CHAPTER 5 Reactions of Alkenes and Alkynes: An Introduction to Multistep Synthesis 1. 4, Or» -O, C NV The ethyl cation is more stable. The ethyl cation has a methyl group in place of one of the hydrogens of the methyl cation. This methyl substituent can donate electrons toward the positive charge which decreases the concentration of positive charge, thereby making the ethyl carbocation more stable. ” (CH;CH,CCH; > CH3CH,CHCHs > CHsCH,CH CH, because a tertiary carbocation is more stable than a secondary carbocation, which is more stable than a primary carbocation. CH; CH; a. CHyCHCHCH, ©. e. Che Br CH, ie b. cHycinccH, 4. CHyCCHRCH:CH, £ CHLCHCHCH, Br Br Br CHS CH; | | a, CH)=CCH; c C=CH) CUACHCHCHACHCH, and CHACH_CHCHCH:CHy 8. CHyCH:CH:CHCH oH OH oH OH ‘oH os CH; Gt i & LCHCCH, 2. cHyCCHy s.cHyCcHy 4 creer, cl Br oH OCH; b. The first step in all the reactions is addition of an electrophilic proton (H’) to the carbon of the CH: group. The tert-butyl carbocation is formed as an intermediate in each of the reactions. 6364 10. Chapter 5 ©. The nucleophile that adds to the tert-butyl carbocation is different in each reaction. In reactions #3 and #4, there is a third step—a proton is lost from the group that was the nucleophile in the second step of the reaction. 3 CHy CHy 4 CH CHy cael croc + H,0* crigect — cHycctt + CH;OH) (OH on ocH 3M ° HOH ~, a. " + cHoH OCH; CH; CH; b. CH=CCH; + CH;OH —!~ CHCCH; b= CCH LOCH OCH ©. CHCH HCH; + CH,CH,oH HS CHACHLCHICH, or OCH,CHs (CHy=CHCH,CH, + CH;CH,OH —!+ CH;CH,CHCH; OCH;CHs CH)CH=CHCH; + H,0 CH CHCH;CH, or ba CH)=CHCH,CH; + #0 —+ CH,CHCH,CH, bu The nucleophile that is present in greater concentration is more apt to collide with the carbocation intermediate. Therefore, if the solvent is a nucleophile, the major product will be formed by the reaction of the solvent with the carbocation, because the concentration of the solvent is much greater than the concentration of the other nucleophile. (For example, in “a” the concentration of H30 is much greater than the concentration of CI.) 8, CHCH,CHICH, and CH,CH/CHCH b, CHCHCHCH, and CHYCH/CHCHs OH a OCH; Br major major CH Gh Br. CH) . O = 0 =O r we cuncucHcH=cH, at crscaicr.cHcHs Be, CincHICHCHCH, CH; CH; CH; Bri. 12. 13. 14, ChapterS 65 CH; CH; . # Br. CH; wt Be a CH; cH; Br CH; 7 we Br CH; CH e Se Be, Br 1-Bromo-3-methyleyclohexane and 1-bromo-4-methyleyclohexane will be obtained in approximately equal amounts because in each case the intermediate is a secondary carbocation. The general molecular formula of a cyclic alkyne is CyH2y-4. Because a compound has two fewer hydrogens for every ring and zrbond, a compound with one ring and 2 bonds (one triple bond) would have 6 fewer hydrogens than the C,Hy-2 formula The molecular formula of a noncyclic hydrocarbon with 14 carbons and no bonds is CisHs0 (CrHansa). Because a hydrocarbon has two fewer hydrogens for every ring and z’bond, a hydrocarbon with one ring and 4z-bonds (2 triple bonds) would have 10 fewer hydrogens than the C)H2,.2 formula. Thus, the molecular formula is CiH2o. i & HCSCcH:CoH, CH; a. 4-niethyl-1-pentyne b. 2-hexyne66 15. 16, 17. 18. 19. 20. Chapter 5 HC==CCH,CH,CH,CH3 (CHyC=CCH,CHCHy (CH;CH,C=CCH,CH; I-hexyne 2-hexyne S-hexyne butylacetylene methylpropylacetylene diethylacetylene cHRCHYCHC=cH CIRCHCH.C=CH CH; CH 3-methyl-I-pentyne 4-methyl-I-pentyne 4-methyl-2-pentyne sec-butylacetylene isobutylacetylene isopropylmethylacetylene CH; cHC= CH CHy 3,3-dimethyl-L-butyne tert-butylacetylene a, 5-bromo-2-pentyne c. S-methyl-3-heptyne b. 6-bromo-2-chloro-4-octyne —d._3-ethyl-I-hexyne a. sp*sp? d. sp-sp* g spsp b. sp-sp* e. sp-sp h. sp-sp* ce. sp-sp? f. sp’-sp” i. sp’-sp Br a, CH)=CCH; e econ br be Br Br Br cater cHecH CHC + emcee be hr te Because the alkyne is not symmetrical, two ketones will be obtained. ° ° i i CH;CH,CH; + H,0 #580, CHCH,CCH,CH;CH;CHs + CHsCH,CH;CCH;CH,CH, <> The best answer for “b” is 3-hexyne, because it would form only the target ketone. 2-Hexyne would form two different ketones, so only half of the product would be the target ketone CH,CH,C: a. CHC=CH b. CH,CHjC=CCH,CH, HI21. 22. 24, 25. 26. 21. ChapterS 67 Note that both of the enols can exist as E and Z isomers. oH OH I I CH)CH=CCH:CHACHCH and CH,CH:E—CHCH:CHCH, CH, CH; Me Sis aN H H Tmia” CHaCH;CH;CH;CH=CH, catalyst b. CH;CH;CH;CH=CH or CHjCH,CH=CHCH; I-pentene 2-pentene (CHs CH; CHy CH or or or I-methyleyclopentene 3-methylcyclopentene 4-methyleyclopentene methylenecyclopentene The reaction of sodium amide with an alkane will not favor products because the carbanion that would be formed is a stronger base than the amide ion. (Recall that the equilibrium favors reaction of the strong and formation of the weak; Section 2.5) CHC; + NH ee CHGH) + NH PK, > 60 PK, =36 weaker acid — weaker base stronger base __ stronger acid Remember: the weaker the acid, the stronger its conjugate base. a. CH;CH,CH,CH, > CHyCH,CH=CH > CH;CH,C: b. Ni, > CHC > CH;CH,O” > F The electronegativities of carbon atoms decrease in the order: sp > sp” > sp*. The more electronegative the carbon atom, the less stable it will be with a positive charge. a. CH;CH, b. H,C=CH Solved in the text.68 28. 29. 30. 31. 32. 33. Chapter 5 1 a, HC Toncucaer — CHxCHsCHsC=CH ° H,0, H,S0, Il b, productofa 55+ CH,CHyCHsCCHs H,/Lindlr catalyst c. HC: a (CHjCH=CH, NaN fg d. productofe | EE cancticH, Br cH. wn BQ CCHS Tine Pa cast H H a 1.Nt excess HC . 2. CHF CHE CHs a —CHACHCH CHCHACHCHCH— OCH; OCH; OCH; OCH; a. CH)=CHCI b. Cih=ecHs ©. CR =CF, ,° OCH; HO—OH ——+ 2HO- 10S — Boeacecel a a o~ ; Ho— cnt Vatu > Homer cncHte a a aoa iN - HO—CHLGHCHCH + CHCH —~ HO CHRFHCHACHCHLCH a ca a aaa Since branching increases the flexibility of the polymer, beach balls are made from more highly branched polyethylene. electrophile nucleophile a CH;CHCHs + — caCHICH, NUChapterS 69 electrophile CHs oe nucleophile. ——» CH;C—6CH; Or It be CHEK + cHGH bash CH a ” 34, a CHC=CHCH, + HBr —~ CH°—CHCH Br os oH b. CHC=CHCH, + HI —+ CHyC—CH:CHy I at Hy th ©. CH;C=CHCH; = cr CHCH—CH,.CH CHy CH trace HCI I d, CH;C=CHCH, + 1,0 Ciiee— crc on CHy CH; trace H,SOy e, CHjC=CHCH; + CH3OH Gig —canCHy OCH; CH; CH; trace H,S04 f. CH\C=CHCH; + CH;CH,OH cre cHcH, OCH,CHy, Br CHy (CH,CH3 CH 35. I I (Frese b. CiygcHCHy c (he a. canccncty Br a 36.70 Chapter 5 CH;CHCHy CH;CH,CH; 37. ben 5 Nese. Hae co CrartiCH, CH)CH= a CHCA, 1804 aaa Cy me oe: on 38. CH;C=CH ou oe b. CHyCH,C=CHCH,CH; and (CHj;CH=CCH,CH;CH) OH oH I e. CHSC CHy=C i i 39. CH\CH)CH;CCH;CH,CH,; and CH;CH,CH,CH,CCHCH3, 40. a. b. noreaction ¢. e cl without an ‘OH Br OCH; acid catalyst CH; 41. a. CH;CCH; Db. CH;CHCH; ce. CH;CH, aa CO CO Ho , b. CH;CH)CH,CH=CH, = CaRCHRCHLCHICH, a CH,CH= CH HCHCHs “ Cy 130 Cy ba 140 CHs = oO CH; Br44. 45. 46. ChapterS 71 To determine their relative rates of hydration, the rate constant of each alkene is divided by the smallest rate constant of the series (3.51 x 10°). propene = 4.95 x 10°/3.51 x 10%= 1.41 (Z)-2-butene =8.32 x 10°%/3.51 x 10° = 2.37 (E)-2-butene = 3.51 x 1073.51 x 10% =1 2-methyl-2-butene = 2.15 x 1074/3.51 x 10% =6.12 x 10° 2,3-dimethyl-2-butene = 3.42 x 1074/3.51 x 10° = 9.74 x 10° a. Both compounds form the same carbocation, but since (Z)-2-butene is less stable than ()-2-butene, (Z)-2-butene has a smaller free energy of activation b. 2-Methyl-2-butene reacts faster because it forms a tertiary carbocation in the rate-limiting step, while (Z)-2-butene forms a less stable secondary carbocation. c. Both compounds form tertiary carbocations. However, 2,3-dimethyl-2-butene has two sp” carbons that a proton can be attached to, but 2-methyl-2-butene has only one. Therefore, 2,3-dimethyl-2-butene will have a greater number of productive collisions with a proton. Ka a, CH,CH,CH-4CH, CH;CH;CHCH, CH,CH,CHCH; cai 1 *OCHs 4 ch cng CHLCHEHCH, OCH; D. the first step e. the sec-butyl cation ce. Ht f. methyl alcohol d. 1-butene ‘As long as the pH is greater than —2.4 and less than 15.9, more than 50% of 2-propanol will be in its neutral, nonprotonated form. ROH; ROH RO- Because when the pH = pKa, half the compound is in its acid form and half is in its basic form. Therefore at a pH less than ~2.4, more than half of the compound will be in its positively charged protonated form. ‘Ata pH greater than 15.9, more than half of the compound will exist as the negatively charged anion. Thus at a pH between -2.4 and 15.9, more than half of the compound will exist in the neutral nonprotonated form.2 47. 48. 49. 50. Chapter 5 a. e e “or ara om #80, = (CH;CHCH: OCH; CH CH CH;O_ CH; ms, or CH,OH CH CHs Br. CH; z ae dene OCH;CH2CH3 CHs CH; 13504, I CH;C=CHCH; “no” (CHyCCH;CH HO 1 ‘OH (CH3C=CCH,CH,CH; ¢, BrC=CCH,CH,CH; CH; CHACHA CEHCH,CHICH g CHC=CCH_CHCH CHCH, cH; a a cl concur, e CanCHcHnecH,CHACH, + Car Cei cri, CH,CHCH, d & & a crrcnscrscercr a51. 52. 54, ChapterS 73 a. S-bromo-2-hexyne c. 5,5-dimethyl-2-hexyne b. S-methyl-2-octyne mos CH,CH;C=CH, + d. 6-chloro-2-methyl-3-heptyne ro CHCA Ce electrophile nucleophile rc: v. onchange — aacbecm «a nucleophile electrophile a ce. cHc=C1H* + NH, —~ cnc: electrophile nucleophile He named only one compound correctly. a, 4-methyl-2-hexyne ——e._correct b. 7-bromo-3-heptyne d. 2-pentyne HC==CCH,CH,CH;CH,CH; CHjC==CCH,CH;CH,CH; CHjCH)C=CCH,CH,CH; -heptyne 2-heptyne S-heptyne pentylacetylene butylmethylacetylene _ethylpropylacetylene cuncincincic CH CH; 3-methyl-I-hexyne concn ‘CH CH 4-methyl-2-hexyne sec-butylmethylacetylene CH; CHy 4,4-dimethyl-2-pentyne tert-butylmethylacetylene CH CHycHCHC=CH CH; 3,4-dimethyl-I-pentyne CHRCIRCHICHC=CH CHScHCH CHC H CHs S-methyl-I-hexyne isopentylacetylene CHEE OCHCH, CH 4-methyl-I-hexyne CHYCHCH:C=CCH CH; S-methyl-2-hexyne isobutylmethylacetylene CH 2-methyl-3-hexyne ethylisopropylacetylene t ia cauectnc cscnge=cH CH; CH 4.4-dimethyl-t-pentyne 3,3-dimethyl-I-pentyne (CH;CH,CHC=CH CH;CHy 3-ethyl-L-pentyne74 55. 56. 57. 58. Chapter 5 dia case aK mh bb. CH3CH)C=CCH;CH, —pye—~ CH3CH2CH2CH;CH,CH3 The molecular formula of the hydrocarbon is Cs2Hse, CrHon2 = Cates With one triple bond, two double bonds, and one ring, the degree of unsaturation is 5. Therefore, the compound is missing 10 hydrogens from CyHz»+2 a, CHy=CCHs fe. CHjCH=CH, br Br b. CH;CCHs f£. CHC Br ° c candor, g. CHjC=CCH,CH)CH;CH,CH3 d.CH3CH2CH3 HAC CH. a. CHyCH=CCH; e ed , | rN Br H Hl Br b. cHcHUcH, f. no reaction br ° ¢. CHsCCH:CH; no reaction d. CHyCH,CHCHy59. RCH;CHy RCH=CH; \H,, Puc wantecan\\ Br Lie HBr RcuCH CHS inter ‘CH Chapter5 75 RC=CH2 Br nou a a “excess HBr h Rao RCCH3 LNA Hy 60. a. CH\CHCH,C=CH CH;CHCH,C=CCH, [=> CH;CHCH,CH=CHCH, ia 2. CBr , inde i is Gy catalyst by #0 1,80, on CHyGHICH,CHCH,CH, CH; 5-Methyl-2-hexanol also will be obtained because in the third step of the synthesis, the proton can add to either of the sp” carbons. 61. Three are named correctly. a. 3-heptyne b. S-methyl-3-heptyne ©. correct oH CHCHCH,CH,CHCH, CH; d._6,7-dimethyl-3-octyne correct correct 62. only bis a pair of keto-enol tautomers. LLNaNH 9 H,0. H:S04 IL aso, 7 CHACCHs 1. NaNH Tancup” CHsC=CCHCH A) aa ~ CHyC=CCH,CH, tue aN76 65. 67. Chapter 5 9° Oo oO I ll i a. CH;CH,CCH; —-B. CH CH;CH)CCH;e. o 4. cH LNaNH a HC=CH SGacgccnar — CHyCH:CH.CHC H 0 H,S0, | H#SOs i (CHyCH;CH;CH;,CCH3 LL NaN, _ b. HC=CH FGpqqpr CHsCHxC=CH | ar CH,CHjCH=CH, cals CH)CH:CHCH, Br LLNaNs © CH Janene, CH;CH,CH,CH=CH) Ho iso. CHCHCHCHCH, OH #0 I G “HS, 50 CCHs The base used to remove a proton must be stronger than the base that is formed as a result of proton removal. A terminal alkyne has a pK,~ 25. Therefore, the base used to remove a proton from a terminal alkyne must be a stronger base than the terminal alkyne. In other words, any base whose conjugate acid has a pK, greater than 25 can be used. She can make 3-octyne by using I-hexyne instead of 1-butyne. She would then need to use ethyl bromide (instead of butyl bromide) for the alkylation step: NaN, CHjCH,CH;CHC=CH Gq” CHsCH:CH,CH)C=CCHCHs Or she could make the 1-butyne she needed by alkylating ethyne: 1L.NaNt cH = cHCH,C=CH TOK : woo cHLcu.cn,cise CH,CH,CH,CH;C=CCH,CHy68. 69. 70. 1. ChapterS 77 8. —CHYCHCH,CHCHCH b. —CHCHCHACHCH ACH FO OF F CO;H CO;H CO; a, CH)=CHCH,CH; b. CH,=CCH; CHCA CH.CH—CHLCHCH:CH—CHCH — When BF; and H;0 are used to generated the H’ electrophile, a negatively charged counter ion is not formed. aR Py BF; + HpQ: === FyB:QH, === FByGH + HY When HCI is used to generated the H’ electrophile, a negatively charged counter ion is formed. HCI Because a negatively charged counter ion can act as a chain terminator, BF; and H,O are used as the source of H’,8 6. Chapter 5 Chapter 5 Practice Test Which member of each pair is more stable? CH, a, CH,CHCH;CH, or CH,CCHy Bb. CH;CHjCH, or CH,CHCH; Which would be a better compound to use as a starting material for the synthesis of 2-bromopentane? CHjCH;CH;CH=CH) or CH CH;CH=CHCH3 What is the major product of each of the following reactions? CH; a, CH)=CCH;CH; + HBr ——~ CH3CH;CH=CH, + HCl —— Indicate how each of the following compounds could be synthesized using an alkene as one of the starting materials: CHs CH; a. ae CHsECHCH, CH OH Draw the enol tautomer of the following compound: or Indicate whether each of the following statements is true or false: a. 1-Butyne is more acidic than 1-butene. TF b. An sp” carbon is more electronegative than an sp* carbon. T ¢. Water is a stronger acid than ammonia. TF d. The reaction of I-butene with HCI will form 1-chlorobutane as the major product. TF1 10. 11. 12. ChapterS 79 What reagents could be used to convert the given starting material into the desired product? #H H c=q “—— oy Give the systematic name for the following compound: CHAFHC= CCH,CH Br CH; What would be the best alkyne to use for the synthesis of the following ketone? i CH,CH,CH,CCH; Rank the following compounds in order of decreasing acidity: (Label the most acidic compound #1.) NH, — CHyC=CH CH;CH;, H,0 CHy;CH=CH) Give an example of a ketone that has two enol tautomers. Show how the target compounds could be prepared from the given starting materials. CH = ——* — CH,CH,CH;CH,CH;CH3 9° b. Il CH = ——* — CH;CH,CCH)CH,CH3