Name: ________________________________ ID #: ________________________________

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EXAM II Organic Chemistry 2302-001 April 3rd, 2013 ! Exam is 7 pages including a Periodic Table and Spectroscopy Tables (make sure that you have them all). ! Do not open your exams until instructed to do so. ! Have your ID in hand when you come forward to turn in your exam. ! Place your last name on all pages of exam in case your exam gets separated. ! You may NOT use calculators, notes, or models for the exam. ! Please raise your hand if you have a question and a TA or I will assist you. ! You will be given 50 minutes to complete your exam. When time is called, all pens/pencils are to be put down and no more written work done. Points will be deducted from exams of those who keep working. ! Read each question carefully and be sure to answer all parts of each question.

1.) 2.) 3.) 4.) 5.) 6.) 7.)

___________/ 6 pts ___________/ 9 pts ___________/ 15 pts ___________/ 36 pts ___________/ 12 pts ___________/ 10 pts ___________/ 12 pts

Total ___________/ 100 pts

Last Name: ___________________________

1. Nomenclature. 6 points Draw the structure corresponding to each name. Indicate stereochemistry where appropriate. a. (S)-2-ethylpentanal b. butanoic anhydride c. methyl benzoate

2. Spectroscopy of Carbonyls. For each of the following pairs of molecules below circle the molecule whose carbonyl absorbs a higher frequency of light in an IR spectrum and then explain what causes this difference in absorption. 9 points a.
O O vs O O

b.

O Cl vs

O N

c.

O H vs

O H

EXAM II

Perkins, Chem 2302-001 Spring 2013

Last Name: ___________________________

3. Multiple Choice. For each of the following questions, clearly circle the correct answer(s). Some questions may have more than one answer, so circle all that apply. 15 points a. Which of the following carboxylic acid derivatives will under go nucleophilic acyl substitution with sodium ethoxide (NaOEt)?
O NH 2 O Cl O OH O O O

b. Which product will be formed from the treatment of the 2-cyclohexenone with one equivalent of hydrogen gas with Pd-C catalyst?
O H 2 (1 equiv) Pd-C O OH O OH

c. The reaction of (R)-3-methyl-2-pentanone with LiAlH4 followed by addition of water yields a pair of stereoisomers. How are these stereoisomers related? Diastereomers Enantiomers

d. Identify the structure of the polyhydroxylaldehyde that can be cyclized to give "-DGlucose.
HO Polyhydroxylaldehyde HO HO O OH OH

!-D-Glucose

OHC HO HO

HO OH

HO OH HO HO

OH CHO OH

HO HO HO

O O

OH

e. Which of the following carbonyl compounds will form the highest percentage of gem-diol at equilbrium with reacted with H3O+?
O H O H O Br O OCH3 O Br

EXAM II

Perkins, Chem 2302-001 Spring 2013

Last Name: ___________________________

4. Contrasting Reactions. For each of the following reaction schemes, draw the product in the box provided. You dont need to worry about stereochemistry. If no reaction will occur indicate No Reaction in the box. 36 points a.
O OH pyridine O Cl 1. LiAlH(OtBu) 3 2. H 2O

b.
1. NaCN 2. NaOH, H 2O Br 1. Mg, ether 2. O 3. H 2O

c.
NaBH 4 CH3OH H O Ph 3P

d.
1. MgBr O 1. (CH3)2CuLi 2. H 2O

2. H 2O

e.
1. CH3CH 2Li 2. H 2O O O excess H 2O H+

f.
NaOH, H 2O O NH 2 1. LiAlH 4 2. H 2O

EXAM II

Perkins, Chem 2302-001 Spring 2013

Last Name: ___________________________

5. Fill in the Starting Reagents. For each of the following molecules, give the starting carbonyl compound and amine or alcohol that are needed to prepare each product. 12 points a.
+ H+ O O

b.
+ H+ N

! 6. Mechanism. Draw a stepwise mechanism for the following reaction. Be sure to show all arrows, reactive intermediates and resonance structures. 10 points
O O H+ + H 2O (excess) O + 2 CH3OH

EXAM II

Perkins, Chem 2302-001 Spring 2013

Last Name: ___________________________

7. Synthesis. How would you synthesize the following ester starting from t-butyl alcohol? You may use any inorganic reagents necessary. Any additional carbons must come from methanol or CO2. 12 points
OH O O

! !

EXAM II

Perkins, Chem 2302-001 Spring 2013

! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !

Last Name: ___________________________

EXAM II

Perkins, Chem 2302-001 Spring 2013