(please print and circle your last name) CHEMISTRY 332 FINAL EXAM. December 11, 2006

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1 Seat No. Name (please print and circle your last name) CEMISTRY 332 FINAL EXAM December 11, 2006 I. (18 points) II. III. IV. (48 points) (50 points) (40 points) V. (26 points) VI. (18 points) TTAL (200 points) YU CAN PICK UP YUR FINAL EXAM IN 2755 GILMAN TURSDAY, DECEMBER 14 R LATER Total of best 5 quiz scores Total of best 4 midterm scores Total course points Course grade APPY LIDAYS! 1

2 I. (18 pts) Nomenclature. Provide a correct name for 6 out of 7 of the following compounds (3 pts each). Clearly cross out the one problem you do not wish to have graded. A. C C CC(C 3 ) 2 B. NC 2 C C 2 C. N C 3 D. N 2 C 3 CC 2 C C 3 E. F. G. C 3 CC 2 C 2

3 A. II. C 3 (48 pts) Predict all major carbon-containing products of 12 out of 15 of the following reactions. Make certain to indicate stereochemistry where it is pertinent. No reaction is a possible answer. Clearly cross out the three problems you do not wish to have graded (4 pts each). (C 3 ) 3 CCl AlCl 3 KMn 4 2 B. C 3 Br 2 FeBr 3 1. Mg 2. C C. (C 3 ) 3 C N 2 1. Fe, Cl 2. Na, 2 (C 3 C) 2 N D. C 3 C 2 CEt 1. NaEt, Et 1. NaEt, Et 2. dilute C 2 Cl E. N 2 NaN 2 Cl F. 2 C CCC 3 Na 1. Me 2 CuLi

4 G. C 3 C 3 PCC N 2 Na 3 BCN. 1. MgBr 1. Na 2. dilute MeI I. C 3 C SCl 2 EtN 2 J. Cl CCl AlCl 3 NaB 4 K. C 2 C I 4 (List all products and their ratio) C 2 4

5 L. C 3 C 3 2 C C C C 2 2 C CCEt 1. LiAl M. C 3 C 2 C Et 1. LiN(i Pr) 2 cat. 2 S 4 2. C 3 C 3. 2 N. NCC 2 CN 2 C CCC 3 cat. NaEt Et Ph 3 P C 2. C 2 C excess PhNN 2 5

6 III. (50 pts) Provide detailed step-by-step mechanisms for 5 out of 7 of the following reactions (10 points each). Provide resonance structures for all intermediates and indicate equilibria where they exist. Clearly cross out the two problems you do not wish to have graded. A. Et 2 NC Cl + LiNEt 2 Et 2 NC NEt 2 + LiCl B. C 3 C cat. 2 S C 3 6

7 C. C 3 C 2 C + C(C 3 ) 3 cat. Cl C 3 C 2 CC(C 3 ) D. EtCC 2 CEt + C cat. NaEt Et C C C 2 Et C 2 Et + 2 7

8 E. C 3 + Br 2 Ac Br C 3 + Br F. + ClC 2 C C 2 AlCl 3 C 2 C C 2 + Cl 8

9 G. N + ClCC 3 AlCl 3 N C C 3 + Cl 9

10 IV. (40 pts) Synthesis. Using as starting materials only benzene, organic compounds containing 4 or fewer carbons, and any necessary inorganic reagents, indicate how 4 out of 6 of the following compounds might be synthesized in the laboratory. Use only reactions expected to go in good yield. Clearly cross out the two problems you do not wish to have graded. F F A. B. CC 2 C NEt 10

11 C. C 3 C 3 (C 2 ) 3 C C C 3 D. (C 3 ) 3 C CN 11

12 E. C 3 C 2 N 2 F. C 2 Et C 2 CC 2 C 2 CC 3 C C 3 12

13 V. (26 pts) Miscellaneous. A. (4 pts) Circle the most acidic compound and underline the least acidic compound. C 3 C 2 C CC 3 CC 3 B. (4 pts) Circle the most basic compound and underline the least basic compound. NMe 2 C 3 N 2 N C N 2 C 3 C 3 C. (4 pts) Circle the one type of polymerization that has most likely been used to prepare each of the following polymers. 1. C 3 C 2 C x a.) ring opening b.) coordination c.) anionic d.) block 2. CN C 2 C x a.) cationic b.) step growth c.) anionic d.) ring opening D. (4 pts) Circle all compounds that will react with NaB 4 to give a secondary alcohol. CC 3 C C E. (4 pts) Circle all compounds that are readily reduced to a primary amine. CN 2 CN C 3 N 2 NMe 2 13

14 F. (6 pts) Identify the type of orbital symmetry controlled reaction given below using appropriate TERMS AND NUMBERS. (Examples: electrocyclic ring closure, 4+2 cycloaddition, 3,3-sigmatropic rearrangement, etc.). You do NT need to identify any additional terms EtCC CCEt C 2 Et C 2 Et 2. 14

15 VI. (18 pts) Carbohydrates. A. (8 pts) 1. Draw all possible D-aldopentoses. Incorrect or duplicate structures cancel out correct structures. (4 pts) 2. Draw all of the osazones that you expect to form when the above D-aldopentoses are allowed to react with excess PhNN 2. (4 pts) 15

16 B. (10 pts) ) Using the letters corresponding to the following structures, provide answers to the questions below. Wrong answers cancel out correct answers. C C 2 C C 2 C C 2 C C 2 C C 2 C 2 C C 2 A B C D E F 1. All D-hexoses 2. All ketoses: 3. All L-aldopentoses: 4. All aldopentoses that will react with 2 and cat. Ni to give an optically inactive product: 5. All aldopentoses which will react with N 3 to give an optically active product: 6. Two aldopentoses which will give the same osazone: 16