) b) c) d) e)

A, C, and D B, C, and E B and E A and B none of the molecules is chiral.

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Chem 210

Practice Exam 2C

25.

(4 pts) Consider the following reaction in which the intermediate carbocation loses H+ to give the final product

H+

Which of the following energy profiles best represents the overall reaction?

a)

b)

c)

d)

e)

26.

(4 pts) How many different stereoisomers are possible for 1,4-difluoropenta-1,2-diene? a) 1 b) 2 c) 3 d) 4 e) 8

End of the exam

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Chem 210

Practice Exam 2C

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 2C

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Chem 210

Practice Exam 2C

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Chem 210

Practice Exam 2C

Answer key: 2C 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.

A B E A A E C D E B B E F A C B C B E D F D (2 pts) A (2 pts) A E D

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