Chapter 1 concepts Octet rule Formal charge Resonance hybrid

o Contributing structures Resonance Bond dipole Constitution/connectivity

o Schrodinger 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 contributoro 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

alkanes…straight 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 conformero Staggered conformero Antio Gauche

Straino Torsionalo Van der waals (steric)o Angle- decreases from cyclo3 to

cyclo6 Conformational analysis graph Chair and boat

o Axial and equatorialo 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 spirocylico fused ringo 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 reactivityo 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 activationo Transition stateo Endo vs exothermic

Electrophile vs. nucleophile Functional groups Induced dipole-induced dipole forces Dipole-dipole attractive force Dipole-induced dipole force Hydrogen bonding Polarizability Hammond’s rule Rate determining step

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 Zaitsev’s Rule Alkene nomenclature

o OH (ol) outrank = (en)o E and Zo 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

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 6 Concepts Reactions– electrophilic addition

o Hydrogenation– syn addition Adds to less crowded face

o Hydrogen halideso Acid catalyzed hydrationo Hydroboration-oxidation– syno Halogens– vicinal dihalide, antio Halohydrins– vicinal, antio Free radical addition, HBR/ROORo Epoxidation– syno Ozonolysis

Regioselectiveo Markovnikov’s ruleo Anti markovnikov’s rule

Free radical stabilityo 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 priority…what to do if 2 groups contain same atom

Optical activityo Ordinary vs plane polarized lighto Optically activeo Optically inactive– achiral o Rotation of light CW (+), CCW (–)

Naming stereoisomer R vs. S Observed rotation…equation for it Optical purity

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

o OP = specific rotationof sample

specific rotation of pure enantiomer∗100

Enantiomeric excess Racemic mixture Physical properties of enantiomers Fisher diagrams– shown as eclipsed

o Vertical– away from youo Horizontal– toward you

Erythro/threoo 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 can’t give optically active products

o Achiral reactants give chiral, racemic products

Absolute vs relative configurationso Absolute- R and So 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

E1 E2 Favored under

acidic conditions/polar protic solvents

Favored with tertiary alcohols and alkyl halides

Possible with secondary alcohols or alkyl halides

Rearrangements are possible and always occur with primary alcohols and alkyl

Favored under basic conditions with all alkyl halides and large bulky bases

Requires high concentrations (e.g.,1M) of strong bases

No rearrangement

halides s are possible

Chapter 8 Leaving group related to basicity

o Strongly basic- poor LGo Weakly basic- good LG

SN2o Backside attacko Inversion of configurationo 1˚ and 2˚ RX with – Nuo steric hindrance

solvolysis– Nu = solvento 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 increases…1˚ 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 baseo 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 Double dehydrohalogenationo Hydrogenation– syn

o Lindlar’s catalyst- Zo Na/NH3 Eo Addition of HXo Hydrationo Halogenso Ozonolysis

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

NBSo HX to conjugated dienes

Kinetic, thermodynamico X2 addition to conjugated dienes

Kinetic, thermodynamico Diels Alder

EWG and s-cis Syn addition

Dieneo Alkadieneo Isolated dieneo Conjugated dieneo Cumulated diene

Chapter 11 Benzene Kekulé structures Ortho, meta, para Benzyl nomenclature Benzyl priority Benzylic carbon Redox reactions

o Birch reductiono Chlorination of benzylico NBS of benzylico Oxidationo SN1o SN2- 1˚ benzylic halideso E1 and E2o Hydrogenationo Halogenationo HX addition

o HBr with ROOR Alkenylbenzenes Aromatic compound

o Anti, non, or aromatic Sp2, conjugated, huckel’s

Heterocylic aromatic compounds

Chapter 12 Electrophilic aromatic substitution Reactions

o Nitrationo Sulfonationo Halogenationo Friedel-crafts alkylation/acylationo Clemmensono Wolf-kishner

Activating and deactivating substituents Partial rate factors ERG vs EWG