NAME:___________________________

Exam 2Answers Organic Chemistry Chem 141 Fall 2013

LECTURE SECTION: Morning / Afternoon (circle one)
This is a closed-book, no notes exam. You may use molecular model kits. No other outside material may be used and you may not discuss the exam with anyone else. All UVM academic integrity policies apply during this exam. The exam has 21 questions for a total of 100 points. The exam duration is 2 hours and 45 minutes. Good luck!

Answer the Multiple choice questions in the spaces below.(2pts each) 1. D 2. B 3. B 4. A 5. A 6. C 7. C 8. B 9. C 10. D
For grading purposes only: Pages 1-2 3 4 5 6 7 8 TOTAL Problems 1 - 10 11-12 13-15 16-17 18-20 18-19 20-21 Points ____ ____ ____ ____ ____ ____ ____ ____ points Grader ____ ____ ____ ____ ____ ____ ____ _____ %

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1. (2R,3S)-Dibromobutane is: A. optically active B. racemic C. dextrorotatory D. a meso compound. 2. Which cyclic compound is likely to be the least strained?

A.

B.

C.

D.

3. A new antibiotic has been extracted from the mold of a Korean soy-sauce. The optical activity of the pure molecule has been measured as +40.3. What does that say about the molecule? A. It has more R chirality centers than S. B. It rotates plane polarized light dextrorotatory. C. It is a meso compound, extracted using acid/base washes and a separatory funnel. D. It has a low melting point so would be good as a human pharmaceutical. 4. Which of the following is the most electrophilic?

A.

B.

C. Na+ -:CC-CH3

D.

5. Which of the following statements is TRUE regarding the sugar D-(+)-galactose? A. It can be degraded to D(+)-glyceraldehyde. B. It is dextrorotatory as indicated by the D. C. It has R chirality due to the (+). D. It is levorotatory due to the (+). 6. Which two factors contribute to ring-strain? I. Angle strain II. Number of groups as dashes/away. III. Inductive effects IV. Torsional strain of eclipsing C-H bonds. A. II, III and IV B. I, III, IV C. I and IV only D. I and II only

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Use the following reaction coordinate diagram to answer questions 7, 8, and 9.

7. Which arrow shows the energy difference between starting material X and the intermediate? 8. Which arrow shows the rate determining step for the formation of the intermediate? 9. Which description best explains the difference between the starting material X and the product Y? A. The product is sp2 hybridized and the starting material is sp3. B. The reaction would need to be run on ice or with a reflux condenser in order to prevent boiling of the solvents. C. The product is lower energy than the starting material and no stereochemical outcome can be predicted without more information. D. The combination of B and D would prevent the formation of Y from being formed unless the two solids were mixed together without solvents. Refer to the following illustration to answer question 10.

10. Which bond is cis to the bond labeled M?

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11. Menthol is naturally occurring compound that can be extracted from peppermint. It is used in many products for its mild anesthetic and counterirritant effects eg. throat lozenges. Menthol has an isomer neomenthol.

a. What is the relationship between menthol and neomenthol? (1pt) DIASTEREOMERS b. Draw the chair structures for both menthol and neomenthol and circle the most stable chair. (9pts).

c. Draw a Newman projection for the neomenthol (in the more stable orientation) looking from the carbon with the isopropyl group toward the carbon with the OH. (2pts)

12. What has been the highlight of your semester so far? Or what do you hope to accomplish by the end of this semester? 1pt Highlight: The warm sunny Fall and getting to hike, bike and sail. Hope for semester: Effectively teach 400 students how to study organic chemistry and maintain a sense of excitement and fun associated with learning.
3

NAME:___________________________
13.a) (S)-Naproxen is an active non-steroidal anti-inflammatory drug (NSAID), but the (R)-enantiomer is a harmful liver toxin. Show the structure of the toxic version with dashes/wedges.(2pts)

b) Penicillamine has two enantiomers the (S) is anti-arthritic, the (R) is toxic. Show the structure of the medicinally useful (S) molecule with dashes/wedges. (2pts)

14. Name the following molecules according to IUPAC rules (include stereochemistry where appropriate). (3pts each/12pts)

a. b. c.

d.

(2R,3S)-2-bromo-3-methylpentane

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15.a) Draw a dash-wedge illustration of (2R,4S)-2,4-dichloropentane. (2pts).

b) Draw a Fischer projection of (2R,4S)-2,4-dichloropentane. (2pts).

c) Draw the most stable orientation of (2R,4S)-2,4-dichloropentane as viewed from carbon-2 to carbon-3. (2pts).

16. Use one word to describe the relationships between the pairs of molecules shown below. (1pt each). a)

_enantiomers_______ b)

_constitutional _ c)

__enantiomers_____

NAME:___________________________
17. Energy from food, can be delivered by fats, carbohydrates or proteins. When carbohydrates are metabolized they are broken-down into sugars and the sugars are oxidized. During an oxidation reaction the end alcohol group is often converted into an aldehyde or ketone. Example

a) Draw the Fischer projections of the following sugars after a similar oxidation has occurred. (2pts each)

b) Circle the compounds that are mesomers. (1pt each, -1pt per error) c) Describe in a few sentences what a racemate (or racemic mixture) is. (2pt). A racemate is an equal mixture of two enantiomers.

NAME:___________________________
18. a) Add curved arrows to illustrate the electron flow for the following mechanism. (1pt per arrow, -1pt per wrong arrow).

b) Place circles around TWO nucleophilic atoms and put squares around TWO electrophilic atoms. (4pts). Other answers possible. 19. Circle the more acidic compound of the following pairs and explain why. (2pts each) a.

The carboxylic acid is more acidic because the conjugate base is able to resonance stabilize the negative charge that is formed. This is not possible for the molecule with two alcohols. b.

The molecule on the left is more acidic because the conjugate base formed by this molecule is neutral (more stable).

NAME:___________________________
20. Explain how to separate the following compounds based on their chemical or physical properties. You have a fully stocked chemical laboratory to use. (4pts)

Filtration: One solid, one a liquid at room temperature. Distillation: Significantly different boiling points. Liquid/liquid extraction: The molecule on the left is water-soluble (ionic) the one on the right is soluble in non-polar solvents (such as ether).

21. Magristatin is a potent anticancer pharmaceutical.

Please make your notes on the left hand structure and write only your answers on the right hand structure. a. Add a star (*) to each chirality center (1pt for correct, -1pt for wrong, no negative scores). b. Assign R/S to each chirality center (1pt each). The End.

NAME:___________________________