TAF HH) Chemistry 303 fall, 2000 SECOND EXAMINATION 7:30 PM, NOVEMBER 13th, 2000 Duration: 2.0 hr Name. key 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: Total: 00 There are 9 pages in this exam, followed by five pages of spectra, All I3C NMR spectra are "proton-decoupled”, as usual. Please check now to be sure you have a complete set. You may detach the Data Sheets for your convenience, but remember to re-staple the rest of the exam securely when you hand it in. If you are using a resonance argument in your answer, draw the relevant resonance structures. ‘Be aware that in Problem I and II, you may "purchase" the unknown structure (X, A) for a point penalty. Go to the front and request the structure of the proctor and he will deduct the appropriate points. Please be aware that a small number of students will be taking the exam at different times up until the afternoon on Tuesday. It would be well not to discuss the exam until after that time.I. (28 pts) Consider the spectral data for molecule X on p 11/12, ‘A. (4 pts) From the 4000-1500 cm! region of the infrured spectrum alone, which of the following functional groups are ruled out? (circle those which wre ruled out, and explain in one sentence how you ‘came to that conclusion.): carbonyl group (C=O) Goto COM_Ae perk for ob seth at 3500 unl Camino NED) We peak for n* type absorptions? a2iSnm —->215nm ~— cannot tell. (circle single best answer) D.(3 pls) Consider protons Hi, and Hi in B. I. Are they equivalent? fo 2. What do you predict for their signal(s) in the !H NMR spectrum [approx. chemical shift and pattern, including approximate coupling constants]? Yao dovblots, with small Coupling Nhs, E. (3 pts) Consider protons He and Hy in L. Are they equivalent? 2. What do you predict for their signal(s) in the !H NMR spectrum [calculated chemical shift and pattern, including approximate coupling constants]? Show any arithmetic. Fanat ti 3 ame l-c-o 4 oe Se OE.F. (2 pts) Consider all of the spectral data and the C43 4 Ch, eb mechanism of the reaction to form A, and o write a [large] structure for A. Draw in © the groups of hydrogens and label groups of aa; equivalent H as a,b, etc. Hee [if you do not know the structure for A, a u ‘you may request it from the proctor for ‘a cost of § pts] y _ 0 iS G. (3 pts) Write the steps involved in the formation of A from B in the presence of triethylamine. Be sure to show the role of the triethylamine. Ve ft, wt Hs “CE ar eee as 8 Y 0 B + 6h a a H. Explain how parts of the 'H NMR spectrum for A are consistent with your structure for A. 1, pts) To which H do you assign the peak at 5 1.05? Specify the number of Hs giving this peak. Ch Ce) EH 2. (3 pts) To which H do you assign the peak at 5 1.95? Give number of Hs. Calculate the expected chemical shift based on your structure and compare with the observed number. chow Cc, 3H a 9 f- c= 0.90 1:30 predicted). —_ 3. (4 pts) To which H do you assign the peaks at 8 2.20? Give number of Hs. Ch, Ce) And (A) =) Total of 4H wi Too peaks 4. (2 pts) to which H do you assign the pattern at 6 5.88? Give number of Hs. Wo ce) 1H1. (2 pts) Explain how the UV data for A is consistent with your structure for A and not with B. for A: pet at 3 237 saggets Caytgton, xt feat foo Chih €) a- bends abjncert, WS ti Far B Wo J2T visibhe, ie J. 3 pts) Explain how the IR spectrum for A, in the region from 1500-1800 cnr'l, is consistent with your structure. Be as precise as you can in defining the structural type suggested by the IR peak position(s). Tee pes: C20 stretch at ~ 135 carl Czo stretch at khsoui =) tyra of Con). C=O het single petoe. K. Consider the /3 C NMR spectrum for A. Re-draw the structure of A here, for reference and number each carbon. LQ pt) How ‘any non-equivalent carbons are oor wAd M1 (circle Tingle bar answes) 2. (1 pt) To which carbon do you assign the peak at 5199? C-7, Arbon! carbon 3. (3 pts) To which carbon do you assign the peak at 8 160? Explain in terms of the structure how you mad« your assignment and take into account the peak at 8125 as well. The Ow te doable bond must be responsible ae f Yak very dfleot Sate Oba c4 Cand peak a $1 9 & keshielled, A ae i # stlowsabsed | yi ‘ee this pesonbdni streuctare, 2 les B “sernahhULL. (22 pts) 7 A. Consider the actual equilibrium constants for the chair flip of the monosubstituted cyclohexanes. Note that there is not a linear change in Keq With atomic number of halogen atom, and that Cl, Br, and I have similar effect on Keg x Koa AG (Keal/mol) (apex Keo A ee 0.25 x ca 0.41 0.53 a B Br oa 0.48 042 047 1. (1 pt) Which isomer has the equatorial halogen? ¢ ) » neither. 2. (2 pts) If X =H, the equilibrium constant Key would be: zero__ >10_ <10_ 3. pts) Which struct, aor, isles favorable for X=CI? Explain carefily the main factor responsible for the difference. A . @ hts Av sxinl 8, with is at niteracioris. 2) [Serpricachs te Aepalnd & fess thaw be 4 Me gio, © hich has Siuiler Size) 4. (4 pts) Give your analysis as to why the AG for F is less than the AG for Cl (expected), but AG for Br and I are about the same as for Cl (not so obvious). Think “outside the box". 7 fu nda, to size of Aton, He bend leah x t & she pa obvious prrntieker — A dpe hur on A Very bay bond wolf Anye “inv, epalioee Soa hugh: FRQ< br SE, Longer bow) congensater tor Inger ftom. B. 1. (4 pts) Use the structure below to draw carefully a diaxial version of 1,3-dichlorocyclohexane. Then show the ring flip (conformational isomer) structure atthe right side of the equilibrium. Considering both structures, circle neatly any chlorine atoms which are equatori i @ diaxial2. (3 pts) The AG for this equlibrium is -2.0 Keal/mol and Keq is 30. Specify which is the less stable isomer and explain carefully why it is less stable than the other, in terms of the two most igerant ypes of repulsive interactions. You may want to re-draw the less stable isomer here. 5 Zi Ce ns two pAtche skint wud ,3- hinxial merch There i alin A Fyple fale pepabiod wi the Gaxial Vers less stdble. 3. (2 pts) Consider the more stable isomer. Are there any elements of torsional or bond angle strain in this molecule? Explain. . He Ob: could newton 4 Z / #e stems, | rauche titterndions WW ce I Win rtselt Cevhich we pever “Cab. suice they Zero out Among sthuchies 4. (3 pts) Use the structure below to draw the div i the ring flip (conformational isomer) at the other side of the equilibrium. The AG for this process is +0.9 Keal/mol, and Keq is ea 0.20. Specify which is the les sible isomer and explain carefully why itis less stable than the other, comparing repulsive interactions in both isomers. @ Ly Aces tqeae @ Ae diaxial less Hable hile the hain! fas the ussil Fauche problen, A Ws0 fas te CC band Epaks dined op % siwinize Kpalinct The spenterial Grasethers ttm chpolr-cbple rpbiel whic 13 stony exoush to sntke thi the lese ofthe cob rer.TV. (14 pts) The conformational analysis for cyclohe: such as the ketone, cyclohexanone, but with some a new dipolar substituents, as in trans-2-chloro-5-methyi O cyclohexanone atives also is useful with related compounds es. It gets particularly interesting with severa lohexanone with chair conformers a and b. : m0 inhexane: Kj,=03 TZ I pimtntabctnt Kyat ‘ > A. (5 pts) Rationalize why the equilibrium as written is unfavorable in hexane solvent. Analyze conformers a and b with regard to the usual repulsive interictivws asa start but there is obviously more to it. Cantforsar (4) ns strony Aye depute; te 2 mf @ ar dey md reel.” Les severe ui the Atel cose. Ge. Aitxial case bes the ws! quucle Weeractrois, but the ipek eect douwatkes Wi herawe Folreute B. (3 pts) Rationalize why the reverse is true in methyl alcohol solvent. Moog 1i 4 polar, pric robeat JPA] The birk sole doh wi CQ) A slebih l by the polar soloat through dipek digo Specibic W- Goudiaiy to Aare ean The smaller m0feculay es neduces Ye S- of 0 0d, | ai Ql Lpartialy Canney bond doh He bond dipale palin WR bss sfbilrecb by the polar soled CC. (6 pts) The infrared spectrum for cyciohex::none shows a strong peak at 1719 cm!- However, trans 2-chloro-5-methyleyclohexanone shows two peaks, wl 1726 cm, ‘Explain carefully in terms of ‘conformations and the effect of different conformations nn the IR spectrum, of aoe L pe > 4 ss ee How, He byek ential. B histaurs te hipolo- pesmmntce Stiucture through eked sth bark) ge bypulsie Stronger fet w~ 4 COS tus!) Han 4 & G78), be both we rowed % kighr energy C5 Dy, dese nore dovile bonSpectral Data for Compound X, Problem I Mass spectrum: mvz 131 (8.0%), 130 (100%). UV spectrum: Amax 210 (e 55) IR spectrum: (NMR spectra on reverse)oor i x prorodaoy(@sraaar uo enoads YN) sumaysads yy (ea) ype * 00pz 3) 6ez *Hy sumspoods An, TT WizIqQ01g ‘Y punodutoy 405 BEG jexyvadg