Chemistry 303, fall, 2002 SECOND EXAMINATION 7:30 PM, NOVEMBER 1 Ith, 2002 Duration: 2.5 hr sane KEY Lab TA Gf you do not know his/her name, give day of lab section, NOT Hooley nor Kim) ‘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: nee 10 Piesics: fae m1 MT IV. 126 i 19 The second part is tough... Total: 100 ‘There are 10 pages in this exam, and a separate Data Sheets section. All '3C NMR spectra are "proton- decoupled”, as usual. 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, Be aware that in Problem I you may "purchase" the unknown structure (1) for a multi-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. PLEDGE:2 L. 10 pts). Consider the structure of compound Z. On the chart below, please draw your best prediction for the !H NMR spectrum. Take into account chemical shift positions, splitting patterns, and iabel each set of peaks with the #H giving rise to it. Use the additivity table to back up your chemical shifts where appropriate; show your calculations, Label cl H Br GC CHy0) He 2 oN Ha methine 1.55 Hg methine alpha-Cl 2.55 alpha-CN alpha-Br 2.20 beta-Cl beta-CN 2 beta-Br total: 86.30 doublet, coupled to Hg, with J = 7 Hz quintet with. Assuming Jap = Jac, and explain coupling patterns. Specify approximate J values. Step 1. Draw in all the individual hydrogens on the structure, and label each hydrogen or group of equivalent hydrogens: A, B, C, e Step 2. Calculate the chemical shifts wherever possible, Specify the approx. chemical shifts for Hs where you cannot calculate them directly. Step 3. Predict the pattern of peaks for each group of equivalent protons, assuming pure Ist order spectra. Step 4. Draw the spectrum, and indicate on your spectrum the relative #Hs responsible for each peak or set of peaks. 135 He methyl 0.90 1.05 beta CN 0.45 O15 total: 6 1.35 0.25 total: 53.00 Doublet, J=7 =7Hz 3H area 1H area 300 MHz Aysusiut If Jap not equal Jgc, observe doublet of quartets or quartet of doublets 1H area 1H 3 2 1 0 perIL. (28 pts) Consider the spectral data for Structure I on the Data Sheets. A. (4 pts) From the 4000-1500 cm*! 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.): carbonyl group (C=O) alcohol (-OH) _ no significant peak at 3200-3600 em! amino (-NH2) __same cyano (+ no pe: a. 2250 emr!— aldeh: special C-H 2. 2800 cor! ether (R-O-R), monosubstituted alkyne (R-C=CH) no peak at ca 2250 cm"!_nor C-H stretch at 3300 en B. (2 pts). 1. From the mass spectral data, what is the molecular weight of the compound? __180 2. Give an estimate of the number of carbon atoms. 3 4 5 6 7 8 9 (circle one) at least, must be less than 6 carbons by M+1 €. (6 pts) From the 1H NMR spectrum, for each set of equivalent protons, give the 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, _Chemical Shift Rel. Area splitting pattern Approx. J ye seer 3H. triplet 7. 2. 2190) 2H. triplet, up ae 3.60. 2H. triplet 7. <= th.20. 2H. quartet 7. * 7. continued4 E. (2 pt) How many non-equivalent carbon atoms are indicated in the !3C NMR spectrum? 3 F. 1. (8 pts) Draw the structure for I 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 I (6 pt penalty). 9° Pelee Bt CH. Br cae so Nou (b) (a) (a) triplet, split by Hy 3H All J =7 Hz, for simple "open chain" compounds (b) triplet, split by He 2H (c) triplet, split by Hj, 2H @ quartet, split by Hy 3H 2. (2 pts) Specify which carbon in your structure gives the peak at 5171 ppm in the !3C NMR eee Ke — the carbonyl carbon ‘c=0 Z 3. @ pts) Explain how your structure fits the IR spectrum, based on the peaks from 4000-1500 cm! ‘The C=0 is an ester type carbonyl (or ketone, aldehyde), consistent with a strong peak at 1735 cmr!. 4. (2 pts) Explain how your structure is consistent with the parent ion region of the mass spectrum. The presence of Br is indicated by two peaks of equal height for M and M+2. The M+ is also consistent with the presence of 5 carbons.LL. (17 pts) Consider the three isomers, M,N, and P, Assume you do not have access to ‘comparison spectra from authentic samples. wen _ po mene base HH OCHy HOW Hyco H M N f A. (4 pts) Could one distinguish N from P using the 'H NMR alone? Explain. NO. The two vinyl H in each would give a singlet. The two MeO in each would give a singlet. Same patterns. (note: using coupling constants would not work, because the H in each compound have the same chemical shift and therefore would show no coupling to each other. They would appear together as a singlet. However, one might argue that the chemical shifts would be predictably different, but there is no additivity table for the vinyl H which might establish this. Qualitatively, one can note the resonance structure for P which places electron density at the CH carbon and therefore would make those Hs highly shielded, showing up perhaps at 4.5-5 ppm. The effect is also present in N, but in P it is doubled. B. (4 pts) Could one distinguish N from P using only the 1500-4000 cnr! region of the IR? Explain. YES N would show NO peak for the C=C stretch due to symmetry, no dipole change. P would show a moderately strong peak, as there is a significant change in dipole moment with the C=C stretch continuedig a ee oa HoH HH OCHs Hyco H u N fs C.G pts) Could one distinguish M from P using !3C NMR with broad band decoupling (the usual)? Explain. YES. M would show only 2 peaks, by symmetry. P would show 3 peaks D.@ pts) Could one distinguish M from N using '3C NMR with broad band decoupling? Explain, NO. Both would show only two peaks, at similar chemical shifts. E. @ pts) Could one distinguish M from N using the parent ion region of the mass spectra? Explain, NO. They have the same molecular formula. The exact MW is the same for each.7 IV. (26 pts) Henry is a closet philatelist and, in the course of that activity, recently ran into an interesting chemical problem. Some stamps can be identified by their "watermark" and this can be visualized by dipping the stamp into a "Philatelic Watermark Fluid". It is described on the bottle as a hydrochloro-fluorocarbon" but no more information is given, He enlisted the help of the master NMR spectroscopist, R. Hooley, and some spectra were collected. Consider the spectra in the Data Sheets for Structure II, pages 5-7. From the boiling point and other hints, the candidate structures seem to be A-C. Fluorine has an effect on chemical shift similar to that of Cl, but it has spin 1/2 and J values similar to H (Data Sheets: p 8, Table 3). ni cl at - ont / Lew aL ae OO OLN A. Considering the pattern of the peaks and the chemical shifts in the 'H NMR spectrum, 1. pts) Is structure A fully consistent with the spectrum? If not, explain what you expect for A. ‘YES. Or: possibly a qualified NO based on a careful chemical shift calculation. However, such a calculation would be suspect because one is adding up several perturbations. ‘The pattern would certainly be consistent with A. . (5 pts) Ls structure B fully consistent with the spectrum? If not, explain what you expect for B. NO. ‘The chemical shift of the CH group would be >4 (one alpha Cl, two beta Cl, one beta F) However, the pattern IS consistent with the spectrum, doublet with Jyp = 18 Hz 3.(5 pts) Is structure C fully consistent with the spectrum? If not, explain what you expect for C. NO Two different H environments. One doublet and one triplet due to H-H coupling, and then additional splitting due to H-F splitting. ‘Two different families of peaks: one methine + o-Cl + 0-F + B-F one methylene + o-F + B-F + B-Cl8 B. (4 pts) It is hoped that you found one and only one structure consistent with the 1H NMR data. /f not, please write a generic answer to this part. If so, please explain how that structure is also consistent with the pattern of the !9F NMR spectrum (do not concern yourself with the chemical shift). 1. e., what coupling gives rise to this !9F NMR spectrum? F is coupled to 3 equivalent H, giving a quartet. J= 18 Hz, consistent with coupling to H on adjacent (not the same) cl carbon C. (4 pts) In the same way, explain how that structure is consistent with the pattern of the !3C NMR spectrum, I. e., what couplings gives rise to this 13C NMR spectrum? i Two peaks, both doublets, due to '°F coupling. HsCs-GaF Cq doublet at 6 118 ppm, J = 300 Hz cl Cy doublet at 5 38 ppm, J = 0.5 ppm or 37 Hz IF B: The splitting patter is consistent, but not the chemical shitis. IF C: Should show two geminal Jcr patterns + vicinal coupling D. @ pts) Draw any ane of the possible staggered conformations of C using a Newman projection. Choose the proper template and fill it in. The key thing is to use the staggered template. Various positioning of the substituents is OK.9 V. (19 pts) Consider the molecules F-J and the selected IR peaks listed for the C=O stretch, Note that there is a change in the frequency as a phenyl group replaces a methyl, and a change when Cl atoms replace H. Note also that in I and J, there are two peaks in this region, of different relative intensity. uchcy, ok. ork. Chu Chow. F G H I J 1720cm™ 1692 cm" 1718 om" 1692 cm’! (larger) 1692 om’ (smaller) 1716 om'" (smaller) 1716 cm'™ (larger) A. (5 pts) Rationalize the difference in position of the peak for F (“normal”) and in G (shifted). It always helps to express you answer with structures. The phenyl group in G can interact with the C=O by resonance: ca, ‘CH, -~cH; <> a ‘CH, : eee eee. @s The contributions from structures 3-5 are not available for acetone and tend to contribute "single bond" character to the C=O. Therefore the C=O stretch is at lower frequency for the phenyl compound. a, £., B. (5 pts) Rationalize the difference in position of the peak for G compared to the peak for H. Standard dogma: Consider resonance structure 2, above. Putting in the CCl3 group raises the energy of structure and makes it a smaller contributor. Therefore, less contribution from a single bond structure, stronger bond, and moves the C=O stretch to higher frequency compared to that for G [BUT: this rationale does not very well account for the fact that with only one Cl (or two Cl), one does not see intermediate changes in the frequency~they are all the same with the added complication of a second peak]10 C. (9 pts) Things are not always so simple. See if you can rationalize the observation of two peaks from I and J compared to one from H. You might need to refine your thinking about the effect of the CCl3 group (structure G) with this analysis, and go beyond the ideas presented in lecture. — ie rotation It might be helpful to analyze the conformations v x of the compounds. The most favored conformation type a is shown here (X or other substituent) both in the Newman, g projection and the sawhorse projection. ‘The alternative, with a |x” 7x Be group eclipsed with the Ph substituent, is an energy maximum Ph as one rotates the front carbon, due to repulsion. favored, energy minimum Hint #2. IR spectroscopy is a "fast" camera, unlike NMR, and the x spectrum can show peaks for separate entities which are rapidly eG a interconverting. Pir # Fr x XPh disfavored, energy max, 1.@ pts) Draw on the templates here the cl H H three energy minima conformations for structure I W H tye cr T H Ph Ph 7 Ph 1 2 3 2.(4 pts) In your discussion, you should explain clearly: (a) why there are two peaks and (b) why each is at the particular position observed. 3. (2 pts) Explain why the relative intensity of the two peaks changes between I and J. Each of the isomers can give a peak in the IR; (2) and (3) are identical by symmetry. (1) has a Cl eclipsed with the C=O; a repulsive interaction of the Cl 8- with the (-) of the O destabilizes this resonance structure: é. cl 5 4H So (1) is at higher frequency, 1716 cm-l: For J, there are two conformations with eclipsed Cl and C=O, and therefore this peak is larger relative to the peak at 1692 cm-l, This is probably the better answer for the IR of G, where all energy minimum conformations have the eclipsed Cl with C=O and therefore a higher energy stretching vibration. Probably have to revise the "dogma" for next year end exam