FIRST MIDTERM EXAMINATION Chemistry 131 Thursday, October 18, 2012 Professor Kool Due to privacy reasons, do NOT

write your name on this exam. Name: ________KEY_______________________________________________________ INITIALS ONLY Stanford University ID No.

TA and section time (example: Ross, Wed 12 pm): ______________________________

INSTRUCTIONS: This examination is 9 pages long, none of them blank. CHECK YOUR COPY. Enter all answers on these pages, using the back of facing pages if you need more space. Answers may be entered in pencil. This examination is due promptly at 8:30 pm. Problem: 01 02 03 04 05 06 07 08 09 /5 /10 /15 /10 /10 /21 /12 /7 /10 Back of page used? yes yes yes yes yes yes yes yes yes

Total

/100

Please sign below before starting this examination. I have observed the Stanford Honor Code during this examination. Signature: __________________________________________________________

1.

The compound below is artemisinin, a natural product shown to have antimalarial properties. Indicate which carbons are at the alkane, alcohol, ketone, or carboxylic acid oxidation levels using the given key. Make sure to mark ALL carbons. (5 points)

* * *
+0.33 for each right answer, rounded to nearest .5 (maximum 4.5 for one mistake, max 4 for two mistakes)

* *

* *

2.

Indicate whether the structures below are aromatic, antiaromatic, or nonaromatic. (10 points)

+1 each

3.

How many 1H NMR signals would you expect to see in each of the following molecules? Assume rapid time averaging of conformations and ignore spin-spin splitting. (15 points)

+3 each

4.

Determine whether the following reactions are oxidations, reductions, or neither. (10 points)

+1 each

5.

Predict the spin-spin multiplicity of ALL of the hydrogens in the molecules shown below. Use the following abbreviations for multiplicity: s = singlet, d = doublet, t = triplet, q = quartet, u = quintuplet, x = sextet, h = heptuplet, dd = doublet of doublets, ddq = double of doublet of quartets, tt = triplet of triplets, etc. (10 points)

6.

Provide the missing reagents and/or products for the following reactions. Some reactions may give more than one product. Some reactions may require more than one reagent. (21 points)

7.

The 1H NMR spectrum for an unknown compound with molecular formula C 9H9OCl is shown below. Propose the most reasonable structure of the compound in the box provided below. (12 points)

Spectral data 9.88ppm, 1H, s 7.71ppm, 1H, d 7.66ppm, 1H, s 7.57ppm, 1H, d 7.45ppm, 1H, dd 3.71ppm, 2H, t 2.83ppm, 2H, t

8.

Draw the detailed mechanism for the following reaction using arrow pushing formalism. Make sure to include all resonance structures of the intermediate. (7 points)

+2 for mechanism +4 for two major resonance forms, +1 for having all five resonance forms Common errors: N exceeds valency, formal charge mistakes.

9.

Styrene forms a dimer in acidic condition under heat. Propose the detailed mechanism using arrow pushing formalism and make sure to show all intermediates. (10 points)