(CHE 325) Organic Chemistry II

Spring 2011

EXAM #1
Name: ID#: KEY

Check your exam to be sure it is complete. There are nine questions in this exam. It is worth 100 points. To receive full credit for your submissions, make sure you do your own work. Read each question carefully, and answer in clearly legible and coherent English. Use the back of the page for additional space if needed. Partial credit will be given, so show your work. Don't fall in love with individual problems. Do the ones first which you can do easily. Pace yourself. Good luck! N. Totah

1. 2. 3. 4. 5. 6. 7. 8. 9.

(of 6) (of 6) (of 8) (of 14) (of 12) (of 12) (of 20) (of 12) (of 10)

Total:

(100)

Name: 1. (6 points) Give IUPAC names for the following compounds: a.

NO2 Br

o-brom onitrobenzene

b.
NH2 Cl Cl

CH2Cl3

2,6- dichl oro-4-e thylaniline

2. (6 points) Write a complete, stepwise mechanism transformation. Use curved arrows to denote electron flow.

for

the

following

H2SO4

OH2 or H H H

HSO4

Name: 3a. (6 points) Consider the compounds below:

CH3

*
O A

CH3 CH3 CH3 CH2 CH B

1

O CH3

i. How many signals would you expect to see in the compound A? Answer: two

H NMR spectrum of

ii. What is the relationship between the two protons marked with an asterisk (*) in compound A? (circle one) different homotopic enantiotopi c diastereotopic

iii. The 13C NMR spectrum of compound B shows five signals. How many signals in the corresponding DEPT-135 spectrum would point up? Answer: four

3b. (2 points) What is the most likely structure of the molecule that gave the following 1H NMR spectrum? Circle your answer.

O C D E

Name: 4a. (8 points) Label the following structures as aromatic, antiaromatic, or nonaromatic.

N H nonaromatic antiaromatic

N O

aromatic

aromatic

4b. (6 points) Which of the following hydrocarbons (A or B) would you expect to be deprotonated most readily in the presence of a base? Briefly explain. For full credit, you will need to discuss both compounds.
H H H H

Compound B is expected to be more acidic. In compound A, loss of a proton re sults in formation of an unstable antiaromati c com pound (8 electrons; cycloheptatrienyl anion). However, deprotonati on of compound B results in f ormati on of an stable, aromatic system (6 electrons; cyclope ntadienyl anion). Due to the stability associatied with aromatici ty, compound B should thus be deprotonated more readily (e.g. is more acidic).

Name: 5a. (4 points) Rank the following compounds in order of decreasing reactivity to Electrophilic Aromatic Substitution. Rank the most reactive compound 1, and the least reactive compound 4. Place the number corresponding to the relative reactivity of each compound in the blank below it.

OCH3 Cl

OCH3 As(CH3)3 NO2 CH3 1

SO3H

5b. (4 points) Rank the following compounds in order of decreasing reactivity to Nucleophilic Aromatic Substitution. Rank the most reactive compound 1, and the least reactive compound 4. Place the number corresponding to the relative reactivity of each compound in the blank below it.
NO2 Cl NO2 1 NO2 Cl NO2 Cl CH3 4 2 Cl

NO2 3

5c. (4 points) Trifluoromethylbenzene undergoes Electrophilic Aromatic Substitution. Do you expect this compound to react faster or more slowly than benzene under identical reaction conditions (e.g. is the -CF3 group activating or deactivating)? Briefly explain your reasoning. CF3

trifluoromethylbenzene Trifluoromethylbenzene will react more slowly than benze ne (CF 3 is deactivati ng. The CF 3 group withdraws electron density from the ring by inducti on making the ri ng a poorer nucleophile.

Name: 6. (12 points) Match each of the compounds A, B, and C with the appropriate broad band decoupled 13C NMR spectra shown below. Briefly explain your reasoning. Note: for full credit, you rationale must unambiguousely exclude the other two compounds. Cite chemical shifts and identify relevant functionality in your discussion. Be specific.

CH3 A

O O

CH3

CH3 B O

OH

CH3 OH C

OH

13

C NMR spectra:

i. Compound:

TMS

ppm

Reasoning: Has a C=O peak (ca. 180 ppm) Does not show peak at ca. 60ppm (C-O linkage)

Name: ii. Compound: C

TMS

ppm

Reasoning: has no C=O at ca. 180ppm or shows C=C peaks ca. 100-150ppm

iii. Compound:

TMS

ppm

Reasoning: shows both C=O (180 ppm) and C-O (60ppm) peaks

Name: 7. (20 points) Predict the major product(s) for the following reactions. Assume reagents are present in equimolar amounts unless otherwise indicated. Clearly depict any stereochemistry. "No Reaction" is a possible answer. CAUTION! Don't confuse reactions that will occur slowly with those that will not occur! a.
CH3 O2N HNO3 H2SO4 CH3 O2N NO2

b.
OCH3
Cl O

OCH3 CH3O
O

CH3O

AlCl3

c.
I2 CuCl2

Me3N

Me3N

d.
SO3H CH3 1. NaOH, 300C 2. H3O+

OH CH3

Name: e.
OH CH3 SO3 H2SO4 HO3S OH CH3 + OH CH3

SO3H

f.
Br CH2 O2N Br2 FeBr3 O2N CH2 O2 N Br CH2

g.
KMnO4 (excess) H2O
(step 1)

CO2H CO2H

product(s) of step 1

CH3Cl AlCl3
(step 2)

No Reaction

h.
Br NBS CCl4, (PhCO)2O

Name: 8. (12 points) Propose a structure that is consistent with the spectral data provided. For full credit, show your work and briefly explain your reasoning. As part of your answer, clearly correlate each peak in the 1H NMR spectrum to the structure of your compound (e.g. label the peaks). F.W.: C10H14 IR: 740 cm-1 1 H NMR: integral values are listed above each peak
3H a a d a a a b c e

4H

3H

d 2H c 2H e

ppm

IR suggests this is a 1,2-disubstituted benzene NMR supports structure as per labelled peaks

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Name: 9. (10 points) Show how you would synthesize the following compounds from benzene or toluene. Use any other organic or inorganic reagents required. Avoid product mixtures if possible, but assume that ortho and para products can be separated. Clearly indicate at what stage (if any) such separations are needed. a.
NH2 Cl HNO3 CH3 CH3 H2SO4 CH3 NO2 (separate) NH2 Cl2 FeCl3 CH3 CH3 Cl CH3 + NO2

NH2 1. Fe, H3O+ 2. NaOH or H2,Pd

b.
SO3H O Cl AlCl3 O

H2 Pd/C

SO3 H2SO4

SO3H

(+ ortho)

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