Review of Chem 205
Chapters 1, 2, 3,
4, 5, 6, 7,
8, 9, 12,
11, 12, 14,
15
Chapter 1 - Structure and Bonding
- Atomic Electronic Structure
- Ionic vs. Covalent Bonding
- In Covalent Bonding - Combination of Atomic Orbitals to form
Molecular Orbitals
- Formation of Hybrid Bond Orbitals - particularly as it
pertains to Carbon, Oxygen, Nitrogen - influence of hybridization
state on bond length, bond angle, molecular geometry, bond
strength
Chapter 2 - Bonding and Moleculare Properties
- Calculation of Formal Charges
- Polarity - Relationship of polarity to intermolecular forces
and physical properties exhibited by a compound
- Acids and Bases - Bronsted-Lowry Definition, Lewis Definition,
Relationship between electronegativity and size and acidity and
basicity, Use of pKa values in predicting acid strength and
direction of acid-base reactions
Chapter 3 - Alkanes and Cycloalkanes
- Concept of functional groups and how they define a family of
organic compounds
- Straight-chain and branched chain alkanes
- Types of consitutional isomers
- Nomenclature
- Relationship of size and branching to physical properties
of alkanes
- Cyclocalkanes
- Nomenclature
- Cis-Trans Isomerism
Chapter 4 - Stereochemistry of Alkanes and
Cycloalkanes
- Conformational analysis of straight chain alkanes
- Newman and Sawhorse projections
- Eclipsed, Gauche, Anti conformations - Dihedral Angle
- Definition and origin of torsional and steric strain
- Conformational anaylsis of cycloalkanes
- Ring Strain - Definition and origin - Angle Strain, Steric
Strain, Torsional Strain
- Conformations of cyclobutane and cyclopentane
- Conformational Analysis of Cyclohexane - Chair
Conformation, Axial and Equatorial Positions, Ring Flip, Boat
Conformation
- Conformational Analysis of mono and di-substituted
cyclohexanes - origin of 1,3-diaxial interactions
Chapter 5 - An Overview of Organic Reactions
- Kinds of Reactions - Addition, Elimination, Substitution,
Rearrangement
- Mechanisms of Bond Breakage and Bond Formation - Homolytic,
Heterolytic bond breakage; Homogenic, Heterogenic bond
formation
- Radical Chain Reactions - Free Radical Intermediates
- Polar Reactions - Nucleophiles and Electrophiles; Ionic
Intermediates
- Energy Changes Associated with Reactions
- Free-Energy Changes and Reaction Equilibria; Enthalpy
Component, Entropy Component - Relationship to endothermic and
exothermic processes and bond dissociation energies
- Transition states and Energies of Activation - Relationship
to rates of chemical reactions
- Distinction between transition states and reaction
intermediates
- Composite Energy Profile Diagrams which describe all energy
changes associated with chemical reactions
Chapter 6 - Alkenes: Structure and Reactivity
- Calculation of the number of degrees of unsaturation in a
molecule
- Nomenclature of Alkenes
- Electronic Structure of the pi bond
- Z and E isomers for alkenes
- Relationship between alkene stability and the number of
substituents
- Reactions of Alkenes - Electrophilic Addition
- Markovnikov's Rule
- Carbocation intermediates and realtionships to
Markovnikov's Rule
- Hammond Prinicple - Relationship between energy of
activation and intermediate stability
- Rearrangement of Carbocation intermediates - 1,2 dihydride
and alkyl shifts
Chapter 7 - Alkenes: Reactions and Synthesis
- Addition of dihalogens to Alkenes - halonium ions and
stereochemistry
- Halohydrin Formation
- Hydration of Alkenes to Form Alcohols
- Oxymercuration-Demercuration - Regioselectivity
- Hydroboration-Oxidation - Regioselectivity
- Free Radical Addition of HBr - influence of peroxides -
Regioselectivity
- Reduction of Alkenes to Alkanes - hydrogenation,
hydrogen/metal
- Oxidation of Alkenes to diols - KMnO4, -OH, cold;
OsO4, NaHSO3
- Oxidative Cleavage of Alkenes
- Ozonolysis
- KMnO4, H2O, heat
- Oxidation of 1,2-diols by HIO4
- Addition of Carbenes
- Preparation of Alkenes via Elimination Reactions -
Dehydrohalogenation and Dehydration
Chapter 8 - Alkynes
- Electronic Configuration of the carbon-carbon triple bond
- Nomenclature of Alkynes
- Reactions of Alkynes
- Addition of HX and X2
- Hydration of Alkynes - Oxymercuration/Demercuration;
Hydroboration/Oxidation - Enol-Keto Tautomerizations
- Reduction of Alkynes to Alkenes
- H2/Lindlar's Catalyst - Stereochemistry
- Li/NH3 - Stereochemistry
- Acidity of Terminal Alkynes - Preparation of sodium acetylides
- Use in synthesis
- Oxidative Cleavage of Alkynes - KMnO4 and
Ozonolysis
Chapter 9 - Stereochemistry
- Optical Activity and Specific Rotation
- Chiral Centers and Chirality
- Enantiomers - Sequence Rules for designating R/S
Configurations - Fischer Projections and Rules for Comparison of
Stereoisomers using Fischer Projections - Racemic Mixtures,
Enantiomer Excesses
- Diastereomers and Meso Structures
- Stereochemistry of reactions that result in the introduction
of a chiral center into an achiral molecule
- Stereochemistry of reactions that result in the introduction
of a second chiral center into a chiral molecule
- Stereochemistry of disubsituted derivatives of cyclohexanes;
cis-trans forms of 1,2; 1,3; and 1,4 disubstituted derivatives,
chiral versus achiral, true versus interconverting
enantiomers
Chapter 10 - Alkyl Halides
- Nomenclature of Alkyl Halides
- Preparation - Free radical halogenation (X2, light
or heat, NBS), Use of HX, PBr3, SOCl2
- Resonance - Rules for Drawing resonance structure -
Relationship of Resonance to Stability of Reaction
Intermediates
- Organometallic Reagents formed from alkyl halides - Coupling
Reactions using Gilman Reagents and its use and limitations for
synthesis
Chapter 11 - Reactions of Alkyl Halides:
Nucleophilic Substitutions and Eliminations
- SN2 Mechanism for Substitution of Alkyl halides and tosylates
- Arrow Mechanism - Concerted Nature
- Stereochemistry
- Characteristics that influence this reaction - nature of
the alkyl halide (steric effects), nature of nucleophile,
leaving group, solvent
- SN1 Mechanism of Substitution - Understand same aspects as for
SN2
- E2 Mechanism of Elimination - Understand same aspects as for
substitution reactions - antiperiplanar stereochemistry and
consequences
- E1 Mechanism of Elimination - Understand same aspects as for
substitution reactions - no antiperiplanar requirement
- Understand Competition between Substitution and
Elimination
Chapter 12 - Mass Spectroscopy and Infrared
Spectroscopy
- Understand basis of I.R. Absorption - Be able to interpret
simple spectra - learn the approximate positions of absorption of
major functional groups given to you in the laboratory
- Understand basis of mass spectrometry - Know how to identify
molecular ion to determine molecular weight and how to interpret
simple fragmentation patterns
Chapter 14 - Conjugated pi Electron Systems and
Ultraviolet-Visible Spectroscopy
- Know Difference between Isolated and Conjugated pi electron
systems
- Understand unique pi electron configuration of a conjugated pi
electron system
- Understand unique chemistry of addition to conjugated dienes -
1,2 and 1,4 addition products - Kinetic versus Thermodynamic
Control
- Diels-Alder Reaction
- Reaction Mechanism
- Important characteristics of dienes and dienophiles
- Types of ring compounds that can be made with this
reaction
- Endo rule when bridgehead compounds are made
- Ortho, Para rule when unsymmetrical dienes are
reactants
- Ultraviolet Spectroscropy
- Basis for absorption of light in this spectral region, pi
-> pi* transition, n -> pi* transition, relative
positions and intensities of these two type absorption
bands
- relationship between length of the conjugated pi electron
system and the position of the absorption band
Chapter 15 - Benzene and Aromaticity
- Nomenclature of Benzene and its derivatives
- Relationship between electronic structure and unusual
stability of benzene
- Use of the Hückel (4n+2) Rule to predict aromaticity in
general
- Aromatic ions
- Polycyclic compounds
- Heterocyclic compounds
- Distinguishing IR and UV absorptions for Benzene