600 Chapter 20 Solutions to Problems 1. a.reduction ¢. oxidation e. reduction b, neither 4d. oxidation f.neither 2, i a, CHjCH,CH,CH,CH,OH @ CH;CH b. CH,CH,CH,CH)NH f. CH\CH,OH ¢. CHjCH,CH), e d, no reaction h C)-sner, OH 3. A terminal alkyne cannot be reduced by Na, because Na donates an electron to the terminal sp carbon, causing a hydrogen atom to be removed. 2 CH;C=CH + 2Na ——> 2H + 2Na* + Hy OH I a (\-cxs, ¢. CHjCHjCHCH;CH, ¢. CHyCHjCHjNHCH,CH; b. pronon d. (ono f. CH,;CH,CH,CH,OH + CH,CH,OH 5. Carbon-nitrogen double and triple bonds can be reduced by LiAIHg because the bonds are polar. The hydride ion will be attracted to the partially positively charged carbon. oe 8.a. solved in the text. ‘e. as 1 a. 1. CHjCHjCCHCH; ii} 2. CH;CH,CH,CH,COH 4. il b. 1. CHsCH;CCH;CH; 3. i 2. CHjCH,CH,CH,CH 3. 4, Chapter 20601 OH CHyCOCH, OH CH,CH,0H + CH,OH Zn(Hg) HCI, A ot Oo A tertiary alcohol is not oxdized to a carbonyl compound. (ro il U 6. HOCCH,CH,COH i I 6. HCCH,CH,CH Nl CH,CCH,CCH,CH, A tertiary alcohol is not oxdized to a carbonyl compound, Il I CH3CCH,CCH,CH,602 10. 1. 12. 13. Chapter 20 Chromic acid needs to be protonated to convert a poor leaving group (“OH) into a good leaving ‘group (0). The alcohol displaces water to form a protonated chromate ester, which loses a proton. The aldehyde is then formed in an elimination reaction. cs Hton gc # i HO-Cr-OH === CH,CH,CH,O—Cr—OH ine Zl ill oO » H = HOH CH,CH,CHO1t f ° il CH,CH;CH=O + H,CrO; | <— cHcH,c-0%—on (AH bP H;0° +250 HO: Solved in the text. g i g = €S—otccn, & ° © CH,CH,CH,COH CH; q 9 CH 7 COn d. CHsCHCOCCH, f. no reaction CH; CH, a, cyclohexene —_bL-butene ©. trans-2-pentene 4. cis-2-pentene °, b. ~N CH A oh CH; =CH’ The reaction forms a product with two new asymmetric carbons. Because only syn addition occurs, only two of the four possible stereoisomers are formed.14. 15. 16. Chapter 20 603 é ZN ae cH I a. cHjcn=cr, ROOM cyicfi—tu, SES cuducnocn, yr on CH,CHCH,OCH, i 2 CH MgB: g b. cH;cH=cH, BOOQH cycfi—bu, acacia CHCHCH,CH, x he ou CH,CHCH,CH, oH I . CH;CHCH,CH, product of "b" HyCrOy Il CH;CCH,CH, ‘The bromonium ion is much less stable than an epoxide, because the C—Br bond of a bromonium ion is a much weaker bond than the C—O bond of an epoxide, and a weaker bond is easier to break. The difference in the strength of the bonds can be understood by comparing the pKa of HBr (~ 9) and the pKa of an alcohol such as CH3OH (15.5). Thus, HBr is a much stronger acid than CH3OH, which means that Br is a much weaker base than “OCH. Being a weaker base, Br” shares its electrons less well (is a better leaving group). The difference in basicity is even greater than this when comparing the leaving group in a bromonium ion and an epoxide, because the Jeaving group in a bromonium ion is a neutral bromine, which is a weaker base than Br The major product results from attack of the Grignard reagent on the less sterically hindered carbon of the epoxide (the one bonded to a hydrogen and to a methyl group). I will be easier to answer this question if you use molecular models. 9 CHS HC. CH, 1. CH;MgBr Howes, - 2H," "7 RCH(CHS)2 CH,CH, H CH3CH) s 9 CH; HC CH, 1. CHyMgBr a To CINCH RCHICH,), cH;CH, =H HO R604 17. 18. 19. Chapter 20 ‘The addition of Br to an alkene is a stereoselective reaction because not all possible stereoisomers are formed: the trans-alkene forms the erythro pair of enantiomers, whereas the cis-alkene forms the threo pair of enantiomers. Itis a stereospecific reaction because a cis-alkene leads to a different set of products than does a trans-alkene. ILis not enantioselective, because if an asymmetric carbon is created, both enantiomers are obtained in equal amounts, and if two asymmetric carbons are created, two pairs of enantiomers (ora meso form and a pair of enantiomers) are obtained. CH i 8, CHsS—GHCH,CHs b. Ce OH OH ‘OH a. Syn addition to the trans isomer forms the threo pair of enantiomers. (See Section 5.19) wh H CHy CH oy C=O + or H——OH Hi A a4 ‘CH, HO--H = H—}-oH CH, CH, . Syn addition to the cis isomer forms the erythro pair of enantiomers. In this case, the product is'a meso compound because each asymmetric carbon is bonded to the same four substituents, so only one stereoisomer is formed. CH; H-}—0H H—}—0H CH, or CH; CH; H-{—OH HO—}—H H——OH HO——H CH,CH; CH,CH; or20. a. Chapter 20605 4. Syn addition to the trans isomer forms the threo pair of enantiomers. HH; H H,, CH, CH3 CH; ‘c—c—OH , HOM, - i H OH HO- H H's \ XN us CH,CH,; — CH,CH, ‘OH HO-—H = =-H——OH CH;,CH, — CH,CH, ‘The fact that only one ketone is obtained means that the alkene must be symmetrical. The cyclic ketone that is obtained is Om Therefore, the alkene is a, The compound on the left is more reactive because when the bulky tert-butyl group is in the more stable equatorial position, the two OH groups are in equatorial positions. In the other compound, the two OH groups are in axial positions and, therefore, are too far away one another to form the cyclic intermediate, = ‘OH OH (CHG)3C (CH3)3C more reactive ° ,OH On On (CHy)3¢ bu (CHs)s\ less reactive606 22. 23. Chapter 20 . The compound on the right is more reactive because when the bulky tert-butyl group is in the ‘more stable equatorial position, the two OH groups are in equatorial positions. In the other ‘compound, the two OH groups are in axial positions and, therefore, cannot form the cyclic intermediate. (wor OH (CH,),C (CHC less reactive C OH 'OH (CH)5E (CHs)s more reactive OH OH ‘OH OH Any alkene that forms two ketones when it is cleaved will form the same products when the ‘ozonide is worked up under reducing conditions as it forms when it is worked up under oxidizing conditions, In other words, each sp? carbon must be bonded to two alkyl groups. CH, SHCA — cHY ‘CH i t {i 1. a. CH,CH,CH,CCH, + CH,CH 4, a HCH + Oe g i i b. CH;CH,CH,CCH, + CH,COH b. HCOH + Oo q i i 2 a HCH + CH,CH,CH,CH,CH 8. a CH3CH,CH;CH 0 (equivalents) i i ° b. HCOH + CH;CH,CH,CH,COH i b. CHCH,CH;COH (2 equivalents) 9 ° i i tL il 1) 3. a. CHsCCH,CH,CH,CH 6. a. CH;C—CH + HCCH,CH,CH 9 il i b. CH;CCH;CH;CH,COH it I i b. CH;C—COH + HOCCH,CH,COHChapter20 607 & CH, ois cHY ‘cH, 2,3-dimethyl-2-butene b. CHyCH)CHy, Jos CH;CH,CH, fA c=c cc NN or Os H H H (CH,CH,CH; cis-4-octene trans-4-octene 25. — Solved in the text. 26. _ It does not tell you whether the double bond has the cis or the trans configuration. 27, Solved in the text. 28. “C 1.050 e a ° oO OH nH LCHMgBr —_— H 2. H,0" 0 ou fire. Drawn 0 29, b. CHjCH,C=CCH,CH,CH;C=CCH,CH,608 Chapter 20 30, KMnO,, HO * HO" H,CrO, bs Baga cold B ou 9 ON T Ton, 2. NaHSO3, H,0 aw Nin VY 1 1. NaBH, 1,RCOOH a ., 21,0 2 HO ‘0! 31. ae H,C=O : " 1. CHCH;Br Mim cH,CH:MgBr 2S cH,CH,CH,O 0, cH,CH,CH,OH co. Ml 1,LiAll, 2. CHyCH,Br eae CH;CH)MgBr —3 CH;CH,CO oor CH,CH,CH,OH Hy H,0 3. CH,CHBr -S=% cu,cH,c=n => CH,CH,COH HCI 1. LiAU EUAN, CH,CH:CH,OH or QO 2.H;0' OH, H,0 i ; a CHCH,Co = i, b. CHCH,Br C=“ cu,cr,c=n ae CH;CH,CH,NH) tert-BuO 1.03 1.NH. € CH;CH;CH,Br = CH,CH=CIh, =F CH,CH=0 Dy CHACH:NH, in, Hy 2. Hy Raney Nickel32. 33. 34, CH, c Cr tert-BuO™ CY 7.6, ° Os A bulky base is used 2. Zn, HO Cy to encourage elimination 9° a. - H,CrO, oo Br HO’ ‘oe OH HyCrOy ‘OH aldehyde acyl halide alkyl halide carboxylic acid acid anhydride ether ester alkene epoxide a. oxidized c. reduced e. oxidized g. reduced b. reduced 4, oxidized f. oxidized M ‘MgBr Et,0 2H 1 “Ai A Chapter 20 1.CO3 ae 1. cngin — has CH; Cry610 Chapter 20 38. t a. CHjCH,CH,CH,COH k. CH;CH;CH), _jH oxidation cae 9 HCH, ' (Sto « reduction 2 oxidation e ° q 1. CH;CH,CH;COH + CH;COH © CH;CH,CH,CH reduction oxidation d. CHyCH,CH;CH,OH Formation of the aldehyde after steps 1 and 2m. €S-cuc.cr, is neither oxidation or reduction, eaten Formation of the alcohol after steps Sand 4 is a reduction. 9 ? a De + HCH ©. CH,CH,CH oxidation oxidation f. CH,CH,CH,CH,NHCH, a reduction aoa 6 oxidation i & ¢S—ton oxidation H CH, H,C H qs P. h. ¢S-cn01 + CH,CHOH oxidation reduction HAC, Q H H, A CH OHO i, HC, MJ L, Px Cs 9 9 PS + *S® tl il H CH, HAC ey q. “OCCH,CH,CH,CH,CO” oxidation oxidation \ in 2 € Sono reduction 1. HOCCH,COH oxidation 36. Tl _HyCrOy i a. CH;CH;CH;CH ———> CH,CH,CH,COH H,CrO, I b. CH3CH,CH)CH,OH ———> CH,CH,CH,COHChapter 20 611 ° eis H,CrO, e CHCH,CH,CHBr HOS cy,cH,cH,cH,0H > cH,CH,CH,COH i. Bit H,CrO, i @. CH;CH,CH=CH, 1 BES cH,CH,CH,CH,OH > CH,CH,CH,COH 2. HO, H,0, 37. 1 LO 1 cuter CCH; becult_{) AlCl, = of 2.0 A 1, CHyMgBr 2. H,0* CH; OH CH, ie i A C=CHC C=CHC: <= I ti CH, CH D c 1. Os, ~78°C 2. HyOy ja c=0 a cr + uote") + CO, °. E 38. & CHYCH,CH,CH=CCH, —& a, ( )ecucr.ce, CH; CH; or “o =CH; “OL “ ‘CO612 Chapter 20 39. 1B a. CH,CH,CH=CH, = CHCH,CH,CH,OH : 2, H20p, HO se A KM 2 orfon 82 cucH=cHcH; + 1,0 H,SO, ° b. CH;CH,Br fe cH,cHMgpr CH,CH,CH,CH,OH 2 a free a CHCH,CH,CH Br oH © O00: 0 substitution product climinaion product xovno [804 9 1 i + HOCCH,CH,CH,CH,COH Ha a Lindlar catalyst 1.NH; a. HC=CCH,CH, ———4= CH;C=CCH,CH, 2. CH3Br41. 42. : i il 1. CHyCCH;CH,CH,CH,CH,COH I th 2m HOCCHCH,CH,CH,CH,COH Chapter 20 613 1.NH. CH,CH3 CH,CH, ———2= CH,C=CCH,CH, Na, / 2. CH3Br NH; \ H ° 9 CH, 1 1 3. CO, + HOCECH:CH,CH,CH,COH oO 9 I tL iil 4. CO, + HOCCCH,COH + HOCCH,COH °O 9 Ih I I I I 3. CO, + HOCCH,CCH,COH + HOC—COH REO =O coos of Nee) RCOO) On = ston O 1.0, GL NaBH, aad weno a 2.Zn, HyO 2. H,0* BS 4 1.03 ae 2. HO,614 Chapter 20 43. Because the compound is produced as a result of ozonolysis of an alkene under oxidizing conditions, it must be a ketone or a carboxylic acid. Since there is no signal for an OH group, the compound must be a ketone. The NMR spectrum shows two signals with splitting that is, characteristic of an ethyl group. Therefore, the compound produced as a result of ozonolysis must be 3-pentanone, The alkene that underwent ozonolysis, therefore, must be 3,4-diethyl-3- hexene. CH;CH2, CECH jo CH;CHY \CH,CH, 3,4-diethyl-3-hexene 44, 9 9 1 Io a 1.CH.CCI CCH; {] OCCH; 9 OH AIC, RCOQH HCl OH Os 0 c A B D socl Bares 1 t g cH,cH,NH, EAB oy Cne, «SEL cHcc. OH on a mvenie H + Br E Br CHsI ['co. F excess CH; CH; CH BY Ag,O. +h A i cucuNcH, = ABS} cHcNcH) = CIN + CH=CH, y Ch or x CH HO” CHy nm L 10,10, i HCOH NChapter20 615 45. The rate-determining step in the chromic acid oxidation of an alcohol is the E2 elimination reaction of the chromate ester. 2-Propanol is oxidized more rapidly than 2-deuterio-2-propanol because it is easier to break the carbon-hydrogen bond than the carbon-deuterium bond. CH; Qo CHs A ou O-CrOH cng" on ° wet 46. 1 va 1 CH;C=CHCH,CH,CCH, 1BHs Gy cHCHcH,cH,Ccry oe 2. HO, H,0, is Hs [isos H,SO. 6 n so, 1 il —_ 4 (CHyCHCCH,CH,CCH,; <7 I CH: cHaCH oma CH, 1. CHyMgBr 2.H,0* HO. CH, cH. CH, 47. ° Hl HyCrOy tl Ree a cHcrcH 2S cucHdon 22% cx,cu,dcr L.NaBH, 2. H,0 cu.cx,cr,ox Oo Il CH;CH,COCH,CH,CH,616 Chapter 20 ° OH 1 I 1 b. CH,CH,CH,CH,On P&S cH,cH,CH,CH pou CH;CH,CH,CHCH,CH, a H,cr044 i CH,CH,CH,CCH,CH OH O, Br NHCH; on™ OT Oo d. NaBH, H,SO, a or cS LNaBEy or eso O+4 Son nobemencrcreon x CH3 CH; ° 9 5 th I “Cys Lenape Cho 18% (TT 42%. noteu,cu,crcxtce 48, CHCH,E=CH, CH, 49. Acyclic intermediate is formed when HIOg cleaves a 1,2-ciol. It is easier to form a cyclic intermediate if the two OH groups are on the same side of the molecule. Therefore, A is cleaved more easily because itis a cis diol, while B is a trans diol. 50. i c=CH CoH a 1.0. Sail + CO, 2. HO onen 9° CCH. 1. disiamyl- cx,Con —bomme NajCr,0.- NaxCr0, DO, HO) os SO,Chapter20 617 51. 9 OH O a. CH,CH,CHOH SS cH,cH,CH cw CH,CH,CHCHCH i CH, af80. Hy il CH,CH,CH,CHCH,OH =o —— CH;CH;CH=CCH CH; CH; NagCr,0. i gE R i — >. CHyGHOH sao cu,ccH, HQ CHs¢CH;CCH, CH; =e CH, 1. NaBH, 2. H,0" CH;C=CHCH=CH, OH OH CH;CHCH,CH,CH, <2 cH. ee cuyton’ yGHCH,CH,CH; = ia 5 a IsCCH;CHCHs CH; Cly=GCH=CHCH, CH; CH; Q,wspame 8, saan he ; al « cncr,on 22S cx,cu SPMTE cy crcncu +S cu,Cucn,ch,on 0 2. H,0" 2. CH,CH NajCr,07 CH,gHOH cucu, |acr Ct, 12804 CH ett oso on618 52. 53. 54, Chapter 20 ‘The compound is either 4-octyne or 2,5-dimethyl-3-hexyne. CH; CH; T I CH,CH,CH,C=CCH,CH,CH; CH,CHC=CCHCH, 4-octyne 2, imethyl-3-hexyne Because oxidative cleavage formed only one four-carbon carboxylic acid, you know the compound is either a symmettical eight-carbon alkene or a symmetrical eight-carbon alkyne. Therefore, the compound has a molecular formula of CgH 4 or CgH6 and, consequently, a molecular weight of 110 or 112. 0.5 g of the hydrocarbon was hydrogenated; this corresponds to 0.0045 mol (0.5/112 = 0.0045, 05/110 = 0.0045). The key here is to remember from general chemistry that 1 mol of a gas has a volume of 22.4 liters at standard temperature and pressure. Knowing this, it can be calculated that 0.0045 mol of Hy = 100 mL Hz. Since about 200 mL of Hg were consumed, the compound must have two bonds. Thus, the unknown compound is an alkyne. a. None was successful. iL i b. 1. CHyCH,CCH, + cu,con 2. noreaction 3. Gn H,C OH c 1, 1.KMnO,,HO,cold 2, 1. LiAlH, 3. 1. KMnO,, HO, cold ee F ae 250 2.30) 2. H,0 or or 1,050, 1,080, ste ste 2.H,0 2.Hy02 The absorption bands at 1600 cm!, 1500 emr!, and > 3000 cm in the IR spectrum indicate the compound has a benzene ring. The absorption band 2250 cm! indicates the compound has a triple bond, and the absence of an absorption band 3200 cm tells you that itis not a terminal alkyne. ‘The two triplets and the multiplet in the 1H NMR spectrum indicate a propyl group. Compound A is I-phenyl-1-propyne and compound B is propylbenzene. H (\-ceceu, a €S-cngen,crs, Puc B A55. 56. 57. Chapter20 619 Diane has enough information to identify diols A, C, E, and F, but not enough information to distinguish between diols B and D. Only the 4th compound will form two products upon cleavage with periodic acid. So it must be F, The 1t and Sth compounds will not react with periodic acid. Because the 1St compound is optically inactive and the 5th compound is optically active, the 1St compound must be C and the 5th compound must be E, ‘The 3°¢ compound is the only optically active compound that forms one compound with periodic acid. Therefore, it must be A. Diane could distinguish between B and D if she analyzed the products obtained from the reaction of B and D with periodic acid. B will form acetaldehyde (a 2-carbon aldehyde), while D will form propanal (a 3-carbon aldehyde). 1 2 3 4 5 6 CH, CH; CH, CH, CH, CHCH; H | OH OH H——OH H—~—OH H—-}~on H—+-on GH; H]-OH HO-]-H HOT —# CH, H—+—on ‘OH CH, CH; CH,CH; HO——H CH,CH, CH, BorD A F CH; BorD c E CHy=CHCH,OH = CHjCH,CH,OH a CH,CH,COH Joe ° 9 1 I CH;CH,COCH,CH,CH, = QHSCHsCHOH oy oH Cc] OH 9 cuycucuca, cyecce, CH)=CCH,CH, — CHyC=CHCH, CH, CH; CH; CH; A B c D i g i CH,CCH,CH, CH;CCH, CH,COH E F G620 Chapter 20 58. HC’ ~CH; 59. a. (2R,38)-Tartaric acid is a meso compound. It will be formed by syn addition to the cis isomer. Syn addition of two OH groups can be carried out using a cold, basic solution of potassium permanganate or using osmium tetroxide followed by an aqueous solution of sodium bisulfite. COOH HOOC HOO H NO 76008 Mind, HO”, HO H-—OH wos ee —ton 1H CooH (2R,38)-tartaric acid b. (2R,38)-Tartaric acid can also be formed by anti addition to the trans isomer. Anti addition of two OH groups can be carried out by first forming an epoxide and then treating the epoxide with an aqueous solution of hydroxide. COOH HOOG 1H 7 * OH #H coon (2R35)-tartaric acid ¢. (2R,3R)-Tartaric acid and (2S,3S)-tartaric acid are the threo isomers. They will be formed by anti addition to the cis isomer. HOOC, COOH il H COOH Ne cf 1, RCOOH oN XH H H HOOC OH Q2R3R)-tartaric acid (25,38)-tartaric acid or COOH COOH H-OH | HOH HO-—-H H—}—0H coon cCooHChapter 20 621 4d. The threo isomers can also be formed by syn addition to the trans isomer. HOOK 7 xin, HO", 20 HOOK. # OH Pc eal wpe + — H ‘COOH HO ‘COOH HOOC QR3R)tartaric acid (25,35)-tartaric acid or COOH COOH HOH | H HO——H H——0H coon coou os 10, CH oa Ors O=Oe Of "Be 1. BH,/THE, Nee CH; CH; 4 a H,02, HQ 1.05 Vos — Oo CH, 2.2n,H,0| CL 7 Oo oO yo so ‘OH 1 il 6. E CH;CCH,CH,CH,CH,CH 2p \ I fr00. CH3 psc. CSrenscrson 9 9° CH CH;CH,OH Ch ayy lt bh oO CHjCCH,CH,CH,CH,COH 3 isCCH,CH;CH,CHy “Pa ° F J CH; [sce OCH,CH, — |CH,CH,NH, 9 ° G OCH,CH; cu CH CCH,CH,CH,CH,CCI 5 K \giuon i i 1H NCH,CH; CH,CCH,CH,CH,CH,COCH, L622 Chapter 20 61. Br ° 5 . i a. CHACHCH, fae CHYCCHy HO, CHRC=CHh, ara CHCCH; CH; CH, CH, ™ b. Note that 2-bromopropane (obtained from the first step) is divided into two portions; one portion is used to form propene, and the other is used to form the Grignard reagent. Br; CH,CH,CH, 3 CH,CHCH, AS cu,cn=cu, Bi . 1.05 male.o 2. Zn, H,O g r CHYCHCH, + CH,CH = CH,CHGHCH; MgBr cH; Hsofa CH,CH=¢CH, CH, 9 Br, LCHCH ou © CH;CH,CH, == CH,CHCHs * CHsCHCHs s—-* CH;CHCHCH, Br 2 Mer 7H CH; NaxCr,0; H,SO, t CHsCHCCH, CH; oO Bry 4. CH,CH, 472 CH;CH,Br fe CH,CH,MgBr ae CH;CH,CH,CH,0H os 2.41 fpos QR 10 io crore + als ha cH,cH,cH=cH, <22 cH,CH,CH,CH,BrChapter20 623 The ethylene oxide needed for the reaction can be obtained from some of the bromoethane prepared in the first step. ° x reooH 0 cu,cH,Br 22. cy,=cu, SOS 62, ° 9 q i CHCHICHNEH OTs Scr —— > CH,CH,CH,CH qi 0 DMSO624 Chapter 20 9 LBB Tae AA PCC Ak a de SHG Eos oH H 2. HO; H0, b. Br, On " es "Temcog Cy NagCrsOp or 2.HCI, ZCI, HO ,s0,— ° ites 2.Zn, HzO ° fo) CY 1, NaBH, Oo Oy Os 1. Bey oe 2.H,0" 2. H,0 Bp ~ OH ‘Br OH Mebr PB Sm I ae CH=CH, a Br - OH f HOF 1, KMnO,, HO; cold a tno oT ‘OH 65. =Chapter 20. 625 66. Three structures (A, B, C) fit the data given. Terpineol is actually C. A B c oy . vaso, ac abe 2. Zn, HO 5. Hc’ an 67. The fact that the HO substituent ends up on the least substituted sp? carbon of the double bond indicates that oxygen is the first species to add to the double bond. That HO» is one of the reagents suggests that the alkene reacts with HOp, forming an epoxide. Br- attacks the epoxide from the backside with the result that the OH and Br substituents form an anti addition product. ‘The fact that Br~ attacks the most substituted carbon of the epoxide suggests that there is an acid catalyst at the surface of the enzyme that causes the epoxide to open to give the more stable partial carbocation,