Chemistry 303 Third Examination December 3rd, 1996 Lab T. 7 This is an “open book" exam; you may use anything which is not alive There are 9 pages in this exam; please check to be sure you have a complete copy. Don’t worry--it is not that long. There is a lot of space for answers and working out. State your assumptions and show your logic. Write complete answers (¢.g., if you claim resonance effects, be sure to draw the relevant structures to illustrate your point). Use arrows to show mechanism, with precision. Sloppy arrows will not be given full credit. L /36 1__ss m___2t IV. 5 total: /100I. (36 pts). Consider the interesting molecule, A. Its reactivity contrasts somewhat with the related compound, B. As awarm up to analyzing reactions of A, please consider the structure and behavior of B. You may add a sentence of explanation if you see ambiguities in the question. ‘A. (3 pts) For each of the carbons in B, indicate with a check if it is a stereogenic center and, if so, whether itis R or $ configuration. Consider the following molecules as possible products from reactions of B. Cy ‘OCH: So % i S ; ose \ U v w x Y Zz B. (2 pts) Which is the most likely product from the Sy2 reaction of B with NaQCH3? Circle single best answer Uv Ww @) YZ C. (2 pts) Which is the most likely product from the E2 reaction of B with NaOCHs? Circle single best answer uv ® Ye 2 D. (2 pts) Which is the most likely substitution product from B with AgNOs in met Circle single best answer U cohol solution? Wexey Z| E. (2 pts) Which is the most likely elimination product from B with AgNOs in methyl alcohol solut Circle single best answer = U V WX Y F. (4 pts) Write a mechanism for the reaction in part D, above. Van 4 ae Hy : é i + ‘ye = ye by TR vv N : # I J ove + @G. (3 pts). If you wished to increase the rate of the Sy2 reaction of B with NaOCH3/CH30H by adjusting the nature of the leaving group, what would be a better choice of leaving group? Explain. Worker C-x bord: BET @ tore stable anren) + cof Ny H. (6 pts) Obviously, the Sy2 and E2 reactions ee give different products: Suppose we change the nucleophile/base to NaOC(CH3)3 in tert-butyl alcohol solvent. 1. Write the product from the simple Sy2 reaction: H pest 2G 2. Write the product from the simple E2 reaction: X 3. How would the relative amount of Sw? produet to E? product differ for this reaction compared to the reaction of B with NiOCH3/CH3OH? More Sn2, More E2, or No Change? Explain in terms of mechanism. More £2. te lager 5 ect) be Aistowred mw the ws ode “a ie seusibve te steme . 7 nN Asti Br . tuo at) Br Hite u he Cr r Me aherache ao fh bre ant 4 f Tm th ir br How are these stereoisomers related: enantiomers?_ x diastereoisomers?__ (check all correct answers) superimposable? mirror images?_& ma pis) Draw in Newman projection gy How is this stereoisomer related to one or the other 0 an tional faker of the isomers in part B, above (pick one for comparison) which snot observed in the reaction) H He a. enantiomers _ bidiastereoisomer — X_ c. non-superimposable _X_ H fh d. mirrorimages = __ i (check all correct answers) r D. (pts) Write the best mechanism to account for the formation of F and G from D. Include a clear function for the irradiation. . af padieal proces Br pitiatin ra irradiat \ + Ply lat 2 Ph Br, _inadiation “YL = fbr —> 2 Bre De FO Br Ae (major) (minor) rh Bia > wat * es a MER : 47 | Sef) aon Lecaleed — v MAA fh ¢ rial rly fA 7X, + br Aho could have resonance yite benene sou) (2)IIL. (21 pts). Consider the reactions of two closely related reactants, G and J, in the presence of aqueous base. The products H and K have different molecular formulas and form at somewhat different rates: K forms faster under comparable conditions. Hi gH | SO fast reaction slow reaction Br wee Ly Bi ‘NaOH, H20 ae NaOH, H20) IR: 290m" IR: 3300 em (s, broad) (3, several peaks) G, C13H2sBrO 2900 em’! (s, several peaks)! J, Cy3sBrO + fingerprint + fingerprint | ‘A. (7 pts) Draw the most stable conformer of G and of J,using the chair representation. Be sure your drawing shows clearly which substituents are axial or equatorial; you need not draw in the hydrogens. Label each substituent (not hydrogens) as (A) axial or (E) for equatorial. Which isomer is more stable, G or J? Explain carefully, b oH E LOT @ E (En © Z br 2 wxts] subst tues Ke ezemeral a says g CoAuthe pstomnabo = fd) pees More. stole. Af B. (2 pts) How are G and J related? Circle all correct answers. stereoisomers xen diastereoisomers X_ enantiomers mirror images C. (6 pts) What is the structure of product H? Write the best mechanism for its formation. What is the name of this mechanism? IR 7 ot ae ol Conpist do mcerval SE, oH hecause He tesatting ting 44 = nL, fixed ae foviaffuotl HO a died Sy x he sertously stramed. 7 " =_—_ at privery be oe chegontenith AS cannot Fh; ee apa wage Te tet-ba ped A rt et ty disfavored disfavored 6D. (6 pts) What isthe structure of product K? Write the best mechanism for its formation. What is the name of this mechanism? br ‘Ar ES A a) Sue 8 wR + Sou 2 - ew. + Br 42 porte chair for IR shows No -OH k IV. (25 pts). A. Consider the following reaction. It proceeds to completion when M is dissolved in CH2Clz, methyl alcohol is added, and the mixture is heated gently. cl Clp OCH3 ar IK Pcron actus ae or ct solvent M N 1, (6 pts) Write the best mechanism for the conversion of M to N. Include a representation of all transition states and intermediates. Show any partial charges in the transition state(s). What is the name of this mechanism?2. (5 pts) Keeping in mind that the disappearance of M is independent of the concentration of methy! alcohol, and depends only on the concentration of M, draw the appropriate reaction coordinate diagram, indicating where your transition state(s) and intermediate(s) appear. Pay attention to the relative energy levels of reactant, transition state(s), and intermediate(s). Label clearly AG# for the rate-determining transition state. pate ~ determing B Extent of reaction. —— B. Consider the related substrate P under the same conditions. Cl CH: "HCl. 3 Hy +cHjon —CCh Gy, na solvent P Q 1. (4 pts) Would this reaction proceed faster, slower, or at the same rate as that from M? Write a mechanism and explain in comparison with your mechanism for M. . lied. by Lyk FASTER © ee chee bol, ne TE fe buor, 264 | * J our Meh LEK Ce wot, colbirerdl bord) ga,2. (S pts) Indicate clearly how the reaction coordinate diagram for this process compares with that for M. Again, the rate is independent of the concentration of CH3OH, and is directly related to the concentration of P. Label clearly AG# for the rate-determining transition state Sith. & B cations Pp D6" bwer thew a for Mo because thin sitien stite ewergy I bower, Extent of reaction. ——— C. (5 pts) Now consider the reaction of T, under somewhat different conditions. The overall process is similar, and it requires acid but only in catalytic amounts. CH; OE CH: Ht CH 34 EOH = ——— (ME ° ‘cH; CHCl, cH T x E\OH = CH3CH,0H Write the best mechanism for the conversion of T to X, making clear how the acid is required but is not consumed. of Os ners a + he \ catalprc HOH