Chem 210

Practice Exam 4D

Organic Chemistry: Chem 210

Practice Exam 4D
There are 27 questions on this exam. Check that you have done all of the problems and filled in the first 27 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 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.

All rights reserved: P. Maslak 2013

Page 1 of 13

Chem 210

Practice Exam 4D

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 = m-chloroperbenzoic acid., TosO = TsO = tosylate

********************************************************************************** 1. (4 pts) Arrange the following phenols in order of increasing acidity (least to most acidic).
OH OH OH OH

CN NO2 A B NH2 C D

CH3

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

2.

(4 pts) Which of the following species are aromatic?

H N N N

II

III

IV

a) I and II

b) II and V

c) IV and V

d) I, II, and III

e) II, III, and V

All rights reserved: P. Maslak 2013

Page 2 of 13

Chem 210

Practice Exam 4D

3.

(4 pts) In the reaction shown below, the carbon marked by a dot () is 13C isotope that can be distinguished from normal carbons (12C) by a special kind of spectroscopy.

H2SO4

Which structure shows the correct position of 13C in the product of the carbocation rearrangement shown above?
a) b) c) d) e)

4.

(4 pts) What is the correct mechanistic designation for the first step of ring-opening reaction of the epoxide shown below?
O 1. CH3MgBr 2. H3O+ Product

a)

H+ O

b)

c)

d)

H3C MgBr

H3C MgBr

H3C MgBr

H3C MgBr

5.

(4 pts) Which of the following statements about A and B is true?

a) b) c) d) e)

They are different conformations of the same molecule. They are constitutional isomers. They are diastereomers. They are enantiomers. They are identical.

All rights reserved: P. Maslak 2013

Page 3 of 13

Chem 210

Practice Exam 4D

6-7.

A Chem-210 student had only the following reagents available to accomplish the transformation given below: a) KMnO4/H+ b) H2/Pd/C c) OsO4; NaHSO3 d) Li/NH3(liquid) e) Hg(OAc)2/H2O; NaBH4 f) BH3; H2O2/ HO g) NBS/DMSO/H2O h) H2/Lindlars catalyst i) HIO4 j) H2SO4/SO3

6. (4 pts) What reagent was employed to carry out the third (III) step?
I II III O H

7. (4 pts) Availability of which reagent would allow to shorten the synthesis to just two steps? a) O3; Zn/AcOH 8. b) KMnO4/HO c) CrO3/H+ d) PCC

(4 pts) Which of the following is the best mechanistic representation of the reaction of primary alcohols with POCl3/pyridine?
H N

a)

H Cl

O P Cl H HH O H Cl Cl Cl

H -H
+

O2PCl2

O H N

O PCl2 O H N Cl -H+ O O PCl2 HH H N

b)

O P

O2PCl2

c)

H HO HH Cl

O P Cl Cl

H -H+

O2PCl2

d)

HH O H

HH O Cl

O P Cl Cl

HH O PCl2 O H N

O2PCl2

e)

H H OH

O P Cl Cl Cl

POCl3 HH

O P Cl Cl Cl

All rights reserved: P. Maslak 2013

Page 4 of 13

Chem 210

Practice Exam 4D

9.

(4 pts) Considering only monochlorides, what would be the yield of the most abundant product in the radical-chain chlorination of 2,3,4-trimethylpentane? a) 10% b) 15% c) 20% d) 33% e) 40%

10-11. The following reagent list applies to questions 10-11. a) b) c) d) e) NaNH2/NH3 H2/Pd/C NBS/H2O/DMSO CH3OH/heat Hg(OAc)2/H2O; NaBH4 f) BH3; H2O2/ HO g) POCl3/pyr h) H2/Lindlars catalyst i) Li/NH3(liquid) j) H2SO4/SO3

What are the correct reagents necessary to carry out each transformation? 10. (4 pts)
Br

11. (4 pts)
OH Br

12.

(4 pts) Which symbol should be used to correctly represent the relationship between the two structures drawn below?

a)

b)

c)

d)

e)

13.

(4 pts) Which structure shows a major intermediate formed in the electrophilic nitration of chlorobenzene?
a) O b) O H NO2 O2N Cl c) d)

Cl

Cl O2N H Cl H

All rights reserved: P. Maslak 2013

Page 5 of 13

Chem 210

Practice Exam 4D

14.

(4 pts) When A and B react in t-BuOH, the following rate expression is observed:
A: -d[A]/dt = k[A][B] B: OK Ph OTos

What is the most likely mechanism of this reaction? a) E2 b) SN2 c) E1 d) SN1 e) it cannot be determined

15 - 16. Consider a 6-carbon system built of an allyl anion and an allyl cation by connecting their central carbons. The -type MOs of that system are shown below in a random order. Note that some orbitals may be degenerate.
A B C

15. (2 pts) Which of the following transitions will have the largestmax? a) A F b) D B c) C B d) D F e) E B

16. (2 pts) How many unpaired electrons are there in the molecule according to this MO scheme? a) 0 b) 1 c) 2 d) 3 e) 4

17.

(4 pts) Select the reagent and solvent combination which would result in the fastest rate of substitution (R = CH3 in all cases).
25 oC I ?

a) ROH, HMPA

b) RS, H2O

c) RO, H2O

d) RS, DMSO

e) RSH, H2O

All rights reserved: P. Maslak 2013

Page 6 of 13

Chem 210

Practice Exam 4D

18.

(4 pts) What is the best representation of the lowest energy conformation of (1R)(2S)-1,2dichloro-1-methylcyclohexane?
a) Cl Cl CH 3 H 3C Cl b) Cl c)
H H H H Cl Cl H CH3 H H H H

d)
H Cl Cl CH3

e) Cl H 3C Cl

19.

(4 pts) The heats of formation, Hf (rounded off to simplify the arithmetic), of cyclohexane and cyclooctane are both 30 kcal/mol. What is the strain energy (in kcal/mol) of cyclooctane? a) 0 kcal/mole b) 5 kcal/mole c) 10 kcal/mole d) 15 kcal/mole e) 20 kcal/mole

20.

(4 pts) What is the major organic product of the reaction shown below?
1. MCPBA ? 2) HBr, Et2O a) Br b) Br OH c) OH Br d) O e) OH OH

21-22. In general, different isotopes of the same atom have almost indistinguishable reactivities. Consider the reaction of 1 equivalent of D-Cl with 1,3-cyclopentadiene where D = 2H.
D-Cl

21. (2 pts) Which is true about this reaction? a) b) c) d) e) The 1,2-adduct is the kinetic product, and the 1,4-adduct is the thermodynamic product. The 1,4-adduct is the kinetic product, and the 1,2-adduct is the thermodynamic product. The kinetic and thermodynamic products are the same, except for isotopic substitution. There is only 1,2-adduct possible in this reaction. There is only 1,4-adduct possible in this reaction.

22. (2 pts) How many isomers, including stereoisomers, form in this reaction? a) 2 b) 4 c) 6 d) 8 e) 16

All rights reserved: P. Maslak 2013

Page 7 of 13

Chem 210

Practice Exam 4D

23.

(4 pts) Select the substrate which would react fastest in the substitution reaction under the indicated conditions (at 25 oC)?
MeNH2 CH3CN

a)

OTos

b) Br

c)

OTos

d) I

24.

(4 pts) (1S, 2S)-1-Bromo-1-deutero-2-methylbutane is converted to 1-deutero-2-methylbutanol in a two-step process. What is the stereochemistry of the major products? Note: deuterium, D = 2H, has a higher priority than hydrogen, 1H, in assigning the absolute configurations.
D Br t-BuOK t-BuOH BH3/THF H2O2/NaOH D OH

a) b) c) d)

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

25.

(4 pts) What is the product of the following sequence of reactions?

KMnO4, H+ NaBH4 Product + CO2

a)

OH

b) O

OH

c)

OH OH

d) O

OH OH

OH OH

OH OH

OH

OH

All rights reserved: P. Maslak 2013

Page 8 of 13

Chem 210

Practice Exam 4D

26.

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

OH OH OH Na2Cr2O7 H3O+

a)

OH O O O

b) O

H O OH

c)

OH O O OH

d)

OH O OH OH

27.

(4 pts) What is the best sequence of reactions to synthesize the desired product?
Pr 1 2 3 NH2

a) b) c) d) e)

Step 1 HNO3/H2SO4 HNO3/H2SO4 AlCl3/PrCl HNO3/H2SO4 AlCl3/EtCOCl

Step 2 PrMgBr/H3O+ AlCl3/PrBr HNO3/H2SO4 H2/Pd HNO3/H2SO4

Step 3 H2/Pd H2/Pd H2/Pd PrMgBr/H3O+ H2/Pd

End of exam

All rights reserved: P. Maslak 2013

Page 9 of 13

Chem 210

Practice Exam 4D

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

All rights reserved: P. Maslak 2013

Page 10 of 13

Chem 210

Practice Exam 4D

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

All rights reserved: P. Maslak 2013

Page 11 of 13

Chem 210

Practice Exam 4D

All rights reserved: P. Maslak 2013

Page 12 of 13

Chem 210

Practice Exam 4D

Answer key for 4D:

1. C 2. B 3. D 4. B 5. E 6. I 7. A 8. A 9. E 10. A 11. C 12. E 13. A 14. B 15. D 16. C 17. D 18. D 19. C 20. B 21. C 22. D 23. A 24. A 25. B 26. C 27. E

All rights reserved: P. Maslak 2013

Page 13 of 13