CH 437/637, Fall 2003 Dr.

Shaughnessy Exam 2 November 25th, 2003 Name: ANSWER KEY

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Problem
1 2 3 4 5 Total

Score
(20) (30) (12) (26) (12) (100)

1) For each structural question below, propose an experiment that would provide a conclusive answer. You should explain what experiment youll use, and what you would expect to observe. Your answer should be brief, but should be as specific as possible about what you would expect to observe in each case (20 points). a. A single stereoisomer of the unsaturated ester below was isolate. Is the product E- or Z?
H H3C CO2CH3 CH2CH3 H H3CH2C CO2CH3 CH3

A NOE difference of NOESY would be the best way to determine which isomer was the correct one. The alkyl group cis to the vinylic H would show a strong NOE interaction with it, while the trans alkyl group would not.

b. Determine whether you have cis-1-bromo-2-methylcyclopropane, or the transdiastereomer?

H3C H H H Br H H3C H H H H Br

In this case, cis versus trans could be determined by measuring the coupling constants between the proton next to the bromine and the proton next to the methyl. Since this is a cyclopropane, the couplings will be small. A cis-coupling would be 4-7 Hz, while a trans-coupling would be 1-3 Hz. Given the complexity of the coupling, obtaining the coupling constants may prove difficult. An NOE or NOESY experiment to determine whether the H next to the bromine was cis or trans (interaction or no interaction) to the methyl group would establish the stereochemistry. c. What is the activation barrier in the following process?

By using VT-NMR and line shape analysis you could determine the rate of interconversion. By measuring the rate at various temperatures, you would get the activation energy of the interconversion. The terminal vinylic CH2 and the alkyl CH2 exchange environments, so they would coalesce at some temperature.

d. Which stereoisomer of the phosphole shown below was isolated.

H P CH3 Ph CH3 P H Ph

The 2JH-P coupling is strongly dependent on whether the H is cis or trans to the phosphorus lone pair. The coupling is much larger (20-30 Hz) in the cis case than in the trans case (5 10 Hz). The coupling constant could be measured in the 1H or 31P NMR. e. Determine whether an unknown sample is ethyl acetate or methyl propionate.
O H3C O O O CH3

In ethyl acetate, the methyl singlet would be near 2 ppm, while the CH2 triplet would be near 4 ppm. In methyl propionate, the methyl singlet would be at 3.7 ppm, while the CH2 would be at 2 ppm.

2) Provided below is the 1H NMR spectrum of phenyl glycidyl ether along with expansions of the alkyl region with peak listings. Calculation of a minimized structure (MM2) gave the low energy conformation shown below (30 points).
O H2 H1 H3 H5 H4 O H2 H3 OPh O H1 CH2

4.2394 ppm (1696.31 Hz) 4.2313 ppm (1693.07 Hz) 4.2118 ppm (1685.27 Hz) 4.2038 ppm (1682.07 Hz) 3.9930 ppm (1597.72 Hz) 3.9789 ppm (1592.08 Hz) 3.9654 ppm (1586.68 Hz 3.9514 ppm (1581.07 Hz)

3.3831 ppm (1353.68 Hz) 3.3755 ppm (1350.64 Hz) 3.3729 ppm (1349.60 Hz) 3.3687 ppm (1347.92 Hz) 3.3654 ppm (1346.60 Hz) 3.3620 ppm (1345.24 Hz) 3.3585 ppm (1343.84 Hz) 3.3543 ppm (1342.16 Hz) 3.3518 ppm (1341.16 Hz) 3.3442 ppm (1338.11 Hz)

2.9217 ppm (1169.06 Hz) 2.9112 ppm (1164.86 Hz) 2.9096 ppm (1164.22 Hz) 2.8991 ppm (1160.02 Hz) 2.7738 ppm (1109.88 Hz) 2.7672 ppm (1107.24 Hz) 2.7615 ppm (1104.96 Hz) 2.7549 ppm (1102.32 Hz)

a. Should the alkyl region of the spectrum be classified as a first order or second order spectrum. Briefly support your answer. None of the alkyl protons are chemically equivalent, so there is no chance of chemically equivalent protons being magnetically inequivalent (note that this is not the case for the aromatic ring). /J = 8.9 for the H1/H2 system, so this would officially be a second order AB pair. You can see the AB nature of this pair in the unequal peak intensities of the dd features. The H4/H5 pair (/J = 12.2) is also close to being an AB system, but officially would be a first order AX system. Both systems are close enough to first order to allow fairly accurate J values and chemical shifts by simple inspection. b. Treating the spectrum as first order, determine all of the coupling constants for the alkyl region and correctly assign each alkyl proton to the correct peak. Draw appropriate tree diagrams on the peak lists above. Use the table below to report your answer. Proton Chemical Shift report to 2 decimal places 3.97 ppm 4.22 ppm 3.36 ppm 2.76 ppm 2.91 ppm Coupling (i.e. 3Ja-b)
2

Coupling Constant

H1 H2 H3 H4 H5

JH1-H2 JH1-H3 JH2-H3 JH4-H5 JH3-H4 JH3-H5

11.02 Hz 5.62 Hz 3.22 Hz 4.88 Hz 2.64 Hz 4.20 Hz

c. Use the coupling constants you determined in part a, to predict the pattern for the complex multiplet at 3.36 ppm. Use a ruler to draw a tree diagram that accurately predicts the position and relative intensity of the peaks.
H3

3J

H1-H3

= 5.62
3J H3-H5

3J 3J H2-H3

H3-H5

= 4.20

= 4.20
3J H2-H3

= 3.22

= 3.22

3J

H3-H4

= 2.86

3J

H3-H4

= 2.86

There are no exact peak overlaps, so in theory all peaks should be 1:1. In reality, though, some of the very close peaks will overlap due to insufficient instrument resolution.

3) Identify the spin system in the molecules, or portions of molecules, shown below (12 points).
CH3 F H Br aromatic ring AA'XX' AX3 F F

H H H3CO OH H H -CH2CH2only AA'BB' The two methylenes would likely have very similar chemical shifts.

H F

F H

AA'XX'

4) Provided below are the 1H NMR spectrum of nona-2-trans-6-cis-dienal, which is a fragrant compound isolated from cucumbers and melons. COSY and HETCOR 2-D spectra are also provided. Using the information provided, correctly assign each peak in the 1H and 13C NMR to the appropriate proton(s) or carbon(s) of the dienal (26 points).
O H

1.99 O H 9.45 6.08 2.36 5.26 6.80 2.22 0.92 5.39 H 194 O

20.5 158.1 25.4 14.2 133.2 133.3 32.7 126.7

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5) Oxidative addition of methyl iodide to Pd(PPh3) would be expected to give either a cis- or trans-(PPh3)2Pd(CH3)I. In the 31P{1H} NMR, a pair of doublets were observed at 26 and 32 ppm with a coupling of 23 Hz. The 1H NMR gave a dd (7 Hz and 5 Hz) at 1 ppm. Which isomer of the product was formed. Briefly support your answer (12 points).
Ph3P Pd(PPh3)4 + CH3I Pd Ph3P I CH3 H3C Pd Ph3P I PPh3

In the trans-isomer, both of the phosphorous atoms are chemically equivalent and are magnetically equivalent relative to the methyl group. Therefore, the two phosphorus nuclei would have identical chemical shifts and the same coupling constant to the methyl group. Therefore, a singlet would be observed in the 31P{1H} NMR and a triplet in the 1H NMR. The observations are actually consistent with the cis-isomer. In this isomer, both phosphorous atoms are chemically inequivalent. Therefore, they would give different chemical shifts and would couple to each other in the 31P{1H} NMR. They would also have different coupling constants with the methyl group (trans > cis). Therefore, the methyl group would give a dd in the 1H NMR spectrum.

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