APPENDIX 2 CHAPTER 8 1(b)CH:OCH2CH3 (c) CH3OC (d) CH3N=N=N (e)CHac=n (f) Ch3SH (g) CH3I 82ClCH,CHCH2C≡N CH CH(CH2)CH3 8.5 Hydrolysis of (R)-(-)-2-bromooctane by the Sn2 mechanism yields optically active(S)-(+)- 8.6(b) 1-Bromopentane;(c)2-chloropentane:(d)2-bromo-5-methy lhexane:(e) 1-bromodecane 8.7 CH3 CH(CH2) CH3 and CH3 CH(CH2) CH3 8.8 Product is(CH3)3 COCH3. The mechanism of solvolysis is SNl (CH3)3C-Br: (CH3)aC+] Br (CH3)3C + OCH3->(CH3)3C-OCH3 (CH3)3C--OCH →(CH3)3C-OCH 8.9 (b)1-Methylcyclopentyl iodide; (c) cyclopentyl bromide;(d) tert-butyl iodide 8.10 Both cis-and trans-1, 4-dimethylcyclohexanol are formed in the hydrolysis of either cis-or 8.11 A hydride shift produces a tertiary carbocation; a methy l shift produces a secondary carbo- -OCH CH3 (c)CH3 CHCH2CH (d) cis-and trans-CH3 CH=CHCH3 and CH,=CHCH_CH3 8.13 CH3(CH2)16CH,OH CH3 scl CH3(CH2)16CH,OS CH+ Hcl 14(b)CH3(CH2)16CH,;(c) CH3(CH2)16CH2CEN;(d)CH3(CH2)16CH2SH (e)CH3 (CH,)16CH2SCH,CH,CH2CH Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
APPENDIX 2 A-21 CHAPTER 8 8.1 (b) CH3OCH2CH3 (c) (d) (e) CH3CPN (f) CH3SH (g) CH3I 8.2 ClCH2CH2CH2CPN 8.3 No 8.4 8.5 Hydrolysis of (R)-()-2-bromooctane by the SN2 mechanism yields optically active (S)-()- 2-octanol. The 2-octanol obtained by hydrolysis of racemic 2-bromooctane is not optically active. 8.6 (b) 1-Bromopentane; (c) 2-chloropentane; (d) 2-bromo-5-methylhexane; (e) 1-bromodecane 8.7 8.8 Product is (CH3)3COCH3. The mechanism of solvolysis is SN1. 8.9 (b) 1-Methylcyclopentyl iodide; (c) cyclopentyl bromide; (d) tert-butyl iodide 8.10 Both cis- and trans-1,4-dimethylcyclohexanol are formed in the hydrolysis of either cis- or trans-1,4-dimethylcyclohexyl bromide. 8.11 A hydride shift produces a tertiary carbocation; a methyl shift produces a secondary carbocation. 8.12 (b) (c) (d) cis- and trans-CH3CHœCHCH3 and CH2œCHCH2CH3 8.13 8.14 (b) CH3(CH2)16CH2I; (c) CH3(CH2)16CH2CPN; (d) CH3(CH2)16CH2SH; (e) CH3(CH2)16CH2SCH2CH2CH2CH3 CH3CHCH2CH3 OCH3 OCH2CH3 (CH3)3C OCH3 H (CH3)3C OCH3 H (CH3)3C OCH3 H (CH3)3C OCH3 H (CH3)3C Br (CH3)3C Br CH3CH(CH2)5CH3 NO2 CH3CH(CH2)5CH3 ONO and HO H CH3 CH2(CH2)4CH3 CH3N N CH3OC N O CH3(CH2)16CH2OH CH3 SCl O O pyridine CH3(CH2)16CH2OS O O CH3 HCl
APPENDIX 2 8.15 The product has the R configuration and a specific rotation (alb of -9.9% CH3(CH2) /CH2)sCH -OTS -HO CH 8.16 CHa CH, C(CH3)2 chaPTeR 9 91=6+uo-H→6=C-H+-0-H Carbide ion Water Hydroxide ion OHCeC-H-9H-0:+H-C=C-H Acetylide ion Hydroxide ion 9.2 CH3 CH2CH2C=CH (1-pentyne), CH3 CH2CECCH3 (2-pentyne),(CH3)2CHCECH (3-methyl-1-butyne) 9.3 The bonds become shorter and stronger in the series as the electronegativity increases N-H longest and weakest, H-F shortest and strongest CHCH HC≡C:+CH3CH3 (stronger acid) (weaker base) ( (c)CH2-CHuk h+NH,KL CH-CH NH3 Amide Vinyl anion (stronger base)(stron d)CH3C≡CCH2O—H CHc≡CCH2O:+:NH anion (stronger acid) (stronger base) aker base) (weaker aci 9.5()HC=CH-2 CH Br NuNH CH3C≡CH NaNH,, NH: 2. CH=CH- CH-CH,Br CHC≡CCH2CH2CH2CH3 (c)HC≡CH CH3CH2CH2C≡CH CH3CH2CH2C≡CCH2CH 9.6 Both CH3 CH2CH,CECH and CH3 CH,CECCH3 can be prepared by alkylation of acety lene. The alkyne( CH3)2CHC=CH cannot be prepared by alkylation of acetylene, because the required alkyl halide, (CH3)2CHBr, is secondary and will react with the strongly basic acetylide Br 9.7(CH3)3CCCH3 or (CH3)3CCH2 CHBr or (CH3)3 CCHCH2B Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
A-22 APPENDIX 2 8.15 The product has the R configuration and a specific rotation []D of 9.9°. 8.16 CHAPTER 9 9.1 9.2 CH3CH2CH2CPCH (1-pentyne), CH3CH2CPCCH3 (2-pentyne), (CH3)2CHCPCH (3-methyl-1-butyne) 9.3 The bonds become shorter and stronger in the series as the electronegativity increases; N±H longest and weakest, H±F shortest and strongest. 9.4 (b) (c) (d) 9.5 (b) (c) 9.6 Both CH3CH2CH2CPCH and CH3CH2CPCCH3 can be prepared by alkylation of acetylene. The alkyne (CH3)2CHCPCH cannot be prepared by alkylation of acetylene, because the required alkyl halide, (CH3)2CHBr, is secondary and will react with the strongly basic acetylide ion by elimination. 9.7 (CH3)3CCCH3 Br Br (CH3)3CCHCH2Br Br (CH3)3CCH2CHBr or or 2 CH3C CCH2O H 2-Butyn-1-ol (stronger acid) NH2 Amide ion (stronger base) K 1 CH3C CCH2O 2-Butyn-1-olate anion (weaker base) NH3 Ammonia (weaker acid) CH2 CH H Ethylene (weaker acid) NH2 Amide ion (weaker base) NH3 Ammonia (stronger acid) K 1 CH2 CH Vinyl anion (stronger base) HC C H Acetylene (stronger acid) CH2CH3 Ethyl anion (stronger base) K 1 HC C Acetylide ion (weaker base) Ethane (weaker acid) CH3CH3 C C Carbide ion C C H Acetylide ion H O H Water O H Hydroxide ion C C H Acetylide ion H O H Water H O Hydroxide ion H C C H Acetylene CH3CH2C(CH3)2 Cl H2O C H3C CH3(CH2)5 H OTs HO C (CH2)5CH3 H CH3 HC CH CH3C CH CH3C CCH2CH2CH2CH3 1. NaNH2, NH3 2. CH3Br 1. NaNH2, NH3 2. CH3CH2CH2CH2Br HC CH CH3CH2CH2C CH CH3CH2CH2C CCH2CH3 1. NaNH2, NH3 2. CH3CH2Br 1. NaNH2, NH3 2. CH3CH2CH2Br
APPENDIX 2 98b) CHaCH,CH,OH=>cHH=CH2→ CH3CHCH,Br-→cHc=CH (c)(CH3)2CHBr NaOCH.C CH3 CH-CH2; then proceed as in parts(a)and(b). (d)CHaCHCI HC≡CHNa (e)CH3CH2OH BrCh,CH,Br -a ≡CH; then pro ceed as in part(d) 9HC≡CH H3CH CH→CHCH1CH2C=CH⊥NNH2 L NINH, NH 2. CH: CHICE CH3 CH, CH,C=CCH,CH2 CH3 CH3(CH2).CH3 orHC= CH-2, CH1(CH2C=CH当、CH1(CH2CH 9.10 Oleic acid is cis-CH3 (CH,)CH=CH(CH,),CO,H. Stearic acid is CH3(CH2)16CO2H. 9.11 Elaidic acid is trans-CH3(CH,),CH=CH(CH,)CO,H 912CH3C≡CH 1. NINH,NH C、 H CH, CH2CHCH CH3C≡CCH2CH2CH2CH3 3c CH,CH,CH, CH3 Lindi 9.13(b) CH,=CHCI CHaCHCI (c)CHaCHBr2 CH3 CHCIz 9.14 CH3C=CCHs H,SO,CH=CHCH CHaCCH, CH3 OH H+CH3CH≠CCH O:+CH3CH2—CCH3 O-H H CH3CH,-CCH3 + O →CH3CH2CCH3+H-0 Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
APPENDIX 2 A-23 9.8 (b) (c) ; then proceed as in parts (a) and (b). (d) (e) ; then proceed as in part (d). 9.9 or 9.10 Oleic acid is cis-CH3(CH2)7CHœCH(CH2)7CO2H. Stearic acid is CH3(CH2)16CO2H. 9.11 Elaidic acid is trans-CH3(CH2)7CHœCH(CH2)7CO2H. 9.12 9.13 (b) (c) 9.14 O H H O H H H CH3CH2CCH3 O CH3CH2 O CCH3 H O H H H O H H CH3CH OH CCH3 CH3CH2 OH CCH3 CH3C CCH3 H2O, Hg2 H2SO4 CH3C OH CHCH3 CH3CCH2CH3 O CH3CHCl CH3CHBr2 2 1. NaNH 2HCl 2, NH3 2. H2O HC CH CH3CHCl CH2 CHCl 2 HCl CH3C CH CH3C CCH2CH2CH2CH3 1. NaNH2, NH3 2. CH3CH2CH2CH2Br H2 Lindlar Pd Li, NH3 C H H CH2CH2CH2CH3 C H3C C H H CH2CH2CH2CH3 C H3C HC CH CH3(CH2)5C CH CH3(CH2)6CH3 1. NaNH2, NH3 2. CH3(CH2)5Br H2 Pt HC CH CH3CH2CH2C CH CH3CH2CH2C CCH2CH2CH3 CH3(CH2)6CH3 1. NaNH2, NH3 2. CH3CH2CH2Br 1. NaNH2, NH3 2. CH3CH2CH2Br H2 Pt CH3CH2OH BrCH2CH2Br H2SO4 heat CH2 CH2 Br2 1. NaNH2 2. H2O HC CH CH3CHCl2 1. NaNH2 2. H2O HC CH CH3C CH 1. NaNH2 2. CH3Br (CH3)2CHBr CH3CH CH2 NaOCH2CH3 CH3CH2CH2OH CH3CH CH2 CH3C CH H2SO4 heat Br2 1. NaNH2 2. H CH3CHCH2Br Br
APPENDIX 2 9.15 2-Octanone is prepared as shown: cH→ CHa (CH,), CH2C=CHH20, H2SO. CH3(CH2)CH,CCH 4-0ctyne is prepared as described in Problem 9.9 and converted to 4-octanone by hydration with 916CH3(CH2)4C≡CCH2CH2C≡C(CH2)4CH CHAPTER 10 10.1(b)CH3-C-CH >CH2-C=CH CH CH3 C(CH3)2← >C(CH3)2 CH3 CI CH 10.2 103(b) CH (c) CH, -Allylic Allylic allylic Allylic- 10.4(Propagation step 1) H+H—Br Propagation step 2) Br 10.5 2, 3,3-Trimethyl-1-butene gives only (CH3)3CC=CH2. 1-Octene a mixture of H,B CHa I( CH2)4CH3 as well as the cis and trans stereoisomers of BrCH,CH=CH(CH2) CH3 10.6(b) All the double bonds in humulene are isolated. (c) Two of the double bonds in cembrene conjugated to each other but isolated from the remaining double bonds in the molecule. (d) The CH=C=CH unit is a cumulated double bond; it is conjugated to the double bond at C-2. 10.7 1, 2-Pentadiene(3251 k/mol, 777.1 kcal/mol);(E)-1, 3-pentadiene(3186 k/mol, 761.6 kcal/mol): 1, 4-pentadiene (3217 kJ/mol, 768.9 kcal/mol) Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
A-24 APPENDIX 2 9.15 2-Octanone is prepared as shown: 4-Octyne is prepared as described in Problem 9.9 and converted to 4-octanone by hydration with H2O, H2SO4, and HgSO4. 9.16 CH3(CH2)4CPCCH2CH2CPC(CH2)4CH3 CHAPTER 10 10.1 (b) (c) 10.2 10.3 (b) (c) 10.4 (Propagation step 1) (Propagation step 2) 10.5 2,3,3-Trimethyl-1-butene gives only . 1-Octene gives a mixture of as well as the cis and trans stereoisomers of BrCH2CHœCH(CH2)4CH3. 10.6 (b) All the double bonds in humulene are isolated. (c) Two of the double bonds in cembrene are conjugated to each other but isolated from the remaining double bonds in the molecule. (d) The CHœCœCH unit is a cumulated double bond; it is conjugated to the double bond at C-2. 10.7 1,2-Pentadiene (3251 kJ/mol, 777.1 kcal/mol); (E)-1,3-pentadiene (3186 kJ/mol, 761.6 kcal/mol); 1,4-pentadiene (3217 kJ/mol, 768.9 kcal/mol) Br CHCH(CH2) CH2 4CH3 (CH3)3CC CH2Br CH2 Br H H Br Br Br H H Br H H Br Allylic CH3 CH3 H H H H Allylic Allylic Allylic Allylic CH3 Br and Cl CH3 C(CH3)2 C(CH3)2 CH2 CH3 C CH2 CH2 CH3 C CH2 HC CH CH3(CH2)4CH2C CH 1. NaNH2, NH3 2. CH3(CH3)4CH2Br H2O, H2SO4 HgSO4 CH3(CH2)4CH2CCH3 O (d) Allylic Allylic H H
APPENDIX 2 10.8 2-Methyl-2, 3-pentadiene is achiral. 2-Chloro-2, 3-pentadiene is chiral 10.9 CH, -=CHCH3(cis trans) and CH,-CHCH2CCH2CH3 10.10(CH3)2CCH=CH2 Cl 10.11 3, 4-Dibromo-3-methyl-l-butene: 3, 4-dibromo-2-methyl-1-butene: and 1, 4-dibromo-2 1013(b)CH2=CHCH=CH2+cisN≡CCH=CHC≡N (c)CHaCH-CHCH-CH2+ COCH COCH3 10.16 There is a mismatch between the ends of the homo of one 1, 3-butadiene molecule and the lumo of the other(Fig. 10.9). The reaction is forbidden CHAPTER 11 CH3 CO,H 111(a) 11.2 1, 3, 5-Cycloheptatriene resonance energy 25 k/mol (5.9 kcal/mol). It is about six times smaller than the resonance energy of benzene CH=CH 113b) Forward Main Menu TOC Study Guide Toc Student OLCMHHE Website
APPENDIX 2 A-25 10.8 2-Methyl-2,3-pentadiene is achiral. 2-Chloro-2,3-pentadiene is chiral. 10.9 10.10 10.11 3,4-Dibromo-3-methyl-1-butene; 3,4-dibromo-2-methyl-1-butene; and 1,4-dibromo-2- methyl-2-butene 10.12 10.13 (b) CH2œCHCHœCH2 cis-NPCCHœCHCPN (c) 10.14 10.15 10.16 There is a mismatch between the ends of the HOMO of one 1,3-butadiene molecule and the LUMO of the other (Fig. 10.9). The reaction is forbidden. CHAPTER 11 11.1 (a) (b) 11.2 1,3,5-Cycloheptatriene resonance energy 25 kJ/mol (5.9 kcal/mol). It is about six times smaller than the resonance energy of benzene. 11.3 (b) (c) NH2 NO2 Cl CH CH2 CH3 CH3 CO2H CO2H CH3 CO2H COCH3 O H H O COCH3 and CH3CH CHCH CH2 O O O Cl O O H H (CH3)2CCH Cl CH2 CHCH2C CH3 CH2 CHCH3 CHCH2CCH2CH3 CH2 and CH2 (cis trans)