Organic Chemistry 432 Cole April 7, 2018 Circle Lab Section: TA M. Singh E. Paulson E. Paulson S. Singh B. Silva B. Silva Anueune No lab Nowesge %3/1SO Exam #3 (55.3%) Name. i ay Fist Last Name Lab Monday 1-4 PM Tuesday 9-12 AM Tuesday 1-4 PM Wednesday 1-4 PM ‘Thursday 9-12 AM Thursday 1-4 PM Students not attending any lab section this semester Notes: Before starting exam, please check that you all 7 questions on 7 pages, with an additional scratch page. Be sure that you have answered the entire question and be brief and concise as possible. Approach each problem systematically and stepwise. Finally, reread the question and your answer, did you fully answer the PERIODIC TABLE OF THE ELEMENTS question? H 1.008 Li | Be 695 | 501 Na 229) fat Co | Ni |Cu 39.0 |40i08 [2496 47.90 |s0.94 |si.99 |s494 5893 ba71_fo3.s4 Rb| Sr | Y | Zr | Nb} Mo| Te Rh |Pd Ag 85.47 |s7.62 [esr |oi.22 92.91 [9594 | [99] 102.91 1064 for: Cs |Ba | La | Hf | Ta | W | Re Ir [Pt | Au 3290 437.34 [3891 7849 fs0.95 fess [1862 192.2 $95.09 $9697 Fr | Ra| Ac (223) | 1226) {12271 Ce | Pr |Nd Sm |Eu | Gd|Tb Dy Ho | Er |Tm| Yb | Lu 140.12 [40.91 £4424 i 50.35 51.96 [57.25 h58.92 for Th | Pa | U Pu |Am/Cm | Bk | Cf | Es |Fm | Md| No |Lw 32.08 | 1231) 38.03 (242i | 243) [ran | i267) |124o) | (254) | 1253) | 256) J 254i [1271Point Summary (For graders only). #110) #2(20) #323)" -#4(25)-#5(12)#6(30)_——-#7(30)-—(148) Total 1.(10) Give in detail the stepwise mechanism for the selective deuteration of monosubstituted cyclohexanone using a slight deficiency of lithium diisopropylamide. Show an acceptable stepwise mechanism, showing all intermediates, indicating all electron pair movement using curved arrows. DO NOT combine steps, unless they are concerted, doing one at a time. 0 - wt yr 1.03 equivalents a u (Glight excess) O° 2 Rurstre pd duct oleveteow pitQe kueivo to fem Q ee hap ave At RU Ra reget fRrun product - One BE TOO S 2s ap, juacien, Of TDD OR, errtere2.(20) Propose din acceptable mechanism for the «-bromination of 1-indanone using acetic acid as the catalyst. Be sure your stepwise mechanism shows all intermediates, indicating all electron pair movement using curved arrows and do not combine steps unless the reaction step is concerted. Oo + By CH;CO,H oe pe : Spek 8 = at. _ - cae 4 WO-Cek, = eu ‘ae Z u oe Ou, basa Y sles ash rmmsidle, eyeam Promuain OB petal Aces te bajas Quiche wee fr Pues Re CONS Ruck Ue tA Species fore a tie3.(23) Propose a laboratory synthesis of the following compounds starting with the indicated starting material and any organic compound containing four or fewer carbons, oxygens, halogens, ete and any inorganic reagents. Note, the desired product may require more than one step. Be sure to include all steps and stable intermediates along with necessary reaction conditions to form the products. co u + Ok 4 De cer Be =Ic ol 97. aalect a! c O Donn 0 — ——~ CAS » ba One ym Me a dholhLo — : oO png Oke oe Wane > BYES Trace how a tke Ho 7 askes @ tar o 0 9 b wn ad ‘OH O ) Naderon LE \) NOR / Et 9 BOB = . — & ay Ae a OF DA | ° mm op 9 y Neifind | Exo OF a \ i ‘= to, eo | 2 tisot4.(25) Indicate the expected major products that are formed in the following reactions, Include whether other regioisomeric products will be formed as well as stereochemistry if required. OC, ae 130°, * He eS rN + a ie Cat neste.) Ni 1. _NaOEvVEtOH B pons __NAOEVEOH ee 2 PN No, ° ° ° 9 7 it a eon, aelt Co u EOH ong Ho at kes wsmrmede— -78°C HO. A, u D. + aa Ze ty THE i UT LDA slight excess aN i EB wh + BINH, — >> AK x S ps tack 5,(12) Evaluate the following pair of compounds for their acidity of the bolded hydrogen using a>, < between eaich pair of compounds. (Do not rearrange the order of compounds, there are 6 comparisons). Sn dhe Ahk dy 2 pts 2acl6.0) __ Give in detail the stepwise mechanism, showing all intermediates, indicating all electron pair movement using curved arrows for the formation of the Dieckmann cyclization shown below using sodium methoxide in methanol, followed by protonation with a dilute acid, Also, indicate which steps are reversible and those that are irreversible. 7 o 0 9 NaOMe 10° om CH,OH 07 r ‘ 5 o”.- a P~ Owe, ul f Ne, CL Me, We a Re HeOL Ome _ OS? Wea Docuct . S sheps Ks He ge Dosusinir Moth tile Witunsac What is the driving force for this reaction? QB Su fs Ha dimtactre Feat OF cer oe Spout: + ORie Meier McS apron Wh accic7.30) Give in detail the stepwise mechanism for the Robinson Annulation reaction between ethyl vinyl ketone and B-tetralone. Show an acceptable stepwise mechanism, showing all intermediates, indicating all electron pair movement using curved arrows. DO NOT combine steps, unless they are concerted, doing one at a time. 9 a Uy NaQEt A HOH OH ‘0