Name (First, Ml, Last): Answer vey Student ID Number: = PeoF cAnTRILL Chem 30B Fall 2003 FINAL EXAM (180 Min) Monday December 8th ***1D0 NOT OPEN THIS EXAM UNTIL INSTRUCTED TO DO SO*** ONLY ANSWERS WRITTEN IN THE BOXES PROVIDED WILL BE GRADED INTERPRETATION OF THE QUESTIONS IS PART OF THE EXAM— ‘DO NOT ASK FOR THE QUESTIONS TO BE EXPLAINED TO YOU "Every day you may make progress. Every step may be fruitful. Yet there will stretch out before you an ever-lengthening, ever-ascending, ever-improving path. You know you will never get to the end of the journey. But this, so far from discouraging, only adds to the joy and glory of the climb” = Sir Winston ChurchillQuestion 1 Rach of these reactions produces ONE MAJOR PRODUCT. In each case, draw this product in the box provided. For multi-step reactions just give the FINAL product, /.¢., no intermediates. (2 points each) (a) (0) ° (©) O° oO (8) oO wae oe (e) ()) 4 eq, Bry —— (ii) NaNHg () HCI/H,0 / Heat —_——_—__—_> (i) NaBH, / MeOH (i) Et,CuLi / E1,0 ——_—— (ii) LDA/ Mel (i) LIAIH, / THF —__— (ii) HgO* (iii) NaOH / H2O {i) Oy / Meg (i) NaBH, / MeOH ——— (li) TSCI/ EtgN (iv) NaS NNN O4 | | Question 1 continued on next page... 1(i) xs Bry / NaOH Q ® (i) HgO* Gi) SOClp (iv) MegCuLi Et,0 /-78 °C @ OD (i) 0804 1 HaO2 E — ——_—+- (ii) HpSO, cat. ce (h) {i) HpSO4 OH —_———_—— oT (il) BHy THE Co Ou (iti) NaOH / H202 @ xs EtMg8r OH —_—_——“- (il) HgO* co ® OMe Cys? Au cr boyveh a SS — CH,Cly Question 1 continued on next page. 2(kK) Oo on (n) (0) Ae Bry / KOH antl H,0 () SOC, Se al (ii) NaNg (il) Heat (i) LiAIH, / Et,0 (i) HzO i) H Be MeOH / H* ——_—_ (i) PhLi/ pentane —_————— (ii) HgO*Question 2 Deuterium (D) is a heavier isotope of hydrogen (H). Chemical reagents in which certain H atoms have been replaced by D are used to perform reactions in which the products are isotopically labeled, For each of the reactions below, draw the structure of the final product, CAREFULLY INDICATING the position of the D atoms in the products. (3 points each) fe) @ ch © _—{ O= (c) @ We aA © o 0 x __ xg DzO / DCI (cat.) — Lindlar /D —> (i) siagBD / THE — (li) CHeCOOH (). NaBD,, —_> (i) HO (i) LAID, / Et, ——__> (i) B90 () Bra (i) -Bu0K ——_> (iil) Na / NDg (!) 4 oO D D> D Pi 2S wD tQuestion 3 Propose a synthesis for each of the transformations shown below, include all intermediates, in addition to conditions and reagents for each synthetic step ~ do not worry about solvents. (8 points each) ‘As many steps ‘as you need — => Heat ( cope ELIMINATION) ®) ph ‘As many steps | as you need Ph, H — —, AN —_ =~ HOEM ANN Bh Hg Ph BUMINATION,Question 4 Propose a synthesis for each of the transformations shown below, include all intermediates, in addition to conditions and reagents for each synthetic step - do not worry about solvents. (10 points each) ‘As many steps as youneed — (re (Tefen ad Dersaniov Nano, Ha HO (b) ’As many steps as you need O~ = == NH, OH WH, Soy Y Caecum Ann) din ~ Lia,Question 5 Propose a reasonable mechanism that accounts for the transformation shown in the box below - SHOW ALL STEPS. (15 points) NH2NH2 KOH / KOH /He0 250°C Wu ms Oo +n “ — | What is the name of this reaction?_ WOLFF ~ KISHNERQuestion 6 Propose a synthesis to convert cyclopentene into the acyclic hydroxy-amide compound shown below. Show all intermediates, and the reagents necessary for each step (do not concern yourself with solvents). Points will be deducted for syntheses that result in a mixture of compounds. (18 points) As many steps ° as you need A ~AX HoN —. — ‘OH NH, o eyQuestion 7 Using ONLY acetylene (C2H,) as your carbon source, and other NON-CARBON containing reagents, propose a synthesis for syn-3,4-hexandiol in the box below. Show all imermediates and reagents for cach transformation (do not concern yourself with solvents). Points will be deducted if your synthesis results in anti-3,4-hexandiol! (18 points) As many steps as you need oH — H eo — OH Yy | LinDLAg a v W 4 a7 _ | Ube Oso. V aa’ Question 8 Propose a reasonable mechunism that accounts for the transformation shown in the box below — SHOW ALL STEPS. (15 points)Question 9. Answer the following questions about 4 novel class of highly branched compounds called dendrimers. (12 points) Large excess AON NH; ——= (a) Explain why the product of the reaction of an excess of acrylonitrile with ammonia gives the tris- nitrile compound A (Show Intermediates) (0) A three step reaction sequence {() B, (i) C, (i) B, £e., steps (i) and (i) are the same] gives the branched polyamine compound B (a 1st generation dendrimer). What are the reagents B and C? Be LAY C= 4 pointe (6) Subjecting compound D 10 a two step reaction [() C, then (ji) B] gives @ 2nd generation dendrimer — What is its structure? WayQuestion 10 Shown below are wo short synthetic schemes, the one on the left results in the formation of compound E (molecular formula C,H,0), and the one on the right results in the formation of compound J (molecular formula C;H);N). When E and J are reacted together (box at bottom of page), 2,6-heptadione is formed. In the large boxes (B, E, G, J), fill in the structures of plausible {intermediate compounds, and in the small boxes (A, C, D, F, H, 1) fill in the reagents necessary to achieve each transformation. (20 points) 1) WE —> (ii) HyO*Question 11 Propose a synthesis of the cyclic five-membered target molecule shown below using propanal as your only starting material. You may use any reagents of your choosing, but all of the carbon atoms in the final product MUST come from propanal. Show all intermediates and reagents for cach transformation (do not concer yourself with solvents). (18 points) As many steps as you need‘Question 12. (EXTRA CREDIT SYNTHESIS QUESTION) Propose a synthesis of hexamethyl- cyclopropane using propyne as your starting material. You may use any reagents of your choosing, but all of the carbon atoms in the final product MUST come from propyne. Show all intermediates and reagents for each transformation (do not concern yourself with solvents). (15 points) As many steps as you need oO. — |x 4Question 13 (EXTRA CREDIT MECHANISM QUESTION) __ Propose a reasonable mechanism that accounts for the transformation shown in the box below - SHOW ALL STEPS. (15 points) {Ane DT FV MVD OR BT Bas BLvig ey () 1 eq EtONa / EtOH cos COnEt (i) HO/HCI 5 (acidic workup) 5 2 Ho | 5 “ i ¥ Eto be ° Sheet 3 L * coer ia % @ co,er < 3 2 Y & | q ENOLATG 2 Vv EXCHANGE 0 (Q pet ° 3 en G S G te ~ Sayre ; “i b 4 o oO ese” Jo ° at j 4 —= 6 —s> THM * en é This is an example of what kind of reaction? DV EK MANN) 5 What is the driving force? FORMATIONS OF MOST > STABLE EVOLATE j (wore: There MAL Be Arete ROUTE VIA WHICH THE RING DOES WS