Chem 2312-003 Midterm II F12 !

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Chemistry 2321-003 Organic Chemistry I

Midterm Examination II
11:00 am 12:20 pm Form A

October 24, 2013 J. Jeon

Name: ___________ Answer Key______________

please print

Total

/100

ID #: ______________________________________
There are 100 points on this exam and the seven exam pages. Please read questions very carefully. For the multiple choice questions 1-12, select the best answer and darken completely with a pencil the space corresponding to that answer in scantron (form # 882-E). You are free to use molecular models during the exam. For questions 13 and 14, I will not reconsider grades for answers written in pencil. Have fun!

Chem 2312-003 Midterm II F12 !

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1. (5 pts) Which of the following compound is not serve as a nucleophile? d) is an electrophile (alkyl halide).
a) b) O H3C OH H3C c) OH CH3 H3C d) Cl e) Li

2. (5 pts) Rank the following carbocations in order of stability. (1 = most stable, 4 = least stable) A 1 2 3 4 2 B 2 1 2 3 4 C 4 4 4 2 1 D 3 3 1 1 2

a) b) c) d) e)

3-4. (10 pts) These problems are about the IUPAC (International Union of Pure and Applied Chemistry) nomenclature of organic compounds. 3. (5 pts) Select the best name for the following molecule. a) (S)-2-bromohexane
Br H3C CH3

b) (R)-2-bromohexane c) (S)-5-bromohexane d) (R)-5-bromohexane e) (S)-1-bromo-2-methylpentane

4. (5 pts) Select the best name for the following molecule. (The stereochemistry of the chloride-bearing carbon is not indicated. Please simply ignore it). a) (E)-3-Chloro-1-methylpent-1-ene
Cl H3C CH3

b) (Z)-3-Chlorohex-4-ene c) (E)-3-Chlorohex-4-ene d) (Z)-4-Chlorohex-2-ene e) (E)-4-Chlorohex-2-ene

5. (5 pts) Which of the following compound contains a Z alkene?

a) H H OH CH3 b) H CH3 OH H c) H HO CH3 H HO H d) H CH3 H CH3 e) H OH

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6. (5 pts) Rank the following molecules in order of reactivity toward a bimolecular elimination (E2) reaction. (1 = most reactive, 4 = least reactive) A
H H Br CH3 H H3C Br CH3 H3C H3C Br CH3

B 2 3 2 1 1

C 3 1 1 3 2

a) b) c) d) e)

1 2 3 2 3

7. (5 pts) Rank the following alkenes in order of stability. (1 = most stable, 4 = least stable) A
H3C H3C Br Br Br H3C H3C Br

D 1 4 2 3

a) b) c) d) e)

2 1 4 1

3 4 2 3 1 3 4 2 all the same

8. (10 pts) Consider the following energy diagram:

Free energy (G)

Eac2 Eac1

A+B C+D
Reaction Coordinate

8. (5 pts) Which of the following statement is not true for the above reaction? a) The reaction is spontaneous. b) Two transition states exist. c) The second step is the rate-determining step (RDS). d) The reaction is a two-step mechanism. e) One intermediate exists.

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9. (5 pts) Lets walk a little further. Consider the following energy diagram showing two possible pathways for the reaction between A and B: 1) A + B > C + D and 2) A + B > E + F

Free energy (G)

Eac4 Eac3 Eac1

Eac2

A+B E+F C+D

Reaction Coordinate

9. (5 pts) Which of the following statement is true for the above reaction? a) The reaction pathway to produce C and D is both a kinetically and thermodynamically favored process. b) In both reactions, the second step is the rate-determining step (RDS). c) The products E and F are kinetically favored over C and D. d) At high temperature, the products E and F will is favored. e) None of above.

10. (5 pts) Consider the following substitution reaction.

Br NaCl H2O (solvent)

CH3

A
Which of the following statements is not true? a) The rate of the reaction is not sensitive to the concentration of the nucleophile. b) The reaction is first order in A. c) The reaction generates an intermediate. d) The reaction is sensitive to the stability of an intermediate. e) The major product is produced as a single enantiomer.

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11. (5 pts) Which of the following is the major nucleophilic substitution product of the reaction shown below?

I H3C CH3

NaSCH3 DMSO H3C

O S CH3

DMSO

a) H3C

NaS CH3

b) H3C

SCH3 CH3

c) H3C

SCH3 CH3 O S CH3

d) H3C

SCH3 CH3

e) H3C

CH3 CH3

12. (5 pts) Which of the following is the major elimination product of the reaction shown below?
Na H3C Br CH3 t-BuOH t-Bu

a) H3C Ot-Bu CH3

b) CH3

c) H3C Br CH3

d) CH3 H3C

e) H3C CH3

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13. (20 pts) Consider the following substitution reaction.

OH H3C CH3 CH3

HBr H2O, heat

1) (15 pts) Draw the Major products and a detailed arrow-pushing mechanism (step by step) of the substitution reaction above. Be sure to show the formation of all the intermediates and products. Specify the correct stereochemistry where appropriate. 2) (5 pts) Indicate the ratedetermining step (RDS) among all the steps in the reaction.

HO

HBr

Br

Br

+
heat SN1 mechanism 1) proton transfer Br H H 2 Br Major products

+
minor products (racemic mixture)

Br H

Br

Br

Br

+ H
O H 3) carbocation rearrangement Br Br major products 4) nucleophilc attack minor products (racemic mixture)

2) Loss of leaving group: ratedetermining step (RDS)

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14. (20 pts) Consider the following elimination reaction.

NaOMe Me Br products MeOH

1) (10 pts) Draw two chair conformations (hint: utilize ring flip). Circle a reactive conformer (i.e. conformational isomer) responsible for the elimination reaction.
* How to draw substituted cyclohexanes above (can be axial and equatorial) H H above (can be axial and equatorial) Me Br below (can be axial and equatorial)

H Me Me Br
Me Me

below (can be axial and equatorial) H

Br thermodynamically more stable conformaiton kinetically active "reactive conformer"

Br

H Br

2) (10 pts) Draw the Major product and a detailed arrow-pushing mechanism (step by step, draw all the intermediates) for the above elimination reaction. Specify the correct stereochemistry where appropriate.

H Me H H these two Hs are not active toward E2 Br kinetically active "reactive conformer" (anti-periplanar geometry) Me NaOMe Me

***** End of Exam ***** You may pick up your exam on Tuesday, October 29 (in class). Thank you!