CHEMISTRY 211 PRACTICE EXAM II – ANSWER KEY 1) Give IUPAC names to the following compounds. I F F H3C Br CH3 Cl CH2CH3 CH3CI2CH2CH2 CH2CH3 I CH3 (5R,6R)-6-chloro-5-ethyl-2,2,5,6-tetraiodooctane (S)-4-bromo-1,1-difluoro-2,2,4-trimethylcyclopentane 2) Draw accurate structural formulas for the following molecules (next to the name). a) cis-1-fluoro-3-iodocyclopentane (both enantiomers) H F H H H I I F b) both diastereomers of the structural formulas drawn in 2a H I I F H H H F c) methylene fluoride CH2F2 d) (3S,4R)-3,4-dibromo-1,6-dichlorohexane (Fischer Projection) CH2CH2 Cl H Br H Br CH2CH2 Cl e) a diastereomer of structural formula 2d (Fischer Projection) CH2CH2 Cl Br H H Br CH2CH2 Cl f) the enantiomer of structural formula 2e (Fischer Projection) CH2CH2 Cl H Br Br H CH2CH2 Cl 3) Indicate whether the following pairs of structural formulas represent structural isomers, stereoisomers or the same molecule. If stereoisomers, classify each pair as conformational or configurational and as enantiomers or diastereomers. In addition, label each compound as chiral or achiral and if appropriate, as cis, trans or meso. H CH2OH H H 3C OH OH CH3 chiral chiral NH2 NH2 H H NH2 H H I I H H H H I I cis achiral meso Conformational Diastereomers cis achiral meso OH H H H HO OH H Identical NH2 trans achiral HO Configurational Enantiomers CH2OH trans chiral Structural Isomers trans achiral H H H Br Br Conformational Enantiomers H Br Br cis chiral cis chiral CH2SH CH2SH F H H F F H F H CH2SH achiral meso CH2SH chiral Configurational Diastereomers 4) Write stepwise, reasonable complete mechanisms for the following transformations. Use curved arrows to indicate the bonding changes taking place. Predict and/or rationalize the formation of the major product. Include stereochemistry where indicated. Cl CH3 CH CH OH H2O CH3 ∆ OH + CH3 CH2 CH CH C + HCl H O H H O H + H O H Cl CH3 CH H3O + CH3 CH CH CH3 CH CH OH CH3 CH CH CH H H O H H CH3 CH H C 2o R+ O H H CH3 CH C + + H H CH3 CH H3O O H H CH3 CH C OH C 3o R+ CH3CH2CH2 CH(CH3)2 + CH3O (E2) ? + CH3OH + I I CH3 HOCH3 OCH3 + H CH3CH2CH2 H CH3 H CH(CH3)2 H H I CH3CH2CH2 CH(CH3)2 CH3 H CH3CH2CH2 CH(CH3)2 CH3 + I 4) continued.................... CH2CH3 CH3 C CH2 Br CH3 C ∆ CH3 CH2CH3 CH2CH3 CH3CH2 OH CH CH3 + CH3 C CH2 CH3 + HBr OCH2 CH3 Major SN1 Faster: CH2CH3 CH3 C CH2 Br + Br CH2CH3 CH3 CH3 C CH2 CH3 CH2CH3 CH3 CH3 C CH2 3o R + O O CH3 C CH2 CH3 OCH2CH3 + H CH2CH3 H O O CH2CH3 H H E1 Slower: CH2CH3 C CH3 CH2CH3 H CH3 CH2CH3 CH2CH3 CH CH3 CH3 C CH CH3 H O + H CH2CH3 H O CH2CH3 H CH3 H 3C + NH3(aq) Cl (E1 Only) ? + ? + ? + NH4Cl(aq) Major NH3 CH3 H H3C CH3 CH3 H3C H3C Cl + NH4 + Cl Major (tetrasubstd'; most stable; fastest formed) CH3 H 3C H CH3 H3C NH4 + H NH3 H H C CH3 CH3 H2C + H NH3 NH4 CH2CH3 5) Draw accurate stereochemical formulas (Fischer projections or dash-wedge formulas) for the products obtained in the following reactions. Label each separable fraction as optically active or inactive. More than one product may be possible. CH(CH3)2 CH(CH3) 2 CH3 Cl CH3 SCH3 CH3SH CH3 (SN1) CH3 CH(CH3)2 SCH 3 + CH3S CH3 SCH 3 CH(CH3)2 CH(CH3) 2 H CH3CH2O H (E2) CH3 C(CH3)3 CH3CH 2 opt. inact. (achiral) F F C opt. act. H C(CH3 )3 H SCH 3 CH(CH3)2 opt. inact. (meso) Br CH3CH2 CH3 NH2 I H2N C (SN2) H opt. act. CH3 6) Circle the one which: a) is the best choice of substrate and conditions which favor an SN1 reaction. CH3NH2 ∆ CH3 CH3 Cl C CH3 C CH2CH3 CH2CH2 Cl CH3NH2 ∆ CH3 CH3 b) are the compounds which would require resolution to separate all of their possible configurational stereoisomers (more than one answer possible). isopropyl fluoride bromoform 1,2-dibromocyclopropane t-butyl iodide isobutyl chloride 1,3-dichlorocyclobutane sec-butyl fluoride 1,4-diiodocyclohexane c) is the correct order of nucleophiles or bases favoring increasing rate of reactions whose kinetics would exhibit first-order dependence on the concentration of the alkyl halide substrate [R-X] only. H2Se 1 4<2<1<5<3 H2As2 3<5<1<2<4 H2O 3 3<5<1<4<2 HSe4 2<4<1<5<3 H2S 5 2<3<1<5<4 4<5<1<3<2 6) continued.............. d) is the best choice of substrate and conditions which favor an E2 reaction. I Br Br DMF CH3 t-BuO DMF CH3 e) is the pair of compounds which would be produced in equal amounts by an optically inactive reaction mixture. CHO H OH & HO CH3 CH3 CH3 CH3 H H H CHO OH OH & HO H H I H Br & OH H CH3 CH3 I I H H Br H Br Br H I Br H Br Br H H & & Br H H H f) is the best choice of substrate and conditions for a bimolecular substitution reaction whose mechanism is a one-step concerted process. PH2 MeCN CH3CH2 CH2 Br CH3 Br (CH3)2P Me2CO g) is a geminal dihalide with three possible stereoisomers, one of which would exhibit no net rotation of plane-polarized light. Cl H3C Cl Cl F Cl F F F H3C CH3 CH3 F F H3C CH3 Cl CH3 CH3 Cl Cl h) is the correct order of decreasing rate of substrate reactivity for substitution reactions whose transition state for the rate-determining step (RDS) involves two molecules. CH3 CH2 Br 1 3>4>2>5>1 CH2 I Br 3 2 1>5>2>4>3 4>1>2>5>3 CH3 CH3 Br F 4 3>5>2>1>4 5 4>2>5>1>3 i) is the best choice of substrate and conditions which favor an E1 reaction. Cl Cl OH OH DMSO H2O 3>1>5>2>4 6) continued.............. j) are characteristics of a first-order elimination (E1) reaction (more than one possible). inversion second-order rate law bimolecular reaction rearrangement stereospecificity base-independent rate anti-coplanar conformation unimolecular reaction stepwise process concerted process carbocation (R+) intermediates k) is an achiral object. human’s hand eagle's wing pig's tail horse’s ass gorilla's foot
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