Organic Chemistry II: Practice Exam #3A Answer Key

1. Reaction of the diene shown below with HBr yields up to four products.

A. Write structures for the four products and a mechanism for their formation.

B. Construct an energy diagram for this reaction. Clearly label your starting materials, intermediates and products in the mechanism for part A and in the diagram.

C. If the reaction is performed at low temperature, which product will be favored? __D__ Product D comes from the most stable resonance form of the most stable intermediate (B). Therefore it will form fastest and will be favored at low temperature, where addition of the Br- nucleophile in the second step of the reaction is irreversible. D. If the reaction is performed at high temperature, which product will be favored? __C__ Product C is the most stable of the four products because its alkene is the most substituted. Therefore it will be preferred at high temperature, where addition of the Br- nucleophile in the second step of the reaction is reversible. This allows the kinetic product (D) to be converted to the more stable thermodynamic product (C).

2. Draw structures for the product of any five (5) of the following reactions. If multiple products are possible, only show the major product. If you answer more than five, you will receive credit for the best five.

3. Reaction of 4-methoxypyridine with Cl2/FeCl3 yields a mixture of two monochlorination products.

A. Write structures for the two products in the boxes above. B. Use resonance forms to predict the major and minor products.

The intermediate leading to the first product (3-chloro-4-methoxypyridine) has four resonance forms, compared to only three resonance forms for the intermediate leading to the second product. This means that the intermediate for the first product will be more stable and will form faster, leading to the major product. (Note that the lone pair of electrons on the nitrogen in the ring cannot be used to draw additional resonance forms. This is because these electrons are in an sp2 orbital in the plane of the ring. There is no overlap between this orbital and the p-orbitals on the other atoms in the ring.)

4. Circle the appropriate compound for each of the following pairs.

5. Complete one of the two following syntheses. If you do both, you will receive credit for the better one.
A. Use benzene and any other reagents to synthesize compound 1.

The keys to solving this problem are to recognize that (1) the nitrogen in the final product most likely was added to the ring as a nitro group and (2) the propyl group must be added by a Friedel-Crafts acylation followed by reduction in order to avoid the rearrangement that would occur if an alkylation reaction were attempted using CH3CH2CH2Cl and AlCl3.

B. Use benzene and any other reagents to synthesize compound 2.

Both substituents in the product are alcohols, so you will need to recall the reactions that produce alcohols in order to do this problem: Grignard or organolithium plus aldehydes/ketones, or reduction of carbonyl groups. There are actually multiple correct routes for this synthesis. The one shown above uses both of these alcohol-forming reactions.

6. Solve one of the two following problems. If you do both, I will count the one on which you do better. (NMR table is on page 9; s = singlet, d = doublet, d of d = doublet of doublets, m = multipled, q = quartet, t = triplet) A. Reaction of compound 1 with diethylamine yields compound 2. Based on the spectral data provided below, propose structures for 1 and 2. 1 (C7H7NO2) 2 (C8H10N2O)
1

H-NMR

8.3 (s, 1H); 7.8 (d, 1H); 7.6 (d, 1H); 7.4 (d of d, 1H); 3.6 (s, 3H)

There are four aromatic protons and a methyl group based on the NMR data. Subtracting the methyl group from the formula leaves you with 6 carbons, which suggests the presence of a benzene ring. A tempting structure to write would have a disubstituted benzene with a methyl group and a nitro group meta to one another. However, the chemical shift of the methyl group in such a molecule would be in the 2.2-2.5 range based on the table. In addition, that compound would not react with dimethylamine so the structure is clearly incorrect. The alternative to a disubstituted benzene is a monosubstituted pyridine. Assuming that the methyl group is attached to an oxygen (to give the downfield shift) leaves CO unaccounted for, meaning a carbonyl is present. Making the substituent the ester shown above satisfies the formula, NMR data, and reactivity, since the amine can react with the ester to make an amide with the correct formula given for 2. B. Reaction of compound 3 with 2-methylpropene and phosphoric acid yields compound 4. Based on the spectral data provided below, propose structures for 3 and 4. 3 (C9H12O) 4 (C13H20O)
1 1

H-NMR H-NMR

7.6 (d, 2H); 7.1 (m, 3H); 4.1 (m, 1H); 1.6 (d, 6H) 7.6 (d, 2H); 7.3 (d, 2H); 4.1 (m, 1H); 1.6 (d, 6H); 1.3 (s, 9H)

3 is clearly a monosubstituted benzene because there are five aromatic protons. The last two peaks are typical of an isopropyl group, with the CH next to a heteroatom. The ether shown above is the only possible structure. The NMR data for 4 indicate that a substituent was added to the para position of the ring since there are four aromatic protons and they have the two 2H- doublet pattern. The new peak at 1.3 is typical of a t-butyl group. The reaction works by first protonating the alkene to make a tertiary carbocation, which then reacts with 3 by electrophilic aromatic substitution.