Dr. Steven Pedersen February 28, 2008 Chemistry 3B Midterm 1 Student name: — Kee Student signature: TA’s name or section number: Problem 1 ------___ (27 pts) Problem 2(a-c) ________ (18 pts) Problem 2(d-g) __. (20 pts) Problem 3 —-----— (9 pts) Problem 4 (a-b) ______ _—— (16 pts) Problem 4 (c-d) (16 pts) Problem 5 (16 pts) Problem 6 ——---—— (14 pts) Problem 7 (14 pts) Total Points = __________ (150 pts) No Calculators Allowed No Molecular Models Allowed Be Sure Your Exam has 10 Pages1. A. Provide a systematic name for the following compounds. Use common nomenclature for any branched substituents. (27 pts) Oo Br dy 3- di hromoacefophoneno Br HO, OH (RS) - ha ~cbipheng| ~ 4 2- ethandiof Or RS) - 1, 2 -eliphang (2 1ha te /2-diol Yorhy lrory-Y-wistlal Cy ole bexanove ‘OH B. Draw a structure for each of the following names. For cycloalkanes use flat rings. For all others use bond-line notation. ee > para-nitrophenol Ken > allyl iodide aut ° > 4,5-dioxcheptanal AON C. Provide a real example of each of the following: + A S-membered ring anti-aromatic compound. + A3-membered ring aromatic compound. @ A reactive conjugated dienophile. The answer a ° mist be & eave deenophie AWD on, jegavecl,2. Predict the product(s) from the following reactions. Where relevant, show all stereoisomers. Pay particular attention to any instructions given in the product boxes. Each redundant answer cancels one correct answer within any given box. (18 pts) ° : by + NEF ————» 0 SOgH AICI +Clp ———__» Ay —_—> So Xe + nd Hint: Not an Sy1 reaction (more problems on the next page) beak SS < A 2 : ‘3. i cy a 0: c H No ¥ S034 So 2products + Br(20 pts) + HBr Oo ° <4 AICly No, 1 a 2 2. excess Zn(Hg), HC! 3, NaNO», HC! 4, CUCN, heat KPO eee rc To ot 3c 6 products including stereoisomers Bc One major product g — Ri { ws 2 products: oN 4 A4. Write logical arrow-pushing mechanisms for the following reactions. Be sure that your mechanism accounts for all products shown. (16 pts) 9 ° heat —— fi = ° v ° “DX ° Y 8° Roe 2. oS 1 the only product formed! No credit for a Styowite mechanism More problems on the next page. 6(16 points)5. Provide the reagents and any other organic compounds necessary to synthesize the indicated product from the starting material shown. For each problem, five boxes are provided in which to place each step of your synthesis. No synthesis will require more than five steps. However, some or all, may require fewer than five steps. (16 pts) 1 30Cly Also, PBrs, HBe, Hee 2 m = 3 Dio 4 5 1 SI 2 NZ 2Dz ,Pble ¥ el D A . —— Some 3 ,, -OMe ory OL <—~ °AZULENE 6. Electrophilic aromatic substitution on azulene leads to only one product, (14 pts) CO A. How many different mono-substituted azulene products are possible?_ azulene B. Three sites where an electrophile, E*, can react with azulene are indicated with a*. In the boxes provided, show'the intermediate that would be formed when the indicated position reacts with E*(do not show the actual product). A c | “ | . é @ je oD LS. C. One of the three intermediates shown in Part B leads to the only product of electrophilic aromatic substitution on azulene. Which site is it, A, B or C? __A__ D. Explain your answer to Part C by comparison with the other two possibilities. You explanation should include words and pictures. . B cannot lead to « substituted aaulene Becaue Vhs 20 sobstiVvate Car. Aand Baw both resonaues stabi fi ged) vuvermesl ater, Maurier, © At aufiaromatic Character (ire) while . “ Fees dittecunces will foe Fol ot a : . ; he banin 4m clan 9 Vlg tencteata, AAD 4 (we on i va vig, tomate Df Zs < Ean ae DOS: : “ mo hyeas gen af Ther cubon ‘a mfiauangartic cetomaarti €7. A. Using shaded/unshaded molecular orbitals, show the transition state picture that leads to the product shown. (14 pts) fe} heat » ASS “ey . B. Is the enantiomer of product X (Part A) formed in this reaction? If your answer is yes, draw the enantiomer. If your answer is no, explain using a few words. Credit is only given for the correct YES/NO answer. / NO, Flee Site is Chiral [non ~racemit , nel Vaca L\ cartrowe Cannes be fered on O ance ewetenn sii an Hho Ditls- Mder Heactorn C. Is product X in Part A best described as resulting from an endo or exo approach of the dienophile? Circle one. —. Product X from the reaction in Part A along with two other possible products is shown below. The following questions are based on these products. ‘O Xo Y z D. Very little of product Y relative to product X is formed in this reaction. Explain this result. vl sferic Gincleranes bloc Sato greg ovsl Sls Me tlegl grep CLC lel will hr iviy tees Pein Pewrtoly proeclue dK E. Very little of product Z relative to product X is formed in this reaction. Explain this result. Tuc us a0 possihil%, QD Steet ABAD over leg (S00, vow Fw Sore $en A 470 pucluct 2» S00 1 ew SfebihiBitty, abe Lorn hat Wess 768 Aransi¥err 0 bih2ig, stale Lungs»