Chemistry 3036 fall, 1999 THIRD EXAMINATION 7:30 PM, DECEMBER 16TH, 1999 Duration: 2.5 hr Name, Lab TA, (GF you do not know his/her name, give day of lab section. NOT Hooley nor Chlenov) This is an “open book" examination; you may use anything which is not alive. Note: if you do not know the complete or specific answer, give a partial or general answer-- WRITE SOMETHING Write only in the space provided for each question. Score: 7 hs CRA aNE KEY 2. /18 3. /1s 4 /12 5. /12 6. ‘16 ae (12 Total: /100 There are 8 pages in this exam. Please check now to be sure you have a complete set. If you are using a resonance argument in your answer, draw the relevant resonance structures. If you are asked to analyze a structure and you have no idea what itis, do a general analysis of the data and propose partial structures. Write mechanisms completely and carefully, We sometimes skip steps in lecture; don't do it on the exal Please be aware that a small number of students will be taking the exam at different times up until the evening on Friday. It would be well not to discuss the exam until after that time. See you tomorrow morning... PLEDGE: =1. (5 pts) Consider the following pairs of reactions, carried out under identical conditions. One of the 2 reactions is much faster than the other for each pair. A. (5 pts) Predict which reaction is the faster, draw the mechanism carefully with a clear representation of the transition state, and explain why the other reaction is much slower. o Restided to 60 > +Nasme HES D-swe A a wis .-E by THE = {common solvent) > + NasmMe OE >-sue a The trnanition! stile nee Ans An saKteAT 5 \ Z bond pagle C12"). ney gr = fa F ir| NS + BP ire thea ot if Pe fr » os + We? pret No delocrhentron, Vory eustableV. (12 pts). Consider the reduction of acetaldehyde by NADH. 6 + CHsCH20H NADH NAD (business end only) mutant NADH A. (7 pts) Write a careful stepwise mechanism for the reduction of acetaldehyde into ethyl alcohol with NADH, the reduced form of the cofactor NAD. 6 pF aha Fe eis fy i, B. (5 pts) The side chain indicated by an arrow in NADH has no apparent role in the process, but Nature would certainly not waste energy putting in such a group for no reason. Obviously, it can have some hydrogen bonding possibilities for molecular association, but it might also have an effect on the intrinsic reactivity of NADH. Compare NADH with "mutant" NADH: which is more reactive in this reduction process? Explain carefully. The beahow epents ow the fash” by te echo pur B a) HMDA, Tye apie site chain stubibect 7 owe parr Aud reduces read’. g o gn dithouk te Apide 7109, te tach And coil i pare readie; fess peacthot shobrti ZottongVL (16 pts). We have several examples where the rate-determining step in a process can proceed in one step 7 (concerted) or in two steps with a reactive intermediate (stepwise). ‘The issue of concerted vs stepwise can be important when analyzing competing reactions on the same general pathway. Zinc chloride is a moderately strong Lewis acid. It reacts with the epoxide to give the products T and U which are compared by spectroscopy. Note that the process strongly favors the formation of T. H AV _2nCle _2nCle (catalyst) OC: co CHeClz (solvent) . aor minor A. (5 pts) Imagine spectroscopy to distinguish the structures of T and U (assuming you do not have authentic samples of each) Can they be distinguished by: if yes, explain with a single key difference) UVa eee — IR_pes—_disabbiteted bond ng Hetrasabs, ‘y mass spec_ “2. tnMR_Y shows sioldob SA: T Shows tur bil seagls of 2h cath, BonmR_7_Shpws ZY Shows 7 perks B. (5 pts) Write a reasonable mechanism to rationalize the formation of U. First, draw both chair forms of the reactant, S. Draw the chair form of cyclohexane for all intermediates. Indicate which is the rate-determining step. Show the catalytic role of ZnCl (no net consumption). AoAC. (6 pts). Write the best mechanism for the formation of T. Draw the chair form of cyclohexane for 8 the reactant and all intermediates. Indicate clearly which is the rate-determining step. Discuss how your mechanism is consistent with the preferred formation of T instead of U. 4 Zl, c _ ff oie, y x g So~200 ‘ aaane — ON To tternatine foe eds anccrtal Me ohitt produce ee ee eee oe VAT. (12 pis). Consider the faflowing conversion. Write a pathway through reasonable mechanisms and intermediates which best rationalizes this process. Shorter pathway via more stable intermediates will get more credit Ht HeSO« Hint: If Ha is a deuterium, one can trace the process and see that rom ‘OH | itends up as Ha in the product, He: Ha g [ |