CHEMISTRY 332 FINAL EXAM. December 14, I. (18 points) II. (48 points) III. (50 points) IV. (40 points) V. (26 points) VI.

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1 Seat No. Name (please print and circle your last name) CEMISTRY 332 FINAL EXAM December 14, 2005 I. (18 points) II. (48 points) III. (50 points) IV. (40 points) V. (26 points) VI. (18 points) TTAL (200 points) 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. 2 C CC B. NCC 3 C. C 3 C (C 3 ) 2 C D. S E. CC CC 2 C 3 F. C 2 C 3 G. 2

3 II. (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). A. C 2 CEt 1. NaEt, Et 2 C CCC cat. NaEt, Et B. C C 3 C 3 C 2 N 2 NaB 3 CN 2 C CC 2 Br C 3 NaCN 1. LiAl 4 C. C C 2. 2 C 3 C 2 Br D. C 3 C(C 3 ) 2 N 3 2 S 4 1. Cl, Fe 2. Na E. 2 N N 2 NaN 2 Cl C 3 F. C 3 C 2 CEt 1. LiN(i-Pr) C CC 2 Br 1. LiAl

4 G. C 2 C 2 I 4 (list all products and their ratio). C3 C 3 NaB 4 N I. C 3 N 1. NaN CCl 2 N J. C SCl 2 C 3 AlCl 3 C 3 K. 2 C CCC 3 Ph 3 P C(C 3 ) 2 L. C Na 1. Me 2 CuLi

5 M. Br 1. Mg 2. C Et cat. 2 S 4 N. PCC t-bun 2. CEt 1. Na C 2 Br 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. (C 3 ) 3 C + BrC 2 AlCl 3 (C 3 ) 3 C C 2 + Br B. N + KC(C 3 ) 3 + KBr Br N C(C 3 ) 3 6

7 C. CEt + Me cat. Cl CMe + Et D. + t-bun 2 cat. Ac N-t-Bu + 2 7

8 E. + EtCEt 1. NaEt 2. mild 3 + CEt + Et F. + Br + 2 Br 8

9 G. C 3 CN 2 Br 2 Na C 3 N 2 + C 2 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. A. C 3 C C 3 C 3 B. C C C 3 10

11 C. C 3 C 2 C 2 N C C 3 D. C 3 CC 2 C C 2 11

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

13 V. (26 pts) Miscellaneous. A. (4 pts) Circle the most acidic compound and underline the least acidic compound. CC 3 C 3 C 2 C 2 C C 2 C 3 CC 2 CC 3 B. (4 pts) Circle the most basic compound and underline the least basic compound. C N N 2N N 2 C. (4 pts) Circle all compounds that will readily undergo cationic chain growth polymerization. 2 C CC 2 Me 2 C CEt 2 C CPh 2 C CC C 2 D. (4 pts) Circle all compounds that will react with NaB 4 to give an alcohol. Me Me 2 C CC 2 C CEt E. (4 pts) Circle all compounds that are readily reduced by LiAl 4. CN C 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 C CC 2 C C 2 2 C CC 2 C 2 C Me Me Me Me 2. 13

14 VI. (18 pts) Carbohydrates A. (8 pts) 1. Draw all possible 2-ketopentoses. Incorrect or duplicate structures cancel out correct structures. (4 pts) 2. Circle all of the above 2-ketopentoses that are D sugars. (2 pts) 3. Draw the osazone that you expect to form from any one of the above 2-ketopentoses when allowed to react with excess PhNN 2. Show both the starting 2-ketopentose and the osazone product. (2 pts) B. (5 pts) 1. Draw all possible 3-ketopentoses. Incorrect or duplicate structures cancel out correct structures. (3 pts) 2. Circle all optically active 3-ketopentoses drawn above. (2 pts) 14

15 C. (5 pts) Circle all of the following terms that correctly describe the following compound (NTE: wrong answers will be subtracted from correct answers). C 2 optically inactive C 3 aldose ketose pyranoside reducing sugar reactive towards Fehlings solution furanoside a monosaccharide a D sugar forms an optically inactive product upon reaction with 3 + reactive towards Tollens reagent an epimer of ß-methyl glucoside 15