178) CHAPTER 4 Reactions of Alkenes I Problems 33. Give the major product of each of the following reactions Oe e b. CHy CHCHy + HBr —— Oe om, 4 cHycHccH= cn, + mBr — CH 34, Identify the electrophile and the nucleaphile in each of the following reaction steps. Then draw curved arrows to illustrate the ‘bond-making and bond-breaking processes. s cuguen, + —— caeuen, oh ». CCH cH, + cucucii cH, cy cuet + Oi cH CH 35, What will be the major product of the reaction of 2-methy- ‘patene with each ofthe following reagents? a HBr b, Hg(OAc)2, H0 followed by NaBH b. Br + peroxide i. 11,0 + tracelIClL oH i. Br/CHCl, 4. H+ peroxide k. Brito Ic 1 Bry/CH,OH /Pa 1m. BH,/THF, followed by H,0;/HO™ & Br; + excess NaCl 1. Hg(03CCF,); + CH,OH, followed by NaBH, 36, Which ofthe following compounds isthe most stable? 3.4-dimethyl-2-hexene: 2,3-dimethyl-2-hexene: 4 5-dimethyl- ‘Which would you expect to have the largest heat of hydrogenstion? Which would you expect to have the lowest heat af hydrogenation? 37, When 3-methyl-I-hutene reacts with HBr, two alkyl halides are formed: 2-bromo--methylbutane and 2-brome-2-methylhutane, Propose a mechanism that explains the formation ofthese products. 38. Problem 30 in Chapter 3 asked you to give the structures of all alkenes with molecular formula Cll. Use those structures to answer the following questions: Which of the compounds is the most stable? b. Which of the compounds is the feast stable?Problems | 179 39, Draw curved arrows to show the flow of electrons responsible for the conversion of reactants into products. eo % I a CH,—C—ocH, —— cH,—C—cH, + cH,o- I cH, © CHCH,—Br + CIs ——> cHCH,—Jem, + Be 40. Give the reagents that would be required to carry cut the following syntheses: cnet on ¥,CHJCH.OH “Oo cng cic HH ort h CH,CH,CH,Br 1 cue, Sy ons cognate Onn 41, For each pair of bonds, which has the greater strength? Briefly explain why. CH, a CH= Cl or CH Br © CHy—CH, or CHy—CH,CH, 1 1 1 t & cHycryeah or cHyeCH 417 Br o& Brae " " 42. Give the major product of each ofthe following reactions ‘HCL 1,0 Her Ch 4 a . pone’ © | J eo tL amor 4 ay ‘Hel Che OT Tae OF he , how would you prepare the following compounds? O oO er b cHLCH,CH.cHCH, é ° cu,etien, £ CLcHccHcH,cH, a on Bc 44, There are two alkenes that react with HBr to give I-bromo-I-methyleyelobexane. 44. Identify the alkenes ‘Will both alkenes give the same product when they seact with HBriperoxide? . With HCI? 4d, With HCUperoxide?180 CHAPTER 4 Reactions of Alkenes 45 46, 41, 48, 49, 50, For each of the following paits, indicate which member is the more stable: ih cu, cH, 2 cxnde, or cHséxerce, e. cIGeCHCHCH, or cHcHecHencH, CH; CH; h encen or cnyenencn, £ CH; a, 6 cH,eHicHt, or cHéticH,c1 B cangresc, or cmeicHyct é & 4. CH,CH,CHLCHCH, or CH CHACH,CH,CH, “The sevonul-order rate constant (in units of M~!s~') for aid-eatalyzed hydration at 25 °C is given for each of the following HC, HAC, CH WLC, u HAC cH HC, cH, \oocu Vd Vd Ved Noe! eee on oN co SNe # W iH H ‘cH iw cH, HAC ‘ens 495 10% asx 108 ssi 215x104 sarc 104 Calculate the relative rates of hydration of the alkenes. Woy does (Z)-2-butene react faster than (E}-2-butene? Way does 2-methyl-2-butene react faster than (Z)-2-but Why does 2,3-dimethyl-2-butene react faster than 2-methyl-2-hutene? ‘Which compound has the greater dipole moment? clon Hon cl ety Nd \ : Nod co PS wa ct wn clon 1 Need \ cN\ # ‘cH, H 4. What five-carbon alkene will form the same product whether i reacts with HBr in the presence of a peroxide or with HBr in the absence of a peroxide? Give three alkenes containing six carbon atoms that fe peroxide or with HBr in the absence of a peroxide the same product, whether they react with HBr in the presence of a ‘Mark Onikoff was about to turn inthe products he bad obtained from the reaction of HI with 3,3,3-titluoropropene when he realized thatthe labels had fallen off his flasks. He didn't know which label belonged to which flask. Another student in the next lab old him that because the product obtained by following Markovnikew's rule was 1,1, l-trifiuoro-2-iodopropane, he should put that label on the Mask containing the most product and label the flask with the least product 1.1, .-tsfluoro-3-iodopropane, the antic ‘Markovnikov product, Should Mark follow the student's advice? 4 Propose a mechanism for the following reaction (show all curved arrows) enayarar + axon A cere, ben, ‘b. Which step is the rate-determining step? What isthe electrophile in the frst step? Wihat isthe nucleophile in th fits sep? ‘What isthe electrophile in the second step? ‘What isthe nucleophile in the second step?