108 6.1 Chapter 6 C. The Hammond postulate (Section 6.10). 1. The transition state for an endergonic reaction step resembles the product of that step. 2. The transition state for an exergonic reaction step resembles the reactant for that step. 3. Inan electrophilic addition reaction, the transition state for alkene protonation resembles the carbocation intermediate. 4. More stable carbocations form faster because their transition states are also stabilized. D. Carbocation rearrangements (Section 6.11). I, Insome electrophilic addition reactions, products from carbocation rearrangements are formed. 2. The appearance of these products supports the two-step electrophilic addition mechanism, in which an intermediate carbocation is formed. 3. Intermediate carbocations can rearrange to more stable carbocations by either a hydride shift or by an alky! shift. 4, Inboth cases a group moves to an adjacent positively charged carbon, taking its bonding electron pair Solutions to Problems Strategy: Because two hydrogens must be removed from a saturated compound to introduce an unsaturation, a compound's degree of unsaturation refers to the number of pairs of hydrogens by which its formula differs from that of the corresponding saturated compound. For example, a saturated alkane with four carbons has the formula CyHio. The compound in (a), C4Hg, which has two fewer (or one pair fewer) hydrogens, may have a double bond or a ring, CgHy4 thus has a degree of unsaturation of I. Degree of Compound Unsaturation Structures (@) Cty 1 CHgCH=CHCHs — CHsCHyCH=CHp (CHy),C=CHp [Dery (0) CyHg 2 CHp=CHCH=CH, CHsCH=C=CH, CHG: (©) Coty 2 b6.2 6.3 6.4 Alken Structure and Reactivity 109 Strategy: Unlike the hydrocarbons in the previous problems, the compounds in this problem contain additional elements. Review the rules for these elements. Solution: (a) Subtract one hydrogen for each nitrogen present to find the formula of the equivalent hydrocarbon — CgHy. Compared to the alkane CgH4, the compound of formula CH, has 10 fewer hydrogens, or 5 fewer hydrogen pairs, and has a degree of unsaturation of 5. (b) CgHsNO>p also has 5 degrees of unsaturation because oxygen doesn't affect the equivalent hydrocarbon formula of a compound. (©) Ahhalogen atom is equivalent to a hydrogen atom in calculating the equivalent hydrocarbon formula. For CsHsCh, the equivalent hydrocarbon formula is CsHi2, and the degree of unsaturation is 3. (4) CoHieBrz — one degree of unsaturation. (©) CjoHr2N203 — 6 degrees of unsaturation. (f) CaoHs2CIN — 5 degrees of unsaturation. ‘A Cig hydrocarbon with 11 degrees of unsaturation (three rings and eight double bonds) has a formula Cy¢H34~ Hz2 = CigHi2. Adding two hydrogens (because of the two nitrogens) and subtracting one hydrogen (because of the chlorine), gives the formula CygH3CIN20 for Diazepam. HG N cl =N Strategy: (1) Find the longest chain containing the double bond and name it. In (a), the longest chain is a péntene. (2) Identify the substituents. There are three methyl groups in (a). (3) Number the substituents, remembering that the double bond receives the lowest possible number. The methyl groups are attached to C3 and C4 (two methyl groups). (4) Name the compound, remembering to use the prefix "tri~" before "methyl" and remembering to use a number to signify the location of the double bond. The name of the compound in (a) is 3,4,4-trimethyl-1-pentene. Solution: @ Gis i ) gis HpO=CHCH—CCH, CHgCH,CH=CcH,CH, SUN sts IsCH20t 1gCHg CH 3,4,4-Trimethyl-I-pentene 3-Methyl-3-hexene © He OH @ OH sGHCHCHy CHgCH=CHCHCH=CHCHCH, CHyCH CH CH= CHCHCH,CH, 4,7-Dimethyl-2,5-octadiene 6-Ethyl-7-methyl-4-nonene110 Chapter 6 6.5 Strategy: It's much easier to draw a structure from a given name than it is to name a structure. First, draw the carbon chain, placing the double bond or bonds in the designated locations, Then attach the cited groups in the proper positions. Solution: 0) @) rs ) uch HyC=CHCH,CHyC=CHy CHgCHaCHCH=CC(CHa)g 2-Methyl-1,5-hexadiene 3-Ethyl-2,2-dimethyl-3-heptene - GMs Gta @ Ge OH CHjCH=CHCH= CHE —C= CH CHC HCH Oty PG 2,3,3-Trimethyl-1,4,6-octatriene on CHs CH 3,4-Diisopropyl-2,5-dimethyl-3-hexene 6.6 0) on 6 CH 1 3 r 2 1,2-Dimethyl- 4,4-Dimethyl- 3-Isopropyl- cyclohexene cycloheptene eyelopentene 6.7 Compounds (c),(e), and (can exist as cis-trans isomers. cis trans oe ee (©) CHgCHyCH=CHCH3 fa pra CHgCHp “CHy = CHgCHp hoa cy (©) ocH=cIcH =e, pan ao a 4 oO H oo \ © ercH=cHeI ‘c=<, Sond” es AAlkenes: Structure and Reactivity 111 6.8 (a) (b) Ho GHaCH HgC = bf = CHgCHCH, =H cis-4,5-Dimethy!-2-hexene trans-6-Methyl-3-heptene 6.9 Strategy: Review the sequence rules presented in Section 6.5. A summary: Rule I: An atom with a higher atomic number has priority over an atom with a lower atomic number. Rule 2: f a decision can't be reached by using Rule 1, look at the second, third, or fourth ‘atom away from the double-bond carbon until a decision can be made. Rule 3: Multiple-bonded atoms are equivalent to the same number of single-bonded atoms. Solution: High Low Rule High Low Rule (a) -Br -H 1 (b) Br Cl i (©) -CH,CH; -CH; 2 (@) -OH -NH, 1 ©) -CHOH -CH; 2 () -CH=0 — -CH,OH 3 6.10 Highest priority ———> Lowest Priority (a) ~Cl, -OH, -CH, -H (b) -CH,OH, ~CH=CH, ~CH,CH3, ~CH3 (©) -CO3H, -CH,0H, -CH)NH) (@) ~CH;0CH3, ~C=N, ~C=CH, ~CH2CH 6.11 (a) Low HC CH,OH_— Low pay Zz High CHgCH, Cl High First, consider the substituents on the right side of the double bond. ~Cl ranks higher than ~CH,OH by Rule I of the Cahn-Ingold-Prelog rules. On the left side of the double bond, ~CH2CHs ranks higher than CH ) High Cl CHC, = Low c=C E ren Low CHxO —CH,CH2CHy High12 Chapter 6 © High sC. Ox Low (POH High Ae \ CHOH Low Notice that the upper substituent on the left side of the double bond is of higher priority ‘because of the methyl group attached to the ring. @ Low H pu cae aaa High HC ‘CHyNHp High COzCHy Low ‘CH2OH More stable (@) 2-Methylpropene disubstituted double bond ) HH CHaCH2CHs c=G E ES Hse H trans-2-Hexene no steric strain oO 1-Methyleyclohexene trisubstituted double bond © High Low High Less stable H HCH, 4 CHoCHs 1-Butene monosubstituted double bond H H 7 PQ 2 Hg CHyCHyCHy cis-2-Hexene steric strain of groups on the same side of the double bond C CHy 3-Methyleyclohexene disubstituted double bondAlkenes: Structure and Reactivit y 3 6.14 Strategy: All of these reactions are electrophilic additions of HX to an alkene. Use 6.15 Markovnikov's rule to predict orientation. Solution: @) H cl : () Br i (CHg)gC=CHCHCHy + HBr ——> (CHg)2CCH2CHCHy 2-Bromo-2-methylpentane In accordance with Markovnikov's rule, H forms a bond to the carbon with fewer substituents, and Br forms a bond to the carbon with more substituents. ©) CHy CHy OH I H20 I I CHyCHCHyCH=CH, ————> CHyCHCH,CHCHs H2804, @ chy Br oe Cr : + HBr ——> 1-Bromo-1-methyleyclohexane Strategy: Think backward in choosing the alkene starting material for synthesis of the desired haloalkanes. Remember that halogen is bonded to one end of the double bond and that more than one starting material can give rise to the desired product. Solution: @) Cyclopentene ) CHCl, Cr ees CHoCHy or HPO, cr4 6.16 Chapter 6 ©) Br i CHgCHCH=CHCH,CHg + HBr ——> CH3CH2CH2CHCHCHy 3-Hexene aoe ‘The more stable carbocation is formed @ @ jee aie ie CHyCHsO=CHCHCHy + HBr = |CHsCHpCCHACHCHs | —> CHCHpCCH CHoHy carbocation intermediate Br (b) 1 KI * Y=cHcH, — \*-cHcHy| > [ S HgPO, ae) (CH,CHy carbocation intermediate ‘Two representations of the secondary carbocation are shown on the left below. This, secondary carbocation can experience hyperconjugative overlap with two hydrogens under normal circumstances. However, in the alignment shown in the drawing, only one hydrogen (circled) is in the correct position for hyperconjugative overlap with the carbocation carbon. Because there is rotation about the carbon-carbon bonds, all of the hydrogens starred in the representation on the far right can be involved in hyperconjugation at some time. Hg ay Hy 5G ig Ig H He ee Ae \CHOHCHg --0-CH-C. fy--0-CH-C. / Ha 1H Wa eH Hae Hye HC 4 HAlkenes: Structure and Reactivity 115 6.18 The second step in the electrophilic addition of HC! to an alkene is exergonic. According to the Hammond postulate, the transition state should resemble the carbocation intermediate. ‘Transition state Reaction progress. ——»= oe co ie « OAS Of ]-COX,, 6.19 r electrophilic addition hydride reaction of to double bond shift carbocation with Br~ Visualizing Chemistry 6.20 (a) (b) S 2,4,5-Trimethyl-2-hexene _ 1-Ethyl-3,3-dimethylcyclohexene 6.21 @) (b) High C. Low High Hs High = E Zo = 1 roe fae teh Low OH Low6 6.22 Chapter 6 Oro cl or He CH2CH; | ——> CHCHy — Either of the two compounds shown can form the illustrated tertiary carbocation when they react with HCI. In the conformation shown, the three circled hydrogens are aligned for ‘maximum overlap with the vacant p orbital. Because of conformational mobility, the three starred hydrogens are also able to be involved in hyperconjugation. Additional Problems 6.23 ‘The purpose of this problem is to give you experience in calculating the number of double bonds and/or rings in a formula. Additionally, you will learn to draw structures containing. various functional groups. Remember that any formula that satisfies the rules of valency is acceptable. Try to identify functional groups in the structures that you draw. (a) CioHig~ 3 degrees of unsaturation. Examples: (CHgCHyCH=CHCH = CHCH=CHCH;CHg CO oreAlkenes: Structure and Reactivity 117 (b) CHO. The equivalent hydrocarbon is CgHs, which has 5 degrees of unsaturation. Ga ketone Qa aldehyde Qa aldehyde CGH CHC or g o Rt rey aromatic aromatic aromatic a a A Cor" tenor Cae bonds bonds (©) CyHoClz has C7H2 as its equivalent hydrocarbon formula. C7H Cl has two degrees of unsaturation. triple double bonds halide = cy bend H CHs\ 4 I 1 \ t / CHsCHCHOHCHEC PoCHCCH=c, Gl = halide Che ci cl halides 7 , double bond double bond 7 1 cH halide es or . oe hali Hc o% halide ci’ ‘cr halide i) cee (d) CioH16O2 ~ 3 degrees of unsaturation. double bonds ester ketones i \ o Os X09 HoC=CHCH=CHCH,CH,CH,CH)COCHs Cor alcohol ketone aldehyde alcohols wast 7 Ss Ho. ¢ a8 6.24 Chapter 6 (e) CsHyNOz — 2 degrees of unsaturation. ketone amide double bond nitro (sie NU NG R4 { eee CH,CH,CCH CNH, HyC==CHCH,CH,CH.NT-O- double bond carboxylic © amide ketone { 9 sed 4 ot NHp Hyc-cHCH,NHCHjCOH HO NH or amine nike atedhot Om ether (9) CgHygCINO — 4 degrees of unsaturation. double bonds amide double bonds. fe ee x + 1 > i eee Ni ihe ol halide amine to H snc halide = C1 ae No amine ¥ bond = double ketone bond oi amine. ketone alcoho] G1 = halide halide ci Compound Equivalent hydrocarbon Degree of Complete ‘formula unsaturation formula (a) CgH2O2 CsHig 3 CgH1202 0) GHN. Cis 2 CHaN (©) CoHNO CoH20 4 CoH)3NOAlkenes: Structure and Reactivity 119 6.25 Solve this problem in the same way as we solved problems 6.3 and 6.24. A C22 hydrocarbon with 12 degrees of unsaturation (four rings and eight double bonds) has a formula C>2H46— Haq = Co2Hap. Adding two hydrogens (because of the two nitrogens) and subtracting one hydrogen (because of the chlorine), gives the formula C2gH23CINzO2 for loratadine. 6.26 (E)-4-Methyl-2-hexene (d@) Gh Jen) \ Gis p=0, a Hoc=CHCHCH CHy (SE)-3,4-Dimethyl- 1,5-heptadiene Oo Sor i cach Loratadine o) Gly GHeCHy CHCHCHSCH.CH Hy ee He eH (Z)-4-Ethyl-3,7- dimethyl-2-octene ©) Hye a CHyCHyCHp —CHg (2Z,4E)-4,5-Dimethy|- 2,4-octadiene © Hae HaC=CCH2CHy 2-Ethyl-1-butene f HgC=C=CHCH, 1,2-Butadiene 6.27 Because the longest carbon chain contains 8 carbons and 3 double bonds, ocimene is an octatriene. Start numbering at the end that will give the lower number to the first double bond (1,3,6 is lower than 2,5,7). Number the methyl substituents and, finally, name the compound. Bas alll, OST eyst-pimetnyt-13,6-cctatrene120 6.28 6.29 6.30 6.31 Chapter 6 aa (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene @ (b) CH. ie KR Ho CH2C=CHp p= paQ ClCH CHO(CHs),CH=CHp HC CHg CHyCH2CH3 (4£)-2,4-Dimethyl-1,4-hexadiene © Dimethyl-4-propyl-1,5-octadiene H H H Hy Feo t Hy Zr 2x ola ‘CHyCHCH=C=CHp oy fe 4 HL 20. H | CHy Ca T H 4-Methyl-1,2-pentadiene (3E,5Z)-2,6-Dimethyl-1,3,5,7-octatetraene © © CHgCH2CHCH, aki ed - (CHa)3Q. ye c=c c=Cc as roy CHgCH{CH,CHp = CHa, H C(CHg)3 3-Butyl-2-heptene trans-2,2,5,8-Tetramethyl-3-hexene x )X Menthene CHgCHy CHa CHC, H CHgCHsCHCH=CHp p= prs H 4 H CHy, 1-Pentene (Z)-2-Pentene (E)-2-Pentene fe HCH oHyCHe MH cHg. Jou HO, PMs eas / ae HC H H q HC H 2-Methyl-I-butene _3-Methyl-1-butene 2-Methyl-2-buteneAlkenes: Structure and Reactivity 121 6.32 CHgCH,CHsCHaCH=CHp —CHgCHpCHy CH CHgCHCHy —H ern an HoH Ho CHy 1-Hexene (Z)-2-Hexene (E)-2-Hexene H CHsCHp _CHaCHs Ort Cmts} an a as HOO HCHgCHg Hye UH (Z)-3-Hexene (E)-3-Hexene 2-Methyl-1-pentene et ge CHyCHCH CHSCHCH, Clg Cy p=Q pao f= H H H H H 3-Methyl-I-pentene 4-Methyl-1-pentene —_2-Methyl-2-pentene ig CHsCHp CH CHyCHe CHyCH CH Pe p= e HC OH HyCCHy H (Z)-3-Methyl-2-pentene (E)-3-Methyl-2-pentene (Z)-4-Meth: e es ii CHyCH cH CHyCcHs fe a Pra H HoH HOH (E)-4-Methyl-2-pentene 2,3-Dimethyl-I-butene 3,3-Dimethyl-1-butene Gis A Hag, a & CHyCH, =H HgC 2-Ethyl-1-butene 2,3-Dimethyl-2-butene122 6.33 6.34 6.35 6.36 6.37 Chapter 6 As expected, the two trans compounds are more stable than their cis counterparts. The cis-trans difference is much more pronounced for the tetramethy| compound, however. Build a model of cis-2,2,5,5-tetramethyl-3-hexene and notice the extreme crowding of the methyl groups. Steric strain makes the cis isomer much less stable than the trans isomer and causes cis AH"aydrog to have a much larger negative value than trans AH hyérop for the hexene isomers. cis isomer trans isomer A model of cyclohexene shows that a six-membered ring is too small to contain a trans double bond without causing severe strain to the ring. A ten-membered ring is flexible ‘enough to accommodate either a cis or a trans double bond, although the cis isomer has less strain than the trans isomer. Build models of the two cyclooctenes and notice the large amount of torsional strain in trans-cyclooctene relative to cis-cyclooctene. This torsional strain, in addition to angle strain, causes the trans isomer to be of higher energy and to have a AFPhydcog larger than the AH" jyézog OF the cis isomer. Models show that the difference in strain between the two cyclononene isomers is smaller than the difference between the two cyclooctene isomers. This reduced strain is due to a combination of less angle strain and more puckering to relieve torsional strain and is, reflected in the fact that the values of AH°hyérog for the two cyclononene isomers are relatively close. Nevertheless, the trans isomer is still more strained than the cis isomer. ‘The central carbon of allene forms two o bonds and two x bonds. The central carbon is sp- hybridized, and the carbon-carbon bond angle is 180°, indicating linear geometry for the carbons of allene. The terminal =CHp units are oriented 90° with respect to each other ae Tons 6.38 The heat of hydrogenation for a typical diene is 2 x (AH hydrog Of an alkene) = ~252 ki/mol ‘Thus, allene, with AHyydrog = ~295 kI/mol is 43 kJ/mol higher in energy than a typical diene and is less stable.6.39 6.40 6.41 Alkenes: Structure and Reactivity 123, (a) ie 420 ie CHgCHyCH=CCH,CH, = —S—> CHgCH2CH,CCH,CHg HS0q 1 oH (v) CHaCHg, CH2CH3, Oo el ee Br Br CH, Br CH. CH. — + Two products are formed because the two possible carbocations are of similar stability. @ (©) a cl | I HyC=CHCH,CH2CHaCH=CHp + 2 HCl ———> CHgCHCH,CH)CHyCHCH, Oo) oe Br CH CY oo Cr (b) Br CO ae CO © CHg Br CHy Br Gs CHgCH=CHCHCHs + HBr ——> CHgCHCH,CHCHg + CHgCH,CHCHCHs Highest priority —————> Lowest Priority (a) -I, -Br, -CHy, -H (b) -OCH,, -OH, ~CO,H, -H (©) -CO;CH;, ~CO,H, ~CH,OH, -CH, (¢) -COCH,, ~CH,CH,OH, -CH,CH;, -CH (©) -CH,Br, -C=N, -CH,NH,, -CH=CH, (f) -CH,0CH3, -CH,OH, ~CH=CH, CH2CH3124 Chapter 6 6.42 0) © sigh HOCH, CH High © Low Hoc HW Low Cae ae ae Zz Low HCH Low High cl OCH. High © (d) High NCQ CHy = Low High HsC0,C. CH=CH High een ‘3 \ a Low CHjCH, CH,OH High Low —HO,C ‘CHyCH, Low 6.43 @ oH, ) 3-Methyleyelohexene 2,3-Dimethyleyclopentene Ethylcyclobutadiene @ ©) 0) 1,2-Dimethy]-1,4- 5-Methyl-1,3- 1,5-Cyclooctadiene cyclohexadiene cyclohexadiene 6.44 is (E,SZ)-1,3,5-Octatriene 6-[(Z)-1-Butenyl]-_3-[(Z)-1-Buteny!]-4- 1,4-eycloheptadiene _vinyleyclopentene6.45 6.46 Alkenes: Structure and Reactivity 125, oo ‘co=c Z (comect) Low H Low (>) Low HCH CH=CH, High p= E (correct) High HyC CHCHICHg)2 Low © High Br _CHaNHp = Low Nome E (incorrect) Low =H CHaNHCH, High @ ® ih NQ fly Low c=C E (correct) en Low (CHg)gNCHp CHyCHg High © High Br =e] ‘This compound doesn't show E-Z isomerism. Low ® Low HOCH —COpH High pam E (comect) High HjCOCH, © COCH, + Low Treatment of the tert-butyl ester with trifluoroacetic acid cleaves the -OC(CHs)s group and replaces it with an -OH group, which has a lower priority than the ~OCH group on the upper carbon and the -OC(CHy)3 group that was removed. The result is a change in the E,Z designation around the double bond without breaking any of the bonds attached to the double-bond carbons. a w. \. Low H. ‘C—OCH, Low Low — ‘c—ocHy High tees 2 OFsCOOH VS oe / He a High HCC OC(CHglg High High HgC 8-0 Low ° °126 Chapter 6 6.47 @ Hl eh + (CHgCH,CHCH, ——> _CHgCHCHCH, primary carbocation secondary carbocation ‘The primary carbocation rearranges to the more stable secondary carbocation by a hydride shift. (b) 4 Ota : OHye—CHCHy ——>_CHg?— CHa CH CHg CHg secondary carbocation tertiary carbocation ‘This hydride shift produces a tertiary carbocation from rearrangement of a secondary carbocation. © oH, CH, CHp Ke — primary carbocation _ tertiary carbocation ‘An alkyl shift forms a tertiary carbocation from a primary carbocation. In this example, rearrangement involves migration of the electrons from one of the cyclobutane ring bonds. 6.48 4 Gi H a * carbocation PSAAEE cartocation 6.49 rst CH, C k ‘CHg > bond shift (alkyl shift)Alkenes: Structure and Reactivity 127 6.50 Hy Br CHg : a pe Attack of the electrons of the double bond on Hi yields the carbocation pictured on the far right. A bond shift (alkyl shift) produces the bracketed intermediate, which reacts with Br- to yield 1-bromo-2-meihyleyclobutane. 6.51 (a) Co7H4gO —_5 degrees of unsaturation (b) CgHoCls 8 degrees of unsaturation (©) CopH340s 4 degrees of unsaturation (d) CgHjpNqO2 6 degrees of unsaturation (©) CoiHag0s 8 degrees of unsaturation (D) Ci7Hy3NO3 7 degrees of unsaturation 6.52 The reaction is exergonic because it is spontaneous. According to the Hammond postulate, the transition state should resemble the isobutyl cation. t i + MAL Heesse HgC-7~CHy == | Hyco Hh = Hero CHs HC HC 6.53 primary transition state (higher energy) secondary transition state a +. (higher energy (CHyCHeCHeCH2CHp intermediate) CHeCHcHecHycHr CHaCHaCHeCH=CHp Reaction progress ———>128 Chapter 6 6.54 Transition State #1 Transition State #2 Q. oe HG H ‘UL ‘2-Bromopentane path = H> é — cH /\ J mae | CoH 30 “E 1-Bromopentane path H oi) -- Pest CO CgHy CaHg The first step (carbocation formation) is endergonic for both reaction paths, and both transition states resemble the carbocation intermediates. Transition states for the exergonic second step also resemble the carbocation intermediate. Transition state #1 for 1- bromopentane is more like the carbocation intermediate than is transition state #1 for 2- bromopentane. + OP:054~ yy Se 3 a 7 : AY Base 6.55 Limonene ‘Step 2, in which the double bond electrons add to the carbocation, is an alkene electrophilic addition.Alkenes: Structure and Reactivity 129 epi-Aristolochene Steps 1 and 2 are alkene electrophilic additions, and steps 3 and 4 involve carbocation rearrangements. 6.57 Reaction of 1-chloropropane with the Lewis acid AICI; forms a carbocation. The less stable propyl carbocation undergoes a hydride shift to produce the more stable isopropyl carbocation, which reacts with benzene to give isopropylbenzene. = [owsonsons" acu | CHyCHCHg i CHCH3130 Chapter 6 6.58 al @ ov gis acid CHCH, CHCHg «+ =HpQ0 = ——» CH4CH2CCHACH. tgCHaC- 's 20 Sayat isCHeGCHECHy OH o) cH, OH i ‘CH 2 catalyst © oi ga of acid CH3CHCH,CH=CHp + H, ——>_ CHgCHCH,CHCH. CHCH CH=CH + 10 Be CHyCHoHgCHoH, 6.59 Ho CH, Hy OH. Hae OH, eae ee ee KOH oF : CHgCH—C=CHp Te cig 0 — GH Guyot CHsO=C—CHy Br 2,3-Dimethyl-I-butene 2-Bromo-2,3- _2,3-Dimethyl-2-butene dimethylbutane ‘The product, 2,3-dimethyl-2-butene, is formed by elimination of HBr from 2-bromo-2,3- dimethylbutane. The product has the more substituted double bond.Alkenes: Reactions and Synthesis 133 Solutions to Problems mW Gs Hs Hy cHycHygory X24» cucH=dctiy + clgCHe =H, Ore OHa EET a OHSCH=CCHy + CHCHC= CHa Br Dehydrobromination may occur in either of two directions to yield a mixture of products. 12 CHC SHH, Crete Pha eae + req + H ‘Hy H CH2CHg (Z)-3-Methyl-3-hexene _(E)-3-Methyl-3-hexene oH ee CHsCHeCHp CH CHsCHaCHp HH HCH HeS04, : LO CHgCoHcly EE CH (Z)-3-Methyl-2-hexene (£)-3-Methyl-2-hexene CHsCHeCtle he CHsCHp 4H 2-Ethyl-1-pentene Five alkene products, including E, Z isomers, might be obtained by dehydration of 3- rmethyl-3-hexanol. 73 HC’ ‘CHs Hee Cc ne = 1,2-Dimethyleyclohexene f trans-1,2-Dichloro-1,2- dimethyleyclohexene ‘The chlorines are trans to one another in the product, as are the methyl groups.134 Chapter 7 7.4 HgC ‘CHy 1,2-Dimethyleyclohexene CHy Addition of hydrogen halides involves formation of an open carbocation, not a cyclic halonium ion intermediate. The carbocation, which is sp’-hybridized and planar, can be attacked by chloride from either top or bottom, yielding products in which the two methyl groups can be either cis or trans to each other. are NBS (Pr — H20/DMSO_ HO. H -Br and -OH are trans in the product. 7.6 Reaction of the alkene with Br2 (formed from NBS) produces a cyclic bromonium ion, ‘When this bromonium ion is opened by water, a partial positive charge develops at the carbon whose bond to bromine is being cleaved. cae Be 1% oe > vs Hom eco [ge iG Noo eN ‘ Hg less favorable Since a secondary carbon can stabilize this charge better than a primary carbon, opening of the bromonium ion occurs at the secondary carbon to yield the Markovnikov product, 7.7 Keep in mind that oxymercuration is equivalent to Markovnikov addition of HzO to an alkene. @ of I CHgCH,CHCH=CH, 1-HO(OAC2 He GH cH CHyCHCH, 2. NaBH b) © or Gis 1. Hg(OAc)p, H, HeCHpCH= A Ha(OAe2 HO Gy cH CH CCH, CHeCHpCH=CCHy > NaBH, CHeCHeGCHs OH18 19 7.10 Alkenes: Reactions and Synthesis 135 Think backwards to select the possible alkene starting materials for the alcohols pictured. @) CHg¢= CHCHECHaCH oH 1 Hs oy A Ha(OAC 2 He, CHEECH CHACHSCH 2. NaBH I GOHaCHECHsCH ‘CHg CHy (b) 1H 1. Ha(OAc)g, He0 (CHg 2. NaBH ‘Oxymercuration occurs with Markoynikoy orientation. Strategy: Hydroboration/oxidation occurs with non-Markovnikov regiochemistry to give products in which -OH is bonded to the less highly substituted carbon. Solutio @ Hy Gite crgc=onorcH, LEMOTHE gy, .O—CHCHCH, OS ONCHACHS 3 HzO, OH ee : HOH less substituted (b) ess substituted OH \ 2 ™CHs 1. BHg, THE ‘CHy ‘2. Hp02, OH Strategy: As described in Worked Example 7.2, the strategy in this sort of problem begins with a look backward. In more complicated syntheses this approach is essential, but even in problems in which the functional group(s) in the starting material and the reagents are known, this approach is effective. All the products in this problem result from hydroboration/oxidation of a double bond, ‘The -OH group is bonded to the less substituted carbon of the double bond in the starting material, Solution: © oy Hs I 1. BHg, THE (CHgCHCH=CH, ~ HCH CHOH 2. Hg09, OH eeeree136 WA Chapter 7 () Hy 's cH, s=cHc1 en cH, Oe oa 2. Hp02, OH : ba 2 This product can also result from oxymercuration of the starting material in (a). ce ee CHjOH 2 2. Hg09, OH 2 The drawings below show the transition states resulting from addition of BH; to the double bond of the cycloalkene. Addition can occur on either side of the double bond. Reaction of the two neutral alkylborane adducts with hydrogen peroxide gives two alcohol isomers. In one isomer, the two methyl groups have a cis relationship, and in the other isomer they have a trans relationship. BRO 4 OWN y pre OH HT CH3 rm H CHS72 714 Alkenes: Reactions and Synthesis 137 Strategy: Reaction of a double bond with chloroform under basic conditions gives a product with a cyclopropane ring in which one of the carbons has two chlorine atoms bonded to it. Reaction of a double bond with CHI yields a product with a cyclopropane ring that has a-CHy~ group. Solution: @) IH cc CHy + CHCl SOL td CHy © ory CHs Cp I Zn(Cu) I CHgCHCH)CH=CHCH + CHylp ———» CHgCHCH,CH—CHCH, Depending on the stereochemistry of the double bond of the alkene in (b), two different isomers can be formed. Catalytic hydrogenation produces alkanes from alkenes. @ fs gis He CHyC=CHCHSCHs Gao Tepgnghr CHsCHCHSCH,CH 2-Methyl-2-pentene 2-Methylpentane (b) Of, amie OC, Pal 1 ‘CHy in ethanol CH 3,3-Dimethylcyclopentene _1,1-Dimethyleyelopentane Epoxidation using m-chloroperoxybenzoic acid (RCO3H) is a syn addition of oxygen to a double bond. The original bond stereochemistry is retained. Hagcget BOs ne Her” SoH, HoH 2 . Hg CHg cis-2-Butene cis-2,3-Epoxybutane In the epoxide product, as in the alkene starting material, the methyl groups are cis,138 71S Chapter 7 Strategy: Reaction of an alkene with a catalytic amount of OsOy, in the presence of N- ‘morpholine N-oxide (NMO), yields a diol product. To pick a starting material for these products, choose an alkene that has a double bond between the diol carbons. Solution: @ CH Catalytic (0504 1-Methyleyclohexene (b) CHgCH)CH=C(CHg)o 2-Methyl-2-pentene (CHy=CHCH=CH 1,3-Butadiene Hy omy i ° ; f° | sMo. a aa oto Tox H H gH oO 0804 cots CCH, ChgCHaGH—EcH CHy Ho OH 0304 0804, HCHCH, = HOCH,CHCHCH,OH Strategy: Both sets of reactants cleave double bonds. Aqueous KMnO, produces a carboxylic acid from a double bond carbon that is monosubstituted and a ketone from a double bond carbon that is disubstituted. Ozone produces an aldehyde from a double bond carbon that is monosubstituted and a ketone from a double bond carbon that is disubstituted. If the double bond is part of a ring, both carbonyl groups occur in the same product molecule, (a)Alkenes: Reactions and Synthesis 139 7.17 Strategy: Orient the fragments so that the oxygens point toward each other. Remove the oxygens, and draw a double bond between the remaining carbons. Solution: (a) 1.03 (CH)eo=CHe Zo pGOr™ (CHsC=O + (b) + O=CHCH,CHy 7.18 Strategy: Find the smallest repeating unit in each polymer. This is the monomer unit. Monomer Polymer ®) 90H 90H 90H) HyC=CHOCH, (Cp CH —CHy —CH—CHp CH e EEEER? CHO=CHCI eee 7.19 One radical abstracts a hydrogen atom from a second radical, and the remaining two electrons create a double bond. Visualizing Chemistry 7.20 ® CH cH, RCO3H fe [ee — CHg0— CHCH,CHCH,CHy ° CHg CHg H3C OH GHg i I KNn0, an al (CH3C=CHCHACHCH,CH, = Se JO=0 + O=CCHACHCH,CHs HO" 2,5-Dimethyl-2-heptene . HyC CH, 1.05 rs 2. Zn, CHgCOH + O=CHCH,CHCHCH3.140 Chapter 7 ° Hye ROOgH 3 HgC ey c Hye c= te ‘Ci KMnOg 7 2 HO" 20 HC Hye ¢ 3,3-Dimethyleyclopentene Hoon Hg C=0 1.03 . 2. Zn, CH3CO2H ZO Hy § 4 7.21 a) . Gs CH OH CHgCHOCH3CH, 1 H9(Ace He cu — SoH,cH fell 2. NaBHg cay 's CH HCH 2-Ethyl-3-methyl-1-butene or Hy GH OH crygHO=CHoH 4. Hg(OACa HO oie Connon er 3 BO NaBH, 1s FCHeCHa Clty H CHy 3,4-Dimethyl-2-pentene Only oxymercuration/reduction can be used to produce an alcohol that has OH bonded to the more substituted carbon. A third alkene, 2,3-dimethyl-2-pentene, gives a mixture of tertiary alcohols when treated with either BHs or Hg(OAc). (o) 0 CH, 7 (CH, CHy HO CH, 1. BHg, THE 2. Hp09, OH or 2 H202, 1. Hg(OAc)g, HyO 2. NaBH . 4,4-Dimethyleyclopentene Both hydroboration/oxidation and oxymercuration yield the same alcohol product from the symmetrical alkene starting material.7.23 Alkenes: Reactions and Synthesis 141 HC. CHg 1.BHg, THE "2rHg03, OH ut H not formed ‘Two possible alcohols might be formed by hydroboration/oxidation of the alkene shown. One product results from addition of BH; to the top face of the double bond (not formed), and the other product results from addition to the bottom face of the double bond (formed). ‘Addition from the top face does not occur because a methyl group on the bridge of the bicyclic ring system blocks approach of the borane. 1,0. 1. ROO3H cae 2. oo 4-Methylcyclohexene RCO3H = meta-Chloroperoxybenzoic acid Since the hydroxyl groups in the diol product have a trans relationship, the product can only be formed by epoxide hydrolysis. (Treatment of the alkene with OsOy yields a product in which the two —OH groups have a cis relationship.)142 Chapter 7 Additional Problems 7.24 @ H é AY Sce XS o) 4 C. Z Scrip al © H é 7 ScHe ia @ ‘ C. (7S ctty S (} rf é Z Sony Sy o 4 é a Son, x RCOsH = meta-Chloroperoxybenzoic acid HalPd Bry 0504 NMO | Cy 10 CHel, Zn/Cu ae RCO3H —» CHyCHyAlkenes: Reactions and Synthesis 143, 7.25 (@ Fs CHgCHpCHyCHzC=CHp —=2-Methy-I-hexene CHsCHyCHCH=C(CH3)p2-Methyl-2-hexene Hy I (CHgCHpCH=CHCH(CHa)p CHgCH=CHCH,CH(CHa)y HyC=CHCH,CHeCH(CHg)2 (b) 3,3-Dimethyleyclohexene Za 4,4-Dimethyleyclohexene NN Brg > _ CHyCH—-CHCH,CH(CHg) ©) (CHgCH=CHCH,CH(CHg)2 5-Methyl-2-hexene 2-Methyl-3-hexene 5-Methyl-2-hexene Ho/Pd 22S CHyCHyCH{CH,CHCHg, 2-Methythexane 5-Methyl-1-hexene CHy (cy . lg Ho/Pd CHg Che | eee {—cH. : 1,1-Dimethyleyelohexane Br Br lel 2,3-Dibromo-5-methylhexane @) MoO CHCHOHSCHSCH,CH, HCl CHyCHGHCH,CHaCHgCHy CH CHy 3-Methyl-I-heptene 2.Chtoro-3-methylheptane ©) OH 1. Ho(OAC)p, H i CHeCH,CHpCH=CH, 2 HaOACa He co cH CHCH, 2. NaBH, 1-Pentene 2-Pentanol © (=o ote z0ou x144 Chapter 7 7.26 (@) CH. CH, 3 oct tT ° H es, Heo (b) KMnOg ‘COZH HgO* COpH © H CH, ACH 1. BHg, THF 2. HzO, OH NH OH Remember that -H and ~OH add syn across the double bond. @ OH CH on 1. Hg(OAc)p, HO i 2. NaBH 7.27 (@) O 030, ot NMO a (b) OH i 1. Hg(OAc)p, HO 2. NaBHg Hydroboration/oxidation is another route to this product.Alkenes: Reactions and Synthesis 145 Gil CHCig, KOH Ob < Soi © H @ CHg on oH _He804. HO heat . ©) Hy ° HC 9 cHycH=cHoHcH, 2-2 CHyeH + CHACHCH 1HgCH=CH¢ sr + co 's BZn, Ago 3 co 2 CHy =o | cH,CHCH,OH eee 2. Ha02, OH eae 7.28 H HBr Br fet H — secondary carbocation a less stable H H HBr Pe Br ee A— CH, ‘CHg SS chs ‘3 tertiary carbocation Br more stable Remember from Section 6.10 that a reaction that forms a more stable carbocation intermediate is faster than a comparable reaction that forms a less stable carbocation intermediate. Thus, the reaction of 1-methyleyclohexene with HBr is faster than the reaction of cyclohexene with HBr.146 7.29 7.30 7.31 732 Chapter 7 Recall the mechanism of hydroboration and note that the hydrogen added to the double bond comes from borane. The product of hydroboration with BD; has deuterium bonded to the more substituted carbon; —-D and —OH are cis to one another. CHs H CH Because ozonolysis gives only one product, we can assume that the alkene is symmetrical. He, fH 4 og HQ, pls = tos =o + ry 2. Zn, HgO ae eae HgC CHg Hy CH 2,3-Dimethyl-2-butene Remember that alkenes can give ketones, carboxylic acids, and CO on oxidative cleavage with KMnOg in acidic solution. (a) ki CHgCH,CH=CHp unos, CHgCH2CO9H + CO 30" (b) KMnOg CHyCHaCHyCH=C(CHg)2 CHgCH2CHaCOnH + (CHy)C=0 H30" () (rece fn (re es @ . a (prone Mie ensonbonerrorocon : (a) Compound A has three degrees of unsaturation. Because compound A contains only one double bond, the other two degrees of unsaturation must be rings. (b). (©) 0s e teiede “221, gO” eee containing two fused | and a shared double bond also or symmetrical diketone products.7.33 7.34 Alkenes: Reactions and Synthesis 147 Don't get discouraged by the amount of information in this problem, Read slowly and interpret the information phrase by phrase. We know the following: (1) Hydrocarbon A (CgHl;2) has one double bond or ring, (2) Because A reacts with one equivalent of Ha, it has one double bond and no ring. (3) Compound A forms a diol (B) when reacted with OsO,. (4) When alkenes are oxidized with KMnO, they give either carboxylic acids or ketones, depending on the substitution pattern of the double bond. (a) A ketone is produced from what was originally a disubstituted carbon in the double bond. (b) A carboxylic acid is produced from what was originally a monosubstituted carbon in the double bond. (5) One fragment from KMnO, ox (a) This fragment was CH3CH)CI A ion is a carboxylic acid, CHsCHxCO2H. (a monosubstituted double bond) in compound (b) It contains three of the six carbons of compound A. (©) (a) The other fragment contains three carbons. (b) It forms ketone C on oxidation, (©) The only three carbon ketone is acetone, O=C(CHs)2. (d) This fragment was =C(CH)2 in compound A. (7)If we join the fragment in 5(a) with the one in 6(d), we get: (CH3CHCH=C(CH3)2 CoHi2 A ‘The complete scheme: CHa CHy CHgcHgcH Cory -OHPITINE O cHon rene ee'S 2. NaHSOg, HzO igCHo Gels - B oH On | Ho/Pd KMInOg Hs Hyo* (CHgCH,CHjCHCH, CHgCH,COZH + O=C(CHs)p c The oxidative cleavage reaction of alkenes with O3, followed by Zn in acid, produces aldehyde and ketone functional groups at sites where double bonds used to be, On ozonolysis, these two dienes yield only aldehydes because all double bonds are monosubstituted. 1.03 103s __ 2. Zn, HO Because the other diene is symmetrical, only one dialdehyde, OCHCH2CHO, is produced.148. 7.35 1.36 7.37 Chapter 7 Try to solve this problem phrase by phrase. (1)CioHisO has two double bonds and/or rings. (2)CjoHisO must be an alcohol because it undergoes reaction with HS, to yield an alkene. (3) When CyoHia0 is treated with dilute HoSOg, a mixture of alkenes of the formula CigHig is produced. (4)Since the major alkene product B yields only cyclopentanone, CsHgO, on ozonolysis, Band A contain two rings. A therefore has no double bonds. dilute | i HS, : 1.03 . 2. an, go? B CHp H-.gag--H __CHale Hep G--H ene area pee Higc Hy ~Zn-Cu-HgC CH cis-2-Butene cis-1,2-Dimethylcyclopropane ob, eH _CHele | eCwg/ Soar onc oor oN Hy Zn-Cu H CHy trans-2-Butene trans-1,2-Dimethyleyclopropane ‘The Simmons-Smith reaction occurs with syn stereochemistry. Only cis-1,2- dimethylcyclopropane is produced from cis-2-butene, and only trans-1,2- dimethylcyclopropane is produced from trans-2-butene. (b) _[ #of valence) _[ #of bonding electrons ] _ [# nonbonding (FC) =[ electrons 1-[ 2 | —L electrons ] Formal Charge 1 oNt N2 NB A 0 0 #4 4 Boe Formal charge calculations show a partial negative charge on Ni.Alkenes: Reactions and Synthesis 149, (©) Addition of IN3 to the alkene yields a product in which —I is bonded to the primary carbon and -N3 is bonded to the secondary carbon. If addition occurs with Markovnikov orientation, I* must be the electrophile, and the reaction must proceed through an iodonium ion intermediate. Opening of the iodonium ion gives Markovnikov product for the reasons discussed in Problem 7.6. The bond polarity of iodine azide is: OK " CHgCHjCH=CH, ——> mee CH, | ——> cH,cHCHCHI 7.38 — Bromo- peroxidase art Brt Gt y-Bisabolene bromonium ion Base Br a oe 10-Bromo-c-chamigrene cyclic carbocation 1.39 i 2 Hala 1 I Danger 2 Hook,cH;cH Cyelooctane 1,5-Cyclooctadiene150 7.40 AL 1.42 Chapter 7 Focus on the stereochemistry of the three-membered ring. Simmons-Smith reaction of 1 L-diiodoethane with the double bond occurs with syn stereochemistry and can produce two isomers. In one of these isomers (A), the methyi group is on the same side of the three-membered ring as the cyclohexane ring carbons. In B, the methyl group is on the side of the three-membered ring opposite to the cyclohexane ring carbons. (a) Addition of HT occurs with Markovnikov regiochemistry — iodine adds to the more substituted carbon. (b) Hydroxylation of double bonds produces cis, not trans, diols. (c) Ozone reacts with both double bonds of 1,4-cyclohexadiene. (@)Because hydroboration is a syn addition, the -H and the -OH added to the double bond must be cis to each other. {a) This alcohol can't be synthesized selectively by hydroboration/oxidation. Consider the {wo possible starting materials. . CHyCH,CHCH=CH, LEE THE cy cH cHycHsCH,O LOHCHOH= OM SS a CHyOHZCH,CHZOH,OH 1-Pentene yields only the primary alcohol. 2. OH OH 1. BHg, THF I 1 CHyCHyCH=CHCHy ———2———» CHgCHpCHCH,CHy + CHgCHsCHyCHCHy 2. HO, OH 2-Pentene yields a mixture of alcohols. o OH 4..BHg, THE i (CHg)gC=C(CHg)o (CHg)CHC(CH3)p — 2. HzO, OH 2,3-Dimethyl-2-butene yields the desired alcohol exclusively. (€) This alcohol can't be formed cleanly by a hydroboration reaction. The -H and -OH added to a double bond must be cis to each other. (d) The product shown is not a hydroboration product; hydroboration yields an alcohol in which “OH is bonded to the less substituted carbon.Alkenes: Reactions and Synthesis 151 7.43 HBr HO! i HO : . i Br Hat 0804 Hg NMO c Ho: Cholesterol HO ; OH | Crise Zn/Cu Ha 1. BHg, THE 2. Hz02, OH Hg 1.44 CHy(CHa) SH CHICH)/CHy FETs CHa(CtHa)12002H + CH(CHa)/COH 7.45 CgHg has five double bonds and/or rings. One of these double bonds reacts with H/Pd. Stronger conditions cause the uptake of four equivalents of H2. CgHe thus contains four double bonds, three of which are in an aromatic ring, and one C=C double bond. A good guess for CgHg at this point is: scm152 Chapter 7 Reaction of a double bond with KMnO, yields cleavage products of the highest possible degree of oxidation. In this case, the products are COz + CgHsCOzH. a ce CH=CH, CHeCH, (OH _KMnO4 He/Pd : + CO, 30 A HolRh ; CH2CHg c 7.46 Hee 9 CHg CHy Hs Hyo=0—6 Lorg—b—cH,—$—oH =¢—cocH; ——> —C—CHy—C—CHy— to 3 eG CH CCH OF, COZCH3 COZCHg CO,CH3 7.47 many HpO=CH = ——> Fotig ocr cco N-Vinylpyrrolidone Poly(vinyl pyrrolidone) 7.48 H—A HA HgC. a u HC. hd 2, 9 ext == SE OMY CHy | SE CHyOCICtHaa HyC Hg CHg protonation of nucleophilic attack loss of double bond ‘of methanol on proton carbocation The above mechanism is the same as the mechanism shown in Section 7.4 with one exception: In this problem, methanol, rather than water, is the nucleophile, and an ether, rather than an alcohol, is the observed product.Alkenes: Reactions and Synthesis 183, 7.49 4 _-OH _-0H ee — ae SASS } Bromo- Br i peroxidase i Laurediol bromonium ion 4 _.0H p _-0H a pos Br Br ON sease I I Prelaureatin cation 7.50 (a) Bromine dissolved in CH2Cl2 has a reddish-brown color, When an alkene such as cyclopentene is added to the bromine solution, the double bond reacts with bromine, and the color disappears. This test distinguishes cyclopentene from cyclopentane, which does not react with Bra. Alternatively, each compound can be treated with Hy/Pd. The alkene takes up Hp, and the alkane is unreactive, (b) An aromatic compound such as benzene is unreactive to the Bri/CHClz reagent and can be distinguished from 2-hexene, which decolorizes Br2/CH,Cl. Also, an aromatic compound doesn't take up Hz under reaction conditions used for hydrogenation of alkenes. 7.51 RP 4 | 2% Ce | oe oe a tc a + C0, In step 1, carbon dioxide is lost from the trichloroacetate anion. In step 2, elimination of chloride anion produces dichlorocarbene. Step 2 is the same for both the above reaction and the base-induced elimination of HC! from chloroform, and both reactions proceed through the trichloromethanide anion intermediate.184 Chapter 7 7.82. (a) a-Terpinene, C1gHj6, has three degrees of unsaturation. (b) Hydrogenation removes only two degrees of saturation, producing a hydrocarbon ‘CigHo, that has one ring. o-Terpinene thus has two double bonds and one ring, | HL 20 2 Hairs Ong ° Btn. Hor CO. Hee. pe a-Terpinene Glyoxal _6-Methyl-2,5- heptanedione 7.53. Make models of the cis and trans diols. Notice that it is much easier to form a five- ‘membered cyclic periodate from the cis diol A than from the trans diol B, The cis periodate intermediate is of lower energy than the trans periodate intermediate because of the lack of strain inthe cis periodate ring. Becayse any factor that lowers the energy of a transition slate or intermediate also lowers AG* and increases the rate of reaction, diol cleavage should proceed more slowly for trans diols than for cis diols. CHg Hg & Hy pie Br trans-1-Bromo-3- _cis-1-Bromo-3- methylcyclohexane methylcyclohexane S/o & trans-1-Bromo-2- _ cis-1-Bromo-2- methyleyclohexane methyleyclohexane 1.84 In the reaction of 3-methylcyclohexene with HBr, two intermediate carbocations of approximately equal stability are formed. Both react with bromide ion from top and bottom faces to give four different products.Alkenes: Reactions and Synthesis 155 a par Re a ~|C>-€>|-5 > Ser y a ‘The most stable cation intermediate from protonation of 3-bromocyclohexene is a cyclic bromonium ion, which is attacked by Br from the opposite side to yield anti product. Core igOAc Hooke —ohe jpore ma ICH3 7.55 ‘OAc | ot (om > NaH oe Cyclohexy! + HOAc methyl ether156 Chapter 7 7.56 60,CH, i G05CHy l ~ o| @ H 4 1 ore or « “one 5 Jone Jo G02CHy 00g 4) "q "q Aco + HOAc Aco ‘The reaction mechanism involves the following steps: (1) Addition of Hg(OAc)z to one ofthe double bonds to form a cyclic mercurinium ion; (Q) Reaction of a second double bond with the mescurinium ion to form a six-membered ring and a different carbocation; G)A second cyclization forms the other ring and yields another carbocation; (@) Removal of -H gives a double bond. 7.57 3r—Br + Br Ho" C7} ai Rote iS ee | rag te af oe HjC—CH,OH HC—CHy 7) HC —CH formation of eyclic nucleophilic atack Joss of Ht bromoniumion of -OHon bromo- nium ion The above mechanism is the same as that for halohydrin formation, shown in Section 7.3. In this case, the nucleophile is the hydroxyl group of 4-penten-1-ol.Alkenes: Reactions and Synthesis 157 7.58 Hydroboration of 2-methyl-2-pentene at 160°C is reversible. The initial organoborane intermediate can eliminate BHs in either of two ways, yielding either 2-methyl-2-pentene or 4-methyl-2-pentene, which in turn can undergo reversible hydroboration to yield either 4-methyl-2-pentene or 4-methyl-1-pentene. The effect of these reversible reactions is to migrate the double bond along the carbon chain. A final hydroboration then yields the most stable (primary) organoborane, which is oxidized to form 4-methyl-1-pentanol. “BH 4-Methyl-2-pentene NaOH, HO ay 4-Methyl-1-pentene 4-Methyl-1-pentanol 7.39 @1 Te a) 1 equiv Br Ss Hess CHeCHCH,CH, Br pn oo CH . (b) 2 equiv Hy (eh CHgCHCH,CH,C: ee = CHyCHCHCH,CH)CHy Pd/C CHy Br (© Lequiv HBr Tt 1 > CHyCHCH,CH,C=CH, Addition of one equivalent of FIX or X2 to a triple bond occurs with Markovnikov regiochemistry to yield a product in which the two added atoms usually have a trans- relationship across the double bond.158 Chapter 7 7.60 050 Se” ps Ge. HQ OH Le NMO. eG WP OcH HP OH Hg CHy HjC CH oO S47 Ok, Qe 0 HesgagerOHs 2804 Sey NMO = He” TH H°3"" 07H Ha ACH He oH Hg oH trans-2-Butene Formation of the cyclic osmate, which occurs with syn stereochemistry, retains the cis- trans stereochemistry of the double bond because osmate formation is a single-step reaction. Oxidation of the osmate does not affect the stereochemistry of the carbon-oxygen bond, and the diol produced from cis-2-butene is a stereoisomer of the diol produced from trans 2-butene. We'll study this type of isomerism in Chapter 9.