Old CH 231 Exams

The questions on these old exams are typical of the kinds of questions you can expect on the exams in CH 231 this semester. For the midterm exam, you should know all of the material in chapters 1-5, with one exception: you will not be tested on Fischer projections (section 5-4). The absence of questions about any particular topics on the old exams does not imply that questions on those topics will also be absent on the midterm exam this fall. The overall degree of difficulty of the midterm exam this fall will be comparable to that on the old exams, although there will undoubtedly be some variations in the degree of difficulty of individual questions on specific topics. You should be able to answer all of the questions on old exam 1 and all of the questions except 9, 12, 13, and the bonus on old exam 2.

L. T. Scott
10/12/2004

B OS TON C OL L E GE
Chem 231 - Organic Chemistry I Exam I - September 27, 2000

name

Please write your answers on the exam. Do not spend too much time on any one question.

question 1. (06 points) 2. (06 points) 3. (04 points) 4. (08 points) 5. (05 points) 6. (06 points) 7. (04 points) 8. (06 points) 9. (06 points) 10. (06 points) 11. (06 points) 12. (10 points) 13. (10 points) 14. (06 points) 15. (05 points) 16. (06 points) total

points

Chem 231

Exam I - September 27, 2000

1. (6 points) Draw a molecular structure for each of the following compounds: (a) t-butylcyclopentane (b) 3-(1-chloroethyl)heptane

2. (6 points) Write the IUPAC name for each of the compounds shown below.

H F H

F

3. (4 points) In the drawing to the right, identify each of the labeled carbon atoms as primary, secondary, tertiary, or quaternary.

4. (8 points) For each of the organic species below, (a) indicate the hybridization of the atoms marked with an arrow and (b) indicate the best description of the geometry at each of the atoms marked with an arrow, choosing from the following list of descriptors: linear, bent, planar, pyramidal, or tetrahedral.

Br H3C N C O

(CH3)2CCH2CH3

5. (5 points) Circle the most acidic proton of those shown explicitly in the molecular structure to the right.

H H N H

O

H

H H

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Chem 231

Exam I - September 27, 2000

6. (6 points) Every covalent bond in the molecule shown to the right can be described as resulting from the overlap of an atomic orbital on N one atom with an atomic orbital on the attached atom. For the bonds marked by arrows, indicate C what atomic orbitals are overlapping to make the bond.

7. (4 points) In the group of five compounds shown below, (a) circle the compound that should have the lowest boiling point and (b) draw a box around the compound that should have the highest boiling point.

8. (6 points) The C2 H4 Br cation is known to have a cyclic structure (3-membered ring). Draw the most reasonable Lewis structure for this cation. Show all the valence electrons around every atom, and be sure to indicate which atoms bear formal charges. 9. (6 points) The heat of combustion of methylcyclopentane is –942.1 kcal/mol, and the heat of combustion of cyclohexane is –937.7 kcal/mol. Which of these two C6 H1 2 hydrocarbons is the thermodynamically more stable isomer? Draw a potential-energy diagram that shows the potentialenergies of each of these two hydrocarbons plus oxygen relative to the potential-energies of their combustion products. 10. (6 points) The halogenation of methane under the influence of heat or light is actually a reversible reaction (equation shown below). When X=Br, the equilibrium constant is greater than 1.0 (Keq > 1.0). When X=I, however, Keq < 1.0. Is the change in Gibbs standard free energy (ΔG°) for the bromination of methane positive or negative? What is the equation that relates Keq to ΔG°?

CH4

X2

CH3-X

H-X

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Chem 231

Exam I - September 27, 2000

11. (6 points) Which of the following four reactions will be the FASTEST? (a) ΔG° = +4.9 kcal/mol and Ea = +2.3 kcal/mol. (b) ΔG° = +4.1 kcal/mol and Ea = +8.7 kcal/mol. (c) ΔG° = -6.8 kcal/mol and Ea = +4.2 kcal/mol. (d) ΔG° = 0.0 kcal/mol and Ea = +5.7 kcal/mol. 12. (10 points) Free radical chlorination of 2-methylpropane (“isobutane”) gives two products with the molecular formula C4 H9 Cl in a ratio of about 2:1. If that mixture of products is then irradiated (hυ) in the presence of elemental bromine, those two compounds are converted to a mixture of four products with the molecular formula C 4 H8 BrCl. (a) Draw bond-line formulas for the two compounds formed with molecular formula C 4 H9 Cl.

(b) Draw bond-line formulas for the four compounds formed with molecular formula C 4 H8 BrCl.

(c) Two of the four C4 H8 BrCl compounds make up more than 99% of the product mixture formed by this sequential halogenation procedure. Circle them. (d) When the order of the halogenation steps is reversed, i.e., the bromination is performed before the chlorination, a single compound of formula C4 H8 BrCl makes up more than 99% of the product mixture. Draw a box around it. [Hint: It might or might not be the same as one of the compounds you have already circled.]

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Chem 231

Exam I - September 27, 2000

13. (10 points) Draw a Newman projection for the lowest energy conformation of 2–bromobutane (looking down the C2-C3 bond). Then draw a plot of potential energy vs torsional angle from 0° to 360° around the C2-C3 bond, with the torsional angle defined so that the lowest energy conformation corresponds to 0°. You do not have to draw Newman projections for any of the other conformations, but be careful to show which energy maxima are higher than others, which energy minima are lower than others, and which conformations have the same energy.

14. (6 points) A Lewis structure for the cyanate ion is shown below. (a) Draw a second reasonable Lewis structure for the cyanate ion, being sure to indicate which atoms bear formal charges. (b) Circle whichever Lewis structure contributes more to the actual structure of the cyanate ion. (c) Briefly justify your answer to part (b).

O C N

15. (5 points) Which of the compounds below will have the largest dipole moment? Briefly show why.

H Cl-C C-Cl H

H CH2Br2 H CS2

16. (6 points) The bond-dissociation energy of H2 O is 119 kcal/mol, whereas the bonddissociation energy of HCl is 103 kcal/mol. When the •Cl radical abstracts a hydrogen atom from an alkane, will it exhibit higher or lower selectivity than the •OH radical in choosing tertiary vs secondary vs primary hydrogen atoms? Briefly tell why.

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B OS TON C OL L E GE
Chem 231 - Organic Chemistry I Exam 2 – October 18, 2000

name discussion section (time or TA) Please write your answers on the exam. Do not spend too much time on any one question.

question 1. (04 points) 2. (04 points) 3. (04 points) 4. (06 points) 5. (08 points) 6. (06 points) 7. (06 points) 8. (06 points) 9. (04 points) 10. (12 points) 11. (06 points) 12. (12 points) 13. (14 points) 14. (08 points) bonus (10 points) total

points

Chem 231

Exam 2 – October 18, 2000

1. (4 points) Draw a molecular structure for each of the following compounds: (a) trans-1-chloro-3-isopropylcyclobutane (b) 4,4-bis(fluoromethyl)heptane

2. (4 points) Write the IUPAC name for each of the compounds shown below.

Br

Cl

3. (4 points) In the group of five compounds shown below, (a) circle the compound that should have the highest boiling point and (b) draw a box around the compound that should have the lowest boiling point.

Cl

Cl Cl

I

CF4

Br

4. (6 points) The heat of combustion for methylspiropentane (compound 1 below) is –782.0 kcal/mol, and the heat of combustion for cyclopropylcyclopropane (compound 2 below) is –778.3 kcal/mol. (a) Which of these two C6 H1 0 hydrocarbons is the more stable one? (b) What aspect of the structure of the less stable isomer would you conclude is causing that compound to be less stable than the other isomer?

1

2

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Chem 231 5. (8 points) For each of the cyclohexane derivatives below, (a) Tell whether the groups are cis or trans, (b) flip the ring and draw the other chair conformation, and

Exam 2 – October 18, 2000

(c) circle the more stable conformation for each compound (i.e., the original drawing vs yours).

Cl OH

CH3

6. (6 points) A colorless crystalline compound isolated from guaiac wood has been given the name “guaiol.” Its molecular formula (C1 5H2 6O) and structure strongly suggest that guaiol is a sesquiterpene. Given this information, which of the following structures is most likely correct for guaiol? Show your reasoning.

HO

HO

OH

7. (6 points) The groups on each stereogenic carbon atom below are labeled in order of decreasing priority according to the Cahn-Ingold-Prelog system (i.e., highest priority = a ... lowest priority = d). Indicate for each center whether it has the R or the S configuration.

b d c a a

b d c b

a c d

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Chem 231

Exam 2 – October 18, 2000

8. (6 points) Circle the “substituent” in each set below that has the highest priority in the Cahn-Ingold-Prelog system for assigning stereochemistry (R vs. S), and draw a square box around the “substituent” in each set that has the lowest priority.
O CH2CH3 O CH2CH2CF3 C OOH

CH2OH

C OOH

N(CH3)2 N

CN

S

N CH3

9. (4 points) Fischer projections are shown below for four of the stereoisomers of 2,3,4trichloropentane.

CH3 H Cl H Cl H Cl CH3 A

CH3 Cl H H Cl H Cl CH3 B

CH3 H Cl Cl H H Cl CH3 C

CH3 H Cl H Cl Cl H CH3 D

Some questions below may have more than one correct answer; circle ALL the correct answers to each question. (a) Which isomers are chiral? (b) Which isomers are meso? A A B B C C D D

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Chem 231

Exam 2 – October 18, 2000

10. (12 points) For each pair of compounds in the list below, circle the word that best describes their structural relationship. Assume that the rings are planar.

O H CH3 O A

H CH3

H CH3

O O H CH3 CH3 H

O O C

H CH3

H CH3

O O CH3 H

mirror

B

mirror

D

A&B A&C A&D B&C B&D C&D

identical identical identical identical identical identical

enantiomers enantiomers enantiomers enantiomers enantiomers enantiomers

diastereomers diastereomers diastereomers diastereomers diastereomers diastereomers

11. (6 points) Refer to the compounds above in question 10. Which of the following samples would be optically active? (Circle all the correct answers). pure A 1:1 mixture of A and D pure D 1:1 mixture of C and D 1:1 mixture of A and B 3:1 mixture of C and D

12. (12 points) Write the major organic product expected from each of the following proposed reactions. If no reaction will occur, write NO REACTION.

(a) (b) (c)

(CH3)2CHCH2-Br Cl-CH2CH2CH3 CH3-I

Na CN K SCN CH3OH DMF

DMSO

Na OCH(CH3)2

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Chem 231 12. (continued)
DMF (d) (e) (f) CH3-I NH3 Na Cl Na CN CH3OH DMSO

Exam 2 – October 18, 2000

CH3CH2CH2CH3 H H3C C CH3 OH

13. (14 points) Predict the effect of the changes given below on the rate of the reaction:
CH3OH

CH3-Cl

O CH3

CH3-O-CH3

Cl

Circle one answer only for each question. (a) Change substrate from CH3 Cl to CH3 I. (b) Change nucleophile from CH3 O– to CH3 S– . (c) Change nucleophile from CH3 O– to CH3 OH. (d) Change nucleophile from CH3 O– to (CH3 )2 CHO– . (e) Change substrate from CH3 Cl to (CH3 )2 CHCl. (f) Change solvent from CH3 OH to (CH3 )2 SO. (g) Double the concentration of CH3 O– . faster faster faster faster faster faster faster slower slower slower slower slower slower slower no change no change no change no change no change no change no change

14. (8 points) Bromination of pure (3R,4S)-3,4-dimethylhexane (shown below) with one molar equivalent of elemental bromine under the influence of light produces 3-bromo3,4-dimethylhexane in good yield. Consider carefully how this reaction would occur and then circle all of the products in the list below that you would expect to be formed.

H CH3 H3C H

(3R,4R)-3-bromo-3,4-dimethylhexane (3R,4S)-3-bromo-3,4-dimethylhexane (3S,4S)-3-bromo-3,4-dimethylhexane (3S,4R)-3-bromo-3,4-dimethylhexane

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Chem 231

Exam 2 – October 18, 2000

Bonus. (10 points) When pure cis-1-t-butyl-4-iodocyclohexane is added to a solution of sodium iodide in acetone (propanone) at room temperature, some trans-1-t-butyl-4iodocyclohexane is formed. Likewise, when pure trans-1-t-butyl-4-iodocyclohexane is added to a solution of sodium iodide in acetone (propanone), some cis-1-t-butyl-4iodocyclohexane is formed. (a) Draw structural representations for the two stereoisomers of 1-t-butyl-4iodocyclohexane in their most stable conformations, indicating clearly the 3dimensional arrangement of atoms in each, and then use the curved arrow notation to show how sodium iodide could convert each isomer into the other.

(b) When starting with the pure cis isomer, the reaction “stops” after only 70% of the starting material has been used up. Even in the presence of excess sodium iodide, about 30% of the cis isomer always remains unconverted to trans. When starting with the pure trans isomer, the reaction “stops” after only 30% of the starting material has been used up. Explain (briefly) why these reactions do not convert the starting materials 100% into the product.

(c) Can you explain why one reaction gives 70% conversion to the product, while the other goes only 30% of the way?

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