Index - INDEX A + rotation, 165—166 — rotation,...

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Unformatted text preview: INDEX A + rotation, 165—166 — rotation, 165—166 Acetaldehyde, 104 Acetic acid, 104 Acetylene. 104 Acids, 53 Acid-base reactions, 53—73 conjugate base in, 53 importance of, 53, 54 induction as factor in. 62—64 orbitals as factor in, 66—67 predicting position of equilibrium in, 7 l—72 protons in, 53 relative importance of factors in, 67—69 resonance as factor in, 57—59 showing mechanism of, 73 type of atom with charge as factor in, 54—56 Acidity: and conjugate base, 53 quantitative method of measuring, 71 Addition reactions, 242—245 Alcohols, 85, 86 Aldehydes, 86 -ald0-, 93 Alkyl groups, 63 Alkyl substituents, 92 Alpha effect, 63 Amines. 86 -am.1'nu—, 93 Ammonia, 67—68, 81 -an-. 88 Anti addition, 186—189 Anti conformations, l 12 Anti—Markovnikov addition, 183, 184, 189 Aprotic solvents, 224, 225 Arrows: curved, see Curved arrows straight (in resonance structures), 21 Atoms: geometry of, see Geometry hybridization state of, 77 periodic table and size of, 55 pi bond between two, with one atom electronegative, 44 Axial substituents, 117 B Bad leaving groups, 221 Base(s). 53. See also Acid-base reactions conjugate, 53 in elimination reactions, 232—235 nucleophiles vs., 179—181 Basicity, 233—234 Bent structure, 82 Bond(s): breaking single (in mechanisms), 168 carbon, 3—4 formation of, 22. 169—172 geometry of, 77 lone pair created by breaking single, 169 pi, 33—35 prohibition against breaking single, 24 sharing of electrons in, 11 Bond-line drawings, [—18 drawing, 5—8 finding undrawn lone pairs in, 14—18 297 298 INDEX Bond-line drawings (Continued) identifying formal charges in, 10—14 mistakes to avoid in, 7 reading, 1—5 showing reactions with, 5 Brackets, 21 Branched substituents, 92—93 —br0mO-, 93 -bm‘—, 89 -butyI-. 92 C Carbocations, 183—184 Carbon atom(s): in bond-line drawings, 1—2 with formal charge. 13—14 lone pairs in. 13 neutral, 3 orbitals of, 7, 13 valence electrons of. 10 Carboxylic acids, 58, 85, 86 Chair conformations, 1 15—132 comparing stability of, 129—132 enantiomers of, 154—155 placing groups on, 118—121 and ring flipping. 123—128 technique for drawing, 1 15—1 17 Chargets): conservation of, 31 delocalized, 58—59 formal, see Formal charges partial positive/negative, 62 Chiral centers, see Stereocenters Chiral compounds. 165 Chlorine, 123—124 -Chiorn-, 93 Cis bonds, 95—96 Cis (conformations), 121, 133 Common names, 103—104 Configurations, 134—135. 138—166 conformations vs., 134 definition of, 134 of diastereomers, 156—157 of enantiomers, 151—155 Fischer projections, 160—164 of meso compounds, 157—160 nomenclature for. 146—150 and optical activity, 165—166 R vs. S, 134 of stereocenters, 138—146 Conformations, 106—132 anti, 1 12 chairs, 115—132 configurations vs.. 1341r definition of, 106 eclipsed. 109 Newman projections, 107—1 14 staggered, 109 Conjugate base, 53 Conservation of charge, 31 Curved arrows (in resonance structures), 21—28 figuring out where to draw, 27—28 head of, 22, 23—24 multiple, 27—28 from a negative charge, 31 and octet rule, 24—25 tail of, 22—23 two commandments for pushing, 24—25 Curved arrows (mechanisms). 168—175 from bond to bond, 170—172 from bond to lone pair, 169 head of, 168 from lone pair to bond, 169 pushing, 173—175 tail of, 168 -cyclo-, 89 Cyclohexane, 1 15 D -deC-, 89 -decyl<, 92 Delocalized charges, 58—59 Deprotonation. 53 —di—, 88, 97 Diastereomers, 156—157 Diethy] ether, 104 Dimethyl ether, 104 Double bonds, 33 in bond-line drawings. 2, 6 drawing, 6 nomenclature for. 87—88 and stereoisomerism, 95 in stereoisomers, 147—150 Z vs. E, 148—150 E E1 and E2 reactions, 230—232. 236—237, 239 Eclipsed conformations, 109 E double bonds (stereoisomers), 148—150 Electrons. See also Orbitals bond as sharing of, l 1 as clouds of electron density, 20 in lone pairs, 11—12. 22 movement of, in reactions, 168 valence, IO Electronegativity: and partial charges, 62 in periodic table, 54—55 Electronics, 228 Electrophile (substrate). 178—179 definition of, 178 in elimination reactions, 231 in substitution reactions. 214—216 Elements, second-row, 7. See also Periodic table Elimination reactions, 229—241 analyzing mechanisms in, 236—237 base in. 232—235 El vs. E2, 230—232, 239 Hoffmann product in, 238 leaving group in, 235 regiochemistry of, 182—183. 238—240 stereochemistry of, 239—241 and substitution reactions, 258—261 substrate in, 231 Zaitsev product in, 238 -en-, 88 Enantiomers: of chair configurations, 154—155 definition of. I35 INDEX 299 diastereomers vs., 156—157 drawing, 151—155 Equatorial substituents, 1 17 Equilibrium, prediction position of (acid—base reactions), 71—72 Esters, 85 -e suffix, 87 -eth-, 89 Ethanal, 104 Ethanoic acid, 104 Ethene, 104 Ethers, 104 ~etllyl-, 92 Ethylene. 104 Ethyl groups, 92 Ethyne, 104 Excellent leaving groups, 220 F Fischer projections, 160—164 Fluoride. 55 Fluorine, 55 —fiuor0-, 93 Formal charges: and finding lone pairs, 14—18 identifying. 10—14 in resonance structures, 29—31 Formaldehyde, 104 Formic acid. 104 Functional groups. 85—87, 98. 100 G Gauche interactions, 112 Geometry, 76—83 of bonds, 77 of hybridization states, 77—83 of orbitals. 77. 80—82 Good leaving groups, 220 H Halogens, 86, 93, 218, 220 —hcpt-, 89 -hepryl-, 92 -hex-, 89 300 INDEX »ltexa—, 88, 97 —hexyl~, 92 Hoffmann product, 183, 184, 238 Hybridization states. geometry of, 77—83 Hybridized orbitals, 66, 77 Hydrogen atoms (in bond-line drawings), 1, 3, 4, 7 —lzydr0xy-, 86, 93 Hyperconjugation. 63 I Induction. 62—64 Intermediates, drawing, 175—177 Iodide, 55 Iodine, 55 -iodo-, 93 Isopropyl groups, 92—93 K —keto-, 93 Ketones, 86 Kinetics, 181 L Leaving groups (LG), 21 l in benzylic vs. allylic position. 216 categories of, 220—221 in elimination reactions. 235 as factor in substitution reactions, 220—222 Linear structure, 81 Lone pair(s), I 1—18 and alpha effect, 63 bond broken to form, 169 bond formed from, 169 in carbon atom, 13 electrons in, 11—12, 22 next to pi bond (in resonance structures). 38—40 next to positive charge (in resonance structures), 41—43 in nitrogen atom, 12, 14. 17—18 in oxygen atom. 1 1—12, 14—16 M Markovnikov addition, 183, 184 Mechanisms, 167—190 in acid-base reactions, 73 in addition reactions, 242—244 as “bookkeeping of electrons,” I67 breaking single bonds in. 168 curved arrows for depicting, 168—175 of E1 and 2 reactions, 230—231 electrophiles, 178—179 in elimination reactions, 236—237 importance of understanding, 167 intermediates, 175—177 keeping a list of, I90 nucleophiles, 178—181 and octet rule, 168 regiochemistry of, 182—185 stereochemistry of, 185—190 in substitution reactions, 226 of substitution reactions, see Substitution reactions templates for, 191—210 Meso compounds. 157—160 ~metlz—, 89 Methanal, 104 Methanoic acid, 104 -methyl—, 92 Methyl groups, 92 Moderate nucleophiles, 218 Molecules: bond-line drawings of, see Bond-line drawings geometry of, see Geometry names of, see Nomenclature Multistep syntheses, 276—277 N Negative charge(s): partial, 62 and prediction position of equilibrium, in acid—base reactions, 62 stability of, in conjugate base, 53 Newman projections, 107—1 14 drawing, 107—110 ranking the stability of, 11 1—1 14 wedges and dashes in, 107 Nitrogen atom: lone pairs in, 12. 14, l7—l8 valence electrons of, 12 Nomenclature, 84—105 cis and trans, 133 common names, 103—104 components of, 84—85 deriving structure from, 104—105 functional group, 85—87 and numbering, 98—102 parent chain, 89—91 for stereocenters, 146—150 stereoisomerism component of, 95—97 substituents, 91—94 unsaturation component of, 87—88 -n0n—, 89 Nonpolar solvents, 223 —nonyl~, 92 Nucleophiles, 178—181 bases vs., 179—181 categories of, 218 definition of, 178, 211 electrophiles vs.. 178 in substitution reactions, 211—214, 217—219, 225 Nucleophilicity, 181. 233—234 Numbering, in molecule names, 98—102 0 -oct-, 89 Octet rule, 24—25, 33—35, 168 -octyl—, 92 -oic acids, 86 -01 suffix, 87 One-step syntheses, 265 Orbitals: of carbon atom, 7. 13 as factor in acid—base reactions, 66—67 geometry of, 77, 80—82 hybridized, 66, 77—79 number of electrons in. 22 INDEX 30 1 -0 suffix, 93 Oxygen, 234 Oxygen atom: lone pairs in, ll—12, l4—l6 valence electrons of. l 1 P Parent chain, 84. 89—91, 98—100 —pent-, 89 -penta-, 88, 97 Pentane, 89 -pentyl—, 92 Periodic table: and atom size, 55 and basicity, 233—234 and electronegativity, 54—55 and nucleophilicity, 233—234 Pi bond(s), 33—35 going around a ring (in resonance structures), 45 lone pair next to (in resonance structures), 38—40 next to positive charge (in resonance structures), 43 between two atoms (one atom electronegative), 44 pKa, 71 Polarized light, 165—166 Polar solvents, 223—225 P orbitals, 77 Positive charge: lone charge next to (in resonance structures), 41—43 partial, 62 pi bond next to (in resonance strucures), 43 Predicting products. 246—262 getting practice in, 247—248 questions to ask when. 246—247 in substitution vs. elimination reactions, 258—261 synthesis as flip side of, 263 templates for. 248—258 Primary substrates, 214 302 INDEX Problems, creating your own. 278—279 Products, predicting, see Predicting products —pr0p—, 89 -pr0pyl—, 92 Propyl groups. 92 Protic solvents, 223—224 Protons: in acid—base reactions. 53 and pKa, 71 R Racemic mixtures, 136, 165 Reactions: acid~base, see Acid—base reactions addition, 242—245 bond-line drawings to show, 5 elimination, see Elimination reactions mechanisms of. see Mechanisms predicting products of, 246—248, 258—262 and resonance structures, 21 substitution, see Substitution reactions Regiochemistry, 182—185, 189, 238—240 Resonance, 20—21, 57—59 Resonance structure(s): assessing relative significance of, 47—50 brackets in, 21 curved arrows in, 21—28 double—checking drawings of, 31 drawing arrows in, 26—28 formal charges in, 29—31 guidelines for drawing, 32—45 lone pair next to pi bond in, 38—40 lone pair next to positive charge in, 41—43 pi bond between two atoms (one atom electronegative'), 44 pi bond next to positive charge in, 43 pi bonds going around a ring in, 45 pi bonds in. 33—35 and reactions, 21 recognizing pattems in, 37—45 straight arrows in, 21 as term, 20 two commandments for pushing arrows in, 24—25 Retrosynthetic analysis, 277—278 Ring flipping (chair conformations). 123—128 R stereocenters, 134. 138 S Secondary substrates. 21-4 Second—row elements. 7 SNl and 8N2 substitution reactions. 211—214, 226, 227—228 electrophile as factor in, 215—216 leaving group as factor in, 220—222 nucleophile as factor in, 217—219 solvent as factor in, 223—225 Solvent shell, 224—225 s orbitals, 77, 78 sp orbitals, 66, 77, 81 sp2 orbitals, 66, 78, 79, 8] sp3 orbitals, 66. 79. 80 S stereocenters, 134, 138 Staggered conformations, 109 Stereocenters: definition of, 134, 135 determining configuration of, 138—146 diastereomers, 156—157 enantiomers, 151—155 finding. 135—137 Fischer projections for depicting, 160—164 importance of, 134—135 meso compounds, 157—160 nomenclature for, 146—150 numbering groups in, 138—142 and optical activity, 165—166 R vs. S. 134 trick for determining configuration of, 142—144 Stereochemistry, 185—190, 239—241 Stereoisomers. 135 naming double bonds in, 147—150 optical properties of, 165—166 Stereoisomerism, 84, 95—97, 101 Sterics, 76, 228 Steric hinderance, 130 Straight arrows (in resonance structures), 21 Strong nucleophiles, 218, 219 Study tips, v—vi Substituents, 84, 91—94r axial, 1 l7 branched, 92—93 equatorial, 1 17 numbering of, 100—101 Substitution reactions, 211—228 analyzing mechanisms in, 226 electrophile (substrate) in, 214—216 and elimination reactions, 258—261 importance of understanding, 227—228 leaving group in, 21 1, 220—222 nucleophile in, 21 1—214, 217—219 SN] vs. 5N2, 211—214 solvent in, 223—225 Substrate, see Electrophile Sulfur, 234 Symmetry, of meso compounds, 158—159 Syn addition, 186, 189 Synthesisbes), 263—278 creating synthesis problems, 278—279 as flip side of predicting products, 263 importance of understanding, 264—265 multistep, 276—277 one—step, 265 and retrosynthetic analysis, 277—278 INDEX 303 T Iert-butyl group, 93, 130—131 Tertiary substrates, 214 -refra-, 88, 97 Tetrahedral structure, 80 Thermodynamics, 18] Trans bonds, 95—96 Trans (conformations). 121, 133 -m'—, 88, 97 Trigonal planar structure, 81. 96 Trigonal pyramidal structure, 81—82 Triple bonds, 33 in bond—line drawings, 2 nomenclature for, 87—88 "Two commandments" (for drawing resonance structures). 24—25 U Unsaturation, 85, 87—88, 100 V Valence electrons, 10 Valence shell. 10 Valence shell electron pair repulsion theory (VSEPR), 80 W Weak nucleophiles, 218, 219 Y -_vn-, 88 Z Zaitsev product, 182—184, 238 Z double bonds (stereoisomers), 148—150 Zigzag format, 2. 6, 7 ...
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Index - INDEX A + rotation, 165—166 — rotation,...

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