EXAMINATION 1 Chemistry 3A Name Kim Lavoie (Print frst name before second! Use capital letersi] Peter Volihardt October 4, 2001 Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. an John Antos 364 Karl Tupper 421 Jennifer Barbarow 374 Etic Schneider 461 Dennis Leung 4tt Amish Patel 474 Dan Weix 424 Jennifer Prescher 244 Scheherazade Le 5tt Stephany Schuck 224 Steve Pham 524 Javier Range! 3i1 David Tang 561 Lianne Beltran 32t Joshua Goldberger Making up an | Grade (if you are, please indicate the semester during which you took previous Chem 3A praviously . Please write the answer you wish to be graded in the spaces provided. Do scratch wark on the back of the pages. This test should have 11 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy! Good Luck! DO NOT WRITE IN THIS SPACE L (20) M (20) uM, (30) Vv. (20) v. (30) vi (30) vu. (20) vil (30) Tota: = —— (200)|. [20 Points] Name or draw, ‘as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary the molecule is chiral or achiral (cis, trans, R, S, or meso). indicate with a circle whether a chiral achiral b. chiral achiral ©. Meso-1,3-dimethyl- cyclohexane 7) 4 chiral achiral d. 2R,38-2-Bromo-3- chlorobutane CHy 2 3 4 CHy chiral achiral| [20 Points] Write the best Lewis resonance structure for each of the following molecules. Remember to assign charges! a FFO b HOH H BON H HOH Eo ] Partial Periodk Table f Halogers Hala gases Fist Ke Second Lit! Bet Be o ne ee Ne Third Nat Mg APES gate pins gas gua arte Fourth KEAN pet gpa | Fink pany ans | Node: Ths sep indewe the mtr of eens eich rnp stl of th tom :Il. [30 Points] Unlike BH,, the molecule HBF has an octet form. a. Draw it. b. Show the orbital overlap picture for the bonding between B and F. Label clearly the overlapping orbitals (e.g. s, p, sp*, etc.), c. Show the orbital splitting associated with the B-F c bond in an energy level. diagram, Label each level clearly (e.g. s, p, sp’, bonding molecular orbital (MMO), etc.]. ——>5 IV. [20 Points] Draw the three staggered rotamers with respect to the 2,3-bond in 2,2-dimethylbutane (filin the blanks below). Hs He Hs Hye’ 4 Hac’ H HC! H Circie the most stable rotamer above and explain your answer in one sentence.V. [80 Points} Consider the following equilibria, B AG = +5 keal mot" c AG’ = ~10 kcal mor! ‘Compound B can be made independently and, when heated, generates A and C in a 1:1 ratio, initially. ‘On prolonged heating, the (essentially) only product is C. Draw @ potential energy diagram describing the progress of the reaction from A to B to C. A—> B —> C reaction progressVI. [30 Points] Hydrogen, H,, reacts, just like alkanes, with bromine to generate HBr. bv +B, —— = 2HBr @. Considering the DH” (Hz) = 104 kcal mol, DH® (Br,) = 46 kcal mot’, and DH? (HB3) = 87 kcal mol", calculate the AH" for the above reaction. Show your work below and enter the result in the box above. b. Formulate the propagation steps for the reaction, including their AH” values. Step 2 : ane ©. What is the minimum E, for the rate determining first step? The &, must be larger than kcal mot8 Vil. [20 Points] Given below are some substituent values for the AG* of the equatorial - axial ring flip of cyclohexane, 4 “Chis ~cHiCHs ~SH-CHs bts Cte ~G-or bs AG? (keal/mole) 0 17 18 2.2 5.0 Calculate 4G” for the following conversions in the large box below and enter the results in the small'boxes in the margin. . — ww: CHs——C-—CH, Chis CH3 be Le Leerseg — eee CH CHs CH: CH: i Now ° CHCHsVIll. [30 Points] Place an X mark in the box preceding the most accurate statement. 2. Fluorine (Pauling scale vaiue 4) is more electronegative than carbon (Pauling scale value 2.6) leading to the conclusion that: all fluorinated compounds are negatively charged. the C-F bond is polarized in the sense *C-F* carbon prefers sp* hybridization compared to fluorine because in this way it can minimize electron repulsion, carbon is a better electron acceptor than fluorine, b. CH,’ is a molecule whose carbon center is a.) sp*hybridized, leaving an empty p orbital aligned perpendicular to the molecular plane, and b.) electron-deficient (Ge), at odds with the octet rule. ‘Therefore: to satisfy the octet rule, the molecule is readily protonated. to satisfy the octet rule, the molecule readily dimerizes. to satisfy the octet rule, the molecule readily dissociates to CH, + H’. to satisfy the octet rule, the molecule readily attacks electron rich species, such 7 + §—> chsOHh). as water (e.g., CHs” + Hy10 c. When considering the following potential energy diagram: ‘compound A will convert to B faster than it will to C. Cis the thermodynamically most stable component of the mixture and will form at the greatest rate from A or B. B will convert to C faster than A will, none of the above d. The following molecule is A-sA* Hc achiral because it has a plane symmetry. achiral because it has rotational symmetry. chiral because image and mirror image are non-superimposable, ‘achiral because it contains no stereocenters. 101 e, Radical bromination of A at C2 will give: an achiral molecule because A is meso. an optically active tribromide. a molecule without stereocenters. « chiral tribromide "Don't womy, Howard. The big questions are multiple choice." * The End * uEXAMINATION 2 Chemistry 3A Name: Kim Lavoie [Print frst name before second! Use capital etteral] Peter Volihardt November 6, 2001 Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 114 John Antos 364 Karl Tupper 124 Jennifer Barbarow 371 Eric Schneider 161 Dennis Leung at Amish Patel 474 Dan Weix zt Jennifer Prescher 244 Scheherazade Le 461 Shahed Ghoghawala 224 Steve Pham. st Stephany Schuck att David Tang 524 Javier Rangel 324 Joshua Goldberger___- | 561 ianne Beltran Making up an | Grade (if you ere, please indicate the semester during which you took previous Chem 3A previously . Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 11 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy! Good Luck’ BO NOT WRITE IN THIS SPACE I (60) u (30) Mm (30) Nv. (30) v. (30) vi. (20) Tota: —— (200)cl «+ «=| CHSCH3 [60 Points) Add the missing starting materials, reagents, or products (aqueous work-up is assumed where necessary). Don't forget stereochemistry! 2 Circle one: Racemic Optically active af |—e 4 CH, we OCs, LIAIH, hei CH, O BpH 3 H | f Fill in the missing CH;OH_ ‘substituents! Ha Pure enantiomer cee Re Pure enantiomer 8 NN ot + CHLi (1 equivalent) CHO | ; | 2, —_—— ?Scti,er Nroaon 7 4 14NaOH, CH;OH ‘An oxacyclopropane ‘Na*"SCH; NS i Br (1 equivalent) HBS |, [30 Points] The following reactions proceed (predominantly) by S.2, Sy1, E2, or £1 pathways, respectively. Give the predominant product (one only) in each case and answer the questions by circling the most applicable statement. Ho. HY, CHAOH, 4 HO An alkene Mechanism: Sy2 ‘Syt E2 Et At lower temperatures one of the following ratios will increase: Sy2/ Sut Sut E1 E2/E1 — Sy2/E2 15we 80:0Hs Hac. | KEFOG(CHads, (CHg)gCOH Mechanism: 82 e2 et Changing the alkoxide to CH,0~K" causes one of the following ratios to increase: E2/e1 8,2/ £2 Sit /E1 E2/ 5,2 ot NH, THE He 4H Mechanism: 82 Sit 52 a1 ‘Changing from ammonia to lithium amide, Li NH,, causes one of the following ratios to increase: £2/ 5,2 E2/E4 Sq2! Sut rearrangement / S,2 16cl Hy CH3Se", CHOH solvent 1H Mechanism: S\2 sd 2 Et ‘Changing the solvent to DMSO will have one or more of the following effects (circle all that apply): rate increases solvation of the Nu: decreases e CH;OH solvent, -20°C {CH3}COH | > | Mechanism: Sy Syt 2 Et Changing the solvent to (CHs),COH causes one of the following ratios to increase: 8x21 Sut E2/E1 E1/Syt 8,21 E2 77 il, [30 Points] Explain the following observations by a detailed mechanism (e., write a scheme with structures, use arrow-pushing, etc.) a HeGy, Lil fo os o optically active optically active (Hint: Note the change in stereoche! b. HC. CHs Hc, acetone Pow CHy optically active racemic 188 IV. [30 Points] Provide a viable synthesis of the following compounds from any starting materials containing four carbons or less. Work backwards! a ‘octis b. Gls ts ‘ Hint: You need to start with a defined stereoisomer of your starting % material. oH CH (racemic) 19V. [80 Points} A researcher treated propane with Ci; in the presence of traces of dibenzoyl peroxide as a radical initiator. Careful separation of the product mixture revealed a minor contaminant with the *H NMR spectrum shown below: a. What is the structure of this compound? b. Assign the spectrum by labeling the hydrogens giving rise to the absorption centered at 5 = 2.2 ppm with the letter “A”, those at 6 = 3.7 ppm with “B" in the drawing in the box above.10 c. Explain your assignment in b. ¢. Explain the muttiplcity of the peaks using the (N+ 1) rule. VL. (20 Points] The hydrogen highlighted by an arrow in the following compounds is expected to give fise to the circled signal pattem in the *H NMR spectrum: a. Ha CH singlet doublet triplet quartet H He’ ‘CHsinglet singlet singlet doublet triplet doublet “The End* triplet quintet doublet of doublets "4 quartet septet quartetf FINAL EXAMINATION Chemistry 34 Name: Kim Lavoie [Prin frst name befere second Use eaplal eter) Peter Vollhardt December 12, 2001 Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 414 John Antos 361 Karl Tupper. 424 Jennifer Barbarow 374 Eric Schneider 164 Dennis Leung att Amish Patel a7 Dan Weix 424 Jennifer Prescher 2i4 Scheherazade Le sit ‘Stephany Schuck 224 Steve Pham s2t Javier Range! att David Tang 561 Lianne Beltran 321 Joshua Goldberger Making up an | Grade (If you are, please indicate the semester during which you took previous Chem 3A previously HeSeaaaEaEED Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 25 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: read carefully over the questions (at least twice); make sure that you understand exactly what ig asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy! Grades will be posted on Wed, December 19, outside 305 Latimer Hall (Lab Q), Good Luck! DONOT WRITE IN THIS SPACE 1 Heees 2 (a0) M (90) mW (30) Nv. 0) v. eee ee w, Beauties (00) vil (80) Tota: = —— (400)* 1, [80 Points) Provide the IUPAC name or draw the structure, as appropriate, of the following molecules. Remember the priority of functional groups in choosing names, indicate the correct stereochemistry (e.g. R, S, and E, Z), and do not forget about the alphabetical ordering of ‘substituents! a HCH, Hs b. 7 (E)-4-Ethyi-5-methyi-4-octene e OH CH=CH,Trans-2-mercaptocyciohexanol e 4 c Il c H—+—r HH HC==CH, ‘Meso-1,2,3,4-tetrachlorobutaneIl, [90 Points} Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (When required) is assumed to be part of a step. Itis ‘ot part of any answer. a Bra,hv — i south P(CHs)3 OSCHs OSCH; —_—_—_—_—_> Nal, CH;OH + CHy CH.BrNa’ ~OCHy,CH,OH 1. HBr, 0°C 2.MgTC —— 2. re OH CHe Wt, THE, =H ICH Most stable isomer i CHsCOOH SN, rn parising Achy LAI, HCH CH HO, CHACHA CH2CHs 7 =O 00H 1. cl HO. 2, HHO aye HC An alkene1H . NaOl we 1 : 2. poe AIll, {30 Points] Consider the anti-Markovnikov hydrohalogenation of propene. ROOR, A x ea a, Formulate the propagation steps of this process: Propagation steps. b. Using the bond strength data below, estimate the AH? values of each propagation step for X = Cl, Br, and. yc DH (keal mol"): x bond «65. 2 a1 oe) Hel 3 Note yl HBr Gre aa 53 HI m1 . 95 31AMP of step 4 : cl: Br AM of step 2: a: Br: follow the normal electrophilic, Markovnikoy addition pathway. Considering your data in b., why shot this be so? 10 c. Under radical chain conditions, only HBr adds to propene in an anti-Markovnikov manner; HCI and Hl ld" IV, [50 Points] A researcher executed the following steps to prepare the alcohol A. 9 Huq Be AL ae pe fo THF H3C Hs: —+» Grignard reagent ——__—__—— A GA Qe loot A In addition to A, another compound B, Cs, was obtained in small amounts, which exhibited the IR and NMR spectra shown, a. Aiter consideration of the spectral data, write the structure of B in the box below. Structure of B . Interpret the spectral data as requested in the spaces provided. 1. IR Spectrum ie i evo wee12 ‘Considering the starting materials of the attempted synthesis, B could be an alkyne, alkene, or alcohol. Confirm or rule out these functionalities. ¥ (C=C) is : present absent at (circle correct statement) ae present absent at a ¥ (C,7-H) is : present absent at cm* ¥(O-H) is : present absent a om"? 2. "C NMR Spectrum A 3B T T T T T T T T T T 200 180 160 140 120 100 80 60 40 20 0 pom 3413 Draw your suggestion for B in the box below and label the carbon atoms A, B, C, and D siving rise to the ‘corresponding signals in the spectrum. Note: You are allowed to make an arbitrary assignment of peaks Cand D, as long as you pick the right pair of carbons in your molecule. 3. 'H NMR Spectrum GH A \ =e 22 ppm | (Cis) al 20pm 1H ah ae 2.6 ‘ppm iH oh T 7 T 7 ; 1 5 3 a 3 2 i 0 ppm 35Draw your suggestion for B in the box and label the hydrogens A, B, and C giving rise to the ‘corresponding signals in the spectrum. , Provide an explanation (guess) for the formation of B. 36 1415 \V, [60 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and “arrow-pushing” techniques. Note: These are nol synthetic problems. Do not add any reagents! What you see is what you have! nO = OD Br b. 7 Bry, CCl, A CH 37© CHgOH + SOCl) ——> CHgCi + SO2 + HCI 38 167 VI. [60 Points] Show synthetic forward connections (reagents, intermediates; no mechanisms!) between the following starting materials and the final (racemic) products. Note: several steps are required in each case; there may be several solutions to each problem, but vou should use only one; itis best to work backwards (retrosyntheticaliy) on the back of the exam pages, to enable you to dissect the products into less complex precursors. However, the answer to be graded should be @ forward scheme. {n addition to the starting structure, you may use any organic and organometallic reagents containing four carbons or less. a (CHaCH SS 39OH 40 CN CH 1819 Vil. (80 Points} a. Draw the best resonance structure for the “dinitramide” anion : ©. N. Oo ee Sy ° ° Don't forget charges! . Alkynyl anions, RC=C", have a lone pair situated on the terminal carbon. What type of orbital does it ‘occupy (e.g. sp*, p, etc.)? 4120 c. The mechanism fo rthe E2 reaction of bromocyclohexane with NaOH proceeds through the axial conformer [AG* (equatorial-axial) = 0.5 kcal mol’, E, (equatorial-axial) = 10 kcal mot] with an activation barrier of 19.5 kcal mot, Draw the potential energy diagram for this process. Show clearly the position of the transition states (use the labels "TS1” and “TS2") and of the axial conformer (use the label “Ax"). Potential Energy Diagram: ea i: Hacer 10 —} Hal ao ail ca 4a oa oo al aa foe oan te con + NaBr + HO24 4, _Using key words or a short sentence, list four techniques or experiments that support the mechanism of the S,2 reaction. 4B22 . Predict the coupling patterns of all of the hydrogen signals in the 'H NMR spectrum of the compound shown below. Label the hydrogens as s, d, t, q or dd, tq etc. Apply the sequential N+1 rule. HG, % 4 H {How many #°C NMR peaks do you expect for tetra-t-butyltetrahedrane : g. Give approximate 'H NMR dvalues (ppm) for the hydrogens in the two functional groups shown. RC=CH R,C=CH,23 h. Aresearcher cleaved the alkylidene side chain of steroid A by treatment with O; in CH,Cl,, followed by NaBH, (instead of the usual Zn-CH;COOH). Distillation of the product led to the isolation of liquid B. Assign a structure using the spectral data shown below. 1. O3 2. NaBH, ‘HNMR Spectrum: IR Spectrum: 100 ; . couch + (CH)sCOH ohh but: CEh=CH2 + (CH3)3COCl ——* (CH3)3CO ca Use the data in the Table above to get some estimates of some of the relevant bond strengths, in addition to DEP(CH=CH}H) = 110 keal mol”, DAP(CH2=CH+CI) = 92 koa mot”, and DEP (q bond) = 65 keal mol”, to give an explanation for this finding 7910 IV. [50 Points] “When ethyne is bubbled through acidic butanol, a new compound X forms, with the spectral data shown below. CHCHCH,CHOH, H* rec | [eee X Céin0 a. After consideration of the spectral data below, write the structure of X in the box ebove. bb. Interpret the spectral data as requested in the spaces provided. 1. IR Spectrum a sneer 100. J J THERE ue. TRON GrETTANCE, 78.22 tesa to 1nsaok oe are as 1200.73 ‘te00 ‘3300 eve see eee 1800 seoa avenues 20.0 80Considering the starting materials, X could be an alkyne, alkene, or alcohol, possibilities: ¥ (C=C) is : presenabsent at (Circle correct statement) ¥Cop-H) is: present/absent at (Circle correct statement) VCpr-H) is present/absent et (circle correct statement) F(RO-H) is : PresentVabsent at (circle correct statement) 81 Confirm or rule out these2 12 2. °C. NMR Spectrum 460 440 420 490 a0 60 40 20 PHO Draw your suggestion for X in the box below, and label the carbon atoms A-F giving rise to corresponding signals in the spectrum.18 3. "HNMR Spectrum Note: E and F are actually each a dd (the second J'is so small, 2Hz, that itis barely visible. Draw your suggestion for X in the box and label the hydrogens A-G giving rise to the corresponding signals in the spectrum. 8314 V. [60 Points] ‘Write detailed step-wise mechanisms for the following transformations, Use only structures and “asrow-pushing” techniques. Note: These are not synthetic problems, Do not add any reagents! “What you see is what you have! FS0x, FO 84oe SCH ‘Note stereochemistry HYbO » Cla = a on "CECH ‘CH racemization 8516 [60 Points] Show synthetic forward connections (reagents, intermediates; no mechanisms!) between the following starting materials and the final (racemic) products. Note: several steps are required in each case; there may be several solutions to each problem, but you should use only one; it is best to work backwards (retrosyntheticaly) on the back of the exam pages, to enable you to dissect the products into less complex precursors. However, the answer to be graded should be a forward scheme. In addition to the starting structure, you may use any organic and organometallic reagents containing four carbons or less. C= HyC-O=CH | BC 8618 VIL [70 Points} a. Draw the best resonance structure for | Boe SCN Fy eo we a Indicate the position of the positive charge. b, Nitiles, CSN: , have a lone pair situated on the nitrogen. What type of orbital does it occupy? c. The mechanism for the acid-catalyzed conversion of cis-2-butene to trans-2-butene is as shown. [N+ AS 7 wi re le ks ‘J 2 3 h>k > b Draw the potential energy diagram for this process clearly labeled with the locations of 1,2, and 3. Potential Energy Diagram: st 8819 4. The mechanism of the oxacyclopropanation of alkenes by peroxycarboxylic acids proceeds in one step as shown below (“Mechanism I") ‘Mechanism of Oxacyclopropane Formation (Mechanism 1) BUR a * a eee eee eee A— HL. AN ‘An alternative mechanism ("Mechanism II") would be rate determining O-O bond heterolysis to give free 2 HO" (and RCO) which could then attack the allcene. Alternative Mechanism (Mechanism II) RC-o-on © HOS ho + ‘on alkene + ‘on 28—» omacyclopropane + HY Indicate one method by which you could rule out the second mechanism. Method: ‘Results for Mechanism I ee Results for Mechanism II | 89sare 20 ‘e. Predict the coupling patterns of the hydrogen signals in the “HNMR spectrum of the compound shown pulow, Label the hydrogens ass, d, t, q oF dd, 19 etc. The simplified N*1 rule does not hold here BL An Ais CHSC H How many "CNMR peaks do you expect for the following compound is CH i. Give approximate pe values forthe two functional groups shown, RC=CH ROH pKa: pKa: A researcher attempted the free radical addition of ammonia to I-butene. Two products of adition ae in principle possible, as shown. The ‘HNMR spectrum of the product obtained is depicted below. Circle the product to which it corresponds. AZ ua MOR ALN, * aa ? ™ NE ” ” ai, Octyne can exist as several isomers. Which one gives rise to the IR spectrum shown below. IR spectrum of an isomer of octyne 100 a) 0 40 | * 20 ° ‘cop 35003000 230030001800 1600 1300 1200 1000” 800 600 ‘wavenumber (em!) J... Consider the following measured heats of hydrogenation : \/ +h Saas Na = -28.6 kal mol” rv +H, Satelyst, NAH = -276 kal mol”! Ifyou were to bum the two starting alkenes to CO; and HO, which one would have « more negative AFeoxt? (circle one) ro 91 24EXAMINATION 4 Chemistry 3A Name: Professor Carolyn Bertozzi {PRINT Fst nare et nn Last rare, Use capa! ters Professor Peter Vollhardt October 1, 1996 Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 461 Baryza.Jeremy 311 Adronov,Alex 111 Goon,Scarlett 321 Mullins, Sarah 421 Yeston,Jake 331 Esker,Todd 431 Gruneich,Jefirey 341 Shaffer; Wendy 141 Richards,Steven 351 Loftus,Christine 481 Berglund, Timna “#11 Lemieux,George 211 Thornton,Joel 421 Essy,Blair 221 Moore,Jennifer 811 Staunton,Joanna HVT 361 Paisner,Sara 521 Magliery, Thomas WATT 371 Tellers,David 831 Marcordes,Belinda Making up an grade. (ifyou are, please indicate the Semester during which you took Chem 3A previously. ) please write the answers you want graded in the spaces provided. Do scratch work on the backs of the pages. This test should have 11 numbered pages. Check to make sure that you have received a complete exam. A good piece of ersee read carefully over the questions at least twice; make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. tis better to be pedantic in accuracy! Good Luck! ‘BO NGT WRITE W THIS PACE \ (39) u (20) wh, (30) W. (20) V. (15) MM. (65) vit (15) vil. (15) Total (200)1. [80 Points} Name or draw, as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary (cis, trans, or R, S). : b . (R)-2-bromobutane (Fischer projection) a (R)-3-Fluoro-1,1-dimethylcyclohexane - 6 Br CHy CH CHCH, Flin the fssing Atoms, Fl inthe Missing Group. 93NL [20 Points} Write the most favorable Lewis octet structure for each of the molecules depicted below (don't forget formal charges). TAOKE Partial Price Table ree a Tiases Nee pe roi_| Le Sot PRT ae sro [rere Te | | AT art gee | ae at ree | BERT EI = TaN | Sai pee a RE Uo pA oT a Si Ons, b. N Ss F © 3 Oo Oo B oO a H N 0 "Ny o° c HeeC ee Heo ep 4 H Fill in the two additional octet resonance structures and circle the strongest contributor to the overall structure.WM, [80 Points) ‘Trifluoroborane (boron trifluoride), BF,, reacts with F- to form the tetrafluoroborate ion, BEE. BFg + BF, Draw the orbital on BF, Involve bond formation and show its overlap with the appropriate atomic orbital of F-. Clearly label these orbitals (e.g. 15, 2s, 2p, 35, 3p,Sp, sp’, Sp", et.). b, Draw the energy diagram for the formation of BF, by the reaction of BF, with F~. Clearly depict the energy levels of the orbitals entering into overlap and label them, and show the resulting bonding and antibonding molecular orbital levels. Place the relevant electrons into the various levels. : c. In view of the above, would you consider the protonation (e.g. reaction with H") of the boron in BF, to furnish a stable bond? Explain. 95WV. [20 Points] Treatment of 2-iodo-2-methylpropane (A) with sodium fluoride (1 equivalent) led to the ‘exclusive formation of 2-fluoro-2-methylpropane (C) via the intermediate 1,1-dimethylethyl (t-butyl) cation (B), according to the following scheme: - CH, : GHe Kt © CH, + nate Ke te - NatF” + Cah 1 CHC. ee etaeet Chee —F + NavT ey CHa + CHs A B c Independent generation of B revealed that it reacts faster with iodide than with fluoride ion. Draw a potential energy diagram describing the progress of the reaction from A to B to C. Clearly label the positions of A, B, and , and the transition states (TS) interconnecting the three reaction components. Circle the rate-determining TS for the conversion of A to C, reaction coordinate _ 96V._ [15 Points] Lewis acids, such as AICI,, can cause isomerization of haloalkanes. TABLE 1 Bond-Dissociation Energies of Various A-B Bonds (DH? in keal mol!) Bin AB Ain AB HO-F Cl Br LOH = we msm 0 cHs— ) CHCHCH- «98s h(a (CHs)2CH— en (CHyysc— om 8 [Now Trews aumben oe inp evad Comin bosase of improved mathe For ee femtemen Sone ofthe vahes uiven here my be twa em Using the table above to estimate the relevant bond dissociation energies, calculate the AH” of the following reaction. Show your work. H i AIC; CHs CHupcH.c! cHegat CH CHs AH = b. Circle one. The two chlorides above are: constitutional isomers ‘stereoisomers c, Do you expect the AS* for this reaction to be large and positive, large and negative, or negligible? Explain your answer. Answer: 97Vi. [55 Points] ‘The free radical bromination of 1-bromopropane, CH,CH,CH,Br, at 200°C results in a mixture of dibromides, as shown below, from which 4,2-dibromopropane, CHLGHCH.Sr, can be separated by careful distillation, r hv, 200°C. Ne Bre ——— Xt OVO 2 Br or a a : Sita - BK AB Br 80% 17% 3% x v, Zz chiral - achiral chiral - achiral chiral - achiral optically active - inactive optically active - inactive optically active - inactive le the appropriate labels to indicate whether the respective product is chiral or achiral, and optically active or inactive. b, From the % yield data, calculate the approximate relative reactivity of the hydrogens at C1, C2, and C3 in the starting material during this transformation. ‘Answer: Relative reactivity of Ht : #2: #3 = ©. Formulate the propagation steps in the mechanism of that part of the reaction that leads to 1,2-dibromopropane. 98Complete the following diagram by adding a qualitative potential energy curve for the rotation about the C1 - C2 bond of 1,2-dibromopropane, starting with the conformal ‘shown at 0° and turning C2 (the back carbon in the Newman projection) by 60° increments. Indicate qualitatively (but clearly) the positions (i.e. relative energies) of the maxima and minima of the curve. Hint: CH, is larger than Br. o eo 120" 180" 220" 00° 360" Fa Br er BF a HBr er Hs n 85, Bye Hyper Hoey TH H CH Br we SO OS or Be F H Gis Hat 7 A B c D E F @VIL. [15 Points] The following values represent AG* for the conversion of the equatorial to the axial conformer of the corresponding substituted cyclohexane, AG? (kcal / mol) - ° —o% e =e ‘8 “oor, fe fu, sa CH calculate AG for the following conversion, CH a AG? = H0-C—CH, Hs HsC.__-CHy GRCHs CHa oH cH AG? = on CH,CH, 10010 VII. (45 points) Place an ‘X' mark in the box designating the most accurate statement. a. The Oo {if | | b. Ci c, The relat e. The AH? of an organic reaction: reflects entropy changes. is highly negative for fast transformations. can be estimated by subtracting the sum of the DH" values of the bonds formed from those broken. is the symbol for the rate in the Arrhenius equation. ‘ovalent bonding is strongest when: [1] Ione electron pairs are involved. [1] the atoms are large. bonding and antibonding molecular orbitals cancel each other. itis the result of overlap between atomic or hybrid orbitals of similar size and energy. compounds cis- and trans-1,3-dimethyicyclohexane art identical. stereoisomers. interconverted by ring flip. rotamers. heat of formation, AH,°, of diamond (a form of carbon) equals +0.45 kcal mo! tive to carbon in its standard state: graphite. This observation means that: the diamond form of carbon is more stable than that of graphite. the combustion (burning) of diamond produces more heat than that of an equal amount of graphite. diamond is harder than graphite. diamond is rapidly converted to graphite. rate of the free radical halogenation of alkanes can be increased by: ‘choosing more selective reagents. (C1 increasing the temperature. diluting the starting materials in an inert solvent. cooling the reaction medium to retard the termination process. 101EXAMINATION 2 Chemistry 3A Name: Professor Carolyn Bertozzi (PRINT Fie name fret, then Lact name, Use eaptal eters) Professor Peter Vollhardt November 5, 1996 Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 161 BaryzaJeremy 311 Adronov Alex 111 GoonScarlett 221 Mullins,Sarah 121 YestonJake 331 Esker,Todd 131 Gruneich Jeffrey 341. Shaffer, Wendy 141 Richards,Steven 381. Loftus,Christine 151 Berglund,Timna 411 Lemieux,George 211 Thomton,Joel 421 Essy,Blair 221 Moore,Jennifer 511 Staunton,Joanna 361 Paisner,Sara 521 Magliery.Thomas 371 Tellers. David 531 Marcordes, Belinda Making up an I-grade. (if you are, please indicate the semester during which you took Chem 3A previously i Please write the answers you want graded in the spaces provided. Do scratch work on the backs of the pages. This test should have 14 numbered pages. Check to make sure that you have recelved a complete exam. A good piece of advice: read carefully over the questions at least twice; make sure that you undorstand exactly what is being asked; avoid sloppy structures or phrases. Its better to be pedantic in accuracy! Good Luck! L ) 4 (10) Via Mm. (60) vib. WV. (35) Vic. Va. v. (40) Vid. Vb. vi (40) Vie. Total Total Total (200) 102I, [15 Points] Name or draw, as appropriate, the following molecules according to the IUPAC rules, Indicate stereochemistry where necessary (cis, trans, R, S, or meso). (2R,38)-2-chloro-3-iodobutane ‘ou 103i. [10 points] a. The reduction of (+)-galactose with NaBH, gives a product A and the reduction of (-)-galactose gives a product B. Draw the structures of A and B in the boxes provided. Are these products optically active or inactive (circle one)? A Ox UH NaBH, active inactive B HO HO—}—H NaBHa H—}—oH H——0H HO——H Cr,OH (galactose active —_ inactive b. What is the relationship between A and B? (Circle one answer) enantiomers —_ diastereomers constitutional isomers _ identical 104I, [60 pe s] Add the missing starting materials, reagents, or products (aqueous work-up is assumed where necessary). Don't forget stereochemistry! Hy ° (CHyCHOH a cHRCHOH Yb cy, — Semel CHaCHe g Circle one: optically active? yes no Br CHS (equiv) i b ‘Acetone Br optically active? yes no / | N | cS "oe eH optically active? yes. no \ on Nag0tz0rHe0,HeSOs | a AA Toe optically active? yes no 1057 Br OH MgB ‘OH OH OH 0, HpS0. CeH 90 HeSO4, A a tettiary alcoholOH (CH3OH, H* Hn Seeeea CHacHe Optically active? Yes No 107[35 points] For each pair of reactions shown below, mark the box on the right with an "X" indicating which will go faster and circle the mechanism by which it proceeds (e.g., Sn2, Su1, E2, E1). Below, circle the letter corresponding to the statement that best explains your choice. No credit will be given for a correct answer in the first part of the question with an incorrect reason in the last part. CHO) Br OCH; ~_ r chs Br SoH, NN ap Sy2 Syi e2 A a. CH; is a stronger base than CHS . b. CHS" is less solvated and more polarizable than CH,” ¢. The S-H bond is weaker than the O-H bond. 1 eos cose Go.» o a CctHg Gis co cHacHa0H i Sy2 Syl B Ee a. T isa weaker base than Cl’. b. T is a better nucleophile than CI. c. Ethanol is a better nucleophile than T 108= a. CH,CH,0” is a better nucleophile than CF{CH,0". b. CH3CH,O’ is a stronger base than CF;CH,0 . c, CH;CH,0 is a weaker base than CF;CH,0. Br cn Nan ‘acetone Br _NaCN TCH:OH Sy2 Syt Et a. Carbocations are more stable in polar solvents. b, CH,OH is a weak base. c. Anions are encumbered by solvation in protic solvents. 109O Sy2 Syt E2 Ei a. The E1 reaction proceeds through a planar carbocation, b. The nucleophile in the Sy2 reaction attacks from the backside. c. The base in the E2 reaction attacks the proton anti to the leaving group. Hi : Draw the chair conformers of the starting materials 11010 Vv. [40 points] Explain the following observations by a detailed mechanism (i.e., write a scheme -with structures, use arrow-pushing to illustrate the flow of electrons, etc.). 7 woh EB gh + me 7 OH | He804,H,0,a HO llvi. Ww [40 points} Provide a viable synthetic route from starting material to product. You may use any additional organic or inorganic compounds in your scheme. Br — ( 1213,14 13FINAL EXAMINATION Chemistry 3A Name: Professor Carolyn Bertozzi (PRINT Firstname ft, then Last name Use capial eters) Professor Peter Vollhardt December 11, 1996 Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 161 BaryzaJeremy 311 Adronov,Alex 111 Goon,Scarlett 321 Mullins,Sarah 421 Yeston,Jake 331 Esker,Todd 131 Gruneich Jeffrey 341. Shaffer, Wendy 141 Richards,Steven 351 Loftus,Christine 151 Berglund,Timna 411 Lemieux,George 211 Thomton,Joe! 421 Essy,Biair 221 Moore,Jennifer 517 Staunton,Joanna 361 Paisner,Sara 521 Magliery, Thomas 371 Tellers, David 531° Marcordes,Belinda ‘Making up an I-grade. (fyou are, please indicate the Semester during which you took Chem 3A previously. and the professor ) Please write the answers you want graded in the spaces provided. Do scratch work on the backs of the pages. This test should have 23 numbered pages. Check to make sure that you have received a complete exam, A good piece of advice: read carefully over the questions at least twice; make sure that you understand exactly what Is being asked; avoid sloppy structures or phrases. Its better to be pedantic in accuracy! Good Luck! ‘DO WOT WRITE WHS SPACE 1 (30) n (90) m. (35) Nv (60) Va v. (45) Via. Vb vl (60) Vib. Ve. vi (80) Vic. Total Total (400) Total 1s~ 1. [80 Points} Name or draw, as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary (cis, trans, R, S, and E, Z). Do not forget about the alphabetical ordering of substituents. (R)-1-hexen: L~Laio Racemic 116(2R)-4-buty!-4-pentyl-2-propyl-1- Ronanethiol cis-3,7-dimethyicycloheptene meso-3,4-dichloro-1,5-hexadiene uyi. [90 points] Add the missing starting materials, reagents, or products (aqueous work-up is assumed where necessary), Don't forget stereochemistry! {1 equiv. CHS WMG ey ° OH 1. BH 2. HO», NaOH b. e 1187 1. HBr, ROOR 2u 8. Cul £ 4, GHsCHeBr 4, FpBH H 2. HpOp, NaOH 8. chet % oe CormeaeaE =a 191. (CHs),CONa. a 2 0; i His PRIN Ng t. Hp, Pd/C cl 2 “SC NMR: 8 22, 29, 123, 132 ppm [a cat. OsO4,H202 show stereochemistry!CoH,g0 | "SC NMR: 8 18, 25, 27, 28, 32, 65 ppm i IR: broad peak at 3200-3500 cm ‘OHI. [35 points] a. Amino acids such as serine (compound A, shown below) are the building blocks of proteins. Serine can undergo an internal acid- base reaction to give the charge-separated species B as illustrated in equation 1. Using the indicated pKa values, calculate the equilibrium constant Keg for Equation 1. Place your answer in the box provided below. Is the Gibbs free energy (AG*) for this reaction positive, negative or zero? (Circle one answer below). OH OH OH = ____> oO HN = 4.1) ° pka=4 A B (Serine) > Circle one: AG< 0 Keg = 122b. Indicate the relative energies of A and B on the potential energy diagram below and indicate AG°. Reaction coordinate c. When serine is treated with one equivalent of sodium amide (NaNH2), a favorable proton transfer reaction takes place. What is the product of the proton transfer reaction? Place your answer in the box provided below. (Hint: consider the indicated pKa's. The pKa of NHg is 32). pka= 15 OH O 4 NaN, = ——» + NH3 * Han qa equiv)Vv. 40 [60 points] Write detailed step-wise mechanisms for the following transformations. Use only structures and “arrow-pushing" techniques. Note: These are NOT synthetic problems. Do NOT add any other reagents. By AsO 21 OCH i = RoOCHs i OCH Octts — + Grae 124¢ , & ey i & OCH: Seen — check” cts 125w as ww 12 [45 points] The reaction of 1-butene in an open reaction flask with HBr gives a mixture of two products, compounds 1 and 2, the NMR and IR spectra of which are shown below. Provide structures for compounds 1 and 2 in the boxes provided using the information in the spectra. Make peak assignments on the 1H NMR spectra for both compounds showing which protons ive rise to which peaks (i.e., label the unique sets of protons a, b, c...et¢. on your structures in the boxes, and label the corresponding peaks in the 1H NMR spectra for compounds 1 and 2 with the same letters). hel __| Compoond | "houme Compesnd 2 “HNMR wou WF 1 a" aa ose aaa ed b bobo 126| Compound 2 Pe ume oma R (EG spectrom) 127b. When compound 2 is stored in a humid environment, it slowly converts to compound 3. Provide a structure for compound 3 in the box provided using the information in the NMR and I spectra below. Explait ir wer ider the ci ictet ic ks inthe 1H NMR and IR spectrum. oe Compound 7 compound 3 nee Compound 3, - c Nm, ® » eee eae anaes as ae ab wok Comptond 3 GQ spectunf p> -——~ 128i | | | | vi. 15 [60 points} Provide a viable synthetic route from starting material to product. Several steps are required in each case; there may be several solutions to each problem but you should use only one. It is best to work backwards first (retrosynthetically), and then formulate your synthesis in the forward direction. in addition to the starting ture, you may use \dditional_organic_oF i junds contal rr roblem_c in which the starti i janic in material. 129130 16as the only organic starting material (L., ‘make all your required ‘organic pieces from this compound). BL HO, 17vu. 18 [80 Points] Mark the answer in each of the following multiple choice problems that you deem most correct. Which of the following resonance structures is the major contril to the overall structure? —_—A, because it retains the triple bond. ——_B5, because the charges are further apart. —_A, because C, N, and B have octets, ———B8, because CH stabilizes the adjacent positive charge. The following potential energy diagram fits which one of the reactions shown? ——_(CHa)sCCI + H20 CH3Cl +-OH (CH3)sCCI + (CHg)3CO- —_(CH3)3COH + No 132,19 " CHE CHaCHCHy CHC 1 2 3 The correct order of increasing strength of the marked bonds is: (.e., weakest, middle, strongest) eau | aug) a ea porta aig a. eesteeeat Sea _—_Other (specify): The 13C NMR spectrum of A shows the following number of lines: na eight four five three 13320 a” Neacs The marked hydrogen is expected to show the following splitting pattern in the 1H NMR spectrum: doublet, Jtrans = 16 Hz gHz doublet, Jeis doublet of triplets septet The heat of formation (AH*) of CH3CHs (-20.2 Keal/mol) and CHsCH20H (-66.3 Keal/mol) differ by 46.1 Kcal/mol. Therefore, their heats of combustion will: not be comparable because they are not isomers. differ by the same amount. be -46.1 Keal/mol. be -(66.3 + 46.1) = -112.4 Keal/mol. 134doo CH.OH H——oH eat H ‘OH H——oH feuun H——0H CH,OH H ° A B Compounds A and B are: diastereomers enantiomers identical constit jonal isomers HH = CHaCE=CH CH;CHg 2 3 The order of increasing acidity of 1-4 is: ——1,2,3,4 ——4, 3, 2,1 —3, 4,21 1, 2, 4, 3 Other (specify): 135 at22 H.C" “cH, Hc" ‘cH, A B ls Can you make a structural assignment of the two isomers A and B using NMR spectroscopy? (i.e., can you distinguish which is which?) ——_yes, because A has a mirror plane. No, because stereoisomers have similar spectra. no, because each compound has four chemically unique hydrogens with identical. connectivity. yes, because A has four, whereas B has only three chemically unique hydrogens. The role of a catalyst is: to shift the reaction equilibrium. to initiate a reaction. to accelerate a reaction. to trap reactive intermediates. 136Chemistry 38 Professor K. Peter C. Vollhardt February 20, 1996 EXAMINATION 1 Name: —__ (PRINT Fist nae ft, then Lastname, Use capa eter]) Please check the. name of your TA and corresponding section number. Complete the remaining information if applicable. 411 Yang, J. 121 Losser, J. 4131 Larson, D. 441 Choong, 451 Goodwin, M. 461 Chan, E. 211 Palkoff, S. 221 Staunton, J. 311 Yang, J. 321 Esker, T. 331 Soll, J. ‘341 Gountchev, T. Making-up an | grade 351 361 art 381 at 421 431 aa Bt 521 531 Bet 551 Holmes, D. Chan. E. Lee.T. Chang, H. Fuller, J. Baxter, B. Chin, J. Schutz, M. Carroll, D. Gray, D. Staunton, Losser, J. Ma Kumaraswamy, S. ({fyou are, please indicate the semester during which you took Chem 8A previously, Please write the answers you want graded in the spaces provided. Do scratch work on the backs of the pages. This test should have 15 numbered pages. Check to make sure that you have received a ‘complete exam. A good piece of advice: jad carefully over the questions at least twice; make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy! Good Luck! DONO WRITE TH SPACE vin, Total (30) (20) (30) (20) (15) (40) (30) (15) (200)1. [80 Points] Name or draw, as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary (cis, trans, or R, S, meso). a (2A, 35)-2-Bromo-3-chlorobutane (Fischer projection) {fil in the missing atoms) 138cis-1-Cyclohexy/-4-methyleyclohexane| 3B.) a 139i, [20 Points] Write the most favorable Lewis octet structure for each of the molecules depicted below (don't forget formal charges). TABLE 11 Partial periodic tabl Hoalogens Noble gases, First | H! ] Ke Second [7 Fe Taide Tae at aer Fours [| 0" Bene | geen ith ERT | eens | "Not: The supenesps inate the sumber a eros in cach energy Hv of the mn. a Fok oO b. F H oe NH F H °. [re | a. ‘There are two octet resonance structures. ° = ° Which one is a HC poe Tp te stronger contributor to NH NH the overall structure? (Circle) 140Ml. [30 Points] ‘Trihydrogen cation Hg* is an ion observable in the gas phase by protonation of Hp and represents the most simple cyclic triatomic molecule in the shape of an equilateral triangle. Hp + HY —— Ht a. Toderive a molecular orbital description of this protonation, first depict an energy diagram of the interaction of two hydrogen atoms giving Hp. Clearly label the energy levels as the appropriate atomic or molecular orbitals, draw an approximate picture of the bonding and { antibonding molecular orbitals, and place the electrons into the correct levels. 141b. Draw the eneray diagram for the formation of H* by the reaction of H* with Hp. Clearly depict the energy levels of the orbitals entering into overlap and label them, ‘and show the resulting bonding and antibonding molecular orbital leveis. Place the relevant electrons into the various levels. In view of the above, would you consider the protonation of helitim to furnish a stable bond? Explain. 142[20 Points] Heating a compound A to 100°C led to the exclusive formation of C. Mechanistic work showed that this reaction proceeds through an intermediate B, according to the following scheme: kK, Ke A —_ B — c Independent synthesis of B revealed that it is converted to A at room temperature, none of C being formed under these conditions. Draw a potential energy diagram describing the progress of the reaction fram A to B to C. Clearly label the positions of A, B and C, and the transition states (TS) interconnecting the three reaction components. Circle the rate-determining TS for the conversion of A to C. reaction coordinate 143[15 Points] ‘We shall learn later in the course that alcohols may react with hydrogen halides to generate haloalkanes: ROH + HX PK + HO ‘TABLE 31 Bond-dissucation energies of some A~B bonds (DH in keat mole™') B a H Foc op ft 8 Ni® 10 BA 105 no sD 3% saree tea esas esse 98 iitnaiane a sesleh een ane Tae ibis eases a (acti op nea SO LEER (CH3)sC 93 nog et BB ‘a. Using the table above, caloulate the AH? of the following reactions. Show your work. CHaCHSCHZOH + HE CHSCHACHAE + HO. a= 1449 b. Do you expect the AS° for these reactions to be large and positive, large and negative, ‘or negligible? Explain. Answer: [40 Points] Hydrogen peroxide, HOOH, converts alkanes to alcohols under free radical conditions with HO- as a chain carrier. For example: ots ho Sts Ct-G-H + HOOH Cte-GOH + HO CH CHs a, Write @ mechanism for this reaction including initiation, propagation, and (one) termination step. Initiation: Propagation: Termination: 145,10 b. The 0-0 bond dissociation energy in HaO2 is 51 kcal mor ? and other relevant DH° values are found in the table depicted in problem V. Caloulate the enthalpies (AH?) of the overall transformation and of the propagation steps. Show your work. AHS of overall reaction: AH of propagation steps: 146" ¢. The selectivity of HO» in attacking C-H bonds is: prim: see: tert = 1: 65: 3500, In the oxidation of 2-methylpropane what is the expected ratio of the observed product, (CHz)gCOH, to the other possible product, (CHa) CH CH20H? GH.0H Ratio (CH)sCOH : CHy-G-H = CHy 4d. The experimental heats of formation of the components of the oxidation in a. are given below. ‘AH; (gas): (CHg)gCH-32.4 Hz02 -826 (CHglCOH -74.8 HzO -57.8 kcalmot’ Calculate again the AHP of the reaction. Show your work. ‘Ane = 14712 Vi. [80 Points] Free radical chlorination of (2S)-1,1,2- trimethyleyclopropane is sluggish, but does furnish products of monochiorination at Ca and Cb, HeQ Cs Ck, hv ——~ _ronctiorinated products Hs JL” ‘a. Drawalll of them. Circle the appropriate descriptor for each product as chiral or achiral. Note: the five boxes may be in excess of what you need. ors HQ. CHa chiral chiral chiral sxsial acta ecrial PH chiral ‘chiral ect achiral 148b. Do you expect chlorination at Ga to furnish optically active products? Explain. , Do you expect chiorination at Cy to furnish optically active products? Explain. 149 1314 Vill, [15 Points] Given the following values for the AG?of the ring flip for cyclohexane, AG? (kcal/mole) +4 ° “CH 17 -CH:CHy, 18 HE CH 2.2 CHa Hg C-Chy 5.0 Ch Calculate AGe for the following conversions. eT * ts 2 — er GDN ace = Hs0-G- CHy CH g b Gt aC CHa Chis ct rs Levels ead ‘ 150es EXAMINATION 2 Chemistry 3A, Professor K. Peter C. Vollhardt Name: April 4, 1996 {PRINT Firstname first, then Lastname, Use capital ers) Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 111 J. YANG 121 J. LOESER 131 D. LARSON 141 1.CHOONG 151 MGOODWIN 161 E.CHAN 171 J. SELL 211 §. PAIKOFF 221 J. STAUNTON S11 J. YANG got T.ESKER 331 J. SELL S41 T.GOUNTCHEV Making-up an | grade (it you are, please incioate which semester you previously took Chem SA. —— 3st age st oe art = 361 — at oe 431 aeons 4a anes sn anne set eau 541 eeueaae sat D. HOLMES: E. CHAN T. LEE H. CHANG: J. FULLER, 1B. BAXTER J. CHIN M. SCHULTZ D. CARROLL, D.GRAY J. STAUNTON J. LOESER, S. KUMARASWAMY ) Please write the answers you want graded in the spaces provided. Do scratch work on the backs of the pages. This test should have 12 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: read carefully over the questions at least twice; make sure that you understand exactly what is being asked; avoid sloppy structures or phrases, It is better to be pedantic in accuracy! Good Luck! Wa, Wb. Subtotal L (25) ee eeedieteee (60) tm (30) vy, (30) Yee eeseeee 40) vi (15) Total (200) 151 Va. Vb. Subtotal[25 Points} Name or draw, as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary (cis, trans, R, S, or meso). (S}-3,3-Dimethyleyclohexanol CHs 152Trans-3-(cis2-hycroxy- cyciopropylimethyijeyctobutanol CHGS. 153M. [60 Points] Add the missing starting materials, reagents, or products (aqueous work-up is assumed where necessary). Don't forget stereochemistry! Bae aoe P(CHa faaecs Circle one: Racemie Optically active 154(CHa)sCH (CHa}g®CHZOH CHgOH CHs optically active Circle one: Racemic Opticaly active 9 + CH (1 equivalent) OH cr HOH NaOH, CHsOH 155NaOH, CHgOH H, est CH yg CHeOHe ‘an oxacyclopropane i CHL (CH) MI, [80 Points] The following reactions proceed (predominantly) by Sn2, Sn1, E2, or Ey pathways, respectively. Give the predominant product (one only) in each case and answer the questions by circling the most applicable statement. a “~ HY, CHOH, a ary anakene Mechanism: Sy2 snt Ep Ey At lower temperatures one of the following ratios will increase: ‘Sn2/Sn1 Sn1/E; Eo / Ey Sn2/ Eo 156re O802CH K"OC(CHs}s, (CHs)sCOH Mechanism: Sn2 ni E2 ey Changing the alkoxide to CHg0°K* causes one of the following ratios to increase: Eo/E1 SN2/Eg SNI/E4 Ep/Sn2 Mechanism: Sn2 Snt E2 Ey Changing the ammonia to lithium amide, Li NH, causes one of the following ratios to increase: E2/Sn2 Eo/E1 Sn2/Sn1 rearrangement / SN2 157a F°, CHgOH solvent Mechanism: ‘Sne2 St Eg Ey Changing the solvent to acetone will have one or more of the following effects (circle all that apply): rate increases SN2/SN1 increases solvation of the Nu:~ decreases 8 We HY, CH OH solvent, -206 Mechanism: Sn2 SNt E2 Ey Changing the solvent to (CHg)3COH causes one of the following ratios to increase: Sn2/SN1 EQ/Ey Ey /Syt Sn2/ Ee 158{30 Points] Explain the following observations by a detailed mechanism (i.e., write a scheme with structures, use arrow-pushing, etc.) LAH, hats > optically active (Hint Note the change in stereochemistry!) acetone starting material, but racemic optically active 15910 [40 Points} Provide a viable synthetic route from starting material to product. a CHy Only organic starting material You may use any required inorganic reagents. b. ° OH You may use any additional organic and inorganic compounds. 160vi [15 Points] Chloromethoxymethane, CICH20CH3, and CH3OH react slowly to give a new compound, C3HgO2, which exhibits two sharp signals in the 'H NMR spectrum at 6 = 5.2 and 3.2 ppm, with an integrated ratio of 1:3. a. What is the structure of this compound? 'b, Assign the chemical shifts by drawing the structure again below and labeling the hydrogens as shown for cyclohexane. Format for assigning 8 values to your Answer: ‘compound: c. The rate of disappearance of CICH20CHs is independent of the CH30H concentration, Write a mechanism for this reaction, 161FINAL EXAMINATION : Chemistry 3A Professor K. Peter C. Vollhardt Name: May 13, 1996 (RIT Fr nro ft, en Laat ame. Use cepa itor) Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 177 J.YANG 351 D. HOLMES yey J.LOESER, 361 E.CHAN 131 D.LARSON 371 T.LEE 141 |. CHOONG 981 H. CHANG 151M. GOODWIN 411 J. FULLER 161 &.CHAN 421 B, BAXTER q71 J. SELL 431 J. CHIN 211 8. PAIKOFF 441M. SCHULTZ 221 J, STAUNTON 517 D. CARROLL 311 J. YANG 521 D.GRAY 321 T.ESKER 531 J. STAUNTON 331 J, SELL 541 J, LOESER (I 341 T.GOUNTCHEV 551 8, KUMARASWAMY P| | Making-up an | grade (Uf you are, please indicate whieh samester you previously ook Chem 3A a Please write the answer you want graded in the space provided. Do scratch work on the back of the pages. This test should have 23 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: read carefully over the questions at least twice; make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy! Grades will be posted on Friday, May 17, outside 305 Latimer Hall (Lab Q). Good Luck! BO WOTWATEW THIS SPACE esa eaeeeeaee (30) Vee H (0) Via. Vee ile eeeenetenane (90) eee eVibee re serenereees Wo. Die sees ee (60) ane Vicaat eareseanoatE Subtotal v. (60) Subtotal vi (60) VIL (80) eTotal jnecieteacennes (400) 1622 [30 Points] Provide the IUPAC name or draw the structure, as appropriate, of the following molecules. Remember the priority of functional groups in choosing names, indicate the correct stereochemistry (e.g. R, S, and E, Z), and do not forget about the alphabetical ordering of substitutents! (Z)-4-Chioro-3-methyl-B-penten-t-o1 163SH OH (S)-1-Bromo-2,4-dimethoxyeyclopentene meso-2,3-Dibromobutane (Draw in a Fischer Projection) 1644 i, [90 Points] Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (when required) is assumed to be part of a step. It is not part of any answer. a. hy, “~~ . By i (* equivalent) | ' b. : | 2 i 1 oH oy Cr | | pie i 9 I 1. Hal CCH )2 | NaBH, oH Ho wee ano | I | THNMA: 8 = 2.01(s) "SC NMR: 5 = 19.4, \ 115.9, 133.4 ppm a. Kr OC(CHsls Lo 165CH3 GH ‘OH crys Hon CHeCHs HOP CHeCHy CH Hy t ‘2 bromoalcohol an alkene 9. a 2. h. NaOH, HO Q oF Hee plicaly active HgSO4, H20, H* 166 HY, H2O.2 H CHg= CHe cH ie k 4.05 2. Ha, Pt C70 eHaOe 19C NMA‘: 3 Cap? signals, 2 Csp3 signals 13C NMR: 1 Cgp2 signal, 1 O5p3 signal THNMR: 6= 6.5 (2H), 1.9 (4H), 2.4 (44) THNMA: 8=20 singlet 1‘ 1 2. He Oy cy mixture of cis and trans 1677 [80 Points] ‘The hydrogenation of alkenes to alkanes requires a transition metal catalyst to proceed at reasonable rates. One could also conceive of a free-radical-initiated chain mechanism. An example would be the peroxide-initiated hydrogenation of propene. “~ : te RO-OR ~ a. Write the two propagation steps for the radical chain reaction: Step 1 Step 2 ‘AH’, (CHgCH = CHa) = 5 kcal molt AH? (CHCH2CHs) = -25 kcal molt Given the above AH®, data, calculate the heat of hydrogenation of propene. AH? 1688 ¢. Considering the following data (in addition to those given in b), estimate the ‘AH? values for the two propagation steps and recalculate the AH? for the overall reaction from these values. DH? H-H 104 keal mol AH LAL +21 kcal mort step1 | AH” Step2 | AH? = ‘AH? (hydrogenation) = 169Nw. [60 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and “arrow-pushing” techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! CHg racemic a 804, HS04, HeO, & on 17010 c. Br HBr, ROOR, A Hint: Remember the free radical polymerization of alkenes. V. [50 Points} Free radical bromination of propane with excess bromine, followed by treatment with Nat -NHz and aqueous work-up, gave a mixture of compounds. Fractional distillation furnished a colorless liquid A, C3H3Br, b.p. 89°C, exhibiting the | | spectra shown. | 4, Bi (excess), ho 2. Nat NH CHsCHeCHs 3. He A a, Write the structure of A in the box above, after analyzing the spectral data. b. Interpret the spectral data as requested in the spaces provided. 7" fe ee i : | _.,, Spectrum » es 90 3 wl qo State whether the indicated funtionality is absent or present (circle the correct statement) and provide the expected or observed position of the corresponding peak in the spectrum. CepS-H present/absent at emt Cop?-H present/absent at om? Csp-H present/absent at cmt present/ absent at omt OH present/ absent at 17212 2. 196 NMR Spectrum é = 82.0(D), 73.8(E), 24.3(F)ppm. Draw your suggested structure for A in the box, and label the carbon atoms D, E, and F giving rise to the corresponding signals in the spectrum. Note: make an arbitrary choice between the assignments for D, E. 17313 3. 1H NMR Spectrum F NMR Spectrun aul yeate iH (peste (CHeSt Draw your suggestion for A in the box, and label the hydrogens F and G giving rise to the corresponding signals in the spectrum. 17414, . The residue of the distillation resulting in A contained (among other products) a liquid B, CgHsBrs, the 1H NMR Spectrum of which is shown below: 28 pe8He a 7 3a aT ae a = . What is B ? 17518 [60 Points} Show synthetic connections (reagents, intermediates; no mechanisms!) between the following starting materials and the final products. Note: several steps are required in each case; there may be several solutions to each problem, but you Should use only one; it is best to work backwards (retrosynthetically), to enable you to dissect the products into less complex precursors; in addition to the Starting structure, you may use any organic and organometallic reagents containing four carbons or less. 1767 Vil. [80 Points} Mark the answer in each of the following multiple choice problems that you deem most correct. a. The best resonance structure for N2O is: b. Allene, H2C=C=CHp, has the orbital arrangement shown below: The hybridization at carbons A and B is, respecti Asp Bap? Asp? Bsp —— Asp? Bsp Asp? Bap? 17818 a § 8 2 £ 3 3 ° £ 5 2 2 5 i 8 2 = é acetone a 17919 . Consider the following conformational equilibrium and the AG® values for axial - equatorial conversion of the given group in substituted cyclohexane: OH i C(CHs)s Ht SICH) A'G(axial + equatorial, keal mol"): HO -0.9 (CH,),C — -5.0 (CH,),CH -2.2 Ais more stable than B by 5 kcal mole? Ais more stable than B by 3.7 kcal mole*t ______ A’is more stable than B by 8.1 kcal mole Ais less stable than B by 2.8 kcal mole e. Draw the produet of the following reaction and circle the appropriate entry below the scheme. 80,0 “ee Ke He"OC(CHa (GHNACOH {CHg)gCOH ‘Mechanism: Sn2 Sut Eo Ey Changing the alkoxide to CH30"K* causes one of the following ratios to increase: Eo/Ey Sn2/ Eo SNt/E1 E2/Sn2 18020 f. The structure of adamantane is shown below: D adamantane The number of 8G NMR signals observed for this hydrocarbon is: one two six nine g. Indicate the correct pKa sequence for the following compounds: | | \ i CH,OH NH, HC=CH | ee wa ae 155 35 25 a4 aes 7 2 185 2 aes 4 ° 16 20 | 181at h. Consider the relative rates of the following rearrangements: xe > G- CHy a i : i 2 He BrD Hs0-G-O- Cy acetone ke Hye Br Ha0-G-G- CH DH k= ky —— kk, kde 0, k,= 4-6 k= i. A compound, C3H¢0, exhibits the *H NMR spectrum shown:- 22 Which isomer of C3He0 fits the spectrum? — An ee be —> HH Potts Cobalt has nine valence electrons. In the cobaltocinium ion A, cobalt has an electron shell of: LS 18 electrons 16 electrons ao 7. 14 electrons 20 electrons bs iy 183(Chemistry 3A, Protessor K. Peter C. Volthardt October 3, 1995 EXAMINATION 1 Name: ee [PRINT frst name before second. Use capital letters!) Please check the namo ol your TA and corresponding section number. Complete the remaining Information i applicable. 10 121 131 1a 151 161 ant 2a zt ait a2 sa Craig Tewot (Chris Caylor Jonathan Nitschite ‘Sarah deForest Paulus Wanandi Chloe Laszlo John Robblee Joanna Staunton, John Cave Robin Fulton Jett Golden Marcel Bruchez Making up an t grado (Ufyou ate, please indicate the semester curing which Please write the answers you want graded in the spaces provided. Do scratch work on the backs of the pages. ‘This exam should have 13 numbered pat good pieces of advice tic in accuracy! Good luck! read carefully over the question: stand exactly what is being asked; avoid sloppy structures or phrases, 941 Evan Werkoma 951 Zachary Sweeny 961 Heather Wages/ Eugene Chan 411 Eric Barchas 424 Nathanael Gray 431 Hala Gobran 44t Jeff Dysard 511. Michael Furlanetto 521 Scott Andryski 531 Ryan Bise 541__Kenneth Kotz estes (60) ee eeeeeee (20) Miseaueieaaaet (20) Wer ees (20) ieeuasaeeaaey (50) Vigoss (30) wo (10) Vill seaaneneaas (10) TOTAL (200) 184 you took Chem 3A previously .ges. Chack to make sure that you have received a complete exam. Atew 15 at least twice; make sure that you und it is better to be pedan-|. 180 points] Name or draw, as appropriate, the following malecules according to the IUPAG rules. Indicate stereochemistry where necessary (cs, trans or Fi. S, meso) ios CHCH, b) racomic a (28)-Bromo-1,1-dimethyi- cycloheptane 1854 Moso-2,6-bisleyciopropyljoctane (Fischer projection) e) 186[20 Points] Write the most favorable Lewis ociat structure for each of the molecules depicted below (don't forget formal charges). th a) HONO (Cyanic acid): | | | 1) CIO," (Chiorite ion: | o ao ( | ©) NO, (Dinitrogen trioxide): i | ° o oN ON ° 4) [CH,CO,)?” (Acetic acid dianion): H ° c c H ° 187ILL. [80 Points] George Olah (University of Southam Calfornia; Nobel Prize 1994) showed that in highly acidic ‘media, methane can be protonated to the methonium ion GH,*. This species is also formed on treatment of CH* with H,, ina remarkably exothermic resto ae + H — CH BH’ = - 40 kcal mot @) Depict the molecular orbitals of CH,*, clearly labeling the hybrids on each carbon, the atomic orbital ot the hydrogans, and the location of the charge. b) Draw the energy diagram for the formation of CH,* by the reaction of CH,* with H,. Clearly depict the ‘nergy levels of the ortitals entering into overlap and label them, and show the resulting bonding and antibonding molecular orbitals. Place the relevant electrons into the various levels, 188«) The BG" forthe reaction in (bis about -33 kcal met Why is ris value ess negative than thal of AH”? Write the relevant thermodynamic equation relating AG" to BH". IV. {20 Points] Draw a potential energy diagram describing the rotation around the C1-C2 bond(underined carbons) in tomethoxypropane, CH,OCH,CH,CH,, using the stencil given below. Complats the Newman projections starting withthe most stable rotamer af 0". indicale gauche and antl forms, transition states, and the relative positions of the maxima and minima ofthe curve. Note: the top three Newman projections are ecipsed forms. AF Bp . i L . ° © 1 130 Degrees of rotation 189f V. [50 Points] iodemethane reacts with hydrogen iodide under tree radical conditions (hw) to give mathane and iodine: \ cyt + om eg 8) Write @ mechanism for this reaction including initiation, propagation, and (one) termination steps. Initiation: Propagation: Termination: 190) The bond strength in iodine is 96 kcal mole" and other relevant OH” values can be obtained from the following table: TABLE SI (CHs)scH— ws 6 OS (Clig)aC— e mw om @ ® Bond-Dissociation Energies of Various A~B Bonds Calculate the enthalpies (AH’) of the overall transformation and ct all the mechanistic steps. Show your work. {aH of overall reaction: 1H” of initiatio ‘44's of propagation steps: ‘AH’ of your termination step: 191) The same reaction of HI with 1,4-diiodo-1-{iodamethyl}cyclohexane (A) gave the following product distribution: 1 1 He, f 1 ’ fe + + i i A 1 : 100 10 ‘What is the relative reactivity for iodine abstraction by the iodine atom? Jpsimary Heecondary Teniary = : @) The experimental heats of formation of the components in the reaction of CH! with HI are given below: AH (eas) = CHA3S© = -HI63° © CH, -179.— 15 keal mol"! Calculate again tho AH” of the reaction. Show your work. 192,10 VL [80 Points] Free radical chlorination of optically active trans-1,2-dichlorocyciohexane (A) gave more than one (but fewer than fiva) 1,2,3-tichloracyciohexanes (among other chlorinated products). IE - active active | inactive Inactive fa) Draw the products using the flat stencils provided above. Note: the four boxes shown may be in excess of what you need. Cleariy label each product as optically active or optically inactive by circling the appropriate descriptor. |b) The energy difference between axial and equatorial chlorocyclohexane is 0.52 kcal mot. Using the chair cyclo hexane stencils on the following page (with the numbering shown) draw the two conformers for each of the answers given in part (a). Label the most stable compound in each pair and the AG" for ring ip. Note: again you may not need all of the equations shown, see next page 193fof #. te12 VII [10 Points] Chlorocyctohexane reacts wih hydroxide ion to form cyclohexanol as shown. G OH ‘The reaction follows second order kinetics and proceeds through the axial form of chlorocyciohexane, Thus the ‘equilibrium below precedes the hydroxide attack above: | 1 10 kcal moie“t a AG" = +05 kcal mot a Draw a potential energy diagram for the overall process, starting with equatorial chioracyciohexane (arbitrarily assigned relative energy = 0) and ending with cyclohexanol. Show (qualitatively) the relative energies of starting material, intermediate, products, and transition statas. Label the rale-delermining transition state and fil in the E, and AG’ values given where appropriate. 30 20 m —> Reaction coordinate —— 19513, VIII [10 Points} Label (in the boxes provided) each ofthe following molecules as chiral (c) or achiral (a). ‘The end 196EXAMINATION 2 : Chemistry 3A = professor K. Peter C. Vollhardt Name: November7, 1895 (PRINT Fist name frst, then Lastname, Use capital lator!) Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 411 Toweli,Craig 831 Bruchez,Marcel 121 Caylor,Chris 841 Werkema,Evan 131 NitschkeJonathan — _ 951 Sweeney,Zachary = _ 141 doForest,Sarah soy 361 Chan,Eugene 151 Wanandi,Paulus — 411 Barchas,Eric 161 Laszlo,Chioe — 421 Gray,Nathanaal ease 211 Robblee,John eee 431 GobranHala ae 221 StauntonJoanna = _ 461° Dysard,Jett — 231 Cave,John 511 Furlanetto,Michae! | 311 Fulton,Robin ieee 521 Andryski,Scott cones 321 Golden,Jeff 631 Bise,Ryan ‘541 Kotz,Kenneth ‘Making-up an | grade at (it you are, please insicate which semester you previously took Ghem 34 Please write the answer you want graded in the space provided. Do scratch work on the back of the pages. This test should have 12 numbered pages. Check to make sure that you have received a complete exam. A good i piece of advice: read carefully over the questions at least twice; make sure that you understand exactly Wwhat is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy! Good Luck BORO WRTE TS TPR 4 — 0) Nag no 1 Mb. eee au pee a Va. | Ie. Heese Nv. EEEEEEeeeeeeeeeEeeeev ‘Vb. i Sibel | eeeaecae ee eee Ure aye cuba | Total (200)4 30 Points] (1S,2R)-2—Methyleyclopentanol CHeCHs Br—-H H——ocHs CHeCHs Name or draw, as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary (cis, trans, FS, or meso). 0 198 21 (@R)-6- [GR)-1-Methoxyethy!] ~6~(2—methoxyethyl) -1— undecanol e a Rt od Br 199U— [60 Points] where necessary). Don't forget stereochemistry! a. Use the stencils in the boxes. Circle the correct answer below the boxes. Cy ra Cha hv — - ‘monochlorination { atc-3 | {Optically active) | active active | inactive inactive b NacNn — = NaBr e ° + CHaMgBr HsCO” “OCHs 200 4 ‘Add the missing starting materials, reagents, or products (aqueous work-up Is assumed + HCIHat, t = ° (equivalent) D Riv K*OCHs, CHO ——> 201CH, 7 h 4. NaOH 2.UAIH, — optically active, terminal optically active ‘alcohol: CateB1O. L 1. PB 2u° 9 Ot ee 4, HY, CHSOH —_ CoaKOH, HO —_ LTP ° CHS [25 Points] For each pair of reactions shown below. x’ the box on the right, indicating which will go fasteyand circle the mechanism by which it proceeds (e.g., SN2, SN1, E2, £1). In one ‘complete, grammatically correct sentence, provide a brief explanation in each case in the fbotiom box provided (ce., explain why so-and-so is a better nucleophile, leaving group, ‘solvent, ete). No credit will be given for the right answer with an incorrect reason. Note: the compound on top of the arrow is the solvent, 1.0. Q — T + —_ Woo “OCtGHs / \ + (CHasCOH H: Q HoT + "OCI “ ‘SN2 SN1 E2 ey 203‘SN2 + PICH3}s SN2 CHCoHy “ i (acetone) ane % (eestor, Br (acetone) L | + ‘SNy £2 I g BF “NICHas CHSCHs {OMSO) Br*PICHals CHsSCHs (MSO) SM 2 eteee 9 OscHs + NaH OME q -NaO SCH ° (CHa}g0C (CHa)gOC! HONCH2 woot OME} HONCHd Siz sii HOH. 500 HOH, 1900, SN2 shi 205 Ea| 10 WV. [45 Points} Explain the following observations by a detailed mechanism (.e., write @ scheme with structures, use arrow-pushing, etc.) a a or oo ° b CICHas (CHa O(CHas Bin, er Bin, Br — NaOH ONLY, Not (equiv Hint: use the chair conformational picture of the starting material.vw " 140 Points) Provide a viable synthetic route from starting material to product. You may use any additional organic and inorganic compounds in your scheme, 207BIZARRO PiraroFINAL EXAMINATION Chemistry 3A Professor K. Peter C. Vollhardt Name: December 11, 1995 (PRINT Firstname fs ten Last name. Use capita iter!) Please check the name of your TA and corresponding section number. Complete the remaining information if applicable. 111 Tewell,Craig — 331 Bruchez,Marcel = __ 121 Caylor,Chris, uses 341 Werkema,Evan = __ 1431 Nitschke,Jonathan __ 351 Sweeney,Zachary ___ 441 deForestSarah _ 361 Chan,Eugene ane 151 WanandiPaulus __ 411 Barchas,Eric — 161 Laszlo,Chloe — 421 Gray,Nathanael = __ 211 RobbleeJohn = __ 431 Gobran,Hala eee 221 StauntonJoanna __ 441 Dysard,Jeff ane 231 CaveJohn ee 511 Furlanetto,Michael _ 311. Fulton,Robin — 521 AndryskiScott = _ 321 Golden,Jeff asa 531 Bise,Ryan pues Making-up an I grade 541 Kotz,Kenneth {ityou are, pase incleate which semester you previously took Chem 3A Piease write the answer you want graded in the space provided. Do scratch work on the back of the pages. This test should have 21 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: read carefully over the questions at | east twice; make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy! Grades will be posted on Friday, December 15, outside 305 Latimer Hall (Lab Q). Good Luck! DO NOT WATE W THEE SPACE \ fotinseeeeaeeeeeaee Wa eee ieee eeaeaaeiat (eo) ca View Vb. wm (20) Vib. vcr eames ive seeeeerae (60) as Vie | Subtotal V2 60) Subtotal | iviiieesanneaasi teas (eg) | Milan (0) | Total (400) | 209[30 Points] Provide the IUPAC name or draw the structure, as appropriate, of the following molecules. Remember the priority of functional groups in choosing names, indicate the correct stereochemistry (e.g. R, S, and , Z), and do not forget about the alphabetical ordering of substitutents! 1-(2- Propenyl)cyclohexanol 1, 5, 9-CyclododecatriyneHs G OH SH4 I [90 Points) ‘Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (when required) is assumed to be part of a step. It is not part of any answer. hv Ch + Fe + Bp equiv tequiv tT equiv ‘amonohalomethane: | ae eo 'S*(CHa)2Br"it (NICH(CHs) la CN f. oH HY, HzO. — “HO Hs WR: no peak at 3360 cm ——— q . 2131. Na, Ns (iq) 2, Bra, CHsOH > xh i amen Av CH,CH,B + HCCiy aH’ =+ 12 keal mol“! 2. Write the two propagation steps for the radical chain react ‘Step 1 Step 2 . Given the AH® of the reaction and the following data, calculate the bromine- carbon bond strength in BrCCls. DHP: — CHsCH2 -$- H 98kcal mole” CHsCH, -§- Br 68kcal mole? CLC -$- H 96kcal mole DH'(Br -8- CCi,):° c. The dependence of rate on temperature is given by the Arthenius equation: k= Ae~=a/RT_ will this reaction speed up, slow down, or proceed at the same rate at 50° C? Explain your answer. ‘at the same rate [60 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and “arrow-pushing" techniques." [50 Points] Catalytic hydrogenation of A with Lindlar's catalyst (I.e. deactivated Pd) gave several compounds, one of which, B, gave rise to the spectra depicted below. O He, Pd (deactivated) —_ A 5 CroH 1602 a. Write the structure of B in the box above. 219bb, Interpret the spectral data as requested in the spaces provided. 2 1. IR Spectrum 4000 3000 2000 1500 M1 1000-900 800 700 na . a aa Vepeleiet : ABSORBANCE Considering the oxygen functionality present in A, the product B could be an alcohol. Confirm or rule out this possibility: Hydroxy peak is: H present/absent at om ‘ (circle correct statement) ‘Considering the double bonds present in A, the product B could be an alkene. Confirm or tule out this possibilty: v is: Cp? present/absent at ont (circle correct statement)2. 1G NMR Spectrum 13 ; ae. Sie ee 290 190 190 mo Ho Draw your suggestion for B in the box, and label the carbon atoms A-F giving rise to the corresponding signals in the spectrum.14 3. 1HNMR Spectrum 0 pp 10 4Hz) Draw your suggestion for B in the box and label the hydrogens A, B, C giving rise to the corresponding signals in the spectrum, 4Hiz) , 4.22 (triplet, J = 5.63. (quintet, J =: © 7 3 216 [60 Points} Show synthetic connections (reagents, intermediates; no mechanisms!) between the following starting materials and the final products. Note: several steps are required in each case; there may be several solutions to each problem, but you should use only one; it is best to work backwards (retrosynthetically), to enable you to dissect the products into less complex precursors; in addition to the starting structure, you may use any organic and organometallic reagents containing four carbons or less.16 Sa0H2- CHy OH HO, ae Gite oe g 3 5 3 ° a avil. 17 [80 Points) Mark the answer in each of the following multiple choice problems that you deem most correct. a, The number of resonance structures for the oyclopentadieny| anion, QO vis: one two three five b. Beryllium hydride in ether solvents (R20) forms ether addition products of the type: H2Be(OR2)2. In these compounds, Be is hybridized as: sp? 53 not hybridized 205| i | 18 ©. Consider the following potential energy diagram. A) ON, Reaction coordinate Indicate which reaction sequence conforms best with the diagram, d. The H NMR spectrum of 1,1-dibromo-1, 2-dichloroethane at -120°C reveals the Presence of the rotamer A by the observation of two doublets for the two hydrogens: a Br ao] Br On warming to room temperature, the onset of “iree rotation’ will change this pattern toa: singlet doublet two singlets doublet of doublets ae19 . Consider the following conformational equilibrium and the AG? values for axial - equatorial conversion of the given group in substituted cyclohexane: b OH Hee, . =—— pe Br eH OH Ho Sou, A B oH ‘AsG(axial + equatorial, keal mol"); HO -0.9 Br -0.6 (CHs),CH -2.2 Ais more stable than B by 0.7 kcal mole? Ais less stable than B by 0.7 kcal mole Ais more stable than B by 2.2 kcal mole Ais more stable than B by 1.9 kcal molet The optically pure starting sulfonate has a specific rotation [=] which is monitored as it reacts with F- by second order kinetics. [=] goes to zero faster than the rate of disappearance of starting sulfonate [=] goes to zero at the same rate as starting sulfonate disappears [=] changes but never goes to zero as the reaction goes to completion —— [=] stays unchanged { 2720 g. In each pair of acids shown below, circle the stronger one: » HOE CCH HeC= CHCHs 2 CHgCHpOH CICH2CH,OH 9 OFGtNHy GigNHe 4 Hes #0 h. Considering what you know about the relative bond strength of C-H versus C-D, estimate the Hcp relative to Toy: i i i Ven =M2 Vp | about the same Ven > Ven Ver < Vou i. Consider the following oxidation and all the possible products. 2 MO = ee een 4 A 1 equivalent What will be the observed product distribution? —— onlyA ABC —— onyB ABC = 11:221 }. For the indicated hydrogen in compound A, what will be the expected 1H NMR | pattem: — —— singlet doublet —— triplet, because the two hydrogens at C-3 are equivalent doublet of doublets Hospitals to avoid + THEEND | SMlercy Christmas! 299