es on ech side of the equation are added together. 1 He caavaton higher than the toa from the Kl side tive). the disociation enthalpy of al the bonds in the mol the bond dissociation enthas total from the right side ofthe equat ofthe equation, then the reaton is exothermic (AH forthe reaction ne (a) CH=CH, + 2Hp + Np —> HyN-CH,—CHo—NHp The bond dissociation enthalpies from the left side of the equation: "727 + (4 x 464) + (2x 435) + 950 = 4403 kJimol (C=C) (4=C-H) (HLH) (NaN) The bond dissociation enthalpies from the right side of the equation: 1338 kJ/mol (4x 391) + (2.x 355) + 376 + (4 x 422) NH) (2GN) (CC) 4-CH) is reaction is endothermic because 4403 KJimol is larger than 4838 kJ/mol, (b) CHo=CH, +CHy —> CH3-CHo-CH, The bond dissociation enthalpies from the left side of the equati 727 + (4x 464) + (4 422) = 4271 kJ/m (C=C) (420-1) 4-C-H) The bond dissociation enthal GCC)” @-C-H) (©) CHy=CHp +(CHs);SiH —» H-CH,-CH,-Si(CH3)3 The bond dissociation enthalpies frm the et side ofthe equation 7214 (dx 464) + (9 422) + (34301) + 818.= 7608 ky/aol y 4 =C-) "2c BES SEH The bond dissoci (9 CHo=CH, + CHI; —e H-CH,-CH,-C()), The bond dissociation enthalpies fro 727+ (4x 464) + (422) + (3 x (C=C) (4=C-H) 1-CH) BCD on enthalpies from the ri x 422) + (3 238) GCM BCD side ofthe equation 16 kJ/mol - m enthalpies from the left side of the Deo. equation: eht side of the equato 154 kJ/mol iReactions of Alkenes 121 (f) G 4 CH=CH, —> O ~ ‘The bond dissociation enthalpies from the left side of the equati (3.x 727) + 376 + (10 x 464) = 7197 kJ/mol C=C) (C-C) (10 =C-H) “The bond dissociation enthalpies from the right side of the equation: 721 + (Sx 376) + (8 x 422) + (2x 464) = 6911 kI/mol c) GCC) (8 -C-H) "This reaction is endothermic because 7197 kJ/mol is larger than 6911 kJ/mol. ‘0 The bond dissociation enthalpies from the left side of the equation: (2.x 721) + 376 + (2 x 803) + (6 x 464) = 6220 kJ/mol (2C=C) (C-C) @C=0) | ) The bond dissociation enthalpies from the right side of the equation: 727 + (3 x 376) + (4 x 422) + (2 x 464) + (2 x 385) + 728 = 5969 kJ/mol (C=C) BEC) G-CH G@=CH) @C-0) (C=0) This reaction fs endothermic because 6220 ky/mol fs larger than 5969 kJ/mol 99 (h) HO=CH+ 0p —> HCH ‘Phe bond dissociation enthalpies from the left side of the equati 5 2576 ky/mol The bond dissociation enthalpies from the right side of the equat 316 + (2.x 728) + (2 x 464) = 2760 kJ/mol ) aC) 0) GC 7 eacion Ts exothermis because 2760 KU imal is Targer than 2576 KUO (i) 20H, + Og ——> 2CH30H “The bond dissociation enthalpies from the left side of the equation: "2(4 x 422) + 498 = 3874 ki/mol H) (O=0) ‘The bond dissociation enthalpies from the right side of the equation: 213 x 422) + 2(385) + 2(439) = 4180 ky/mol 2-H) 2(C-0) (0-H) 5s Fonction Ir exothermic because 4180 Ki/mol is larger than 3874 KW/mol. -ctrophilic Additions He eeee LS: Draw structural formulas forthe isomeric carbocation intermediates formed on 1 HCL Label each carbocation 1°,2°, oF 3°, and state which ofthe isomeric carbocations forms more readily e z (a) CHy-CHy-G=CH-CHy —CHy~CHp-CHCH—CHs + CHa “CHa CH-CH— CHa rs nent of each allkene with Tertiary Secondary (Formed more readily) co 014 Cengag Lzaring A Rigs Reed Nyt came copid or ape ops apbicy ass wei nw ein, OOCH5-CHp-CH-CH,-CHy + CHs-CHe-CHp-CH-CHs Both secondary carbocatic (Formed at equal rates) oor a Tertiary Secondary (Formed more re “O- Oe- Om Primary Tertiary (Formed more readily) (0) CH;-CH,~CH=CH-CH, © the alkenes in each set inorder of increasing rate of reaction with HI, and explain the basis for your ich case Problem 6.16 Arra ranking. Draw the structural formula of the major product formed in Hs nd CHs—C=CH-CH, 1 + I. CHs—CH=CH-CH; —> CH;—CH.—CH-CH, — o4-o t- ott 2-Butene A secondary 2-Jodobutan: carbocation (see-Butyl iodide) so racemic mixture Hs CH Hy CH-C=CH-CH, —> CH;—C—CH.—CHy > Ober CH, 2-Methy! patene A tertiary i carbocation 2-lodo-2-methylbutan (Major product deca peti buen he nly one that cn forma etry carbon, so 2-methy bute ‘the compound that reacts faster with HL. ge “0 O- O- 1-Methyleyclohexene A tertiary arbo« ithyleyelo- hexane (Major product)Reactions of Alkenes 1 Om Oa Cyclohexene A secondary Todocyclohexane ‘carbocation (Only product) can form a tertiary Only 1-n h HI. srbocation, so I-methyleyclohexene reacts fast Problem 6.17 Predict the organic product(s) ofthe reaction of 2-butene with each re (a) 130 FSO.) (Br Och £ Br 1 CHy-CH-CHeCH cH C-ti-c cry fiedi-cy OH Br cl (@) Brin 0 ou (Ch in 30 OH : OH CHs-Gt dics CHs HCH CHa ciate Br 1 (2) Hg(OAc)s, HO (hy product (g) + NaBH, CHj—CH-CH,—CH H H gle chiral center is created so the products are racet centers are created. Racemic mixtures will be the result, the exac ig material is cis or frans (not given in the problem). In parts (a), ( (a), (D,, and (g) two chi is on whether the 2-butene sta Problem 6,18 Draw a structural formula of an alkene that undergoes acid-catalyzed hydration to give each alcohol asthe major product ( more than one alkene may give each alcohol as the major product) a) 3-Hexanol (b) 1-Methyleyclobutanol He Ns CH3CHCH=CHCH>CHs o [| (cis or trans) (©) 2Methy-2-butanl (a) 2-Propanol CH CH; H2C=CCH2CH3 CHj¢—CHCHs CHsCH=CHe Problem 6,19 Reaction of2-methy-2-pentene with each reagent is regioselective. Draw a structural formula fr the prodet reach reaction, and account forthe observed regioselectivity rechanism involves formation of a carbocation [(a),(b), and (c)] or a positively ntermediate [(d),(e)] F ctrophlic addition step. These ‘of greatest positive c! e the product shown ry carbocations are more stable the 0 the reactions will give In each (o) HBr CHs a CHy—F-CHa—CHeCHs CHy~€—CHa-CHa-CHs 1 Br eee) HO in the presence of HS. 4) Bryn #0 CHs HC Br 1 CH;—C-CH,—CH)—CH OH -C-CH-Ch CH ou HO 6) Hg(OAe)s in 0 HjC HgOAc cH;—¢-CH-CH,-CHs HO ic mixtures are produced. new chiral center is created. so racet In parts (@) and (e lem.6.20 Account forthe regioselectivty and stereoselectvity observed when I-methyleyclopentene is treated with a each reagent (a) BH Attack of the borane occurs in a concerted fas the same face of the double bond, a process referred to as syn addition (make (x bond) and an electrophile with simultaneous bond formation to H). ends up on the more hin cH me oth vig 74 \ BH. Md approuch from either the top or the on products as shown. thyl group (make a new bond. 1s the transep cel mater ete gh an pty eee EMR BS oars Reactions of Alkenes 12s (©) Hg(OAc), in H,0 ater on the bridged mercurinium ion intermediate (make a new bond between a nucleophile and rwed by loss of a proton (take a proton away) results in -OH trans to -HgOAc. Note that the ¢ of the alkene, leading to a racemic mixture of the two enantiomers Attack by lectrophile) fol ‘mercurinjum fon could form on either f shown. H,0 (cH Pls "erg Ac oS sata nya Note that a chiral center is ereated so the product is actually a racemic mixture. cH (©) Crthe, + HO > oe ce Si ee addition of HCI to 1-bromopropene gives exclusively I-bromo- I-chloropropane. Problem 6.22 Account forthe fact that CH,CH=cHBr = + HC! ——® CH,CH,CHBrCl 1-Bromo-I-chloropropane 1-Bromopropene e product must be derived from the si {y more stable carbocation is the one with the despite the fact that this carbocation is pr vefatom must be able to stabilize an adjacent cationic carbon ato ily a resonance effect, involving the lone pairs of the bromine llustrates how the positive charge is partially dé The exch 's shown. Note how ‘alized onto the bromine ict or duplicated, or posted 10 a ply accesible website, eeeProblem623 Account forthe fact that treating propenoic acid (acrylic ac I HCl——» CICH,CH,COH 3-Chloropropenoie acid The exclusive product must be de significantly m the fact that this attached to the int that the destabilization withdraw carbocation adjac the izing since r the enthalpy oft 0 Br NS A chiral center is created i mixtures, oj ach case, so the products of these bromin ) with HC! gives only 3-chloropropanoic acid ef cH,cHloH 2-Chloropropenoic acid (this product is not formed) 1 carbocation. In this case, the ge on the terminal carbon atom, despite Thus, the carbonyl ent cationic carbon atom, It turns 0 that a carbonyl group is electron removing charge density from a he carbocation even further Not formed be of the destabilizing +1 HaC—CHCOH induct 9 vy HeC=CHCOH + HEI ¢ ee wc -crton Ihe sinc Faabm624 Draw strat om forthe alkene of mca fomula CM at ect with Bs —— @ Xe saul r &) 8K © arian Tala i WR "addition reactions are actually racemicReactions of Alkenes Problem 6.25 Dra the altemative chair conformations forthe product formed by the addition of bromine to 4-tert butyleyclohexene. The Gibbs free energy differences between equatorial and axial substituents on a cyclohexane ring are 21 13 (49 ealymol for tert-butyl and 2.0 2.6 KJ (0.48 - 0.62 kcal)/mol for bromine. Estimate the relative percentages of the alternative chair conformations you drew in the first part ofthis problem. Br (CH3)3C: (Cy) 3€ es br (yc Be H Note that the bromine atoms are trans with respect to each other in the product due to anti addition geometry of the bromination reaction. Recall that large substituents are sterically disfavored in axial positions. The upper product has the large tert-butyl group in the strongly favored equatorial pesition along with both bromine Prone in the somewhat disfavored axial positions. The lower product has the large tert-butyl in the strongly disfavored axial position along with both bromine atoms in the somewhat more favored equatorial positions ‘The conformational energy difference based on the axial 21 kj/mol, and we will ac an intermediate value of 23 ky/mol for the conformational energy difference for the axial vs. equatorial bromine atoms. Thus, the relative conformation energy can be estimated as being favorable for the upper Mructure by an amount equal to the value that is favorable for the feri-butyl group (21 kJ/mol) minus the Gisfavorable contributions of the two bromine atoms (2x +23 kJ/mol) for a total of 164 kJ/mol, At equilibrium the relative amounts of each form are given by the equation: AG?=-RTINK Here Kea refers tothe rato of the alternative chair conformations. Rearrat prea? ky = 9 Solving gives: Ky =e Plugging in the values for AG®,R, and 298 K gives the final answer: i: (qatar). 2750x108 ‘hus, the structure with the er-butyl group equatorial will be favored by about 750 to 1 at equilibrium at room temperature. Problem 6.26 Draw a structural formula forthe cyeloalkene with the molecular formula CH, that reacts with Clz wo give ‘each compound. cl Cin mo a " oS acl @ ©) lO (©) @ [< el ‘CH,CI Hs, Note that the chlorine addition reactions in parts (a) (b), and (c) actually a produce racemic mixtures of intiomers, only one of which is shown. 24 Cengge Lexing A Rigs seed. May mote sane, opr pe rps x ably acs wese, wtchloride gives a ans bromide, In bot (a) and rblem 27 Reaction ofthis bcylalkene wih bromine in carbon tetrachloride gives a {by thom stormy ar rast each ter. However only one ofthese proc i formed. CH; OH; Be a Z ogee or BS fi er A co) o) ‘Which sransdibromide is formed? How do you account for the fact that itis formed tothe exclusion ofthe other zrans Product (a) is formed. Make a new bond between a nucleophile (x bond) and bromine occurs via a bridged bbromonium ion intermediate and anti addition of the two bromine atoms, In a cyclohexane ring, anti addition corresponds to rans and diaxial addition. Only in formula (a) are the two added bromines trans and diaxial. {In (b) they are trans, but diequatorial, so this isomer cannot be formed. In this case, the starting material is a single enantiomer, so only one enantiomer is produced as the product. Br CHs 4 CHs Wi r Mm Br, BH HOH @ @ (b) trans-Diequatorial Erblem 628 Terpin, prepared commerally bythe acidcaalyzed hydration of limonene, used medic cexpectorant for coughs lly as an H2S0, + 2H20 ——> Cyghtag0, Terpin (@) Propose a trcural formula fortrpn anda mechanism fo its formation, Ada water to cach double bond by protonation to g ad loss of the protons o give tern andra hee carbocation, reaction of each carbocation Which double bond would actually react feat, kee ‘carbocations are produced in either ease Ite oon? AW Rohe Reserved May tbe sane cope, Sete pedo pubic cable ete, wb———————— ll Reactions of Alkenes 129 Step I: Make a new bond between a nucleophile (x bond) and an electrophile-add a proton. Step 2: Make a new bond between a nucleophile and an electrophile a ~ ser OU fee eags eattaiast 0h La : — Os Xx Attn Step 5: Make a new bond between a nucleophile and an electrophile 30H 304 _————Step 6: Take a proton away Verpin (b) How many cis, rans isomers are possible forthe structaral formula you propose? There € two cis, rans isomers, shown here as chair conformations with the (CHs);COH- side chain OH CH; oot on ‘OH owt ond CHs CHs e a CHy—CmcH + Ic) ——_» Hef Ctl ci first as Step 1: Make a new bond between a nucleophile (x bond) and an electrophile CH; pret es kim.6.0 Treating 2-methylpropee with methanol in he presence of sulfa CH. Acid gives rert-butyl methyl ether . $0, ft Me don cH, Propose a mechanism for the formation ofthis ether Proton transfer to the of met ene gives ter nol followed by tra lary carbocation nsier of a proty Reaction of this inter Meters mathe mae th thelll = Reactions of Alkenes BI Step I: Make a new bond between a nucleophile (x bond) and an electrophile-add a proton. CH at CH3 Ss 1 SH*OCH: i :0cH. CH3-C=CH2 i ET recoils yin ah aie a $ Swep2: Make a new bond between a nucleophile and an elecropile. es —> CHy-C-CH, *9 Hy Problem 631 When 2-pentene is treated with Cl; in methanol, three products are formed. Account forthe formation of ceach product, (you need not explain their relative percent ‘ G1 Ochs HCO @ i, CHyCH=CHCH,CHs —— cH udhicH.chs + CHyCHCHCH,CH, + CH;CHCHCHCH, (CH30H 50% 35% 15% In this reaction, the chlorine reacts with the alkene to produce the chloronium jon intermediate (make a new saad berwcen'a nucleophile (bond) and an electrophile) that can then react at either carbon atom (mabe a ew acfecphile and an electrophile) to pive the three different products shown. Note that chlorine is = 2,3-dichlorope only a minor product. The reactions produce two new chiral eens oeircjoes "The structures shown actually represent a pair of enantiomers, the identity of which nds on whether the starting alkene is cis or trans (not specified). = eat a/\t CHSCACHCH, (CH; ——> CHG sor congge ering A Rigs Rik Mayme semen pel rps tpl ceil web nwo rnp, eeeCH;CHCHCH,CH; —> cr.cathicrscs 3c 3C1* HY * aS HDF coigittcnc | Sav wih lenschucnscr, > CHEHCHCHCH, Problem 6,32 Treating cyclohexene with HBr inthe presence of acetic acid gives bromocyclohexane (85%) and cyclohexy sett (15%, 9 AN 9 Br 0-C-CH, Qn. Cyclohexene Bromocyclohe Cyclone (65%) (18% Propose a mechanism forthe formation of the later produc Step 1: Make a bond between « nucleophile (x bond) and an electrophile - add a proton. Reaction of proton wives a secondary carbocation intermediate, ateen ol nan new ond between a nucleophile and an electrophile Reaction ofthis ‘atom of acetic acid, followed by proton transfer gives eyclolveel kan. mediate with an oxygenReactions of Alkenes 133 Problem 6.33 Propose a mechanism for this reaction: OH Ar + Bre tO moe + HBr 1-Pentene 1-Bromo-2-pentanol (racemic mixture) Step I: Make a new bond between a nucleophile (bond) and an electrophile. Reaction of 1-pentene with bromine gives a bridged bromonium fon intermediate. + z Pi CH,ACHCH,CH,CH, —» CH—CHCH,CH,CH; + Step 2: Make a new bond between a nucleophile and an electrophile. Anti jermediate at the more substituted secondary carbon, followed by proton transfer, ttack of water of - I-bromo-2-pentanol. z 20, sir H_C—CHCH,CH,CH; —» H,C—GHCH,CH,CHs 5 +2 Step 3: Take a proton away. aes aes HoC—CHCH2CH2CHs | ——> Eg crete + HO tos ee ona A new chiral center is formed, so the product is a racemic mixture. Problem 6.34 Treating 4-penten-1-ol with bromine in water forms a eyclic bromoether 0. E ANOS "*s On Be Ce re 4-Penten-1-o1 (aracemic mixture) Account for the formation of this product rather than a bromohydrin as was formed in Problem 6.32 Step I: Make a new bond between a nucleophile (x bond) and an electrophile. Reaction of the alkene with bromine tives a bridged bromonium ion intermediate. H Bre e ‘A bridged bromonium, jon intermediate ss Rwred May not eae copie or dict, o pose 0 publicly cess webs, a whole orp eeeaction ofthis intermediate with the oxygen 2 bond between «nucleophile and an electropie. Reaction of his atermediat with he hy dau group flowed by proton transfer ives te observed ec th tetrahydrofuran, H i thc, — CY Step 3: Take a proton away ic mixture is produced. A chiral cen iso, > AWE Step 1: Make a new bond between a nucleophile (x bond) and an electrophile- add a proton _— 1-080,4 es th Ne Ps Stop 2: Make a new bond between a nucleophile and an elecrophile a Oh ZA tt — Step 3: Take a proton away, A chiral center is created, so a racen served. May mt be same,Reactions of Alkenes H Br () Bae H H NaOH o-«, \ HS) Sy Step I: Take a proton away Step 2: Make a new bond between a nucleophile (x bond) and an electrophile. The stereochemistry of the product is set by the stereochemistry of the starting material. 3 es oe Propose a mechanism forthe formation ofthis product.to form a more stable tertiary lly formed secondary carbocation can reart Siep2: 12-Shif The ‘ nbered ring as shown. cearbocation and a six-m meee Step 3: Make a new bond between a nucleophile and an electrophile. This new cation reacts with Cr: to give the product Draw a structural formula forthe alcohol formed by treating each alkene with borane in tetrahydrofuran lowed by hydrogen peroxide in aqueous sodium hydroxide, and specify stereochemistry where appropriate oe Hs () ee () Cl. ayn ana ee: 0 CEE (Racemic mixture) 2 @) ANNAN HO, SO +3 (Racemic mixture) Balas Lore “iReactions of Alkenes 137 with alka Problem 6.38 Reaction of a-pinene with borane followed by treatment of th Fickopenpetonde gives the folowing alcohol 1) BH; oH 2) H202, NaOH Cf the four possible cs, rans isomers, one is formed in over 85% yield resulting trialkylbora o-Pinene (a) Draw structural formulas forthe four possible cis, trans isomers of the bicyclic alcohol. CHs CHs CH; CH3 we $ «OH eo ny 4sOH oO 2) BI (4) (b) Which isthe structure ofthe isomer formed in 85% yield? How do you account for its formation? Make a model to help you make this prediction. CH eo &. (4] part (a) are perspective formulas for the four possible cs, trans it with alkaline hydrogen peroxide results in syn (cis) addition of ‘adds to the less substituted carbon and from the less hindered side. In to the disubstituted carbon of the double bond and fro bridge. Compound [4] is the product formed in 854% mers. Hydroboration followed by ‘and -OH. Furthermore, boron ‘droboration of a-pinene, boron adds Oxidation Problem.6.39 Write structural formulas forthe m ‘each oxidizing agent. (a) 0s0,/H,0; jor organic product(s) formed by reaction of I-methylcyclohexene with “ GH; OH Macy OH Ce H,02 =0H 4 a) ‘OH Note that even though the two OH groups are added syn with respect to each other, there are stil wo \ comers produced in the reaction. ‘The OsO, reagent can attack from ether face of the double bond. (b) 0, followed by (CH5)2S 1H: ihe: H —— oy 2. (CHs)2S sed tpl accessible west. in whole or in part.sulfide to give each with ozone followed by dimethyl Problem 6.40 Draw the structural formula ofthe alkene that reacts with pradut ost of predict ° 0 1.05 (@) Gy, <2 TUS 2. (CHs)2S came A Joe nou Pape Cio), — (9 Cathy AR) a Problem 6.41. Consider the following reaction. m3 oe 1 LOL 2. (CH3)2S Cyclohexane-1 44 {@) Draw a structural formula for the compound with the molecular formula CyH, Following is a representation of the (©) Do you predic the prt tobe the ci isomer, the rans isomer, oa mixture of cis and ons isomers? Explain | ‘The product is the cis isomer, because the alker He sereorepesitaton for the more tbl char confomation ofthe dicarbaldehy de formed in this is om one face of the starting bicycloalkane. oxidation, Uacither of the alternative chair conformations of the product, one carbaldchyde group is axial and the other is ‘equatorial. t C-H | t : i H-C H «is-Cyclohexane-1 4-dicarbald fe Re May tee cope decall on Reactions of Alkenes 139 Red Prahlem 6.42 Predict the major organic products ofthe following reactions, and show stereochemistry where appropriate. HOH H20H 2 CH,OH ichenepace Geraniol methyl-I-octanol (a racemic pair of enantiomers) Reduction of geraniol adds hydrogen atoms to each carbon-carbon double bond. (b) + He Te ‘a-Pinene Major product He CHs ly from the less hindered side of the double bond, therefore, that the Reduction of a-pinene adds hydrogen atoms preferen Ly the side opposite the one-carbon bridge bearing the two methyl groups. Predi major isomer formed is the first one shown. Problem 6.43 The heat of hydrogenation of cis-2.255-tetramethyl-3-hexene is -154 KJ (36.7 kealy'mol while that ofthe trans isomer is only -113 KI (-26.9 keal)/mol. (a) Why is the heat of hydrogenation ofthe cis isomer so much larger (more neg ative) than that ofthe trans isomer? 1 value means the cis-22,5,5-tetramethyl-3-hexene is ess stable than the ¢rans isomer. there is so much nonbonded interaction strain due to the alkyl groups smashing into This makes sense th other in the Severe non-bonded interaction strain-41 kJ/mol, Using the e The difference in the answer to proble ea iss vor of the rans isomer. Thes, at oor temperature, the rit would be 15x 107 IS Sie corm cs ests (eine H H Brace 4H, CH;CHy H 4 Ethane () Bihanot H, H R= + 10 HS. cr cron 4 4 E ol Hg(OAc),, HO 5 eee CHAGHLOH Ethanol Or sCCHGC HOH WOH 2. Hea, Rao” Cisco H ul eC + Her ———_+> CH3CH.Br H H Bromoethane Die JH...) / 1,0 Re CICH2CHOH a EClerpetenal H 2 col, yey + Bre ——* arcu cher ees 12-Dibromocth 12th H Se on | = a HochcH, HS” Hee CHOW 1.2-EthanediotReactions of Alkenes 141 2) Chlorveth Hive dite DOHC Ea tse HCI eae CHS CHSC H H Chloroethane 6.5. Show how to conve s-1,2-Dibromocyclopentane Br oer Cee eee , Br cyclopentene into these compounds, “Br trans-1.2-Dibromocyclopentane Note that the product of the reaction is actually a pair of enanti s-1 2-Cyclopentanediol OH 080)" Hors ‘OH cis-12-Cyclopentanediol Oa Cyclopentanot OH OH 1. Hg(OAc)z, H20 2. NaBH, Cyclopentanol 1, BHs |) Wrieoz, Naon O io Todocyclopentane OH Cyclopentanol ) Cyclopentane Cyclopentane2. (CHs)2S CJ o_ levels nedial Ri that Produce Chiral Compo 2 trated tereoisomers formed when (R)-3-methyl-I-pentene is - Tapes, Aso nc sang els coiamely ps sc pte sce. Wil each proc bs opal ()3-Methy-t-pentene Hg(OAe)s, #30 followed by NaBH The alcohol produced in this QS3R)-Rmethyl-2-p solution will be optica Or HW. aH & cer “Fn, & cHy 1-Hg(0Ac)e, HO p ® CH; Hye .sOH CHCH “FS, ®) CH; QRIR)-3Methyl-2-pentanol b) Hy/Pt The alkane produced is methylpen any new chi the product is not ehir centers, and the only product, 3- {he production solution will ot be optically entane (achiral) eS not have any new ¥ alcohol produced do B ome enantiomer in the ® ——_, HoH 2. H:0,, NaOH Se a (R)-3-Methyl-1-pent——————— Reactions of Alkenes 143 (@) Br: in CCl, (2R3R)-1,2-dibromo-3-methylpentane and (2S,3R)-12-dibromo-3-methylpentane. Because these are diastereomers, the product solution will be optically a eins: nee oe HieC gH CH3CHS coy, © cH,Br (28 38-12 Dibromo-d-methylpentane ccs eee @% HoeC 9B cHCHE “Sy, CHBr (25,3R)-1,2-Dibromo-3-methylpentane Problem647 Describe the stereochemistry of the bromohydrin formed in each reaction (cach reaction is stereospecific) (@) cis-3-Hexene + Bry/H;0 CHsCH,. _,CHCH3 Some’ Br / HO H 4 ae pat CH3CH, CHSCH, ‘ee aa is th On Sof Be pc—CluCHZCH fs the same as CC “CHACHs On Br ately GRAR)-4-Bromo-3-hexanol HO. pCHoCHs aba Br, CHeCH3 [gCHaiC—C=aH Kethesameat!’ CH,CH2»-C—C—aH Pats cd fo Br Ph ‘OH Remember that the anti addition geometry is that the Br and OH groups add to opposite ices of the double bd Thee ars onto prods ease of simmer, Ne OR AR)-Foromo-Sexa an S)-4-bromo- hexanol (b) trans-3-Henene + Bry CH3CHo, 4 So=cl Bry / H20 H DCH:CHeraamerereor HCH, Se ea Ox #O ® Hee Cot isthesameas _ CH3CHpt™C—C=CH CH Ho” YCH,CHs HOH {GR AS)-4-Bromo-3-hexanol ® CH3CH> HoH ‘ 4S z isthe same as cca poe So CaCHCHy 7 naa ®@ Hec—co foe Br (35 4R)-4-Bromo-3-hexanol Remember that the anti addition geometry means that the Br and OH groups add to opposite faces of the double Remember that the iy two products because of symmetry, the (3R 4S)-4-bromo-3-hexanol and (38 4R)-4-bromo- aoa eae Nate that cis and trans-3-hexene give different stereoisomer products, explaining why the aanexdnation reaction is referred to as being stereospecific as well as just stercosel 204 Cones Lenin A Rigs eer May ae enn xpi pie opel os aisle wean wk win pu. —| | ye structural formula ofthe product i ablem 6.48 In each of these reactions, te organic starting material is achiral. Th five, Foreach econ deemintie flowing (1) How many stereoisomers ar possible forthe product? (2) Which ofthe possible stereoisomers is‘are formed inthe reaction sh (G) Whether the preduct is optically active or optically inactive? Hy 1: Hg(OAC, HO be batlOAea HOS @ la o:NSBH, ‘The product has no chiral centers so no stereoisomerism is possible. The product mixture will therefore be ‘optically inactive. Br CCl, Ie Nee7 + Gr, oe Br omers, a meso compound relationship of the added and because they will be lly inactive even though each ‘The product molecule has two new chiral centers for a total of three possible stere (cis addition) and a pa jomers (trans addition). However, due to the bromine atoms, only the RR and Ne / = 4 Be, oO, Br The product molecule has wo new chiral centers for atta of 4 total of fou pos anti eationship ofthe added bromine atom te ha ey enantiomery and bec: ai a Bevopcly inact le sterevisomers. However, due tothe s canbe formed. These are se they wil be produced in equal amounts (aoe oduct Solution wil en though each enantiomer Bf isl einai eae) Owrenore, Oey @ JOR + Hol ——» or ‘cl The product molecule has wo new chiral centers fore on ant elatonip of he added crn and OH fo enantiomers and beause they will be Produced in equal ne Ocal inactive eventhough each eaanner ty fen oan wn de tothe the product solution will be 2 ne ABR et ts go,Reactions of Alkenes 145 OH 80H ‘ ae acl cl OH 1.080, (f) ao ieee 2. ROOH OH Because of symmetry in the molecule, the product has no chiral centers. However, there is till the possibility of cis, rans isomers, s0 two products are possible. Because of the mechanism of the OsOg reaction, only the isomer will be formed. The product is achiral so there is no optical activity QH IH is the same as 1. BHs oH @ es 2 2. Hz02, NaOH centers for a total of four possible stereoisomers. However, due to the ethyl groups must be trans leading amounts itself would ‘The product molecule has two new syn addition geometry observed with the reaction of borane, the -OH an to only the two products shown. These are enantiomers and since they will be produced in equ (racemic mixture), the product solution will be optically inactive even though each enantiomer display optical ac on i (s0H “Hy CH Looking Ahead paplené49 ‘The 2-propenyl cation appears to bea primary carbocation, and yeti is considerably more stable than carbocation such as the I-propyl cation H,C—=CH—CH;* HyC—CH,—CH* 2-Propenyl cation 1-Propyl cation How would you account forthe differences inthe stability ofthe two carbocations? ‘The 2-propenyl cation, also called the allyl cation, is stabilized by resonance with the adjacent «bond. HAC: ZcHScHt =<—» H,C—CH=CH2 The resonance distributes the positive charge onto both terminal carbon atoms. The greater the degree of charge we, Thution the more stable the ion, so the 2-propenyl cation is considerably more stable than the I-propy! Cation in which the positive charge & localized on one primary carbon atom. i Rerved. May nt be samed, copied or duplicated, o posted 10 a pubily aces OO