Chemistry 303, fall, 1996 SECOND EXAMINATION 7:30 PM, NOVEMBER STH, 1996 Duration: 2 hr om GRADING KEY Lab TA, Gf you do not know his/her name, give day of lab section) 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 I35 Total: 100 ‘There are § pages in this exam; please check now to be sure you have a complete set. ‘There is also a Data Sheet for Molecule X handed out separately. Please be aware that a small number of students will be taking the exam at different times up until the aftemioon on Wednesday. It would be well not to discuss the exam until after that time. PLEDGE:* 1 (35 pts) (PAF pts) Consider the two molecules below. Predict she NMR chemical shift and sping pattern for each proton. Show your calculations. (s = singlet, d= doublet, t = triplet, q = quartet) cl 4, tks Hy-¢-Cl H.-C-Cl “Fo i cl le chemical | pattem chemical | pattern shift (ppm | (eicle) shift (ppm)| (circle) Hse 4, t, q, other | 2% @ 4 tq, other Hy 3.20 d, t, g, other H.3:20 4, t, q, other B. (3 pts) It should be clear that there is a dependence of the chemical shift position on the number of Cl substituents. Considering our usual parameters of resonance, inductive, hybridization, and steric effects, what do ‘you think is the most important parameter in determining the change in chemical shift for hese compounds? Plein. Stroy eletroang. atoms cuttdraw ekctrns (iidudtive ed), hurcrisg wnidaced Fed, terathnp mw Jess shicldrap 2 more deshiclded, C. Consider the molecule, cis-I-ethoxypropene, A ‘HNMR data: § 1.4 ppm, 3H, triplet, J=7Hz H, H, H 31.9 ppm, 3H, doublet, J=7Hz aN vy i. " 83.8 ppm, 2H,quaret, J=7Hz 4, \Y eH 84.5 ppm, 1H, quintet, J=7Hz | % \ aa 85.9 ppm, 1H, doublet, J=7 Hz WA Co—=Cg gH 8C NMR data: 8 9.5, 15.5, 67.0, 101.0, 144.0 ppm Vy \ a /\ Hg He Hi Hg 1 (15 pts) Correlate the structure with the 1H NMR data: a. Consider the signal which shows up at 81.4 ppm Circle the H which is(are) responsible for this peak: Hy Hy He Ha 8 OG Ky) Bi Hy Circle the H which cause it to be a triplet: Hy Hy He Ha He Hr Hg Fa NG)b. Consider the signal which shows up at 61.9 ppm Circle the H which is(are) responsible for this peak: Hy{H)ey He Hy Hy Hh Hj Hie Circle the H which cause it to be a doublet: Ha H{ Ha) Hy Hg Hy Hj Hy Doa chemeial shift calculation for these protons to back up your assignmeR Cue CH, bee 9.70 df sgprx for TG $ a d- ore 7p 7 c. Consider the signal which shows up at Circle the H which is(are) responsible for this peak: | Hg Hy He Ha He Hr igh) Circle the H which cause it to be a quartet: Hy Hp Hy Ha CHA (HL) Hj H 4. Consider the signal which shows up at 84.5 ppm Circle the H which s(are) responsible for this peak: Hy Hiy HCH) 6 Hy Hy Hh Hj Hy Circle the H which cause it to be a quintet: Hy Hy Hy Hj He €. Consider the signal which shows up at 55.9 ppm Circle the H which is(are) responsible for this peak: Ha Hy He Ha @ Hr Hy Hh Hj Hk Circle the H which cause it 10 be a doublet: H, Hp Hy Hg Bh Hj He 2. @ pts) Note that a simple alkene, such as cis-2-butene, shows NMR peaks at 6 1.85 (d, 6H) and 654 (q, 2H). Considering our usual parameters of resonance, inductive, hybridization, and steric effects, rationalize the difference in chemical shiftfor the H at 645 ppm and the H at 55.9 ppm in molecule A compared to the analogous H in cis 2-butene? Coup red to 2- bude Kesonance atreckures yr @ de a Z pa me ‘f 1 2s yer Hehe A little wore we ay oy “ electron poor y ie cartes x le wae rth, \witedi at # ot Fhictbel, kar te Ksonlaaxe delenit) tohatthy 3 G pls) Correlate the structure of A with the observed ™C NMR data: write the chemical shift value below the appropriate carbon number. It may be helpful to keep in mind your analysis in #2, above. Explain any {cis 2-butene ambiguity. = i 5 assignments oN Ppserred waines? G1 ¢2 63 C4 cs y ao 59.5, 15.5, 67.0, 101.0, 144.0 | § yss Jo) (yy 627 PS~ C1 Md CF cold be reversed. C2 15 thiclbed; C-3 13 Leshiothed > nz Bscussed ry (2) Above, 4. 3 pts) How would thé 1H NMR spectrum of the trans isomer B differ feqm that for the cis isomer, A? Give the single most important difference. NAGE He ay & 5 Me. Much larger for trans D IL 10 longer shneple iad ered to Ss, @ dovblet & ols Und ae =TI. (14 pts) Consider the 60 MHz 1H NMR spectrum below, and the list of structures, A-D. Which structure is best correlated with the NMR spectrum? Take each structure in turn (except for the "right" structure) and point cout the most clear-cut inconsistency between the structure and the spectrum. Identify the "right" structure, and correlate that structure with the spectrum in terms of chemical shift, relative peak areas, and splitting pattern. W pee Yo 4 olla ro px a A Cl CN [ost Ess | i Fee ee eee aE EE Fill groups Foal wt Oerlap coxa Cl wert < Flow 2 b. J vial H tee small C7 4 IF exyecked ) go ee <. 5 Lrviny! wrong > would be Oe C4 wept E at 19 H i ti TTT imitans By le etkal; ond ke Git wW are aaa MH Lxcaptins dette SmemreC: Methine 220 Aum. CS. bas Wo Sbsenmble Tom B. Would UV allow you to differentiate G from H? No. both would Shou MAT* omy j pilistinnsha de C. Would IR allow you to differentiate F from G? tee Sr con}. helowe i F ak 1680-1680 cui] X=6 br womal bebowe mw Cat 70) D. Would IR allow you to differentiate G from H? Yes: cee stretch strong Or H, weak tr €. Hise: cech bend for nt 760-780 coi Coch bends fer Hat 990-370 eau? E. Would 1H NMR allow you to differentiate G from H? ) Lenys. Ks Z Severn iA. =" E has Meas heoblel ot 208 HY tus we doublets Miso; é hns onhy 2 vinnl Hy HM has 3 wml 4. END EXAM.