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33_569023 bindex.qxd 6/3/05 11:33 PM Page 373

Index

classifying, 195–196 • Numbers • definition, 361 dehydration, 201–202 1s orbital, shape, 22 dehydration, alkene formation, 154 2s orbital, shape, 22 Diels-Alder reaction, 210 3D ethanol, 84 chiral center, 96–97 ethers, 202 constitutional isomers, 94–95 Grignard reaction, 200–201 diastereomers, 104–105 naming, 196–197 enantiomers, 95–96 oxidation, 202–203 Fischer projections, 105–108 parent chain, 197 introduction, 93 reactions, 198–201, 201–203 drawings, 94 sugars and, 84 plane-polarized light, 103–104 water across double bonds, 198 stereoisomers, 94–95 water loss, mass spectrometry, 260–261 symmetry, 101–103 Williamson ether synthesis, 202 aldehydes, 86–87, 361 alkanes • A • branching alkanes, 115–118 acetone, 87 bromination, 139 acetylide , alkynes, 172–173 cycloalkanes, 130–134 achiral , 95, 108, 361 definition, 361 acid, 361 free radical halogenation, 136–139 acid base chemistry functional groups, 77 arrhenius acids, 66–67 hydrogens, saturated, 143–146 introduction, 65 nomenclature, 113–120 pKa scale, 65 smashing, mass spectrometry, 259 acid-base mechanisms, 357 straight-chain, 114 acidity substituent naming, 119–120 aromatic compounds, 228–229 alkenes comparing, 228–229 bromination, 164 acids C-H absorptions, 277 Brønsted-Lowry definition, 67 carbenes, 166–167 comparing acidities of organic molecules, carbocation, 156–157, 157–161 69–73 cis stereoisomers, 149 conjugate acids, 67 COPYRIGHTEDcommerical MATERIAL uses, 79 conjugate bases, 70 common names, 148 electrophiles (Lewis acids), 68 compounds from, 143 Lewis acids, 68–69 conjugated (See conjugated alkenes) values, pKa scale, 73–74 coupling, 154–155 activation energy, 181–182 cyclopropane rings, 166–167 acylation, Friedel-Crafts, 235 definition, 142–143, 361 alcohols dihydroxylation, 163–164 alpha cleavage, 259 double bonds, hydration, 161–164 C-H absorptions, 276 double bonds, multiple, 148 carbonyl compounds, 198–199 epoxides, 167 33_569023 bindex.qxd 6/3/05 11:33 PM Page 374

374 Organic Chemistry I For Dummies

alkenes (continued) answer checking, five commandments of formation, 153–155 multisynthesis, 351 , 157 anti addition, 361 hydroboration, 162–163 anti-aromatic, 361 hydrogenation, 168 anti-aromatic rings, 218 hydrohalic acids, 156–157 anti conformation, 361 multiple bonds, 151 anti conformers, butane, 129 nomenclature, 146–148 anti-periplanar, 362 nomenclature, E/Z system, 150–151 anti-periplanar geometry, 192 ozonolysis, 165 antibonding molecular orbitals, 220 parent chain, numbering, 146–147 anticoplanar, 362 permanganate oxidation, 165–166 antifeedants in plants R groups, 78 caterpillars and, 12 reactions, 156–168 organic molecules and, 12 rings, 79 aprotic solvents, 362 stabilities, 152–153 aromatic compounds stereochemistry, 149–151 acidities, 228–229 steric repulsion, 153 basicities, 229–230 substituents, 151 characteristics, 218 substitution, 152 common, 232 trans stereoisomers, 149 diversity of, 217–218 Wittig reaction, 154–155 heteroatoms, 217 alkylated benzenes, oxidation, 236 Hückel, Erich and, 218–219 alkynes Hückel number, 225 acetylide chemistry, 172–173 naming, 230–232 bond angles, 81 nucleophilic aromatic substitution, 243–245 brominating, 173–174 overview, 216–219 C-H absorptions, 277 planar molecules, 225 common names, 170 reactions and, 216 definition, 361 regions, benzenes, 312 dehydrohalogenation, 172 rings, 225 forming, 171–176 aromatic substituents, 241 hydroboration, 176 hydrogenation, 174–175 determining, 225–228 internal, 172 theory, 219–225 nomenclature, 169–170 pi , 227 orbitals, 170–171 rings, magnetic field, 289 oxymercuration, 175–176 aromatics, 362 R groups, 80 aromatics (arenes) rings, 171 benzene, 215 terminal, 172 C-H absorptions, 277 allylic carbon, 361 Kekulé and, 215 alpha cleavage, mass spectrometry, 259–261 rings, 81 amides, 90, 361 Arrhenius acids amines dissociation, 66 alpha cleavage, 260 hydromium and, 66 C-H absorptions, 276 hydroxide ions and, 66 definition, 361 arrow pushing, 51 Diels-Alder reaction, 210 arrows introduction, 91 double-headed arrow, 52 -ane suffix, 146 equilibrium arrow, 52 anion mechanisms, 357 fishhook, 52 anions, 20, 361 reaction arrow, 52 33_569023 bindex.qxd 6/3/05 11:33 PM Page 375

Index 375

resonance arrow, 52 Kekulé, August and, 215 single-headed arrow, 52 mass spectrometry, 261–262 aryls, 362 MO diagram, 221–222 aspirin MOs, 222–224 COX enzymes and, 16 naming benzenes, 230–232 willow bark as natural product, 16 p orbitals, 222 rings, aromatic region and, 312 hybridization, 71 structure, 216–217 reaction center, drawing, 355 substituted, 231 atomic number, Periodic Table, 20 substituted, synthesis, 241–242 atomic orbitals, molecular orbitals and, 220 benzopyrene, fused rings, 217 benzyl group bonding, 24 benzenes, 230 comparison, 70–71 definition, 362 covalent bonding, 27 benzylic position, 362 moments, 29 benzyne, 362

dipole moments, predicting molecule, 31–32 Be(OH)2 (beryllium hydroxide), dissociation dipole vector, 30 and, 66–65 , 19 betaine, 155 , 27–29 bicyclic, 363 electronegativity effects, 72 bicyclic products, Diels-Alder reaction, energy shells, 20 211–212 hybridizing, predicting, 35–36 bioorganic chemists lone pairs, structures, 51 COX (cyclooxegenase) enzymes, 16 orbitals, 19 description, 15–16 protons, 20 enzymes, 15 resonance structures, 54 bonding size, negative charge and, 70 angles, Alkynes, 81 substituents, hybridizing and, 35 classifications, 28 VSEPR Theory, 32–36 covalent bonding, 27 attitude, success and, 323 dipole moment prediction, 30 Aufbau chart, orbitals and, 23 double bonds, 37 axial bonds, 362 homolytic cleavage, 136–137 axial hydrogens, chair conformation and, 132 introduction, 24 ionic, 25–27 orbitals, hybrid, 33–35 • B • pi bonds, 36–39 sigma bonds, 36–39 bases single bonds, 37 conjugate bases, 67 torsional strain, 128 definition, 362 triple bonds, 37 Lewis bases, 68–69 VSEPR Theory, 32–36 nucleophiles (Lewis bases), 68 bonding molecular orbitals, 220 basicities, aromatic compounds, 229–230 bonds beer, fermentation and, 330 Hooke’s law, 268–269 benzaldehyde, 87 infrared absorption, 268–271 benzene vibration, IR light absorption and, 269–270 alkylated, oxidation, 236 branching alkanes carbanions and, 243 chain length, 115 carbon atoms, 221 chain numbering, 116 disubstituted, synthesis of, 236–241 isomers, 115 electrophilic aromatic substitution, 232–236 substituents, 116–118 fused rings, 217–218 33_569023 bindex.qxd 6/3/05 11:33 PM Page 376

376 Organic Chemistry I For Dummies

bromination C-H absorptions, 276 alkenes, 164 carboxylic acid, 89 alkynes, 173–174 Diels-Alder reaction, 210 selectivity of, 139 esters, 89 bromine, isotopes, 256 ketones, 87–88 Brønsted acid, 363 nitriles, 91 Brønsted base, 363 nitrogen-containing functional groups, 90 Brønsted-Lowry definition of acids and carbonyl group, 363 bases, 67 carboxylic acids, 89, 363 Buckyballs, 332–333 catalytic cracking reaction, alkanes, 136 butane, structure, 114 caterpillars, antifeedants and, 12 butane cations chlorination, 138 definition, 363 conformations, 128–130 description, 20 resonance structures and, 57 chain reactions, 137 • C • chair conformation axial hydrogens and, 132 C-H absorptions, IR spectroscopy cyclohexane, 131 alcohols, 276 definition, 363 alkenes, 277 diaxial strain, 133–134 alkynes, 277 drawing, 132–134 amines, 276 ring flip, 133 aromatics, 277 stable, drawing, 134–135 carbonyl groups, 276 chemical equivalency, NMR, 286–287 calicheamicin molecules, 80 chemical reactions, organometallic chemists carbanion and, 17 benzenes and, 243 chemical shifts, 363 definition, 363 chemical shifts, NMR carbenes diamagnetic anisotropy, 288 alkenes, 166–167 fragment combining, 308 definition, 363 introduction, 285–286 carbocation molecular structures and, 319 alkenes, 156–157, 157–161 chemists definition, 363 Corey, E.J., 339–340 , 158 Fischer, Emil, 340–341 mechanisms, 357 Hodgkin, Dorothy, 340 rearrangements, 159–161 Kekulé, August, 338 resonance stabilization, 159 Kolbe, Adolf, 342 carbon Nicolaou, K.C., 338–339 benzene, 221 Pasteur, Louis, 340 carbon-carbon bonds, 17 Pauling, Linus, 341 carbon- bonds, 17 Pople, John, 341 configuration, 24 Wöhler, Friedrich, 342 line-bond structures, 47 Woodward, Robert Burns, 337–338 multistep synthesis and, 348–349 chiloglottone, 88 organic molecules and, 14 chiral center carbon NMR, 296–298 definition, 108, 363 carbonyl compounds diastereomers, 104–105 alcohols and, 198–199 introduction, 96 aldehydes, 86–87 R/S nomenclature, 97–98 amides, 90 thumb technique, 101 amines, 91 33_569023 bindex.qxd 6/3/05 11:33 PM Page 377

Index 377

chiral molecules constitutional isomers definition, 108, 363 definition, 364 introduction, 95 stereoisomers and, 94–95 plane-polarized light, 103–104 core electrons, 25 chlorination Corey, E.J., background, 339–340 of butane, 138 coupling of methane, 136 alkenes, 154–155 selectivity of, 139 constants, 293, 299 , molecules, isotopes and, 256 integration comparison, 320 cis, 363 n + 1 rule, 292–293 cis isomer, stability, 152–153 NMR, 291–292, 298 cis stereoisomer NMR, ethanol, 292 alkenes, 149 NMR, tree diagram, 295–296 description, 131 NMR mistakes, 319–320 class attendance, success and, 326 non-equivalent hydrogens, 293–295 CN (cyano groups), Diels-Alder reaction, 210 singlets, 293 complete dissociation, acids, 66 coupling constants, 364 compounds coupling protons, 364 from alkenes, 143 covalent bonding computational chemists and, 17 definition, 364 natural products, 16 electronegativity and, 27–28 natural products chemists and, 16 organic compounds, 29 computational chemists COX (cyclooxegenase) enzymes description, 17–18 aspirin and, 16 relational drug design and, 18 bioorganic chemists and, 16 in silico drug design and, 17 Curl, Robert, 332–333 condensed structures, 46–47 cycloalkanes configuration, 363 introduction, 130 conformations stereochemistry, 131 anti conformers, 129 cyclobutadiene, MO diagram, 224–225 butane, 128–130 cyclodecapentaene, aromaticity and, 225 cyclohexame, 131–134 cyclohexane, conformations, 131–134 definition, 363 cyclooctatetraene, aromaticity and, 225 eclipsed, 128, 129 cyclopropanes gauche interactions and, 129 alkenes, 166–167 Newman projections and, 127–128 Simmons-Smith reaction, 167 staggered, 128 straight-chain alkanes, 126–130 conjugate acids, 67, 364 • D • conjugate addition daily practice, success and, 327 kinetics and thermodynamics, 209 decane, structure, 114 reaction diagrams, 207–208 degenerate orbitals conjugate bases introduction, 22 acids and, 70 MOs, 221 definition, 364 degree of unsaturation introduction, 67 molecular formulas, 145–146 conjugated alkenes molecular structure and, 310–311, 316 Diels-Alder reaction, 209–212 NMR problem solving, 303 hydrohalic acids and, 206–209 structures and, 144–145 conjugated double bonds dehydration of alcohols definition, 364 alkene formation, 154 introduction, 205–206 overview, 201–202 33_569023 bindex.qxd 6/3/05 11:33 PM Page 378

378 Organic Chemistry I For Dummies

dehydrohalogenation molecule, predicting, 31–32 alkenes, 153–154 predicting, 30 alkynes, 172 dipole vector, 30 definition, 364 dipoles, 19 delta value, 364 discoveries deshielded hydrogens, NMR, 285 aspartame, 333–334 detector, mass spectrometer Buckyballs, 332–333 mass to charge ratio, 253 Diels-Alder reaction, 331–332 overview, 250 dynamite, 329–330 deuterium, NMR, 296 explosives, 329–330 deuterons, NMR, 296 fermentation, 330 diagrams handedness of tartaric acid, 331 3D, 94–109 penicillin, 334 chair conformations, 132–134 soap, 333 dots, electrons, 26 Teflon, 334–335 Frost circles, 221 urea synthesis, 330–331 mistakes in resonance structures, 62–63 dissociation, acids, 66 MO diagram of benzene, 221–222 disubstituted benzenes, synthesis, 236–241 MO diagram of cylobutadiene, 224–225 divalence, 44 molecular orbital diagrams, 220–221 dodecane, structure, 114 reactions, atoms at center, 355 double bonds structures, 41–42, 45–46 aromatic compounds, 216 structures, tips for interpreting, 122 cleavage, 165–166 diamagnetic anisotropy, 288 conjugated, 205–206 diamine, 91 electronegative atoms, resonance diastereomers, 104–105, 108, 364 structures, 58 diaxial strain, chair conformation, 133–134 equivalents, 144 Diels-Alder reaction hydration, 161–164 alcohols, 210 hydrohalic acids across, alkenes, 156–157 amines, 210 identical groups, 150 bicyclic products, 211–212 introduction, 37 carbonyl compounds, 210 Lewis structure, 43 conjugated alkenes, 209–212 mass spectrometry, 261–262 cyano groups (CN), 210 multiple, alkenes, 148 definition, 364 resonance structures, 57 dienes and dienophiles, 210–211 resonance structures, alternating around discoveries, 331–332 ring, 58 ethers, 210 double-headed arrow in diagrams, 52 EWG, 210 doublets, 364

nitro groups (NO2 ), 210 dynamite, 329–330 products, 212–214 stereochemistry, 211 dienes • E • definition, 364 E1 elimination reaction, 193, 365 Diels-Alder reaction and, 210–211 E2 elimination reaction, 192–193, 365 dienophiles E isomer, 365 definition, 364 E/Z system of nomenclature, alkenes, 150–151 Diels-Alder reaction and, 210–211 eclipsed conformations dihydroxylation, alkenes, 163–164 definition, 364 diketone, 88 description, 128 dipole moments totally eclipsed, 129 definition, 364 EDG (electron-donating groups), 210 introduction, 29 33_569023 bindex.qxd 6/3/05 11:33 PM Page 379

Index 379

EIMS (electron-ionization mass endo addition, 211–212 spectrometry), 251–252 -ene suffix, 146, 169–170 electron ionization, mass spectrometer, enzymes, bioorganic chemists, 15–16 251–252 epoxide electron shielding, NMR, 284 alkenes and, 167 electron-withdrawing groups, 238–241 definition, 86 electronegativity equatorial, 365 atoms, 27–29 equatorial hydrogens, chair conformation, 133 definition, 365 equilibrium, reactions, acid-base, 74–75 effects of, 72 equilibrium arrow, 52 increases, 70 esters, 89, 365 polar covalent, 27–28 ethane, structure, 114 purely covalent, 27–28 ethanol, 84 resonance structures, 58 ethers electrons alcohols and, 202 arrows and, 53 definition, 365 atoms, protons and, 20 Diels-Alder reaction, 210 carbon configuration, 24 introduction, 85–86 ground state , 23–24 EWG (electron-withdrawing groups), Heisenberg Uncertainty Principle, 21 Diels-Alder reaction, 210 Hund’s rule, 23–24 exams, success and, 328 ions, 20 exo addition, 211–212 Lewis structures, 43 explosives, 329–330 location, 21 external magnetic field, NMR theory and, 281 meta directors, 238–241 MOs and, 220 , 25 • F • orbitals, 21 falling behind, success and, 324–325 orbitals, filling, 23 fermentation discovery, 330 ortho-para activators, 238 fingerprint region, 366 pi-withdrawing groups, 241 first-order substitution quantum mechanics and, 21 rate-determining step, 188 shells compared to orbitals, 21 S 1 reaction, 187–191 spin, 21 N Fischer, Emil, 340–341 spin, Hund’s rule and, 24 Fischer projections valence electrons, 25 meso compounds, 108 VSEPR Theory, 32–36 R/S nomenclature, 106–107 electrophiles rules for, 105–106 definition, 365 stereoisomers, 107 Lewis acids, 68 fishhook arrows, 52 electrophilic aromatic substitution of five commandments of multistep synthesis benzene answer checking, 351 Friedel-Crafts acylation, 235 carbon skeletons, 348–349 Friedel-Crafts alkylation, 233–234 mechanisms, 347 introduction, 232 multiple problems, 351 nitro group reduction, 235–236 reactions, 348 electrophilic attack, benzenes, 240 retrosynthesis, 349–351 elimination reactions formal charges, Lewis structures, 43–45 E2 reaction, 192–193 formation of alkenes substitution and, 193–194 dehydration of alcohols, 154 enantiomers dehydrohalogenation, 153–154 3D drawing and, 95–96 formation of alkynes, 171–176 definition, 108, 365 33_569023 bindex.qxd 6/3/05 11:33 PM Page 380

380 Organic Chemistry I For Dummies

formulas and, 82 degrees of unsaturation, 145–146 insecticides, 83 molecular, drawing isomers from, 123–126 halogens, degree of unsaturation and, 303 fragmentation patterns, mass spectrometry halogens chlorine, isotopes, 256 alkanes, 259 handedness of tartaric acid, 331 alpha cleavage, 259–260 Haworth projections, stereochemistry benzenes, 261–262 and, 131 double bonds, 261–262 heat mechanisms, 356 McLafferty Rearrangement, 261 Heisenberg Uncertainty Principle, electron molecular structure, 311–312 location and, 21 peaks and, 258 heptane structure, 114 water loss, alcohols, 260–261 heteroatoms free radical halogenation alcohols, 84 bromination, 139 aromatic compounds, 217 catalytic cracking reaction, 136 ethers, 85–86 chlorination, 139 halides, 82–84 initiation, 136–137 thiols, 85 propagation, 137 hexane free-radical mechanisms, 357 IR spectrum, 273–274 Friedel-Crafts structure, 114 acylation, 235 Hodgkin, Dorothy, 340 alkylation, alkyl substituents, 233–234 homolytic cleavage, bond dissociation, Frost circles, ring systems, 221 136–137 functional groups Hooke’s law, bond vibration and, 268–269 alkenes, 141–168 HRMS (high-resolution mass spectrometers), carbonyl compounds, 86–91 compound weight, 255 definition, 366 Hückel, Erich, aromatic rings, 218–219 description, 77 Hückel’s rule, 366 heteroatoms, 82–86 Hund’s rule, orbitals, 23–24 hydrocarbons, 78–82 hybrid orbitals IR absorption, 273 bonding and, 33–35 IR absorption, appearance, 274–275 definition, 366 IR spectrum, 303 naming, 34 molecular structure and, 311 hybridizing atoms waypoints, 143 atom comparison and, 71 predicting, 35–36 rule for determining, 36 • G • hydration, double bonds and, 161–164 hydroboration gas, inlet, mass spectrometer, 251 alkenes and, 162–163 gauche conformation, 366 alkynes and, 176 gauche interaction, conformations and, 129 hydrocarbons genetic coding, organic molecules and, 12 alkenes, 78–79 Grignard reaction, alcohols, 200–201 alkynes, 80–81 ground state electron configuration, orbitals aromatics, 81–82 and, 23–24 hydrogen NMR chemical shift, 288–290 introduction, 281 • H • hydrogenation halides alkenes, 168 alkenes, 157 alkynes, 174–175 definition, 366 33_569023 bindex.qxd 6/3/05 11:33 PM Page 381

Index 381

hydrogens ions chair conformation, 132 anions, 20 coupling, non-equivalent, 293–295 cations, 20 deshielded, NMR and, 285 electrons and, 20 equivalent, 144 negatively charged, 20 index of hydrogen deficiency, 144 protons and, 20 integrations, 305 spectator, mechanisms, 356 line-bond structures, 49–50 IR (infrared) spectrometer peak ratio, 305–306 absorption, functional groups, 273 saturated (See saturated hydrogens absorption, intensity, 270–271 [alkanes]) C-H absorptions, 275–276 shielded, NMR and, 285 IR inactive vibrations, 271 hydrohalic acids molecular structure and, 315–318 alkenes, 156–157 spectrum, hexane, 273–274 conjugated alkenes and, 206–209 spectrum, light transmittance, 271–272 hydronium , Arrhenius and, 66 spectrum generation, 270 hydroxide ions, Arrhenius acids and, 66 IR (infrared) spectroscopy, 366 hydroxyl (OH) groups, alcohols, 195–196 absorption, bonds, 268–271 hyperconjugation IR light, bond vibration and, 269–270 carbocations, 158 NMR spectroscopy and, 267 definition, 366 sensitivity, 255 IR (infrared) spectrum functional groups, 303 • I • structures, NMR and, 308–309 isolated double bonds, 366 in resonance (NMR), 283 isomers in silico drug design, computational chemists branching alkanes and, 115 and, 17 cis stereoisomer, 131, 149 index of hydrogen deficiency, 144 drawing from molecular formula, 123–126 inductive effects, 366 trans stereoisomers, 131 infrared absorption, bonds, 268–271 isotopes initiation step, reactions, 136–137 bromine, 256 inlet, mass spectrometer definition, 256 gas phase and, 251 halogens chlorine, 256 overview, 250 iodine, 256 inorganic compounds, ionic bonds, 29 nitrogen rule, 258 integration, NMR, 298 IUPAC nomenclature, alkenes, 148 baseline noise, 305 coupling comparison, 320 integration curve, peak ratio and, 304–306 intermediates • J–K • definition, 366 J value, 367 resonance structures, mechanisms and, 355 jargon, structures and, 41 internal alkynes, 172 interpreting structures, tips, 122 Kekulé, August, 338 iodine, isotopes, 256 Kekulé structures ionic bonding benzene and, 215 definition, 366 introduction, 45 electronegativity and, 27–28 ketones, 87–88, 367 inorganic compounds, 29 kinetic product and chlorine, 25–27 conjugate addition, 208 ionization, smasher, mass spectrometer, definition, 367 251–252 33_569023 bindex.qxd 6/3/05 11:33 PM Page 382

382 Organic Chemistry I For Dummies

kinetics mass spectrometry definition, 367 alpha cleavage, 259–260 physical organic chemists and, 17 definition, 250, 367 thermodynamics, conjugate addition exam sample, 262–264 and, 209 fragmentation patterns, 258–264 KOH (potassium hydroxide), dissociation introduction, 249–250 and, 66–67 isotopes, 256–258 Kolbe, Adolf, 342 key ideas, 264–265 Kroto, Harry, 332–333 sensitivity, 255 mass to charge ratio, mass spectrometer weigher, 253 • L • materials chemists, 18 McLafferty Rearrangement, mass leaving group, S 2 reaction, 186–187 N spectrometry, 261 Lewis acids, 68–69, 367 mechanisms Lewis bases, 68–69, 367 acid-base, 357 Lewis structures. See also Kekulé structures anion, 357 conversion to line-bond structure, 48–49 base scavengers and reagents, 355 description, 43 carbocation, 357 double bonds, 43 example problem, 357–360 electrons, 43 free-radical, 357 formal charges, 43–45 heat mechanisms, 356 single bonds, 43 intermediates, resonance structures, 355 triple bonds, 43 multistep synthesis comparison, 354 life, organic molecules and, 13 multitasking, 355 line-bond structures nucleophile-electrophile, 356–357 conversion from Lew structures, 48–49 reaction mechanisms, 353–360 hydrogens, 49–50 reagents, 355 introduction, 47 solvents and reagents, 355 lone-pair atoms, structures and, 51 spectator ions, 356 lone-pair electrons, resonance structures, tips for working, 354–356 54, 57 mercurinium ions, 162 meso, 367 meso compounds • M • definition, 108 magnetic movement, NMR theory and, 281 Fischer projections, 108 Markovnikov’s rule, 367 symmetry and, 101–103 Markovnikov, Vladimir meta, 367 hydroboration, 162–163 meta-directing substituent, 367 introduction, 156 meta directors, electrons, 238–241 oxymercuration-demercuration, 161–162 metabolism, organic molecules and, 12 mass spectrometer methane, structure, 114 detector, 250 methane chlorination, 136 EIMS (electron-ionization mass methyl groups spectrometry), 251–252 loss, 262 inlet, 250 prefixes, 118–119 molecular ion peak, 254 mixing orbitals, 34 overview, 250–251 MO (molecular orbital) theory radical cation, 251–252 antibonding molecular orbitals, 220 smasher, 250, 251–252 atomic orbitals and, 220 sorter, 250, 252–253 benzene diagram, 221–222, 222–224 weigher, 252–253 bonding molecular orbitals, 220 33_569023 bindex.qxd 6/3/05 11:33 PM Page 383

Index 383

cyclobutadiene, 224–225 naming degenerate orbitals, 221 alcohols, 196–197 electrons and, 220 aromatics, 230–232 introduction, 219 benzenes, 230–232 molecular oribital diagrams, 220–221 structures, 120–123 overview, 220 natural products rings, Frost circle, 221 caffeine and, 16 valence bond theory and, 220 chemists, 16 models, molecules and, 42 definition, 368 molecular formula, molecular structure and, nicotine and, 16 315–318 peyote and, 16 molecular ion peak willow bark and, 16 mass spectrometer and, 252 Newman projections mass spectrum and, 254 butane conformations, 128–130 molecular ions, 367 conformational analysis and, 127–128 molecular orbital theory, 368 Nicolaou, K.C., 338–339 molecular structure nitriles, 91, 368 confirmation, 313–314 nitro groups, electrophilic aromatic degrees of unsaturation, 316 substitution of benzene, 235–236 fragments, 311–312 nitrogen, degree of unsaturation and, 303 function groups, 311 nitrogen-containing functional groups, 90 IR and, 315–318 nitrogen rule, isotopes, 258 molecular formula and, 315–318 nitroglycerin, 329–330 molecular formula and NMR, 310–311 NMR (Nuclear Magnetic Resonance) peak ratio, 311 spectroscopy molecules carbon NMR, 296–298 3D drawings, 94 chemical equivalency, 286–287 achiral, 95 chemical shift, 288–290, 299 aromatic, characteristics, 218 chemical shifts, standardizing, 285–286 chiral, 95 coupling, 291–296 dipole moment prediction, 31–32 coupling, n + 1 rule, 292–293 formulas, drawing isomers from, 123–126 coupling, singlets, 293 mirror images (enantiomers), 95–96 coupling constants, 293, 299 models and, 42 coupling tree diagram, 295–296 organometallic chemists, 17 definition, 368 VSEPR Theory, 32–36 deshielded hydrogens, 285 monovalence, 44 deuterium, 296 multistep synthesis deuterons, 296 answer checking, 351 electron shielding, 284 carbon skeletons, 348–349 exchange, 296 definition, 368 external magnetic field, 281 five commandments, 347–351 hydrogen NMR, 281 mechanisms comparison, 354 integration, 290–291, 299 problem solving tips, 345–351 introduction, 279 retrosynthesis, 349–351 IR spectrum functional groups, 303 synthetic organic chemists and, 15 magnetic movement and, 281

Vitamin B12, 347 molecular structure and, 310–311 MRI (magnetic resonance imaging) and, 299 NMR active nuclei, 281 • N • NMR inactive nuclei, 281 overview, 281–284 n + 1 rule peak intensity, 290 coupling, 292–293 peak ratio, integration curve and, 304–306 definition, 368 peaks, fragmenting, 306–307 33_569023 bindex.qxd 6/3/05 11:33 PM Page 384

384 Organic Chemistry I For Dummies

NMR (nuclear magnetic resonance) electron spin, 21 spectroscopy (continued) electron spin, Hund’s rule and, 24 problem solving mistakes, 318–320 ground state electron configuration, 23–24 problems, clues, 302–309 Hund’s rule, 23–24 radio waves, 283 hybrid orbitals, 33–35 reasons for, 280 mixing, 34 in resonance, 283 numbers in naming, 22 sensitivity, 255 p orbitals, 21 shielded hydrogens, 285 quantum mechanics and, 21 spectrum, 284–287 s orbitals, 21 spin and, 281 shells and, 21 spin flipping, 283 sp3 hybridized, 33 structures, IR spectrum and, 308–309 syntax, 22 symmetry, 286–287 orchid, diketones, 88 TMS (tetramethylsilane) and, 285–286 organic chemistry

NO2 (nitro groups), Diels-Alder reaction, 210 introduction, 11–12 noble gases, 24 special fields for chemists, 15–18 node, 368 organic compounds nonane, structure, 114 covalent bonds, 29 note cards for reactions, drawing, 142 definition, 368 nucleophile-electrophile mechanisms, 356–357 natural products chemists and, 16 nucleophiles organic molecules benzenes, 240 acidity comparison, 69–73 definition, 368 carbon and, 14 Lewis bases, 68 life and, 13 protic solvents and, 186 overview, 12 reactions, 194 plants, 12 roles, 183–184 synthetic organic chemists and, 15 steric hindrance and, 184 vital life force, 14 nucleophilic aromatic substitution, 243–245 organometallic chemist, 17 nucleophilicity, 184, 368 ortho, 368 numbering parent chain, alkenes, 146–147 ortho-para activators, 238 numbers, orbital types and, 22 ortho-para directors, 369 oxaphosphetane, 155 oxidation • O • alcohols, 202–203 definition, 369 octane, structure, 114 oxyanion, 155 octet rule oxygen, degree of unsaturation and, 303 atom bonding, 25 oxymercuration, alkynes, 175–176 filled, resonance structures and, 61 oxymercuration-demercuration, 161–162 resonance structures and, 55 ozonolysis, alkenes, 165 optically active, 109, 368 orbitals. See also MO (molecular orbital) theory 1s, 22 • P • 2s, 22 p orbitals alkynes, 170–171 benzene, 222 Aufbau chart, 23 shape, 21 bonding and, 21 pain, COX enzymes and, 16 carbon electron configuration, 24 para, 369 definition, 368 parent chain degenerate, 22 alcohols, 197 description, 19 alkenes, numbering, 146–147 33_569023 bindex.qxd 6/3/05 11:33 PM Page 385

Index 385

partial dissociation, acids, 66 protons Pasteur, Louis atoms, electrons and, 20 background, 340 definition, 369 handedness of tartaric acid, 331 ions, 20 Pauling, Linus, 341 number of, 20 peak ratios fragmenting, 306–307 fragments, combining, 308 • Q–R • integration curve height and, 304–306 quantum mechanics, electrons and, 21 molecular structure, 311 questions, success and, 327 peak splitting, 308 penicillin, 334 R group, 369 pentane, structure, 114 R/S nomenclature Periodic Table, atomic number, 20 chiral centers, 97–98 permanganate oxidation, alkenes, 165–166 configuration, 98–101 phenyl group, benzene, 230 Fischer projections and, 106–107 phenyl ring, 369 R-SH groups, 85 photochemical reaction, 136 racemic mixture photochemistry, physical organic chemists definition, 369 and, 17 introduction, 109 physical organic chemists S 1 reaction, 190–191 kinetics, 17 N radical cation, mass spectrometry, 251–252 photochemistry, 17 radicals, 369 spectroscopy, 17 radio waves, NMR and, 283 termodynamics, 17 rate determining step, 188 pi bond, 369 rate equation pi (π) bonds, orbital overlap and, 36–39 S 1 reaction, 187–189 pi electrons N S 2 reaction, 181–182 aromaticity and, 227 N rational drug design, computational chemists resonance structures, 54 and, 18 pi-withdrawing groups, 241 reaction arrow, 52 pKa scale reaction diagrams acid base chemistry, 65 conjugate addition, 207–208 definition, 369 introduction, 181–182 values of common acids, 73–74 reaction mechanisms plane of symmetry, 369 reagents, 355 plane-polarized light types, 353–354 definition, 369 reactions introduction, 103–104 acid-base, equilibrium, 74–75 Pasteur, Louis and, 340 alcohols, 198–201, 201–203 plants alkenes, 156–168 antifeedants, 12 aromatic compounds, 216 organic molecules and, 12 chain reactions, 137 polysubstituted benzenes, synthesis, 241–242 drawing atoms at center, 355 Pople, John, 341 multistep synthesis and, 348 prefixes, methyl groups, 118–119 note cards, 142 primary carbocations, alkenes, 156 nucleophiles, 194 problem working, success tips, 323–324 propagation, 137 propagation, reactions, 137 Simmons-Smith, 167 propane, structure, 114 substitution reactions, 179–180 protic solvents substrates, 194 definition, 369 termination, 137–139 nucleophiles and, 186 transition state, 182 33_569023 bindex.qxd 6/3/05 11:33 PM Page 386

386 Organic Chemistry I For Dummies

reactions (continued) second-order substitution, SN2 mechanism, waypoints, 143 180–187 Wittig reaction, 154–155 secondary carbocations, alkenes, 156 reagents sensitivity base scavengers, 355 IR, 255 solvents, 355 mass spectrometry, 255 rearrangements, carbocation NMR, 255 introduction, 159–161 shells (electrons), orbitals and, 21 mass spectrometry and, 261 shielded hydrogens, NMR, 285 McLafferty Rearrangement, 261 sigma (σ) bonds, 370 reduction, 370 Simmons-Smith reaction, cyclopropanes, 167 resonance arrow, 52 single bonds resonance effects, 72–73 introduction, 37 resonance stabilization of carbocations, 159 Lewis structure, 43 resonance structures single-headed arrow, 52 benzene, 216–217 singlet, 370 cations, 57 singlets, coupling and, 293 charges on best atoms, 60–61 size, relating to, 42 definition, 370 Small, Richard, 332–333 double bonds, 57 smasher, mass spectrometer double bonds, alternating around ring, 58 alkanes, 259 drawing, 56–58 EIMS (electron-ionization mass drawing multiple, 59 spectrometry), 251–252 electronegative atoms, 58 electron ionization, 251–252 fewest charges, 60 overview, 250

filled octets, 61 SN1 reaction importance assignment, 60–61 definition, 370 intermediates, mechanisms and, 355 rate equation, 187–189

introduction, 53 SN2 comparison, 191 lone-pair electrons, 57 solvents, 190 mistakes in drawing, 62–63 stereochemistry, 190–191 molecule stabilization and, 72 substrates, 189

octet rule, 55 SN2 mechanism, second-order substitution, pi electrons, 54 180–187

rules, 54–55 SN2 reaction triple bonds, 57 definition, 370 retinal, 87 leaving group, 186–187

retrosynthesis, 349–351 SN1 comparison, 191 rings solvents and, 185–186 alkynes, 171 stereochemistry, 185

anti-aromatic, 218 SN2 reaction rate, 181–182 Frost circle, 221 SN2 reactions, substrate and, 182–183 fused rings, benzene, 217–218 soap discovery, 333 sodium, chlorine bonding, 25–27 sodium borohydride, aldehydes and • S • alcohols, 199 solvents s-cis conformation, 370 aprotic, 362 s orbitals, shape, 21 protic, 186 s-trans conformation, 370 S 1 reaction, 190 saturated hydrogens (alkanes) N S 2 reaction and, 185–186 degree of unsaturation, structures, 144–145 N sorter, mass spectrometer introduction, 143–144 molecular ion peak, 252 molecular formulas, 145–146 overview, 250 33_569023 bindex.qxd 6/3/05 11:33 PM Page 387

Index 387

sp hybrid orbitals, 370 drawing, 41–42, 45–46, 122 sp2 hybrid orbitals, 370 interpreting tips, 122 sp3 hybrid orbitals, 33, 370 line-bond, 47 specialized areas lone pairs on atoms, 51 bioorganic chemists, 15–16 names, 120–123 computational chemists, 17–18 NMR, IR spectrum and, 308–309 introduction, 14–15 resonance structures, drawing, 53–63 materials chemists, 18 solving, 310–318 natural products chemists, 16 as words of organic chemist, 41 organometallic chemists, 17 studying, success and, 325–326 physical organic chemists, 17 substituents spectator ions, mechanisms and, 356 alkenes, 151 spectroscopy alkyl, Friedel-Crafts alkylation, 233–234 mass spectroscopy, 250 atoms, hybridizing and, 35 physical organic chemists and, 17 branching alkanes, 116–118 spin, NMR theory and, 281 complex, naming, 119–120 spin flipping, NMR, 283 curve drawing, 100–101 stabilities definition, 371 alkenes, 152–153 electron-donating, rings and, 237 resonance stabilization of carbocations, 159 electron-withdrawing, 238–241 staggered conformations meta-directing, 367 definition, 371 priority, R/S configuration and, 98–99 description, 128 substitution gauche interaction and, 129 benzenes, 231 stereochemistry benzenes, synthesis, 241–242 alkenes, 149–151 elimination comparison, 193–194 cis stereoisomers, 131 first-order, 187–191 cycloaklanes, 131 nucleophilic aromatic substitution, definition, 371 243–245 Diels-Alder reaction, 211 rate-determining step, 188 Haworth projections, 131 second-order, 180–187 introduction, 93 substitution reactions, 179–180

SN1 reaction, 190–191 substrates SN2 reaction and, 185 reactions, 194 terminology, 108–109 SN1 reaction, 189 thalidomide and, 109 SN2 reactions, 182–183 trans stereoisomers, 131 success tips stereoisomers attitude, 323 constitutional isomers and, 94–95 class attendance, 326 definition, 371 daily practice, 327 Fischer projections and, 107 exams, 328 steric hindrance falling behind, 324–325 definition, 371 problem working, 323–324 nucleophilicity and, 184 questions, 327 steric repulsion, alkenes and, 153 studying, 325–326 straight-chain alkanes, 126–130 tutoring, 326 straight-chain alkenes, 114 suffixes structures -ane, 117, 146 benzene, 216–217 -ene, 146, 169–170 chemical shifts and, 319 -yl, 117 condensed structures, 46–47 -ylene, 148 degrees of unsaturation, 144–145 -yne, 169–170 33_569023 bindex.qxd 6/3/05 11:33 PM Page 388

388 Organic Chemistry I For Dummies

sulfur, degree of unsaturation and, 303 triple bonds symmetry electronegative atoms, resonance meso compounds, 101–103 structures, 58 NMR and, 286–287 introduction, 37 syn addition, 163, 371 Lewis structure, 43 synthesis resonance structures, 57 disubstituted benzenes, 236–241 triplets, 371 multistep, problem solving tips, 345–351 trivalence, 44 substituted benzenes, 241–242 tutoring, success and, 326

Vitamin B12, 347 Woodward, Robert Burns, 337–338 synthetic organic chemists, 15 • U–V • Undecane, structure, 114 • T • urea synthesis, 330–331 tartaric acid, handedness, 331 valence electrons tautometers, 371 description, 25 Teflon dots in drawing, 26 discovery, 334–335 molecular orbitals and, 220 introduction, 83 valency of atoms, bonds and, 44 terminal alkynes, 172 vibrating bonds termination, reactions, 137–139 Hooke’s law and, 268–269 tertiary carbocations, alkenes, 156 IR inactive vibrations, 271 tertiary cations, alkyl substitutents and, 234 IR light absorption and, 269–270

tetravalence, 44 Vitamin B12, synthesis, 347 thalidomide, 109 VSEPR Theory (Valence Shell Electron Pair thermodynamic product, 371 Repulsion), bond geometry, 32–36 thermodynamics definition, 371 kinetics, conjugate addition and, 209 • W • physical organic chemists and, 17 water loss, alcohols (mass spectrometry), thermodynamic product, 208 260–261 thiols, 85, 371 waypoints, functional groups, 143 thumb technique, chiral center and, 101 wedges, 3D drawing, 94 ties, alkenes, 151 weigher, mass spectrometer and, 252–253 TMS (tetramethylsilane), NMR and, 285–286 Williamson ether synthesis, alcohols, 202 torsional strain, bonding and, 128 willow bark, aspirin, 16 totally eclipsed conformation, 129 Wittig reaction, alkenes, 154–155 trans isomer, stability, 152–153 Wöhler, Friedrich, 330–331, 342 trans stereoisomers Woodward, Robert Burns, 337–338 alkenes, 149 description, 131 transition state definition, 371 • X–Y–Z • reactions, 182 -yl, 117 tree diagram, NMR coupling, 295–296 -ylene suffix, 148 trigonal planar geometry, bonding and, -yne suffix, 169–170 32–33 Z isomer, 371