CHEM 234, Spring 2016 COMPLETE THIS SECTION : Up to TWO POINTS will be removed for incorrect/missing information!

Transcription

1 EM 234, Spring 2016 FIAL EXAM MPLETE TIS SETI : Up to TW PITS will be removed for incorrect/missing information! Ian R. Gould PRITED FIRST AME PRITED LAST AME a Mg Person on your LEFT (or Empty or Aisle) Person on your RIGT (or Empty or Aisle) **YU ARE T ALLWED T TAKE SPARE PIES F TIS EXAM FRM TE TESTIG RM** 1 /12 10 /40 PRIT YUR AME EA PAGE! 2 /20 11 /30 READ TE DIRETIS AREFULLY! 3 /20 USE BLAK PAGES AS SRAT PAPER 12 /35 4 /10 work on blank pages will not be graded /40 5 /20 WRITE LEARLY! 14 /20 MLEULAR MDELS ARE ALLWED 6 /24 15 /8 D T USE RED IK 7 /72 Points Removed (cover errors) /2 D'T EAT, USE MM SESE! 8 /8 Extra redit /5 9 /16 Total (incl Extr /175+5 e Li Be B F e Interaction Energies, kcal/mol Al Si P S l Ar K a Sc Ti V r Mn Fe o i u Zn Ga Ge As Se Br Kr Rb Sr Y Zr b Mo Tc Ru Rh Pd Ag d In Sn Sb Te I s Ba Lu f Ta W Re s Ir Pt Au g Tl Pb Bi Po At Rn R 2 R (δ, ppm) variable and condition dependent, ca. 2-6 δ R R ASU or Posting ID lass you are REGISTERED FR (onground or hybrid) Room you would take this test in if you were in class (LS A-191 for onground and PS -152 for hybrid) Aromatic R 2 R 2 Xe R 2 Aromatic Ar mainly R Eclipsing / ~1.0 /Me ~1.4 Me/Me ~2.6 Me/Et ~2.9 Infrared orrelation hart small range usually range of values strong broad peak peaks R 2200 broad with spikes ~ broad ~ broad ~ R (cm -1 ) 1500 MR orrelation harts 2 X R R 2 R Gauche Me/Me ~0.9 Et/Me ~0.95 i-pr/me ~1.1 t-bu/me ~2.7 Alkyl X Alkyl 3 > 2 > > 2 > 1 0 0

2 M 234, Spring 2016, FIAL EXAM AME Question 1 (12 pts.) Provide a IUPA name for the following structure, do not forget to use E/Z and R/S as appropriate. Br Question 2 (20 pts) Rank the following in order of increasing Bronsted acidity, and provide a BRIEF explanation. You MUST draw the structures of ALL F the conjugate base anions including ALL reasonable resonance contributors A B < < weakest strongest Extra redit Question (5 pts). What kind of functional group is hydrolyzed to form soap? carboxylic acid ester amide aldehyde

3 M 234, Spring 2016 FIAL EXAM -3 - AME Question 3 (20 pts.) For the following acid/base equilibrium: draw the curved arrows showing bond making/breaking b) indicate which is the STRGER and the WEAKER acid and base on each side c) give a BRIEF explanation for your choice of stronger/weaker that includes the phrase "energy of the electrons" + + d) Indicate which reaction (left to right or right to left) is faster and which is slower and indicate on which side the equilibrium lies e) Draw a PRPERLY labelled reaction energy diagram, indicate the position of the transition state and include a drawing of the transition state Question 4 (10 pts.) Rank in order of increasing equilibrium constant for formation of a hydrate. Give a BRIEF explanation. A B < < smallest largest

4 M 234, Spring 2016, FIAL EXAM AME Question 5. (20 pts.) Give a curved arrow-pushing mechanism for the reduction of the provided ester to butanol and methanol. You must draw the Lewis structure of the Al 4 anion and you MUST show exactly where each proton comes from and goes to here, no ++ and -+ notation, and you must also show how the methanol is formed. Me 1. LiAl Me Question 6 (24 pts.) For the reaction between structures A and B below, you are going to determine whether the PRVIDED product is allowed or forbidden, using F.M.. theory. Draw the curved arrow-pushing that describes the bond-making and breaking processes. D D Me Me Δ Me + Me Me D A B D Me b) Was the PRVIDED PRDUT (which may or may not be allowed) formed via suprafacial or antarafacial reaction for reactant A? c) Was the PRVIDED PRDUT (which may or may not be allowed) formed via suprafacial or antarafacial reaction for reactant B? d) Draw the M for A and the LUM for B on TP of the structures that are redrawn for you below, for EA, give the number of vertical nodes Me D D Me Me # vertical nodes = # vertical nodes = M for A LUM for B e) Is the cycloaddition reaction shown above allowed or forbidden. Give a BRIEF explanation that includes the words "suprafacial" and/or "antarafacial" as appropriate

5 M 234, Spring 2016, FIAL EXAM AME Question 7 (72 pts) Provide the missing major organic products for the following reactions. Do not forget to include stereochemistry as appropriate and IDIATE AY RAEMI MIXTURES. heat (electrocyclic ring closure reaction) b) 1. Excess PhMgBr c) 2 S 4 d) 2 Ph l 1 equivalent Br 1. Mg. TF e) (ignore stereochemistry for this problem) 2 f) + F 3 heat F 3

6 M 234, Spring 2016 FIAL EXAM AME Question 7, ontd... Provide the missing major organic products for the following reactions. Do not forget to include stereochemistry as appropriate and IDIATE AY RAEMI MIXTURES. h) 2 1. Excess MeI 2. Ag 2 /heat (ignore stereochemistry for this problem) 1. a + - Me/Me i) Ph + Ph Me excess (ignore stereochemistry for this problem) j) + excess Ts cat. / heat Question 8 (8 pts) Give all reactants/reagents and conditions that would be used to give the provided structure below. Indicate whether the reaction is a Aldol reaction or a laisen reaction. ignore stereochemistry Me Question 9 (16 pts.) I TE BXES, give the missing reagents/conditions or structures, as required, to complete the following Stork (enamine) alkylation of cyclopentanone give reagents give reagents give structure give reagents Ph

7 EMISTRY 234, Spring 2016 FIAL EXAM AME Question 10 (40 pts.) Show how you would make the target componds on the right from the starting compounds on the left. Show reagents and conditions where appropriate, and the structures of important intermediate compounds. Do not show any (arrow pushing) mechanisms. If necessary, you must indicate steps that require separation of isomers l Br 2 These questions use only reactions from the "minimal" sets that were provided on the class website b) (ignore stereochemistry) c) Br Ph

8 EMISTRY 234, Spring 2015 FIAL EXAM AME Question 11 (30 pts.) Give a curved arrow-pushing mechanism for the following reaction Show where all protons come from and go to (no + + /- + ) Show all resonance contributors to the intermediate structures Label the Lewis acid/base and and Bronsted acids/bases as appropriate 3 + b) 2 /a

9 M 234, Spring 2016, Final Exam AME Question 12 (35 pts). Give a curved arrow pushing mechanisms for the following two reactions. 1) Add non-bonding electrons and - bonds to the line-angle structures as required. 2) Indicate the Lewis acid/lewis base (LA, LB) at each ITERMLEULAR step as appropriate, and whether they are also Brønsted acids/bases (LA/BA, LB,BB) 3) YU D T AVE T DRAW RESAE TRIBUTRS for intermediates 4) GIVE TE UMBER F STEPS I YUR MEAISMS 5) Show where ALL protons come form and go to, no abbreviated + + /- + notation 3 + eat + b) a + Et Et Et

10 M 234, Spring 2016 FIAL EXAM AME Question 13 (40 pts.) Show how you would make the target componds on the right from the starting compounds on the left. Show reagents and conditions where appropriate, and the structures of important intermediate compounds. Do not show any (arrow pushing) mechanisms. dopamine 2 b) Ph

11 M 234, Spring 2016 FIAL EXAM AME Question 14 (20 pts.) Synthesize the (target) molecule on the right from the starting molecule the left. this can not be done in one reaction. Give reagents and conditions and the intermediate molecules at each step. Do not show any mechanisms or transient intermediates. Ignore stereochemistry! Br Question 15 (8 pts.) Give the structure of the ketone and ALL TER reagents/conditions you would use to synthesize amphetamine via a reductive amination 2 amphetamine