Final Fall 02.pdf

page 1 —— ptsNAME:________________________Chemistry 233 FINAL 12/18 FALL 2002Associate Professor: Dr. Gergens1. (52) Circle the most (highest); underline the least (lowest)acidic alpha protonOOOOOOCH 3 CH 2 CH 3EtO CH 2 OEtCH 3 CH 3 CH 3 OEtbasicatom12 3ONH 2 C NH NH 2semicarbizidestable sigmacomplexN••⊕HEN••⊕HEreactive position inS E Ar reactionsA B C D••CH 3 CN••NH 2OboilingOOC-NH 2 C-OHCH 2 OH CH 2 NH 2ABCDQuestions g-i refer to the structure of Olestra.RCOOCH 2BRCOOCO AORCOO CORRCO O OCH 2 O-COREDRCO OCH 2OO COROlestraf. g.h.polyesterpolyetheri. The heterocyclic ring B is a ______________ ring.A. furan B. tetrahydrofuran C. tetrahydropyran D. dihydropyran E. pyrole

page 2 —— pts2. (32) Mechanisms and ResonanceDraw the mechanisms for the following trans formations. Your mechanism should show individual steps inthe reaction that lead to all the products formed. Use curved arrows, indicate all formal charges, and showall resonance forms.DO ONLY ONE. CLEARLY MARK YOUR CHOICECH 3 CH 2 CH 2 C N••1.CH 3 MgBr2. H 2 OCH 3 CH 2 CH 2N-HC CH 3+ MgBrOHCH 3 CH 2 CH 2N-H H + ,H 2 OOC CH 3 CH 3 CH 2 CH 2 CCH 3+ NH 4+

4. (20) Mechanisms and Resonancepage 3 —— ptsDraw the mechanisms for the following trans formations. Your mechanism should show individual steps inthe reaction that lead to all the products formed. Use curved arrows, indicate all formal charges, and showall resonance forms.DO ONLY ONE. CLEARLY MARK YOUR CHOICEOOHO - , ∆CH 3 CH 3CH 3 CH 3CH 3OCHCCH 3CH 3+H 2 OCH 3OOHH + , ∆CH 3 OH CH 3 OCH 3O+H 2 O

page 5 —— pts6. (48) COMPLETE SIX . Give the most appropriate immediate synthetic precursors for the compound inthe box at the right for the name reaction given at the left.. Clearly mark your choices by circlingthe corresponding letter.name reaction synthetic precursors for the synthesis compoundA. acetoacetic estersynthesisCH 3OB. S E Ar reaction OC. iodoform reactionOCH 3O -CHI 3D. reductive-aminationNHE. HofmannrearrangementNH 2F. nitrile synthesis CH 2 CH 2 CNG. Grignard synthesisHO(protecting grouprequired)HOCH 2OHH. 1,4 AdditionBrI. Hofmann eliminationN(CH 3 ) 2

page 7 —— pts7. (36) Complete the following reactions by adding the starting material(s), conditions, and/or product(s).Ca(OH) 2COOHCOOH∆thermodynamicproductMgBrCH 32CH 3O1.CH CH CH 3 1.cold KMnO 4OBr 2OO2. + H ,H2 O2.Ph 3 PCH 2show correctstereochemistry

page 8 —— pts8. (34) Synthesize TWO of following compounds from the given starting materials.Clearly mark your choices.CH 3COOHCH 3para-amino-benzoic acidPABAbeginning from any 2 carbonstarting materialCH 3C O-CH 3CH 3 MTBENH 2CH 3OC-OEtCH 3O O OH NH 2C-CH-C-OEtCH 3

9. (32) Synthesize a total of TWO of the following compounds from the given starting materials.Clearly mark your choices.page 9 —— ptsCH 2 CH 2 CN CH 2 -NH 2 O CH 2 -OHCH 3CH 3NH 2OHCOOH C-N(CH 2 CH 3 ) 2ON,N-diethyl-meta-toluamide(DEET; mosquito repellent)