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Chemistry 211 Exam 4 Fall 2015 Linda Waldman ) ) J) 4) ) 6) 1 2 Name Last, First Counting this cover sheet, there are a total of 9 pages- check to ensure you have all 9. All 9 pages must be turned in for grading. Use the backside of preceding pages for scratch paper. Any cheating will result in the dismissal from c/ass with an "F" grade. Please put your name or initial on each page You must sign below to receive a grade on this exam. I have read and understand the above instructions for this exam. Signature Page 1 Cover page Page 2 114 tvlo Page 3 /06 Page 4 116 MC Page 5 t10 Mc Page 6 /08 Page 7 118 Short answer Page 8 126 Products/ Mechanism Page 9 /08 Total 1100 (actually 106) MC MC NMR LSW F15 I. ln it ia ls 11E'l Multiple Choice. (2 points each): Write the best answer in the box provided. l. Which of the following alkenes is expected to have the highest heat of hydrogenation? (Least stable isomer) A) l-pentene B) trans-2-pentene C) cis-2-pentene D) 2-methyl-2-butene ofthe following is not a possible reaction ofa carbocation? addition of a nucleophile rearrangement to a more stable carbocation tt' C) addition of a proton to form an alkane D) loss of a p-hydrogen to form an alkene A 2. Which ./1 A) B) + - C)' t x^ --+ ofHCl to 3-methyl-l-pentene gives two products. One ofthese is 2-chloro-3methylpentane. What is the other product? (Think rearrangement). l 3-chloro-2-methylpentane 2-chloro-2-methylpentane 3. Addition A) B) -chloro-3-methylpentane 3-chloro-3-methylpentane 4.Predictwhichofthefollowingalkenesreactsthefastestwith A) B) o C) D) CH:CHzCHzCHzCH=CHz C) cIs-CH:CHzCH=CHCHzCH: D) HClLtA"t]':Y:kJ'"b-\ trans-CHtCHzCH:CHCHzCH: (CH:)zC=CHCHzCH: D 5. Which of the following alkenes gives 1-bromo-2-methyl-2-pentanol upon reaction with Br2/II2O? gr dt niY I A) CHICH:CHCH(CHrh B) CH3CH2CHCH:CHz D I I q. C) CH-r oll =C1ar.,x CHTCHT Cu / g D) cH3cHzcH2 C:CH I CH: I 6. Which of the following is least likely to react with an alkene? A) H3O+ B) BrCt C) CII3CII2 (cthyl radical) D) Na(X)H2CH3 7. Which of the following gives acetone, (CH:)2C=O, as one of the products of its ozonolysis? A) B) c) D D) A fr'rPn' 2 LSW F15 8. Which ofthe following series ofreactions would convert cyclohexanol to epoxycyclohexane? lnitials 1,2- H€Y c olt 2 o A) (l) #,*rr,.r, (2) Br2,l'l2O B) (l) 84, rsht (2) NaOCI{2CI{3 C) (l) o 1r' / (2) CH3COOH, CH3CO2H H2soi,heat V D) (l)H2Soa,heat (21 Q) ZI,H2O h 9. A compound is treated with ozone followed by zinc in water to give the following three products. Which structure below best fits the data? o o lt c il nrc'i-cn, Htc- 2y 7 2 A A) / I o $ II o a c0 0 H ,c(crrrb Ag c9 r' t\cti 3 h ac I B) (CH3bHHCH2CH2CH{HCH3 c) H2c{cH2cH1f1n"r' o t, ? l-Lilt tt C!-t cHr F l)) HzC{IICIIzCH2C{(CH3h -..-t 10. Which of the \ following does not give 1-bromo- 1-methylcyclopentane as the major product? CH HBr It()()R CHr c) 6r Ar B) light Ht) HBr ----------------> D) A Br, CHt / 6r IIBr 3 (_.) LSW F15 I l. Which species below ln itia ls KEY acts as the nucleophile in the acid-catalyzed addition of water to an alkene? .x x - .q: -I) -A) H:O' B) rhecarbocation QL $\ D) Hzd D 12. The rearrangement which occurs in the + (CH3)2CHC^H{H2 }vz I HBr ------------> I following reaction can be described as a A) hydride shift from C-2 to C-l C on shift from C-2 to CB) h dride shift from C-3 to C-2 methyl group shift from C-3 to C-2 a 3. Identify the nucleophile in the following electrophilic addition reaction. d,r , JI (CH3)2C:CH2 + [N3 ?,, -------------) a A) N? B)N o CH3CCH2I I Ni C) ICI cr D) Io following is the rate-determining step in the acid-catalyzed addition of water to 14. Which of the 2-methylpropene? +H l -{) l(lH-r).C=CH, B) (('H-r),r(l@ + H,(_) ------------> @ (l) (cH3)lc-()H, + H'o I)) (CHl)-l(l@ + H,() i(_lH-r)3c@ + H.,O A @'' ((lH-r.)3c-()H. ........- (.C-HJ3C-()H -.............. +H (rlH3).'(l=cH.' -l ofthe following gives only one organic product on acid-catalyzed hydrolysis? A) 2-hexyne B) 3-hexyne C) 2-heptyne D) 3-heptyne 15. Which -B SYnnehlc 16. Identify the electrophilic species in the f,, lIzC-C, H2O, H3O+ .--------------- following reaction. (cII3)3COII CIIr c A) HzC:C(CHI) B H o c) H: ot (CH3)3COH following are conjugated dienes? 1.2-octadiene II. 1.3-octadiene III. 2,s-gctadiene ,I. A) only B) only II I C) I and D) II hnd 17. Which of the I I Y.,.r"^ ebn', 18. Which of the A) B) II rll lV. lso B T I,7-octadiene .1 l5o following compounds most readily undergoes solvolysis with methanol?, (E)-l-bromo-l-butene Vif C) 3-bromo-l-butenr2-bromo- I -butene " 1' ,,.a1 ..,7--.2' D) 4-bromo- l -buten to e L ...-{"t ' Y ar 4 t^iti"t LsW F15 19. What major product would you expect from this reaction? I CH: Hzo I --7 ,| C +lzo CH: A) B) -dimethyl-2-butanol 3,3-dimethyl- l -butanol 3, r) t cat. H2SO4 CH: H L + H H-c//c KEy' 3 D) I 3-dimeth v 1-2-butanol 2,2-dimethyl-3-butanol 20. Ozonolysis of an alkyne gave the two compounds shown below. What is th the original alkyne? CHTCHzCHzCOzH and (9Hr)rQ of Ltlrcl/ A) B) 2.2-dimethyl-3-fftyne 3,3-dimethyl-4-fftyne ,a7 C-. ,2-dimethyl-llnl v -3- / 21. Which reaction sequence below would work best in converting 3-pentanol into 2,3dibromopentane? A) (1) HzSO+, heat B) (1) H2SOa, U) (1) Br2, v (2) IIBrY heat/ (2) Hztptx lightX I D) (1) HzSOr, heat (3) Br'2, (3) 2 Br2, tight light (2) H2SOa, heat (3) H2lPt X (2) tsr2 22. Which sequence of reactions works best in_qlnthesizing ci^s-3-nonene? A) (1)l-bufyne,NaNH2 (2) l-bromopentane (3) Na, NHj 4zr5 C) (1) l-pent"vne, NaNH2 (2) l-bromobutane (3) H2O, H2SOa/HgSOa x B) (1)l-butynelNaNH2 C (2) l-bromopentane (3) H2, Lindlar Ptl f,tr CeLl:g ' € ---- D) (1) l-pentvne, NaNH2 (2) l-bromobutane (3) 2 HCt (4) NaNH2,[21af 23. What reagents would be required to accomplish the conversion shown below? Br Br make CH: CH: A) B) b into c) r'Nuocgr,tt.r,g# and light. peroxr S s 5s KOtBu. then Brz and lieht. 6ap"e.rtc' 5 LSW F15 ln it ia ls KE 24. Which one of the following compounds fits the C-I3 NMR spectrum shown below? 3(Yt la, l@ l() txt l(D Hrl zB) Nb q 6 to d, & x 06 i H2 -7 D TMS 3 qv .) ? 3 D) q 4 of I -butene wi bromine, Br2, in aq us solution gives primarily 1-bromo-2butanol. Identify the nucleophilic species in the reaction tlzO 25. The reacti n A) Brz B) Br C) HzO D) HOBr i) = e\ cAz 26. The product(s) in the following reaction is (are): cHz tt2lPd C. L a*3 { C\5 c llrc A) B) C) D) only trans-l-4-dimethylcyclohexane. onlycrs-1-4-dimethylcyclohexane. both trans and cis-l -4-dimethylcyclohexane. It's impossible to tell. --'i C) 27. What product results from this reaction? (a h Clz -.cH V OH ...toH CH: A ts \ CI 3 , oil Hzo -+? OH A B e cl OH CH: C P,' cHr D 6 LSW F15 lnitia ls II. Short Answers: (3 pts each) Mark the correct answer in the box provided. I . e A compound, C sHzq, is reacted with excess hydrogen using a metal catalyst. One equivalent ofthe compound consumed]!ryff cuivalents.of-lrydroele.u.--How many rings did the original r compound have? fHD" 2. A 4 t/z -fr2 t4 \>3 H2 f ltD,l a u5ed -- 4-z t' 982 3 // a Propyne is treated with sodium amide in ammonia then methylbromide is added. The reaction proceeds quickly and the product, K, is treated with a poisoned (Lindlars) catalyst on palladium. After purification the major product compound L is isolated. L is then treated then treated with bromine in the dark to produce M. Identify compound M using its IUPAC name to indic a* the stereochemis try. \riflElt. / 4 -1 -/.- -CU 3. 2> +z-.\a ,Ufri* j A B) 6rR t C H3 CH 3 ) cHr cHr CH: ?o 'N" ,2 -) 2 r) tr fr,ff III decre^t3$nytth (stropr]lFfirst). II. CHrCH: III. NH2 IV. HC:C: Stroya$ Arrange the foflowing in orderof L CH3CH2O l)€iYl91 5. 1,,3),6.*ob.tb*c Rank the following in order of decreasing reactivity with bromine, Brz. 30 4. 2 5' fr 4 Compound X, CrHr:Cl, is reacted with sodium ethoxide and gives a single elimination product Y, CrHrz. Treatment with ozone followed by zinc and water gi ves the compound below. Identiff both X and O Y. x)Y) X o I Z , 5 II 3 Y +e lllte:''I) 7 L? l- LSW F15 III. ln itia ls KfY Predict the Products: (4 pts each) Write the major product for each of the following write in the stereochemical designation rather than draw it, if you prefer. If a racemic mixture is predicted please write "racemic". H2O, H2SO1 CII3CH2C=CH dfi u3 chTc,+3 I ..( ni4 bt el ,rc--t cl HBr --------------t, tl 6r (.) (lH.l H-r(' i' ll (lH (l Hj(l acld cH.r lr ) ,r ,$1 cb lllt( clz ub n*) --------------) cHr a ttt il l)BH3/TSF' ,,,,,,;|ru tut .--------------- , tlg tI E o tl IV. Mechanism (6 pts): Draw the complete correct mechanism for the following reaction including all electrons and the correct arrow type. l. Bromination of e by Bf2 1no p",o,.16"g. + oO +:B oo ?ta B.i +rbf 6 ) .r;l I s6;Y 8 0 Bri Cll z lnitia ls LSW F15 KEY provides the lH NMR spectrum shown below, identifu the compound. (The numbers above the peaks are integration values.) V. Spectroscopy: (8 pts) A CsHr compound 1.00 3.00 CsHs 1.99 1.98 4.5 tltrt I 43.532.52 1.5 0.5 1 The information from the lH NMR tells me: Peak Chemical shift Split lntegration Equivalent Group Hydrogens (E) 2.L5 Group with neighbor Neighbor Hyd rogens PPM A Number of t 2 B 1.86 s 1, c 7.47 M(6) 2 D 0.98 t 3 L -.-) ct@'t a oL /-L-lnl 1 L ZZ \ C#, Cilz Clls 2 cilt The structure of the product with appropriate labels (A, B, C, D) is: crta cb ch+" DE h 9 l-t