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Chapter 1 concepts Octet rule Formal charge Resonance hybrid o Contributing structures Resonance Bond dipole Constitution/connectivity o Schrodinger

dinger equation Wave function Quantum numbers o Nodal surfaces Pauli exclusion Isoelectronic Electronegativity Electropositive Electrostatic potential map red and blue Partial charge vs formal charges vs full charge Constitutional isomers, structural isomers Isomers Condensed structural formula Bond line formulas VSEPR, effect of lone pair of e Rules of resonance o Determining major contributor o When to draw resonance contributors Localized vs. delocalized Molecular dipole Nonpolar vs polar Equation for polarity Net dipole Arrhenius vs. Bronsted Lowry vs. Lewis pKa and Ka and their relation to acidity What are strong acids and what should their pKa be o Weak acids and their pKa guideline ISHARE Equilibrium, shifts in side of weaker acid Chapter 2 Concepts Hydrocarbons aliphatic and aromatic Valence bond theory Molecular orbital theory Antibonding vs bonding Boiling point of straight vs. branched alkanesstraight more VDW contact points and surface area Isopropyl, isobutyl, secbutyl, tertbutyl

Cycloalkane vs. alkane Functional groups

Chapter 3 Concepts Conformation Cyclic conformers Strain Alkyl halide Alcohol Alcohol naming priority over alkyl or halogen Conformer o Eclipsed conformer o Staggered conformer o Anti o Gauche Strain o Torsional o Van der waals (steric) o Angle- decreases from cyclo3 to cyclo6 Conformational analysis graph Chair and boat o Axial and equatorial o Chair chair interconversion Newman projection Stereoisomers 1,3 diaxial repulsion (van der waals strain) cis and trans isomer which has more vdw strain heterocyclic compounds and heteroatoms polycylic ring system o spirocylic o fused ring o bridged ring Chapter 4 Concepts alkyl halide alcohol substitution reaction Reactions o Halogenation Alcohols alkyl halides SN1 (3, 2) and SN2 (1, methyl) Nonacidic reagants Alkanes alkyl halides Free radical, hv Cl2 promiscuous Br2- 3 H

Halogen reactivity o F2 > Cl2 > Br2 > I2 Hydrogen halide reactivity o HF < HCl < HBr < HI Relative rates of substitution (ROH) o Methanol < 1 < 2 < 3 PE of halogenation of alcohol SN1 and SN2 o Energy of activation o Transition state o Endo vs exothermic Electrophile vs. nucleophile Functional groups Induced dipole-induced dipole forces Dipole-dipole attractive force Dipole-induced dipole force Hydrogen bonding Polarizability Hammonds rule Rate determining step

o Dehydrogenation of alkyl halides Leaving group rate o RI > RBr > RCl >>>>>> RF Stereoelectronic effect- affect on spatial arrangement of orbitals or bonds Rate of elimination 1 < 2 < 3 Carbocation stability Alkyl shift (adjacent C) rearrangement Hydride shift

Chapter 5 Concepts Alkenes o Mono, di, tri, tetra substituted Elimination reaction Stereoselective reaction- single starting material can give 2 or more stereoisomeric products but gives one more than other o Trans and cis Regioselective reaction o Zaitsevs Rule Alkene nomenclature o OH (ol) outrank = (en) o E and Z o Z destabilized by VDW Methylene, vinyl, allyl Cahn-ingold-prelog system for alkenes Electronic effects degree of substitution Steric effects van der waals strain Reactions o Dehydration of alcohols Acidic conditions E1 (2, 3) and E2 (1) o Dehydrohalogenation of alkanes Under basic conditions E2- anti coplanar (1, 2, 3) Absence of base (alcohol solvent) E1 (2 or 3) PE Diagram for E1 and E2

Chapter 6 Concepts Reactions electrophilic addition o Hydrogenation syn addition Adds to less crowded face o Hydrogen halides o Acid catalyzed hydration o Hydroboration-oxidation syn o Halogens vicinal dihalide, anti o Halohydrins vicinal, anti o Free radical addition, HBR/ROOR o Epoxidation syn o Ozonolysis Regioselective o Markovnikovs rule o Anti markovnikovs rule Free radical stability o 3 > 2 > 1 For ones its not stereoselective, you get racemic mixture cause it can add to either face More substituted double bonds react faster Chapter 7 Concepts Stereoisomers geometric isomers, enantiomers, diastereomers Chiral molecule Enantiomers Cahn-ingold-prelog system o assigning prioritywhat to do if 2 groups contain same atom Optical activity o Ordinary vs plane polarized light o Optically active o Optically inactive achiral o Rotation of light CW (+), CCW () Naming stereoisomer R vs. S Observed rotationequation for it Optical purity

o OP= % enantiomeric excess = % major % minor o OP =

possible and always occur with primary alcohols and alkyl halides

No rearrangement s are possible

Enantiomeric excess Racemic mixture Physical properties of enantiomers Fisher diagrams shown as eclipsed o Vertical away from you o Horizontal toward you Erythro/threo o Erythro- same (or analogous) substituents on same side of Fischer projection o Threo same (or analogous) substituents on opposite sides of Fischer projection Meso Max number of stereoisomers 2n o N = number of chiral centers and double bonds capable of E & Z Optically inactive starting materials cant give optically active products o Achiral reactants give chiral, racemic products Absolute vs relative configurations o Absolute- R and S o Relative degrees (+ or ) Prochiral addition to either face converts achiral reactant to chiral product Enantiotopic product from reaction at one face is the enantiomers of the product from reaction at the other Stereospecific reaction reaction in which stereoisomeric starting materials yield products that are stereoisomers of each other E2

E1 Favored under acidic conditions/polar protic solvents Favored with tertiary alcohols and alkyl halides Possible with secondary alcohols or alkyl halides Rearrangements are

Favored under basic conditions with all alkyl halides and large bulky bases Requires high concentrations (e.g.,1M) of strong bases

Chapter 8 Leaving group related to basicity o Strongly basic- poor LG o Weakly basic- good LG SN2 o Backside attack o Inversion of configuration o 1 and 2 RX with Nu o steric hindrance solvolysis Nu = solvent o SN1 forms C+ 1 and methyl never by SN1, 3 never by SN2 solvent- protic or aprotic SN vs E o Structure of alkyl halide As crowding decreases, SN2 rate increases1 RX with strong bases more SN2 over E2 But if base is crowded, 1 RX go E2 3 RX so sterically hindered to SN2 that any anionic lewis base favors E2 SN1 predominates over E2 when anionic bases are absent o Basicity of anion Nu less basic than OH- react with 1 and 2 via SN2 o E2- 2 RX with strong base o Heat increases E more than SN SN of Alkyl sulfornates ROH + tosyl Cl alkyl tosylate Chapter 9 Nomenclature double + triple Carbide- strong strong base Carbanion, C Greater s character of bond to H, more acidic b/c E.N. increases Reactions o Alkylation of acytelene via SN2

o o o o o o o o

Double dehydrohalogenation Hydrogenation syn Lindlars catalyst- Z Na/NH3 E Addition of HX Hydration Halogens Ozonolysis

o HX addition o HBr with ROOR Alkenylbenzenes Aromatic compound o Anti, non, or aromatic Sp2, conjugated, huckels Heterocylic aromatic compounds

Chapter 10 Allyl vs vinyl SN1 o Allylic halides more reactive than SN1 nonallylic Allylic rearrangement SN2- 1 RX with good Nu Allylic free radical Reactions o Allylic halogenation Cl2 or Br2 NBS o HX to conjugated dienes Kinetic, thermodynamic o X2 addition to conjugated dienes Kinetic, thermodynamic o Diels Alder EWG and s-cis Syn addition Diene o Alkadiene o Isolated diene o Conjugated diene o Cumulated diene Chapter 11 Benzene Kekul structures Ortho, meta, para Benzyl nomenclature Benzyl priority Benzylic carbon Redox reactions o Birch reduction o Chlorination of benzylic o NBS of benzylic o Oxidation o SN1 o SN2- 1 benzylic halides o E1 and E2 o Hydrogenation o Halogenation

Chapter 12 Electrophilic aromatic substitution Reactions o Nitration o Sulfonation o Halogenation o Friedel-crafts alkylation/acylation o Clemmenson o Wolf-kishner Activating and deactivating substituents Partial rate factors ERG vs EWG