APPENDIX A ANSWERS TO THE SELF-TESTS CHAPTER 1 A-1. (a) P; 1s 2 2s 2 2p 6 3s 2 3p 3 (b)S 2H11002 ; 1s 2 2s 2 2p 6 3s 2 3p 6 A-2. (a) (c) (b) A-3. (a) (b) (c) The more stable Lewis structures are A-4. (a)(b) HOCC H H H HHNC H H H (a)(b)(c)NCS ONO HC NH 2 O H11001 H11002 HC Formal charge: NH 2 O0 0 0 Net charge: 0 OO Formal charge: 0 H110011 0 Net charge: H110011 N NCS Formal charge: 0 0 H110021 Net charge: H110021 ONO Formal charge: H110011 H110011 H110021 Net charge: H110011 HC Formal charge: NH 2 Net charge: 0 OH110021 0 H110011 NS H110021 0 0 Net charge: H110021 Formal charge: C 775 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website 776 APPENDIX A A-5. (a)(c) (b)C 10 H 22 (d) A-6. (a) (b) (c) A-7. A-8. A-9. (a) (b) A-10. (a) Linear (b) Linear (c) Bent A-11. (a)D (c) None (e) None (g)A (b) A, B (d)B (f )A, D (h)C A-12. HCHN O H N H Pyramidal; yes, it is polar.N Cl Cl Cl HCC C HOC H H H H H H Tetrahedral Bent Tetrahedral Trigonal planar OCN Formal charge: H110021 0 0 Net charge: H110021 O S 2H11001 O H11002 O H11002H11002 O O O S 2H11001 H11002 O O O S 2H11001 H11002 H11002 has only one sp 2 -hybridized carbon atom O has only sp 2 -hybridized carbon atoms N Br has only sp 3 -hybridized carbon atoms N Br C 9 H 6 BrN O C 14 H 24 O OH C 12 H 20 O Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 777 A-13. (a)11 H9268; 1 H9266 (b)9 H9268; 2 H9266 (c) 12 H9268; 4 H9266 (d) 13 H9268; 4 H9266 A-14. (a)(c) All carbons are sp 2 . (b)(d) B-1. (b) B-2. (b) B-3. (c) B-4. (d) B-5. (a) B-6. (b) B-7. (a) B-8. (d) B-9. (b) B-10. (d) B-11. (b) B-12. (e) B-13. (d) B-14. (b) B-15. (d) CHAPTER 2 A-1. A-2. (a) 28 (8 CGC; 20 CGH) (b) 27(9 CGC; 18 CGH) A-3. (a) Oxidized (b) Neither (c) Neither (d) Reduced A-4. (a)(b) Six methyl groups, three isopropyl groups A-5. (a) 3,4-Dimethylheptane (b) (1,2-Dimethylpropyl)cyclohexane A-6. Primary Secondary Tertiary (a)4 3 2 (b)3 5 3 A-7. (a) 1,3-Dimethylbutyl; secondary (b) 1,1-Diethylpropyl; tertiary (c) 2,2-Diethylbutyl; primary CH 3 CHCHCHCH 3 CH 3 CHCH 3 CH 3 CH 3 CH 3 CHCH 2 CH 3 Isobutyl 2-Methylpropyl Common: Systematic: tert-Butyl 1,1-Dimethylethyl CH 3 C CH 3 CH 3 CH 3 CH 2 CH 2 CH 2 n-Butyl Butyl Common: Systematic: CH 3 CH 2 CHCH 3 sec-Butyl 1-Methylpropyl sp 2 sp 2 sp O CN sp 3 HCC CH 2 CH 3 sp sp 3 H 3 C CH 3 CH CH sp 3 sp 2 sp 3 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-8. A-9. A-10. (a)(c) (b) A-11. (a)CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 (c) (b) (CH 3 ) 3 CC(CH 3 ) 3 (d) (CH 3 ) 3 CC(CH 3 ) 3 A-12. A-13. Alcohol, alkene, ester, ketone A-14. 10,049 kJ/mol B-1. (a) B-2. (d) B-3. (d) B-4. (c) B-5. (b) B-6. (a) B-7. (c) B-8. (c) B-9. (a) B-10. (a) B-11. (b) B-12. (e) B-13. (d) B-14. (d) 3,3-Dimethylpentane 3-Ethylpentane 2,3-Dimethylpentane 2,4-Dimethylpentane 2,2-Dimethylpentane (CH 3 ) 2 CHCHCH(CH 3 ) 2 CH 3 (2-Methylbutyl)cyclohexane 3-Ethyl-2,3- dimethylhexane 4-Ethyl-3-methylheptane 1,2-Dimethylcyclopropane1,1-Dimethylcyclopropane EthylcyclopropaneMethylcyclobutane Cyclopentane C 7 H 16 11O 2 7CO 2 8H 2 OH11001H11001CH 3 CHCHCH 2 CH 3 C 7 H 16 H11013 CH 3 CH 3 778 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 779 CHAPTER 3 A-1. A-2. A-3. (CH 3 ) 3 CCH 2 C(CH 3 ) 3 H11005 2,2,4,4-tetramethylpentane A-4. A-5. A-6. A-7. (a)C (b) A and B (c)D (d)A A-8. A-9. cis-1-Ethyl-3-methylcyclohexane has the lower heat of combustion. A-10. Tricyclic; C 10 H 16 More stable CH(CH 3 ) 2 H CH 3 H CH(CH 3 ) 2 H H 3 C H OH HO H OH H HO H O H CH 3 H CH 3 (CH 3 ) 3 C H EquatorialEquatorial Axial H CH 3 (CH 3 ) 3 C H (Eclipsed) Cl Cl H Cl H Cl H 3 C CH 3 H H H H Cl H Cl (b)(a) Cl H Cl Gauche Cl H H H CH 3 H Anti Cl H H CH 3 H H Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-11. The form of the curve more closely resembles ethane than butane. A-12. B-1. (d) B-2. (b) B-3. (c) B-4. (a) B-5. (c) B-6. (a) B-7. (d) B-8. (e) B-9. (c) B-10. (e) B-11. (b) B-12. (a) B-13. (d) B-14. (b) CHAPTER 4 A-1. (a) trans-1-Bromo-3-methylcyclopentane (b) 2-Ethyl-4-methyl-1-hexanol A-2. (a)(b) A-3. (a) Functional class: 1-ethyl-3-methylbutyl alcohol Substitutive: 5-methyl-3-hexanol (b) Functional class: 1,1,2-trimethylbutyl chloride Substitutive: 2-chloro-2,3-dimethylpentane A-4. Conjugate acid ; conjugate base A-5. (a) (b) CH 3 CH 2 C(CH 3 ) 2 OH CH 3 CH 2 CH 2 Cl CH 3 O H11002 CH 3 OH 2 H11001 OH CH(CH 3 ) 2 ICH 2 CCH 2 CH 2 CH 2 CH 2 CH 3 CH 3 Cl S Potential ener gy Torsion angle H HH CH 3 CH 3 H H H H CH 3 CH 3 H H HH CH 3 HH 3 C 780 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 781 A-6. (a) (b) A-7. (a) Three (b, c) A-8. A-9. A-10. H9004H ° H11005H1100257 kJ (H1100213.5 kcal) A-11. (a) (b) (c) Water is displaced directly from the oxonium ion of 1-butanol by bromide ion. A pri- mary carbocation is not involved. A-12. (a) 3-Methyl-3-pentanol (c) Fluorine (F 2 )(e)Cl 2 (b) KOC(CH 3 ) 3 (d) Ethyl radical, CH 3 C . H 2 B-1. (e) B-2. (c) B-3. (b) B-4. (c) B-5. (e) B-6. (c) B-7. (d) B-8. (a) B-9. (c) B-10. (d) B-11. (c) B-12. (e) B-13. (a) B-14. (c) B-15. (c) B-16. (c) H11001H 2 OCH 3 CH 2 CH 2 CH 2 CH 3 CH 2 CH 2 CH 2 BrOH 2 H11001 Br H11002 C H 3 C H 3 C CH 3 O H H H9254H11001 H9254H11001 (CH 3 ) 3 C H11001 BrH11001 H11002 (CH 3 ) 3 C Br (CH 3 ) 3 C H11001 H11001H 2 O(CH 3 ) 3 COH 2 H11001 (CH 3 ) 3 C (CH 3 ) 3 COH H BrH11001 Br H11002 H11001OH 2 H11001 H11001 H11001Br 2 Br Br H11001 H11001Br HBr CH 3 CCH 3 H11001 Cl 2 CH 3 CH 3 CH 3 CCH 2 Cl H11001 HCl CH 3 CH 3 CH 2 CHCH 2 CHCH 3 CH 3 CH 3 (Least stable) CH 3 CHCHCHCH 3 CH 3 CH 3 CH 3 CCH 2 CHCH 3 CH 3 CH 3 (Most stable) CH 3 CH 2 ONH 2 H H9254H11002 H9254H11002 CH 3 CH 2 O H11002 CH 3 CH 2 OHNH 3 NH 2 H11002 (K H11021 1)H11001H11001 Stronger base Stronger acid Conjugate acid Conjugate base Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website CHAPTER 5 A-1. (a) 2,4,4-Trimethyl-2-pentene (c)(E)-2,7-Dibromo-3-(2-methylpropyl)- 2-heptene (b)(E)-3,5-Dimethyl-4-octene (d) 5-Methyl-4-hexen-3-ol A-2. (a c) (b)(d) A-3. (a) (b) Isomer 5 (c) Isomers 1 and 4 (d) Isomers 2 and 3 A-4. Two sp 2 C atoms; four sp 3 C atoms; three sp 2 H33526 sp 3 H9268 bonds A-5. (a)(c) (b) A-6. A-7. (a) (b) (c) (d) CC(CH 3 ) 3 H 2 C CH 3 (X H11005 Cl, Br, I) (CH 3 ) 2 CHCHCH(CH 3 ) 2 X H11001 (major) CH 3 CH 2 CCH 2 CH 2 CH 3 CHCH 2 CH 3 (major)(CH 3 ) 2 CH11001H 2 C CH 3 (Z)-3-Methyl-3-hexene (E)-3-Methyl-3-hexene Cl Cl OH 1 2 3 4 5 6 OH 4-Methyl-4-penten-2-ol 5-Chloro-2-methyl-1-hexene Cl 1,6-Dimethylcyclohexene 2,3-Dimethyl-2-pentene 782 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 783 A-8. A-9. Step 1: Protonation Step 2: Dissociation Step 3: Deprotonation A-10. A-11. A-12. Cis isomer: Trans isomer: The trans isomer will react faster because its most stable conformation (with the isopropyl group equatorial) has an axial Cl able to undergo E2 elimination. A-13. Rearrangement (hydride migration) occurs to form a more stable carbocation. H 3 PO 4 H11002H H11001 OH H11001 H OH 2 H H11001 H 2 OH11001 Cl (CH 3 ) 2 CH CH(CH 3 ) 2 Cl Cl(CH 3 ) 2 CH (CH 3 ) 2 CH Cl H11001 H Br CH 3 CH 3 Br H11002 CH 3 O H11002 NaOCH 2 CH 3 CH 3 CH 2 OH Br (major) H11001 H11001 HH OH 2 H11001 H 3 O H11001 OH 2 H11001 H11001 H11001 H 2 O H11001 OH H OH 2 H11001 OH 2 H11001 CH 2 BrCH 3 CH 2 C CH 3 CH 3 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-14. B-1. (c) B-2. (c) B-3. (d) B-4. (c) B-5. (a) B-6. (b) B-7. (a) B-8. (a) B-9. (a) B-10. (d) B-11. (b) B-12. (c) B-13. (a) B-14. (c) B-15. (a) CHAPTER 6 A-1. Five; A-2. (a)(c) (b) HBr, peroxides (d) A-3. (a) CH 3 CH 3 OH CH 3 OH H 2 SO 4 (conc) heat 1. B 2 H 6 2. H 2 O 2 , HO H11002 CH 3 Br OH (CH 3 ) 2 CCH 2 CH 3 OH (Z)-3,4-Dimethyl- 2-pentene 2,3-Dimethyl- 1-pentene (E)-3,4-Dimethyl- 2-pentene 2,3-Dimethyl- 2-pentene 3,4-Dimethyl- 1-pentene B Br A 3-Ethyl-4,4-dimethyl-2-pentene 784 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 785 (b) (c) A-4. Initiation: Propagation: A-5. A-6. A-7. Step 1: Protonation to form a carbocation Step 2: Nucleophilic addition of chloride ion A-8. A-9. OH CH 3 CCH 2 CH 3 Cl CH 3 2-Chloro-2- methylbutane (CH 3 ) 2 C CHCH 3 2-Methyl-2-butene H 2 C CCH 2 CH 3 CH 3 2-Methyl-1-butene or HCl H11001 H11001 Cl H11002 Cl H11001 H11001H11001 Cl H11002 HCl CC H CH 3 CH 2 H CH 2 CH 3 CC HH CH 3 CH 2 CH 2 CH 3 O CH 3 COOH O CC H 3 C H H CH 3 (E)-2-Butene Cl 2 H11013 CC CH 3 H 3 C H H Cl Cl CC HH 3 C H CH 3 Cl H11001 Cl H11002 CC H 3 C H HCl H 3 C Cl HBrCH 3 CH 2 CHCH 2 Br CH 3 CH 2 CH 2 CH 2 Br BrH11001H11001 Br H11001 CH 2 CH 3 CH 2 CH CH 3 CH 2 CHCH 2 Br light or heat ROOR 2RO HBrRO ROH BrH11001H11001 CH 3 O H11002 Na H11001 CH 3 OH (CH 3 ) 3 CCH CH 2 HBr Peroxides (CH 3 ) 3 CCH 2 CH 2 Br (CH 3 ) 3 CCHCH 3 Br NaOCH 3 CH 3 OH CH 3 CH 2 CH C(CH 3 ) 2 CH 3 COOH O CH 3 CH 2 CH C(CH 3 ) 2 O CH 3 CH 2 CHCH(CH 3 ) 2 Cl Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-10. A-11. B-1. (c) B-2. (a) B-3. (c) B-4. (d) B-5. (d) B-6. (e) B-7. (b) B-8. (b) B-9. (b) B-10. (b) B-11. (a) B-12. (e) B-13. (e) CHAPTER 7 A-1. (a) 1 and 2, both achiral; identical (b) 3 and 4, both chiral; enantiomers (c) 5 chiral, 6 achiral (meso); diastereomers (d) 7 and 8, both chiral; diastereomers (e) 9 and 10, both chiral; diastereomers A-2. 3: (R)-2-Chlorobutane; 4: (S)-2-Chlorobutane 5: 6: 7: (2S,3R)-2,3-Dibromopentane; 8: (2R,3R)-2,3-Dibromopentane 9: (2E,5R)-5-Chloro-2-hexene; 10: (2Z,5S)-5-Chloro-2-hexene A-3. (a) Three; meso form is possible. (c) Four; no meso form possible. (b) Eight; no meso form possible. HO HO R S OH OH R R C (CH 3 ) 2 C O (2 mol) 1. O 3 2. H 2 O, Zn (CH 3 ) 2 CHCCH 3 CH 3 Br B (CH 3 ) 2 C C(CH 3 ) 2 C (CH 3 ) 2 CHC CH 2 CH 3 A NaOCH 2 CH 3 CH 3 CH 2 OH HBr H11001 HCl hydride shift H11001 H11001 Cl Cl Cl H11002 Cl H11002 786 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 787 A-4. (a)(b) (c) A-5. Chiral stereoisomers: Meso stereoisomer (achiral); plane of symmetry indicated with dashed line A-6. (a)[H9251] H11005H1100231.2° (b) 30% S A-7. (a) (b) (c) A-8. (a)(2S,3S)-1,3-Dibromo-2-chlorobutane (b)(R)-1-Ethylcyclohex-2-en-1-ol H11001 CH 3 COOH O HH H 3 C CH 2 CH 3 O CH 2 CH 3 H 3 C HH O H11001 Cl 2 CC H H 3 C CH 3 H Meso form (only stereoisomer) CC Cl H 3 C H CH 3 Cl H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 Br CH 3 CH 3 Br H11001 HBr CH 3 CH 3 H ClH Cl meso-2,3-Dichlorobutane and CH 3 CH 3 H HCl Cl (2S,3S)-2,3- Dichlorobutane CH 3 CH 3 Cl ClH H (2R,3R)-2,3- Dichlorobutane CH 3 CH 3 H BrH H CH 3 CH 3 HO ClH H H Br HH CH 3 CH 3 Cl H H 3 C CH 3 H OH CC Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-9. Two: (2R,3S)-2-bromo-3-chlorobutane and (2S,3S)-2-bromo-3-chlorobutane; they are di- astereomers. A-10. B-1. (c) B-2. (c) B-3. (b) B-4. (d) B-5. (b) B-6. (c) B-7. (d) B-8. (d) B-9. (b) B-10. (c) B-11. (d) B-12. (d) B-13. (e) B-14. (b) CHAPTER 8 A-1. (a)CH 3 CH 2 CH 2 CH 2 OCH 2 CH 3 (e) (b)(f ) (c) (g) (d) A-2. (CH 3 ) 2 CHO H11002 Na H11001 H11001 CH 3 CH 2 CH 2 Br A-3. (a) (b) A-4. Step 1: Ionization to form a secondary carbocation H 3 C CH 3 CH 3 C CHCH 3 Cl CH 3 CH 3 CH 3 C CHCH 3 H11001 Cl H11002 H 2 O H11001 C H OH CH 3 CH 2 CH 2 H 3 C C H OTs CH 3 CH 2 CH 2 H 3 C pyridine H 3 C SO 2 Cl CH 3 S H11002 C H CH 2 CH 2 CH 3 CH 3 CH 3 S CH 3 CH 2 CH 3 HOTs CH 3 CH 2 CH 3 Br H CH 3 CH 2 CH 3 HCN NaBr DMSO NaCN CH 3 CH 2 CH 3 HS FH H CH 3 CHCH 2 CH 2 I CH 3 CH 3 S H (X H11005 OTs, Br, I) X CH 3 N 3 C(CH 3 ) 3 OH Racemic mixture 788 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 789 Step 2: Rearrangement by methyl migration to form a more stable tertiary carbocation Step 3: Capture of the carbocation by water, followed by deprotonation A-5. (a) S N 1, unimolecular substitution; rate H11005 k[(CH 3 ) 3 CBr] (b) S N 2, bimolecular substitution; rate H11005 k[C 6 H 11 Cl][NaN 3 ] A-6. (a) Sodium iodide is soluble in acetone, whereas the byproduct of the reaction, sodium bromide, is not. According to Le Chatelier’s principle, the reaction will shift in the direction that will replace the component removed from solution, in this case toward product. (b) Protic solvents such as water form hydrogen bonds to anionic nucleophiles, thus stabi- lizing them and decreasing their nucleophilic strength. Aprotic solvents such as DMSO do not solvate anions very strongly, leaving them more able to express their nucle- ophilic character. A-7. A-8. fast H11002H H11001 H 3 C OCH 2 CH 3 H H11001 H 3 C OCH 2 CH 3 CH 3 H11001 H11001 fast HOCH 2 CH 3 H 3 C OCH 2 CH 3 H H11001 BrH 3 C CH 3 H11001 slow OH CH 3 CH 2 OH A O H11002 Na H11001 BC CH 3 CH 2 Br D Cl N 3 NaN 3 CH 3 OH (CH 3 ) 3 CBr (CH 3 ) 3 COCH 3 CH 3 CH 3 CH 3 C CHCH 3 H11001 H 2 O H11002H H11001 H 2 O CH 3 CH 3 C CHCH 3 OH (CH 3 ) 2 C CH(CH 3 ) 2 CH 3 H11001 CH 3 CH 3 CH 3 C CHCH 3 H11001 CH 3 CH 3 CH 3 C CHCH 3 H11001 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-9. Dissociation to give a secondary carbocation Rearrangement by hydride migration to give a tertiary carbocation Capture of the carbocation by water to give product B-1. (b) B-2. (c) B-3. (d) B-4. (c) B-5. (d) B-6. (a) B-7. (c) B-8. (d) B-9. (c) B-10. (a) B-11. (a) B-12. (c) B-13. (c) B-14. (c) CHAPTER 9 A-1. (a) 4,5-Dimethyl-2-hexyne (c) 6,6-Dimethylcyclodecyne (b) 4-Ethyl-3-propyl-1-heptyne A-2. (a)(e) (b)(f ) Na, NH 3 (l) (c)H 2 O, H 2 SO 4 , HgSO 4 (g) (d)(h) A-3. Reaction (2) is effective; the desired product is formed by an S N 2 reaction. Reaction (1) is not effective, owing to E2 elimination from the secondary bromide. H11001H11001H11001 NaBrCH 3 C CNaCH 3 CH 2 CHCH 3 Br CH 3 CH CHCH 3 CH 3 CCH H11001 CH 3 I H11001 NaICH 3 CH 2 CHC CH 3 CNa CH 3 CH 2 CHC CH 3 CCH 3 CH 3 CH 2 CO 2 HH11001CH 3 CH 2 CH 2 CHCO 2 H CH 3 CC H H 3 C CH 3 H CC Cl H 3 C Cl CH 2 CH 3 CH 3 CH 2 CH 2 CCH 3 Cl Cl (CH 3 ) 2 CHC CH CH 3 CH 2 CH 2 C Cl CH 2 CH 3 CH 2 CH 2 CH 2 C(CH 3 ) 2 H11001 H11001 CH 3 CH 2 CH 2 CH 2 C(CH 3 ) 2 OH (H11002H H11001 ) OH 2 CH 3 CH 2 CH 2 CH 2 C(CH 3 ) 2 H11001H11001 CH 3 CH 2 CH 2 CHC(CH 3 ) 2 H CH 3 CH 2 CH 2 CHCH(CH 3 ) 2 H11001 CH 3 CH 2 CH 2 CHCH(CH 3 ) 2 Br 790 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 791 A-4. (a) (b) (c) (d) A-5. A-6. A-7. A-8. B-1. (a) B-2. (c) B-3. (a) B-4. (d) B-5. (b) B-6. (b) B-7. (e) B-8. (c) B-9. (b) B-10. (a) B-11. (d) B-12. (b) CCH CH CH 2 CH 2 CH 2 OH H 2 Lindlar Pd 1. B 2 H 6 2. H 2 O 2 , HO H11002 CCH 2 CH 3 CH 3 CH 2 CF:CCH 2 CH 3 HCE: CH 3 CH 2 CH 2 Br D CH 3 CH 2 CH 2 OH C CNa H11001 (CH 3 ) 3 CC H11002 B CH(CH 3 ) 3 CC A CC H H 3 C CH 2 CH 2 CH 2 CH 3 H (E)-2-Heptene CCH 2 CH(CH 3 ) 2 HC H 2 O, H 2 SO 4 HgSO 4 CH 3 CCH 2 CH(CH 3 ) 2 O CHHC CNaHC CCH 2 CH(CH 3 ) 2 HC NaNH 2 (CH 3 ) 2 CHCH 2 Br CCH 2 CH 3 HC As in part (b) CCH 2 CH 3 CH 3 CH 2 C CHCH 2 CH 3 H 2 C ClCH 2 CHCH 2 CH 3 Cl 2 1. 3NaNH 2 , NH 3 2. H 2 O CCH 2 CH 3 HC Cl CCH 2 CH 3 HC CCH 2 CH 3 NaC NaNH 2 CH 3 CH 2 Br CCH 2 CH 3 CH 3 CH 2 C HC CH HC CCH 2 CH 3 BrCH 2 CH 2 Br 1. NaNH 2 , NH 3 2. H 2 O 1. NaNH 2 2. CH 3 CH 2 Br H 2 CCH 2 CH 3 CH 2 Br BrCH 2 CH 2 Br Br 2 KOC(CH 3 ) 3 DMSO Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website CHAPTER 10 A-1. A-2. A-3. A-4. (a) (b) (c) (d) (e) A-5. (cannot adopt the required s-cis conformation) CO 2 CH 3 CO 2 CH 3 (NBS), heatBr O N O H11001 O O O H11001H 2 C CHCHCH 3 Cl ClCH 2 CH CHCH 3 H11001CH 3 CH CHCHCHCH 3 Br Br (Direct addition) CH 3 CHCH CHCHCH 3 Br Br (Conjugate addition) Br CH 3 H11001 CH 3 OH H 2 O H 2 O OH CH 3 CH 3 H11001 CH 3 H11001 CC HH CH 3 CHH 2 C (3Z)-1,3-Pentadiene CC H CH 3 HCHH 2 C (3E)-1,3-Pentadiene H 2 C CHC CH 2 CH 3 2-Methyl-1,3-butadiene H 2 C CHC CH 2 CH 3 (Conjugated) H 2 CCCHCH 2 CH 3 H 2 CCC(CH 3 ) 2 CH 3 CH C CHCH 3 Allenes H 2 C CHCH 2 CH CH 2 H 2 C CHCH CHCH 3 (Conjugated) 792 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 793 A-6. A-7. A-8. B-1. (b) B-2. (c) B-3. (a) B-4. (c) B-5. (a) B-6. (d) B-7. (a) B-8. (a) B-9. (a) B-10. (d) CHAPTER 11 A-1. (a) m-Bromotoluene (c) o-Chloroacetophenone (b) 2-Chloro-3-phenylbutane (d) 2,4-Dinitrophenol A-2. (a)(b)(c)(d) A-3. (a)(b) A-4. (a) Eight H9266 electrons. No, the substance is not aromatic. (b)6 H9266 electrons. Yes, it is aromatic. (c) 14 H9266 electrons. Yes, it is aromatic. H11002 (14 H9266 electrons) (10 H9266 electrons) H11001 CH 2 Cl Br NH 2 CH 3 CH 3 OCH 3 NO 2 CO 2 H ClCl Br 2 light, heat NBS heat CH 3 CH 2 ONa CH 3 CH 2 OH Br Br A: Br B: I H11002Br H11002 H11002Br H11002 CBr CH 3 CH 3 C CH 3 CH 3 H11001 C CH 3 CH 3 H11001 C CH 3 CH 3 Br Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-5. A-6. (a)(d)Na 2 Cr 2 O 7 , H 2 SO 4 , H 2 O, heat (b)C 6 H 5 CH 2 X (X H11005 Cl, Br, I, OTs) (e) (c) ( f ) A-7. (I) (II) A-8. A-9. A-10. B-1. (c) B-2. (c) B-3. (a) B-4. (b) B-5. (a) B-6. (d) B-7. (b) B-8. (d) B-9. (b) B-10. (d) B-11. (a) B-12. (b) B-13. (c) B-14. (d) B-15. (c) CHAPTER 12 A-1. CH 3 Br H H11001 H11001H11001 CH 3 Br H CH 3 Br H (CH 3 ) 3 CCH 2 CH 3 H11001 H11001 H11001 H11001 H11001 CH 3 CH H11001 CH 3 CH H11001 CH 3 CH H11001 CH 3 CH H11001 C 6 H 5 CH 2 CH 2 CH 3 C 6 H 5 CHCH 2 CH 3 Br Br 2 light (or NBS, heat) C 6 H 5 CH C 6 H 5 CHCH 2 CH 3 Br CHCH 3 HBr C 6 H 5 CHCHCH 3 Br OH OH O Br H11001 H11001 H11013 H11002 H11002 794 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 795 A-2. (a)(c) (b) A-3. (a)NO 2 H11001 (b)(c)SO 3 A-4. (a)(d) (b)(e) (c) A-5. (a)(c) (b)(d) OHCH 3 CH 2 Cl H11001 CN OCH 3 Cl CN Cl OCH 3 O Cl H11001 O Cl NO 2 CH 3 Cl C 6 H 5 CCl, AlCl 3 O or CH 3 COCCH 3 , AlCl 3 O O S Cl CH 3 H 3 C NO 2 OCCH(CH 3 ) 2 C(CH 3 ) 3 O Br Br FeBr 3 H11001 H11002 Br CH 2 CH 3 H11001 Br CH 2 CH 3 Faster H11001 Cl SO 3 H Cl HO 3 S Slower NO 2 NO 2 Slower Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-6. (a) (b) (c) (d) (e) A-7. (a) (b) Br 2 light NaOCH 2 CH 3 NO 2 (CH 3 ) 2 CH [Prepared from benzene as in Problem A-6(e)] NO 2 (CH 3 ) 2 C Br NO 2 H 2 CC CH 3 Na 2 Cr 2 O 7 H 2 O, H 2 SO 4 , heat HNO 3 (excess) H 2 SO 4 CH 3 CO 2 H O 2 N CO 2 H NO 2 (CH 3 ) 2 CH (CH 3 ) 2 CH NO 2 (CH 3 ) 2 CHCl AlCl 3 HNO 3 H 2 SO 4 SO 3 H SO 3 H Br Br 2 FeBr 3 H 2 SO 4 heat N 2 H 4 , KOH, heat or Zn(Hg), HCl CH 3 (CH 3 C) 2 O AlCl 3 O CH 3 CH 3 C O CH O C 6 H 5 CH 2 CCl AlCl 3 O CCH 2 C 6 H 5 O Zn(Hg), HCl or N 2 H 4 , KOH, heat Cl CCH 2 C 6 H 5 O Cl CH 2 CH 2 C 6 H 5 Cl 2 , FeCl 3 CH(CH 3 ) 2 CO 2 HHO 3 S SO 3 H 2 SO 4 Na 2 Cr 2 O 7 , H 2 O H 2 SO 4 , heat CH(CH 3 ) 2 HO 3 S (H11001 ortho isomer) 796 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 797 (c) A-8. B-1. (c) B-2. (b) B-3. (c) B-4. (b) B-5. (a) B-6. (b) B-7. (c) B-8. (b) B-9. (c) B-10. (a) B-11. (e) B-12. (c) B-13. (c) B-14. (c) B-15. (c) CHAPTER 13 A-1. 1: 6.10 ppm 3: 200 MHz 2: 1305 Hz 4: 0.00 ppm A-2. (a) Two signals BrCH 2 CH 2 CH 2 Br aba a: triplet b: pentet (b) Two signals a: triplet b: quartet (c) Three signals, all singlets A-3. A-4. (a)(c) (b) (d) A-5. Seven signals: a: H9254 10–30 ppm b: H9254 20–40 ppm c: H9254 190–220 ppm d–g: H9254 110–175 ppm CCH 2 CH 3 O abc d e f g (CH 3 ) 2 CCN OH (CH 3 ) 2 C C(CH 3 ) 2 HO OH HC(COCH 2 CH 3 ) 3 O CH 2 CCH 2 CH 3 O CH 3 COC(CH 3 ) 3 CH 3 OCC(CH 3 ) 3 A: B: O O CH 3 CH 2 CCH 2 CH 3 Cl Cl aabb CH 3 O CH 3 ONO 2 Br CH 3 O NO 2 Br 2 FeBr 3 HNO 3 H 2 SO 4 (H11001 ortho) CH 3 (CH 3 ) 2 CHCCl AlCl 3 O CH 3 CCH(CH 3 ) 2 O CH 3 Cl CCH(CH 3 ) 2 O Cl 2 FeCl 3 CH 3 Cl CH 2 CH(CH 3 ) 2 Zn(Hg), HCl Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-6. Pentane: three signals; 2-methylbutane: four signals; 2,2-dimethylpropane: two signals A-7. 2,3-Dimethylbutane: (CH 3 ) 2 CHCH(CH 3 ) 2 B-1. (d) B-2. (a) B-3. (b) B-4. (b) B-5. (b) B-6. (a) B-7. (b) B-8. (a) B-9. (c) B-10. (a) B-11. (c) B-12. (c) B-13. (a) B-14. (a) B-15. (d) CHAPTER 14 A-1. (a) (b) (c) A-2. (a) (d) (b)(e) (c) A-3. (a) (b) A-4. (a)(CH 3 CH 2 CH 2 ) 2 CuLi (c)CH 2 I 2 , Zn(Cu) (b)(CH 3 ) 2 CHMgX (X H11005 Cl, Br, I) andH11001 O CH 3 CH 2 CH 2 CH CH 3 CH 2 CH 2 CH 2 MgX (X H11005 Cl, Br, I) H11001CH 3 CH 2 CH 2 CH 2 CH O CH 3 CH 2 CH 2 MgX (X H11005 Cl, Br, I) C 6 H 5 CH H11001H11001C 6 H 5 MgX(CH 3 ) 3 CMgX and (CH 3 ) 3 CCH O O (X H11005 Cl, Br, I) (X H11005 Cl, Br, I) H 3 C CH 2 OH H 3 C CH 3 Br Br H H (CH 3 ) 2 CHCH 2 D CH 2 CH 3 HO H11001 CH 3 CH 2 OH(C 6 H 5 ) 2 CCH 3 OH 2C 6 H 5 CH 2 Li (C 6 H 5 CH 2 ) 2 CuLi LiXH11001H11001CuX (X H11005 Cl, Br, I) (CH 3 ) 3 CBr Mg (CH 3 ) 3 CMgBrH11001 2Li LiX (X H11005 Cl, Br, I) H11001 LiXH11001 798 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 799 A-5. Solvents A, B, and E are suitable; they are all ethers. Solvents C and F have acidic hydrogens and will react with a Grignard reagent. Solvent D is an ester which will react with a Grignard reagent. A-6. A-7. (I) (II) (III) A-8. A-9. (a)(c) (b) B-1. (c) B-2. (a) B-3. (d) B-4. (a) B-5. (e) B-6. (c) B-7. (b) B-8. (a) B-9. (e) B-10. (b) B-11. (b) B-12. (b) CHAPTER 15 A-1. (a)(d) OsO 4 , (CH 3 ) 3 COOH, (CH 3 ) 3 COH, HO H11002 (b e) (c) 1. B 2 H 6 ; 2. H 2 O 2 , HO H11002 H 2 NCNH 2 S C 6 H 5 CO 2 CH 2 CH 3 O OH CCH 3 OH C CCH 2 CH 3 OH CH 3 C 6 H 5 CHMgBr CH 3 C 6 H 5 CHCHCH 3 CH 3 OH 1. CH 3 CH 2. H 3 O H11001 O C 6 H 5 CHCH 3 C 6 H 5 CHMgBrC 6 H 5 CH 2 CH 3 NBS peroxides, heat Mg diethyl ether CH 3 Br H11001 O (CH 3 ) 2 CHCCH 3 CH 3 MgBr H11001 O CH 3 CCH 3 (CH 3 ) 2 CHMgBr H11001(CH 3 ) 2 CHCO 2 CH 3 2CH 3 MgBr 1. diethyl ether 2. H 3 O H11001 OH (CH 3 ) 2 CHC(CH 3 ) 2 2CH 3 (CH 2 ) 3 Li CuBr (C 4 H 9 ) 2 CuLi CH 3 (CH 2 ) 6 CH 3 CH 3 (CH 2 ) 3 Br H11001 CH 3 (CH 2 ) 3 OH CH 3 (CH 2 ) 3 Br CH 3 (CH 2 ) 3 Li LiBr PBr 3 or HBr 2Li H11001 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-2. (a) (c)(C 6 H 5 CH 2 CH 2 ) 2 O (b) (d)K 2 Cr 2 O 7 ,H + , H 2 O, heat A-3. (a) (CH 3 ) 2 CHO H11002 Na H11001 (e) (b) (CH 3 ) 2 C H5007 H5007 O(f ) (c) (CH 3 ) 2 C H5007 H5007 O(g) (d) A-4. (I) (II) A-5. (a)(c) (b) A-6. (a) PCC or PDC in CH 2 Cl 2 (b)Na 2 Cr 2 O 7 , H H11001 , H 2 O, heat (c) 1. LiAlH 4 ; 2. H 2 O (d) OsO 4 , (CH 3 ) 3 COOH, (CH 3 ) 3 COH, HO H11002 A-7. O CO 2 CH 3 C O CO 2 H B OH OH A HO OH CC H H 3 C H CH 3 H O O (CH 3 ) 2 CHCH 2 MgBr (CH 3 ) 2 CHCH 2 CH 2 OH 1. H 2 CO 2. H 3 O H11001 (CH 3 ) 2 CHCH 2 Br H11001 Mg (CH 3 ) 2 CHCH 2 MgBr (CH 3 ) 2 CHBr H11001 Mg (CH 3 ) 2 CHMgBr (CH 3 ) 2 CHCH 2 CH 2 OH 2. H 3 O H11001 O 1. H 2 C CH 2 CH 3 COCH(CH 3 ) 2 O CH 3 COCH(CH 3 ) 2 O COCH(CH 3 ) 2 O CH 3 CH 2 CH 3 (CH 3 ) 2 CHOSO 2 (CH 3 C) 2 O; or CH 3 CO 2 H, H H11001 O CH 3 CCl, pyridine; or O C 6 H 5 CH 2 CH O 800 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 801 A-8. (a) (b) (c) B-1. (e) B-2. (d) B-3. (c) B-4. (c) B-5. (b) B-6. (b) B-7. (a) B-8. (a) B-9. (d) B-10. (a) B-11. (b) B-12. (d) B-13. (e) B-14. (a) B-15. (c) CHAPTER 16 A-1. CH 3 OCH 2 CH 2 CH 3 Methyl propyl ether CH 3 OCH(CH 3 ) 2 Isopropyl methyl ether CH 3 CH 2 OCH 2 CH 3 Diethyl ether A-2. (a)(d) (b)(e) C 6 H 5 SCH 2 CH 3 (c) ( f ) C 6 H 5 SCH 2 CH 3 O H11002 H11001 C 6 H 5 CHCH 2 OH I C C H 3 C H OH H HO H 3 C CH 3 CH 3 OH SCH 2 CH 3 C OCH 3 CH 3 H CH 3 CH 2 C 6 H 5 CH 3 C 6 H 5 CH 2 Br C 6 H 5 CH 2 MgBr NBS peroxides, heat C 6 H 5 CH 2 CH 2 CO 2 HC 6 H 5 CH 2 CH 2 CO 2 CH 2 CH 3 C 6 H 5 CH 2 CH 2 CH 2 OH K 2 Cr 2 O 7 H H11001 , H 2 O heat Mg O 1.H 2 CCH 2 2. H 3 O H11001 CH 3 CH 2 OH H H11001 Na 2 Cr 2 O 7 H H11001 , H 2 O 1. CH 3 CH 2 MgBr 2. H 3 O H11001 CH O CCH 2 CH 3 O CHCH 2 CH 3 OH (CH 3 ) 2 CHCHCH 3 OH (CH 3 ) 2 CHCCH 3 O (CH 3 ) 2 C CHCH 3 PDC CH 2 Cl 2 1. B 2 H 6 2. H 2 O 2 , HO H11002 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website 802 APPENDIX A A-3. (a) A-4. A-5. (a) (b) A-6. A-7. A-8. B-1. (a) B-2. (a) B-3. (c) B-4. (d) B-5. (d) B-6. (e) B-7. (a) B-8. (c) B-9. (d) B-10. (d) CHAPTER 17 A-1. (a) 3,4-Dimethylhexanal (b) 2,2,5-Trimethylhexan-3-one (c) trans-4-Bromo-2-methylcyclohexanone (d) 5-Methyl-4-hexen-3-one A-2. (a)(b)(c) C 6 H 5 CHCHCH 2 CH CH 3 CH 2 CH 3 OO CH 3 CCHCCH 3 O C O C H CH 3 C H CH 2 CH 3 H 3 C HO H 2 N H H 3 O H11001 CH 3 H 3 C OH OH CH 3 COOH O O H 3 C H 2 SO 4 heat CH 3 O H 3 C OH 1. CH 3 MgBr 2. H 3 O H11001 A: CH 2 OH B: CH 2 OCH 2 CH 3 H 2 SO 4 heat CH 3 COOH O CH 3 CH 3 COH CH 3 CCH 2 CH 3 CCH 2 O NaOH NaSCH 3 O HO Br SCH 3 HO CH 3 CH 2 OH CH 3 CH 2 OCH 2 CH 2 OH Na CH 3 CH 2 O H11002 Na H11001 CH 3 CH 2 OH H 2 CCH 2 O CH 3 CH 2 OH H 2 SO 4 heat CH 3 COOH H 2 CCH 2 O H 2 CCH 2 O OH OCH 2 CH 3 O H11002 Na H11001 Na CH 3 CH 2 I Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 803 A-3. (a)(e) (b f ) (c)(g) (d h) A-4. (a) (b) A-5. (a) (1) CH 3 MgI; (2) H 3 O H11001 ; (3) H 2 SO 4 , heat (b) (c) HOCH 2 CH 2 OH, H H11001 (cat), heat (d) A-6. (a) (b) A-7. (a) (CH 3 ) 2 C (CH 3 ) 2 C(C 6 H 5 ) 3 P H11001 H11001 CHCH 3 CHCH 3 H11002 O CH 3 COOH O (CH 3 ) 2 C CHCH 3 O (C 6 H 5 ) 3 PCH 3 CH 2 II H11002 (C 6 H 5 ) 3 P H11001 CH 2 CH 3 H11001 C 4 H 9 Li (C 6 H 5 ) 3 P H11001 CHCH 3 H11002 H11013 H 3 C H 3 C HO O OH CH 3 CCH 2 CH 2 CH 2 CCH 2 OH O OH CH 3 O CH 3 H 3 C H11001 OHHO CH 3 COOH O ]CH 3 IH11001(C 6 H 5 ) 3 P H11001 CH 2 [from (C 6 H 5 ) 3 P H11002 C 4 H 9 Li D C 6 H 5 CH 2 CCH 3 O E C 6 H 5 CH 2 OCCH 3 O (C 6 H 5 ) 3 P H11001 CH 2 CH(CH 3 ) 2 Br H11002 A (C 6 H 5 ) 3 P H11001 B CHCH(CH 3 ) 2 H11002 C C 6 H 5 CH CHCH(CH 3 ) 2 CH 3 CH 2 CH 2 COH O (C 6 H 5 ) 3 P H11001 CHCH 2 CH 3 H11002 C 6 H 5 CCH 2 CH 3 (CH 3 ) 2 NHH11001 O HOCH 2 CH 2 CH 2 OHH11001(CH 3 ) 2 CHCH O CH 3 CH 2 CH 2 CH(OCH 2 CH 3 ) 2 NH 2 OH CH 3 NNHC 6 H 5 OH CN Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website (b) (c) A-8. A-9. B-1. (c) B-2. (d) B-3. (a) B-4. (c) B-5. (b) B-6. (b) B-7. (a) B-8. (b) B-9. (e) B-10. (c) B-11. (c) B-12. (c) B-13. (d) B-14. (e) B-15. (a) B-16. (c) CHAPTER 18 A-1. (a)(c) (b) O O O O H11002 H11002 Na H11001 O H9007H 2 C CCH 2 CH 3 and OH CH 3 C CHCH 3 OH CH 2 CCH 3 O CH 3 CH OH OCH 3 H H11001 H11002H H11001 CH 3 CH H11001 OH 2 OCH 3 CH 3 CHOCH 3 H11001 CH 3 CH HOCH 3 OCH 3 H11001 CH 3 CH OCH 3 OCH 3 CH 3 OH O CH 3 CH OH H11001 HOCH 3 CH 3 CH OH OCH 3 CH 3 CH H H11001 H11002H H11001 H11001 OH CH 3 CH CH 3 OH PBr 3 H 3 O H11001 CH 2 Br CH 2 Br OO CH 2 OH OO O O CO 2 H H H11001 (cat) HOCH 2 CH 2 OH 1. LiAlH 4 2. H 2 O CO 2 H OO CH 2 OH OO O CH 3 OH H H11001 CH 2 Cl 2 PCC 1. CH 3 MgI 2. H 3 O H11001 CH 3 OH CH 3 O O CH 3 HO CH 3 OO OO HOCH 2 CH 2 OH 804 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 805 A-2. A-3. A-4. A-5. A-6. (a) (b) (c) (d) CHCH 2 C SCH 3 O CH O CH 3 CH 3 CH 3 CH 2 CH 2 CH 2 CHCHCH CH 2 CH 2 CH 3 OOH CH 3 CH 2 CH 2 CHCH Br O K 2 CO 3 H11001 CH 3 CH 2 I O O CH 2 CH 3 O O CH 2 CH 3 CH 2 CH 2 CCH 3 O O O CHCCH 3 H 2 C KOH O NaOH 2CH 3 CH O CH 3 CHCH 2 CH OOH CH 3 CHCH 2 CH 2 OH OH NaBH 4 , CH 3 OH or 1. LiAlH 4 2. H 2 O CH 3 CH O CH 3 CH 2 OH PCC CH 2 Cl 2 CH 3 CH 2 CHCHCH CH 3 OOH CH 3 CHCHCHCH CH 3 OOH CH 3 CH 3 CHCHC(CH 3 ) 2 HC O OH CH 3 CH 3 CH 2 CHC(CH 3 ) 2 HC O OH A C 6 H 5 CH 2 CH C 6 H 5 CCH O B (CH 3 CH 2 ) 2 CHCH 2 CCH 2 CH 3 O Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-7. A-8. B-1. (a) B-2. (c) B-3. (b) B-4. (b) B-5. (a) B-6. (c) B-7. (c) B-8. (e) B-9. (c) B-10. (b) B-11. (a) B-12. (a) CHAPTER 19 A-1. (a) 4-Methyl-5-phenylhexanoic acid (b) Cyclohexanecarboxylic acid (c) 3-Bromo-2-ethylbutanoic acid A-2. 4-Phenylbutanoic acid is C 6 H 5 CH 2 CH 2 CH 2 CO 2 H. A-3. A-4. A-5. (a) (b) (c) (d) CH 3 CH 2 CH CN OH H H11001 , H 2 O heat CH 3 CH 2 CHCOH Br O Br 2 , P CH 3 CH 2 CH 2 CH 2 OH 1. LiAlH 4 2. H 2 O MgBr Mg A (CH 3 ) 2 CHCH 2 CHCO 2 H Br B (CH 3 ) 2 CHCH 2 CHCO 2 H I C C 6 H 5 CC(CH 3 ) 2 CO 2 H O C 6 H 5 CH 2 CO 2 HC 6 H 5 CH 2 COCH 2 CH 3 O CH 3 CH 2 OH H 2 OH11001H11001 H H11001 (cat) C 6 H 5 CH 2 CH 2 CH 2 Br 1. Mg 2. CO 2 3. H 3 O H11001 C 6 H 5 CH 2 CH 2 CH 2 Br 1. CN H11002 2. H H11001 , H 2 O, heat C 6 H 5 CH 2 CH 2 CH(CO 2 H) 2 heat H11001CH O CH 3 CH 2 CCH 2 CH 3 O H11001CH 3 CHCH H O OH H11002 CH 3 CHCH CH 2 O O H11002 CH 3 CHCH CH 2 OH O CH 3 CHCH O H11002 H 2 CO HO H 806 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 807 A-6. A-7. A-8. B-1. (b) B-2. (a) B-3. (c) B-4. (d) B-5. (c) B-6. (d) B-7. (c) B-8. (d) B-9. (e) B-10. (c) B-11. (e) CHAPTER 20 A-1. (a) Propyl butanoate (c) 4-Methylpentanoyl chloride (b) N-Methylbenzamide A-2. (a)(b) (c) A-3. (a) SOCl 2 (b) Br 2 , NaOH, H 2 O(c) A-4. (a)(d) (b) (e) (c) COCH 2 CH 3 O COH O CH 3 NH 3 HSO 4 H11002 H11001H 3 CCO 2 H H11001 C 6 H 5 CO O CH 3 CH 2 OHH11001CH 3 CH 2 CN(CH 3 ) 2 O CH 3 CO 2 H H11001 OH C 6 H 5 COCH 3 O C 6 H 5 COC 6 H 5 O CH 3 CNHCHCH 2 CH 3 O CH 3 C 6 H 5 COCC 6 H 5 O O H11001CH 3 COH OH OCH 3 H H11001 H11002H H11001 CH 3 COCH 3 OH H11001 CH 3 COCH 3 O H 2 OCH 3 COH 2 OH OCH 3 H11001 CH 3 COH O H11001 CH 3 COH OH OCH 3 H H11001 H11002H H11001 CH 3 COH OH H11001 HOCH 3 CH 3 COH OH HOCH 3 H11001 OH HCOH OCH 2 CH 2 CH 2 CH 3 CH 3 CH 2 CHCO 2 H Br Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-5. A-6. A-7. (a)(b) A-8. A-9. CH 2 OH Benzyl alcohol CO 2 H Benzoic acid 1. LiAlH 4 2. H 2 O CH 3 Toluene CO 2 H Benzoic acid Na 2 Cr 2 O 7 H 2 SO 4 , H 2 O, heat H 3 CBr H 3 CNH 2 H 3 C MgBr H 3 CCO 2 H H 3 C CCl O H 3 C CNH 2 O Mg 1. CO 2 2. H 3 O H11001 NH 3 Br 2 , NaOH H 2 O SOCl 2 CH 3 COCCH 3 OHO NH 2 CH 3 COCH 3 OH OH NH 2 CH 3 C Br 2 , NaOH H 2 O P 4 O 10 heat D C CH 3 N B BA SOCl 2 NH 3 CO 2 H CH 3 O CCl CH 3 O CNH 2 CH 3 fromOC C 6 H 5 H 3 C N CH 2 CH 2 OH HN CH 3 CH 2 CH 2 OC 6 H 5 C O 808 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 809 A-10. The compound is 2-chloropropanamide. The compound may be prepared from propanoic acid as shown. B-1. (a) B-2. (b) B-3. (b) B-4. (c) B-5. (d) B-6. (c) B-7. (d) B-8. (d) B-9. (b) B-10. (a) B-11. (d) B-12. (b) B-13. (b) CHAPTER 21 A-1. (a)(e) (b) ( f ) (c)(g) (d) A-2. BA CH 3 CH 2 OC(CH 2 ) 4 COCH 2 CH 3 OO O O COCH 2 CH 3 CH 2 CH 3 (CH 3 CH 2 O 2 C) 2 CHCH 2 CH 2 COCH 2 CH 3 O CH 3 CCH 2 CH 2 CO 2 H OCO 2 H Cl CO 2 H Cl H11001 1. HO H11002 , H 2 O 2. H 3 O H11001 3. heat C 6 H 5 CH 2 COCH 2 CH 3 O CH 3 CCHCOCH 2 CH 3 O CH 2 C 6 H 5 O CH 3 CH 2 CH 2 CCHCOCH 2 CH 3 O O CH 2 CH 3 Cl 2 P SOCl 2 NH 3 O CH 3 CHC Cl Cl 2-Chloropropanoyl chloride O CH 3 CHC Cl NH 2 2-Chloropropanamide CH 3 CHCO 2 H Cl 2-Chloropropanoic acid CH 3 CH 2 CO 2 H Propanoic acid 2-Chloropropanamide CH 3 CHC Cl NH 2 O Benzyl benzoate CH 2 OH Benzyl alcohol CO 2 H H11001 Benzoic acid H H11001 COCH 2 O Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-3. (a) (b) A-4. 2CH 3 CH 2 COCH 2 CH 3 NaOCH 2 CH 3 O CH 3 CHCOCH 2 CH 3 O CH 3 CHCOCH 2 CH 3 O CH 3 CH 2 COCH 2 CH 3 O CH 3 CH 2 C OCH 2 CH 3 CH 3 CHCOCH 2 CH 3 O CH 3 CH 2 CO CH 3 CCOCH 2 CH 3 O CH 3 CH 2 CO O H11002 H11001 H11002CH 3 CH 2 O H11002 H11002H H11001 H11002 H11002 H11001C 6 H 5 CCH 3 O C 6 H 5 CCH 2 COCH 2 CH 3 O O CH 3 CH 2 OCOCH 2 CH 3 O NaOCH 2 CH 3 C 6 H 5 CCH 2 CH 2 CH 2 CCH 3 O O C 6 H 5 CCHCOCH 2 CH 3 CH 2 CH 2 CCH 3 O O O 1. HO H11002 , H 2 O 2. H 3 O H11001 3. heat 1. NaOCH 2 CH 3 O 2. H 2 C CHCCH 3 CH 3 CCH 2 COCH 2 CH 3 O O CH 3 CCHCOCH 2 CH 3 CH 2 COCH 2 CH 3 O O O O 1. NaOCH 2 CH 3 2. BrCH 2 COCH 2 CH 3 CH 3 CCH 2 CH 2 COH O O 1. HO H11002 , H 2 O 2. H 3 O H11001 3. heat CH 3 CH 2 CH 2 CCH 2 CH 2 CH 3 O E CH 3 CH 2 CH 2 CCHCOCH 2 CH 3 O O CH 2 CH 3 CD O CH 2 CH 3 810 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 811 A-5. Enolization of the Claisen condensation product is necessary for completion of the reaction. The condensation product of ethyl 3-methylbutanoate can enolize; the product from con- densation of ethyl 2-methylpropanoate cannot. B-1. (b) B-2. (d) B-3. (c) B-4. (b) B-5. (c) B-6. (c) B-7. (b) B-8. (d) CHAPTER 22 A-1. (a) 1,1-Dimethylpropylamine or 2-methyl-2-butanamine; primary (b) N-Methylcyclopentylamine or N-methylcyclopentanamine; secondary (c) m-Bromo-N-propylaniline; secondary A-2. (a) NaN 3 (b) KCN (c) A-3. (a) (e) (b)(f ) (c)H 3 PO 2 (g) (d) (CH 3 C) 2 Oor O CH 3 CCl O O NCH 2 CH 3 N N(CH 3 ) 2 O NBrH 3 C NHCCH 3 CH 2 CH 3 O 2 N NHCCH 3 O NO 2 CH 2 CH 3 H11001 O N 2 H11001 Cl H11002 H 3 C N H11002 K H11001 O O NaOCH 2 CH 3 CH 3 CH 2 CCOCH 2 CH 3 O O CH 3 CH 2 CHC CH 3 H 3 C Claisen product cannot enolize 2CH 3 CH 2 CHCOCH 2 CH 3 O CH 3 Ethyl 2-methylbutanoate CH 3 CHCH 2 C CH 3 CHCHCOCH 2 CH 3 O O CH 3 CH 3 NaOCH 2 CH 3 H11002H H11001 H11002 CH 3 CHCH 2 C CH 3 CHCCOCH 2 CH 3 O O CH 3 CH 3 2CH 3 CHCH 2 COCH 2 CH 3 OCH 3 Ethyl 3-methylbutanoate Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-4. (a) (b) A-5. (a) (b) (c) A-6. In the para isomer, resonance delocalization of the electron pair of the amine nitrogen involves the nitro group. A-7. Strongest base: C, an alkylamine Weakest base: D, a lactam (cyclic amide) NH 2 H11001 NH 2 N H11001 O H11002 O H11002 O O H11002 N H11001 C 6 H 5 NH 2 C 6 H 5 N N N(CH 3 ) 2 C 6 H 5 N 2 H11001 Cl H11002 NaNO 2 , HCl H 2 O C 6 H 5 N(CH 3 ) 2 C 6 H 6 HNO 3 H 2 SO 4 Cl 2 , FeCl 3 1. Sn, HCl 2. NaOH NO 2 NO 2 Cl NH 2 Cl C 6 H 6 (CH 3 ) 3 CCl AlCl 3 HNO 3 H 2 SO 4 NaNO 2 , HCl H 2 O KI 1. Sn, HCl 2. NaOH C(CH 3 ) 3 NO 2 C(CH 3 ) 3 NH 2 C(CH 3 ) 3 I C(CH 3 ) 3 N 2 H11001 Cl H11002 C(CH 3 ) 3 D NHCH 2 CH 3 E NO NCH 2 CH 3 CH 2 CH 3 N A CH 2 CH 3 H 3 C N I H11002 H11001 B CH 2 CH 3 H 3 C N OH H11002 H11001 C 812 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 813 A-8. B-1. (b) B-2. (d) B-3. (c) B-4. (d) B-5. (c) B-6. (e) B-7. (d) B-8. (c) B-9. (d) B-10. (e) B-11. (c) B-12. (b) B-13. (c) B-14. (c) CHAPTER 23 A-1. (a)(c) (b) A-2. (a)(c) (b) A-3. (a) (b) (CH 3 ) 2 CHCl AlCl 3 NaNH 2 , NH 3 Cl CH(CH 3 ) 2 CH(CH 3 ) 2 Cl NH 2 (H11001 ortho isomer) (H11001 meta isomer) HNO 3 , H 2 SO 4 heat NaOCH 3 Cl NO 2 NO 2 Cl NO 2 NO 2 OCH 3 CH 3 O Cl N H11002 O O H11002 Cl H11001 C(CH 3 ) 3 CF 3 NO 2 Cl CH 3 O H11001 C(CH 3 ) 3 C(CH 3 ) 3 NH 2 NH 2 H11001 CF 3 CF 3 NH 2 NH 2 C(CH 3 ) 3 NHCCH 3 O A C(CH 3 ) 3 NH 2 B C(CH 3 ) 3 ClCl NH 2 C C(CH 3 ) 3 ClCl Br D Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-4. The mechanism for para substitution is similar. A-5. B-1. (a) B-2. (a) B-3. (c) B-4. (d) B-5. (b) B-6. (a) B-7. (a) B-8. (a) CHAPTER 24 A-1. p-Hydroxybenzaldehyde is the stronger acid. The phenoxide anion is stabilized by conjuga- tion with the aldehyde carbonyl. A-2. HNO 3 p-Cresol OH CH 3 OH CH 3 NO 2 m-Cresol HNO 3 OH CH 3 NO 2 OH CH 3 OH CH 3 O 2 N H11001 o-Cresol HNO 3 OH CH 3 NO 2 OH CH 3 OH CH 3 O 2 N H11001 OH C HO H H11001 H11001 C HO O H11002 C HO O H11002 Product: Intermediate: NO 2 Y H11001 X H11002 NO 2 H11002 X Y NO 2 X Y H11002 N O H11002H11002 O H11001 N X Y X Y O H11002 O H11001 H11002 814 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 815 A-3. A-4. (a)(c) (b)(d) A-5. A-6. B-1. (d) B-2. (d) B-3. (b) B-4. (a) B-5. (c) B-6. (b) B-7. (b) B-8. (c) CHAPTER 25 A-1. (a)(b) or OHH HO H CHO CH 2 OH L-Threose HHO HOH CHO CH 2 OH D-Threose HHO HO H CHO CH 2 OH L-Erythrose C(CH 3 ) 3 C(CH 3 ) 3 NO 2 HNO 3 H 2 SO 4 1. Sn, HCl 2. NaOH C(CH 3 ) 3 NH 2 C(CH 3 ) 3 OH 1. NaNO 2 , H 2 SO 2 , H 2 O 2. H 2 O, heat CHCH 2 CH 3 CHCH CH 2 CH 2 CH 3 OH B OCH 2 CH A OH Br H11001 BrCH 2 CH(CH 3 ) 2 O H11002 Na H11001 CH 3 CO 2 , 125H11034C, 100 atmOH H11001 BrCH(CH 3 ) 2 (absence of AlCl 3 ) OH CH 3 H11001 CH 3 CH 2 CCl O (Esterification) OCCH 2 CH 3 CH 3 O AlCl 3 OH CH 3 H11001 CH 3 CH 2 CCl O (Friedel–Crafts acylation) OH CH 3 CCH 2 CH 3 O Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website (c)(e) (d) A-2. (a)(b) (c) 5HCO 2 H H11001 H 2 C?O A-3. (a) (c) (b) A-4. H9252-D-Idopyranose (H9252-pyranose form of D-idose) A-5. The products are diastereomers. B-1. (b) B-2. (d) B-3. (b) B-4. (a) B-5. (c) B-6. (c) B-7. (a) B-8. (c) B-9. (c) B-10. (c) H11001 HCl H11001 OHH HOH CH 2 OH HHO HO H CHO D-Mannose CH 3 OH Methanol HOCH 2 H HO HO OCH 3 O OH Methyl H9251-D-mannopyranoside HOCH 2 OCH 3 HO HO H O OH Methyl H9252-D-mannopyranoside H HOCH 2 OH H HHO OH H O HO H H OH OH H H OH O H HO H OH H OH HO H O OHH HOH CH 2 OH HHO HO H CO 2 H11002 OHH HOH CH 2 OH HHO HO H CH 2 OH H9252-D-Erythrofuranose OH H HH OH OH O OHH R R HOH CHO CH 2 OH H9251-D-Erythrofuranose H OH H H OH OH O 816 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 817 CHAPTER 26 A-1. A-2. Fats are triesters of glycerol. A typical example is tristearin, shown in the preceding problem. A wax is usually a mixture of esters in which the alkyl and acyl group each contain 12 or more carbons. An example is hexadecyl hexadecanoate (cetyl palmitate). A-3. (a) Monoterpene; (b) Sesquiterpene; (c) Diterpene; A-4. CC H CH 3 (CH 2 ) 7 H (CH 2 ) 7 CO 2 H Oleic acid HC C(CH 2 ) 6 CH 2 OO H CO 2 H C 15 H 31 COC 16 H 33 O 3NaOH CHOH CH 2 OH CH 2 OH C 17 H 35 COCH O CH 2 OCC 17 H 35 O CH 2 OCC 17 H 35 O H11001 3C 17 H 35 CO 2 H11002 Na H11001 H11001 Tristearin Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website A-5. Geranyl pyrophosphate B-1. (b) B-2. (a) B-3. (c) B-4. (c) B-5. (a) B-6. (a) CHAPTER 27 A-1. (a) (b) (c) DCCI A-2. A-3. (a) CH 3 CNHCH(CO 2 CH 2 CH 3 ) 2 O NaOCH 2 CH 3 ethanol 1. H 3 O H11001 2. heat CH 3 CNHC(CO 2 CH 2 CH 3 ) 2 O H11002 (CH 3 ) 2 CHCH 2 Br CH 3 CNHC(CO 2 CH 2 CH 3 ) 2 CH 2 CH(CH 3 ) 2 O H 3 NCHCO 2 H11002 CH 2 CH(CH 3 ) 2 H11001 NHCHCO 2 H CH 2 C 6 H 5 O 2 N NO 2 O C 6 H 5 CH 2 OCNHCHCO 2 H CH(CH 3 ) 2 O C 6 H 5 CH 2 CH OPP H11002H H11001 H11001 OPP Limonene HC C(CH 2 ) 6 CH 2 OO H NaNH 2 H 3 O H11001 CH 3 (CH 2 ) 6 CH 2 Br C(CH 2 ) 6 CH 2 OO HNa H11001 H11002 C C(CH 2 ) 6 CH 2 OO HCH 3 (CH 2 ) 7 C C(CH 2 ) 7 CHCH 3 (CH 2 ) 7 C O CC H CH 3 (CH 2 ) 7 H (CH 2 ) 7 CO 2 H H 2 Lindlar Pd CH 3 (CH 2 ) 7 C C(CH 2 ) 7 CO 2 H Na 2 Cr 2 O 7 H 2 SO 4 , H 2 O 818 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX A 819 (b) A-4. Leu-Val-Gly-Ala-Phe A-5. (a) Pentapeptide (c) Serine (e) Ser-Ala-Leu-Phe-Gly (b) Four (d) Glycine A-6. (a) H11001H11001H11001 NO 2 O 2 N NHCHCOH CH 3 O DNP-Ala H 3 NCH 2 CO 2 H11002 H11001 Gly H 3 NCHCO 2 H11002 H11001 CH 2 C 6 H 5 Phe H 3 NCHCO 2 H11002 H11001 CH 2 CH(CH 3 ) 2 Leu CH 2 CH(CH 3 ) 2 OO O CH(CH 3 ) 2 H 3 NCHCNHCHCO 2 H11002 H11001 CH 2 CH(CH 3 ) 2 O CH(CH 3 ) 2 C 6 H 5 CH 2 OCNHCHCNHCHCOCH 2 C 6 H 5 H11001Couple: Z-Leu O H 2 NCHCOCH 2 C 6 H 5 CH(CH 3 ) 2 DCCI Deprotect: CH 2 CH(CH 3 ) 2 OO O CH(CH 3 ) 2 C 6 H 5 CH 2 OCNHCHCNHCHCOCH 2 C 6 H 5 H 2 , Pd C 6 H 5 CH 2 OHC-Protect valine: CH(CH 3 ) 2 H 3 NCHCO 2 H11002 H11001 CH(CH 3 ) 2 H 3 NCHCOCH 2 C 6 H 5 H11001 H11001 H H11001 O 1. NaOH, H 2 O 2. H H11001 C 6 H 5 CH 2 OCClN-Protect leucine: CH 2 CH(CH 3 ) 2 O H 3 NCHCO 2 H11002 H11001 H11001 C 6 H 5 CH 2 OCNHCHCO 2 H O CH 2 CH(CH 3 ) 2 (Z-Leu) Leu-Val H11005 H 3 NCHC CH(CH 3 ) 2 CH 2 CH(CH 3 ) 2 H11001 O NHCHCO 2 H11002 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website (b) (c) Same as part b; Ala-Gly-Phe H11001 Leu (d) B-1. (c) B-2. (c) B-3. (a) B-4. (d) B-5. (c) B-6. (b) B-7. (c) B-8. (a) O O O O CH 2 CH(CH 3 ) 2 C 6 H 5 CH 2 OCNHCHCNHCH 2 CNHCHCNHCHCO 2 H CH 3 CH 2 C 6 H 5 Z-Ala-Gly-Phe-Leu H11001 H 3 NCHCO 2 H11002 H11001 CH 2 CH(CH 3 ) 2 Leu O O H 3 NCHCNHCH 2 CNHCHCO 2 H11002 H11001 CH 3 CH 2 C 6 H 5 Ala-Gly-Phe 820 APPENDIX A Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website APPENDIX B TABLES Table B-1 Bond Dissociation Energies of Some Representative Compounds* Bond dissociation Bond dissociation energy, kJ/mol energy, kJ/mol Bond (kcal/mol) Bond (kcal/mol) Diatomic molecules H@H 435 (104) H@F 568 (136) F@F 159 (38) H@Cl 431 (103) Cl@Cl 242 (58) H@Br 366 (87.5) Br@Br 192 (46) H@I 297 (71) I@I 150 (36) Alkanes CH 3 @H 435 (104) CH 3 @CH 3 368 (88) CH 3 CH 2 @H 410 (98) CH 3 CH 2 @CH 3 355 (85) CH 3 CH 2 CH 2 @H 410 (98) (CH 3 ) 2 CH@CH 3 351 (84) (CH 3 ) 2 CH@H 397 (95) (CH 3 ) 3 C@CH 3 334 (80) (CH 3 ) 3 C@H 380 (91) Alkyl halides CH 3 @F 451 (108) (CH 3 ) 2 CH@F 439 (105) CH 3 @Cl 349 (83.5) (CH 3 ) 2 CH@Cl 339 (81) CH 3 @Br 293 (70) (CH 3 ) 2 CH@Br 284 (68) CH 3 @I 234 (56) (CH 3 ) 3 C@Cl 330 (79) CH 3 CH 2 @Cl 338 (81) (CH 3 ) 3 C@Br 263 (63) CH 3 CH 2 CH 2 @Cl 343 (82) Water and alcohols HO@H 497 (119) CH 3 CH 2 @OH 380 (91) CH 3 O@H 426 (102) (CH 3 ) 2 CH@OH 385 (92) CH 3 @OH 380 (91) (CH 3 ) 3 C@OH 380 (91) *Note: Bond dissociation energies refer to bonds indicated in structural formula for each substance. 821 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website 822 APPENDIX B Table B-2 Acid Dissociation Constants* Conjugate Dissociation Acid Formula base constant pK a Hydrogen fluoride H@FF H11002 3.5 H11003 10 H110024 3.5 Acetic acid CH 3 CO 2 @H CH 3 CO 2 H11002 1.8 H11003 10 H110025 4.7 Hydrogen cyanide H@CN CN H11002 7.2 H11003 10 H1100210 9.1 Phenol C 6 H 5 O@H C 6 H 5 O H11002 1.3 H11003 10 H1100210 9.8 Water HO@H HO H11002 1.8 H11003 10 H1100216 15.7 Ethanol CH 3 CH 2 O@H CH 3 CH 2 O H11002 10 H1100216 16 Alkyne (terminal; R H11005 alkyl) RC>C@H RC>C H11002 10 H1100226 26 Ammonia NH 2 @H NH 2 H11002 10 H1100236 36 Alkene C@H RCH?CH@H RCH?CH H11002 10 H1100245 45 Alkane C@H RCH 2 CH 2 @H RCH 2 CH 2 H11002 10 H1100262 62 *Note: Acid strength decreases from top to bottom of the table; conjugate base strength increases from top to bottom. Table B-3 Chemical Shifts of Representative Types of Protons Chemical shift Chemical shift Type of proton (H9254), ppm* Type of proton (H9254), ppm* 0.9–1.8 2.2–2.9 1.6–2.6 3.1–4.1 2.1–2.5 2.7–4.1 2.5 3.3–3.7 2.3–2.8 H—NR 1–3 ? 4.5–6.5 0.5–5 ? 6.5–8.5 6–8 ? 9–10 10–13 ? *These are approximate values relative to tetramethylsilane; other groups within the molecule can cause a proton signal to appear outside of the range cited. ? The chemical shifts of protons bonded to nitrogen and oxygen are temperature- and concentration-dependent. OCH O C O H OArHArH ORH CH C CArH COH CCH CBrHCH C O CClHCCCH CNRHCRH Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website Table B-4 Chemical Shifts of Representative Carbons Chemical shift Chemical shift Type of carbon (H9254), ppm* Type of carbon (H9254), ppm* RCH 3 0–35 100–150 R 2 CH 2 15–40 R 3 CH25–50 110–175 RCH 2 NH 2 35–50 RCH 2 OH 50–65 190–220 @C>C@ 65–90 * Approximate values relative to tetramethylsilane. Table B-5 Infrared Absorption Frequencies of Some Common Structural Units Structural unit Frequency, cm H110021 Structural unit Frequency, cm H110021 Stretching vibrations Single bonds Double bonds @O@H (alcohols) 3200–3600 1620–1680 @O@H (carboxylic acids) 2500–3600 3350–3500 Aldehydes and ketones 1710–1750 sp C@H 3310–3320 Carboxylic acids 1700–1725 sp 2 C@H 3000–3100 Acid anhydrides 1800–1850 and 1740–1790 sp 3 C@H 2850–2950 Acyl halides 1770–1815 Esters 1730–1750 sp 2 C@O 1200 Amides 1680–1700 sp 3 C@O 1025–1200 Triple bonds @C>C@ 2100–2200 @C>N 2240–2280 Bending vibrations of diagnostic value Alkenes Substituted derivatives of benzene Cis-disubstituted 665–730 Monosubstituted 730–770 and 690–710 Trans-disubstituted 960–980 Ortho-disubstituted 735–770 Trisubstituted 790–840 Meta-disubstituted 750–810 and 680–730 Para-disubstituted 790–840 NH CO CC C O CC APPENDIX B 823 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website