ig Chemistry 303 fall, 2001 SECOND EXAMINATION 7:30 PM, NOVEMBER 12th, 2001 Duration: 2.5 hr Name. Lab TA, (if you do not know his/her name, give day of lab section. NOT Hooley) 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: 1 28 IL [4a rid ng IV. 10 v. ‘9 Total: 1100 There are 10 pages in this exam, followed by four pages of spectra and one page containing a Table of Natural Isotopes, and a Table of Spin Quantum Numbers for common nuclei. All $C 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. 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. Be aware that in Problem I, you may “purchase” the unknown structure (X) for a 6 point penalty. Go to the front and request the structure from the proctor and he will deduct the appropriate points. PLEDGE: _23 ‘onsider the spectral data for molecule X on p LL A, (4 pts) From the 4000-1500 cnr! region of the infrared spectrum alone, which of the following ‘functional groups are ruled out? (circle those which are ruled out, and explain in one sentence how you ‘came to that conclusion.): exon oun 0) he pet W the begin dete Ce-e stretch) amino(CNH) Mo petk six the. tegun 350 = pho 0-0, strcteh) cyano -CN)___[Wiolally preseat — 229 eux! aldehyde(@CHO). €=0 $0 =; + Mo = ‘250 — ether (R-O-R). )_ Lue peaks capecteD soi this reyeis) disubstituted alkyne (e.g., Me-C=C-Me). yee A ths oad stretch $2- 3300; B. (2 pts). 1. From the mass spectral data, what is the molecular weight of the compound? 2. Give an estimate of the number of carbon atoms. 4 @Q 6 7 8 9 (circle one) C. (6 pts) For each set of equivalent protons, give the 'H NMR chemical shift, the relative area, and describe the splitting pattern (singlet, doublet, triplet. quartet, quintet, sextet, etc) including approximate coupling constants. You should estimate the J values as best you can. Area ing pattem A 1 A) 3 Z “3 3 7 3 Lé Zz pointe 2 “ 4 26 Z 2 D.(2 pts). From the UV data alone, which of the following structural nypes are ruled out? Cross out your choices. RAL AAS FS continuedx 3 E. (1 pt) How many non-equivalent carbon atoms are indicated in the !3C NMR spectrum? F. 1. (8 pts) Draw the structure for X which best fits all the data (review your IR conclusions). Explain in detail how your structure fits the pattern of peaks (splitting) in the !H NMR spectrum, Label the groups of equivalent H in your structure for reference. You need not show calculation of chemical shift positions, but you might do this to confirm your structure. You can buy structure X (6 pt penalty). HK wet ted HCEN [Re Gaple to ty 7H # Hy 7h “7 Tot H He Ay My ‘hilt part k-al(hos) = 2-40 Ne thift: 0.904 6-w Ger) = LAE Ae shift) bee +ew lor) = bo 2. (3 pts) (a) Specify which carbon in your structure gives the peak at 8 123 ppm in the '3C NMR spectrum. Explain any ambiguity. —C2N (b) Specify which carbon in your structure gives the peak at 5 11 ppm in the !3C NMR spectrum. Explain any ambiguity. Melly he dod gph chy with Ny abacked; least perturbed by -w 3. (2 pts) Explain how your structure fits the IR spectrum, based on the peaks from 4000-1500 cm!. Irak vt 2232 wl tr WV stretch24 pis) Consi e spectra Yon the Data Sheets, p 12 and 13 + With a little work, you should be able to come to the conclusion thatthe structure consists of a benzene ring attached to a C=C unit, a CH3 group. and -OCH3 group connected somewhere, Exactly where the CH3 and CH;0 groups are attached will take a little more work. A. (6 pts) There are six peaks or multiplets in the 'H NMR spectrum, centered at the chemical shifts shown below. Fill in the rest of the table. The patterns could include: singlet, doublet, triplet, quartet, doublet of doublets, doublet of triplets, doublet of quartets, or other. nie ue: cs 1 L82 ppm __2. A Z 2. 3.80. 2 x. oan 3.61 er eeness 4} fiz dd) hyo (th) 5. 2 Zz df Z 6_125 Zz df Z B. (2pts) How many non-equivalent carbons due to are evident from the '3C NMR spectrum? 9 C. (2 pis) Give nvo peaks in the IR spectrum which are consistent with the presence of an alkene. Explain which type of vibration gives rise to each of those two peaks. & (lO Cc stretch; curyamctrical j2-disubsttated alkewe nyo sp eH stretch [itt Pe-sica Se tau jndindstied alter D. (4 pts) On the next page, write large the structure which best fits the spectral data, showing all H, the location of the CH3 and the OCH; groups, and the E/Z relationships on the alkene unit. (2 pts) On your structure, label the proton or group of equivalent protons to correlate with the table in part A (e.g., Hj for entry 1, H for entry 2, etc.) (6 pts) On your structure, show clearly which H is coupled to which other H, and give the magnitude of that coupling constant. (2 pts) On your structure, indicate clearly pairs of carbons which are equivalent and give a single peak in the '3C NMR spectrum, You may draw a second structure if it makes the answer clearer.G. YOUR STRUCTURE, labeled: (draw twice or more if necessarity for clarity) 4, Hes) oy H ‘5 7 Me o HH hre-o 4 4 Hy Hy) Neva) My ant Mubiguoes; could be reversed, & cal by, Jag sho coupkd to b ER PE arn: & ® dooblet of guards Y coupled to hy, JES My coupled 40 ty, Jee, Ladlcbaial Coupling of ty with t J~2 tes enh ty ich dy Mp coupled to He, 27a Hy coped to Ht, J?, 4 be yn wot coupel; sitet poy’ 6 carbons = Are egervabad. jour bare eguivalewt Bonus (3 pts): What are those teeny-weeny little peaks in the 'H NMR spectrum at 8 3.60 and 3.95 ppm due to? Thi resets floor the 11% of '% at etch carb. Keadily vinbhe wh tr stron, shawn fetes. . The S cauples tb the whacked H (i3e-04 Predacing A doublet rymmetrica] a . i dowd He tii Singlet. dtl, So ok:TIL_U9 pts), 6 There are stable molecules formed by replacing one of the carbon atoms in a ring with heteroatoms. and they are called heterocycles. For six-membered heterocycles, one can do the same conformational analysis (chair-chait interconversion, etc) as with cyclohexane, There are differences, some due to the fact that the C-O bond is shorter (1.43A) compared to the C-C bond (1.544). Consider the molecules 2-methyl-1,3-dioxane (2), 4-methyl-1,3- _ficxane (4), 5-methyl-| 3-dioxane (8), methyleyclohexane and 5ter-butyl- | 3-dioxane (S-Bu). The energy 4ifferences for the axial/equatorial equilibria are given, in kcal/mol, PO-9-03g S1Bu AG given for the equilibrium: aG 35 29 AT 14 ‘axial $= equatorial A. (3 pts) Draw the equilibrium for methyleyclohexane, indicate which is the more stable conformer, and explain why itis more stable. Label the isomers as (a) for axial or (e) for equatorial. CNS feJ d io) “ wore stale! 76 axial covbormer Mas quiche witendrns with tow mage ploips ud the ping Awd 3-dinwial veyed sen with te axial Cnty, Subetitucas. B. (4 pts) Draw the equilibrium for 2, indicate which is the more stable conformer, and explain why itis more stable. In particular, explain why the difference in energy is now larger compared to methyleyclohexane. Label the isomers as (a) for axial or (e) for equatorial. ‘fy — +S, 4 ON Lo the same tomy, The arial catbrier & deste bias by 2 gevke éhenctis sin Too 42—diavia) sikertobois Th shorter 0-0 bons fi the urtous closer together and peretse The repubtor tim these effects,C. (3 pts) Draw the equilibrium for 5, indicate which is the more stable conformer, and explain 7 why it is more stable. In particular, explain why the difference in energy is now smaller compared to methyleyclohexane. Label the isomers as (a) for axial or (e) for equatorial oh fxf¥ — Wa a Crani,, 2 goecle xB Ey iiherpet ais pore ste, Le shabiize He sel ait bt ww OC af 5 Setter that a-ly~ wel Hs eprdvan & tees, Mh 4 4. nae Saloon 43 thade 5s a0 43-drarial sroup. D. (4 pts) Aiote the AG value for the 5-t-butyl isomer, 5-tBu. Draw the equilibrium for 5-tBu, indicate which is the more stable conformer, and explain why it is more stable. In particular, explain why the difference in energy is now smaller compared to 2-methyl-1,3-dioxane, 2. Label the isomers as (a) for axial or (e) for et — Yor The Arial — a dastaiized kee ts Sucks Wteenobnis wthe the 2 tous. Dy 2 He vetly/ grep mi tal arial Positions & Lesh lized v9 on witeradms th 2% gigs aed tare 43- oe wher acho — Me E. (5 pts) Note the AG value for the 5-t-butyl isomer, 5-tBu. Now consider the molecule, cis-2-methyl-5- t-butyl-1,3-dioxane. Draw the wo chair forms here, circle the one which is more stable, and explain your choice. J t 4 SF — Wot Curb Or fs fess stable snve te 4 poy 1 axial wath qaude wberadisis ath 2 c& pinged & fi-deveal rudin, tu QD, the axial t-Baty) sop hes Bess, teypuh ind, ae seew wi 2 thor,LV. uctures A, B, ar Note also the IR and 'H NMR spectral data here, entries | (for C), 2. and 3 20. vinyl H ) 4 | A} 2. 1720cm 8 §.89 for Hy and 6.94 for Hs Ha He Hy se ats AA B 4° | 3 1760 em? 85.24 for Hy and 7.02 forty A. (5 pts) Which set of spectral data is correct for compound B. J. Why isthe C=O systching frequency for B different from? Explain carefull He oy reoure eect br siufle ester peowance effecd Gr comigatel exter a y ay < shes Hore C-O shake 6 4 chumekes, impr bowl bw V. 2. Note the specific chemical shifts for Hy and Hy in your choice, and explain differences from the corres sonny Hs in. = Te eon tice yh heseyzets or eechow deny \ Ge. sty dashicdiy B. (5 pts) Which set of spectral data are correct for compound A? (5, 1. Why is the C=O stretching frequency for A different from C Explain carefuly. Q Mew resoutnce Andure shou lectin par Ade cr au oxygens delocalired wre T-bnd. Bes G fs AVAildhle to Lolosline Mito coe, less bond- hartley, of exe, nelle bd chance blr Bo” 2. Note the specific chemical shifts for Ha and Hy in your choice, and explain differences from the corresponding Hs in C. Thie vesew ance Struchire Whe shous rbdea cleckrou © tushy 1D etrhen of My, My 8 Hore shiclheel, le paves Yield to S524 ho av arln with wtucbie wittdinanny sop C-Eo-) al hechictled | doy to Rez,V, (19 pts) Consider the spectral data for Compound D jin the data sheets, p 14. ‘Compound D has two carbons, four hydrogens, and two halogen atoms. 1. (2 pts) Consider the mass spectral data for D and determine the molecular formula, Circle the correct formula: CoHyBrCl — CoHaClp CoHsF) — CoHyCIF_-—- NONE OF THESE 2. (6 pts) Consider the !H NMR data (p. 14) and draw the structure for D. fl 4 Label the groups of equivalent Hs in your structure as Ha, Hp, ete a 6 Give the integral ratio for each group. FE c ie - br & > 24 rot = oy 3. (8 pts) Correlate your structure with the 'H NMR data. a. Which Hs give rise to the pattern around 83.5 ppm? Explain the pattern carefully, pointing out coupling relationships, and stipulating coupling constants, Tho H wet to br CO) nypert ot $35. Coupled hb A127) at to F Ch, J he) Dbobdet of triplels b. Which Hs give rise to the pattern around 54.7 ppm? Explain the pattern carefully, pointing out coupling relationships, and stipulating coupling constants The W net to F Cla) ayer it $47 CE wore eked pn withtrunds than wr), Coupled to Mb a J?) Wd eoghd to F Ch JFe Wd Hotel of tnplds continued...4. (3 pts) Consider the '3C NMR data given for D on p 14. 10 Please explain how the 4 peaks arise in the spectrum by correlating with your structure. 17 8 doe at Fite Fauld t p< Wet AS 72 F cued t w—% do ”y end exam