Virtual Textbook of Organic Chemistry Reusch •

Structure& Bonding

Intro to Organic Chemistry Atomic Structure Molecular Orbitals Sigma and Pi Bonds Octet Rule Bonding Preferences Formal Charges Skeletal Structure Lewis Structure Condensed Structural Formula Isomer Degrees of Unsaturation Constitutional Isomers Resonance Structures Hybridization Molecular Geometry Electronegativity Polar Vs. Nonpolar Covalent Bond Polar Bond Functional Groups

Intermolecular Forces

Intermolecular Forces London Dispersion Force Van Der Waals How To Determine Solubility

Chemical Reactivity I

Organic Chemistry Reactions Reaction Mechanism Acids and Bases Give the conjugate acid for each compound below pKa Acid Base Equilibrium Ranking Acidity Lewis Acids and Bases

Aliphatic Hydrocarbons

IUPAC Naming Alkyl Groups Alkyl t-Butyl, sec-Butyl, isobutyl, n-butyl Naming Cycloalkanes Naming Bicyclic Compounds Naming Alkenes Decalin Radical Reaction Radical Stability Free Radical Halogenation Radical Selectivity

Stereoisomers Part I

Cis vs Trans Conformational Isomers Newman Projections Drawing Newman Projections Barrier To Rotation Ring Strain Axial vs Equatorial Cis vs Trans Conformations Equatorial Preference Chair Flip Calculating Energy Difference Between Chair Conformations A-Values

Chemical Reactivity II

Energy Diagram Gibbs Free Energy Enthalpy Entropy Hammond Postulate Hyperconjugation

Alkenes and Alkynes I

Alkene Stability Carbocation Stability Carbocation Intermediate Rearrangements Addition Reaction Markovnikov Hydrohalogenation Halogenation Hydrogenation Oxymercuration Hydroboration

Alkenes & Alkynes II

Acid-Catalyzed Hydration Halohydrin Carbene Epoxide Reactions Dihydroxylation Ozonolysis Ozonolysis Full Mechanism Oxidative Cleavage Alkyne Oxidative Cleavage Acetylide Hydrogenation of Alkynes Anti Markovnikov Addition of Br Allylic Bromination Alkyne Hydrohalogenation Alkyne Halogenation Alkyne Hydration Alkyne Hydroboration Alkynide Synthesis

Conjugation & Aromaticity

Diene Conjugation Chemistry Stability of Conjugated Intermediates Allylic Halogenation Conjugated Hydrohalogenation (1,2 vs 1,4 addition) Diels-Alder Reaction Diels-Alder Forming Bridged Products Diels-Alder Retrosynthesis Aromaticity Huckel's Rule Pi Electrons Aromatic Hydrocarbons Annulene Aromatic Heterocycles Naming Benzene Rings Acidity of Aromatic Hydrocarbons Basicity of Aromatic Heterocycles Ionization of Aromatics

Stereoisomers Part II

Constitutional Isomers vs. Stereoisomers Chirality Test 1: Plane of Symmetry Test 2: Stereocenter Test R and S Configuration Enantiomers vs. Diastereomers Atropisomers Meso Compound Test 3: Disubstituted Cycloalkanes What is the Relationship Between Isomers? Fischer Projection R and S of Fischer Projections Racemic Mixture Optical Activity Enantiomeric Excess Calculations with Enantiomeric Percentages Non-Carbon Chiral Centers Achiral

Alkyl Halides

Naming Alkyl Halides Alkyl Halide Nucleophilic Substitution Good Leaving Groups SN2 Reaction SN1 Reaction Substitution Comparison E2 Mechanism Zaitsev Rule Beta Hydrogen Dehydrohalogenation E2 - Anti-Coplanar Requirement E2 - Cumulative Practice E1 Reaction Solvents Leaving Groups Nucleophiles and Basicity SN1 SN2 E1 E2 Chart (Big Daddy Flowchart) Cumulative Substitution/Elimination

Alcohols & Ethers

Naming Alcohols Hydroxyl Group Naming Ethers Naming Epoxides Naming Thiols Alcohol Synthesis Dehydration Reaction POCl3 Dehydration Leaving Group Conversions - Using HX Leaving Group Conversions - SOCl2 and PBr3 Leaving Group Conversions - Sulfonyl Chlorides Leaving Group Conversions Summary Oxidizing and Reducing Agents Oxidizing Agent Reducing Agent Williamson Ether Synthesis Making Ethers - Alkoxymercuration Making Ethers - Alcohol Condensation Making Ethers - Acid-Catalyzed Alkoxylation Making Ethers - Cumulative Practice Ether Cleavage Epoxidation Epoxide Reactions Alcohol Protecting Groups t-Butyl Ether Protecting Groups Silyl Ether Protecting Groups Sharpless Epoxidation Thiol Reactions Sulfide Oxidation

Benzene & Derivatives

Electrophilic Aromatic Substitution Benzene Reactions EAS: Halogenation Mechanism EAS: Nitration Mechanism EAS: Friedel-Crafts Alkylation Mechanism EAS: Friedel-Crafts Acylation Mechanism EAS: Any Carbocation Mechanism Electron Withdrawing Groups EAS: Ortho vs. Para Positions Acylation of Aniline Limitations of Friedel-Crafts Alkyation Advantages of Friedel-Crafts Acylation Blocking Groups - Sulfonic Acid EAS: Synergistic and Competitive Groups Side-Chain Halogenation Side-Chain Oxidation Birch Reduction EAS: Sequence Groups EAS: Retrosynthesis Diazo Replacement Reactions Diazo Sequence Groups Diazo Retrosynthesis Nucleophilic Aromatic Substitution Benzyne Phenol Acidity

Amines

Naming Amines Amine Alkylation Gabriel Synthesis Amines by Reduction Nitrogenous Nucleophiles Reductive Amination Curtius Rearrangement Hofmann Rearrangement Hofmann Elimination Cope Elimination

Aldehydes and Ketones

Naming Aldehydes Naming Ketones Oxidizing and Reducing Agents Oxidation of Alcohols Ozonolysis DIBAL Alkyne Hydration Nucleophilic Addition Cyanohydrin Organometallics on Ketones Overview of Nucleophilic Addition of Solvents Hydrates Hemiacetal Acetal Acetal and Hemiacetal Acetal Protecting Group Thioacetal Imine vs Enamine Addition of Amine Derivatives Wolff Kishner Reduction Baeyer-Villiger Oxidation Acid Chloride to Ketone Nitrile to Ketone Wittig Reaction Ketone and Aldehyde Synthesis Reactions Tautomerization Tautomers of Dicarbonyl Compounds Enolate Acid-Catalyzed Alpha-Halogentation Base-Catalyzed Alpha-Halogentation Overview of Alpha-Alkylations and Acylations Enolate Alkylation and Acylation Condensation Reactions Aldol Condensation Directed Condensations Crossed Aldol Condensation Intramolecular Aldol Condensation

Carboxylic Acids and Carboxylic Acid Derivatives

Carboxylic Acid Carboxylic Acid Derivatives Naming Carboxylic Acids Diacid Nomenclature Ester Naming Esters Naming Nitriles Acid Chloride Nomenclature Naming Anhydrides Naming Amides Nucleophilic Acyl Substitution Carboxylic Acid to Acid Chloride Fischer Esterification Acid-Catalyzed Ester Hydrolysis Saponification Transesterification Lactones, Lactams and Cyclization Reactions Carboxylation Decarboxylation Mechanism Claisen-Schmidt Condensation Claisen Condensation Conjugate Addition Michael Addition

Organometallic Chemistry

Preparation of Organometallics Grignard Reaction Protecting Alcohols from Organometallics Organometallic Cumulative Practice

Spectroscopy

Purpose of Analytical Techniques Infrared Spectroscopy Infrared Spectroscopy Table IR Spect: Drawing Spectra IR Spect: Extra Practice NMR Spectroscopy 1H NMR: Number of Signals 1H NMR: Q-Test 1H NMR: E/Z Diastereoisomerism H NMR Table 1H NMR: Spin-Splitting (N + 1) Rule 1H NMR: Spin-Splitting Simple Tree Diagrams 1H NMR: Spin-Splitting Complex Tree Diagrams 1H NMR: Spin-Splitting Patterns NMR Integration NMR Practice Carbon NMR Structure Determination without Mass Spect Mass Spectrometry Mass Spect: Fragmentation Mass Spect: Isotopes

Introduction to Synthesis

Synthetic Cheatsheet Moving Functionality Alkynide Alkylation Alkane Halogenation Retrosynthesis

Pericyclic Reactions

Molecular Orbital Theory Drawing Atomic Orbitals Drawing Molecular Orbitals HOMO LUMO Orbital Diagram: 3-atoms- Allylic Ions Orbital Diagram: 4-atoms- 1,3-butadiene Orbital Diagram: 5-atoms- Allylic Ions Orbital Diagram: 6-atoms- 1,3,5-hexatriene Orbital Diagram: Excited States Pericyclic Reaction Thermal Cycloaddition Reactions Photochemical Cycloaddition Reactions Thermal Electrocyclic Reactions Photochemical Electrocyclic Reactions Cumulative Electrocyclic Problems Sigmatropic Rearrangement Cope Rearrangement Claisen Rearrangement

Carbohydrates, Proteins and Amino Acids

Monosaccharide Monosaccharides - D and L Isomerism Monosaccharides - Drawing Fischer Projections Monosaccharides - Common Structures Monosaccharides - Forming Cyclic Hemiacetals Monosaccharides - Cyclization Monosaccharides - Haworth Projections Mutarotation Epimerization Monosaccharides - Aldose-Ketose Rearrangement Monosaccharides - Alkylation Monosaccharides - Acylation Glycoside Monosaccharides - N-Glycosides Monosaccharides - Reduction (Alditols) Monosaccharides - Weak Oxidation (Aldonic Acid) Reducing Sugars Monosaccharides - Strong Oxidation (Aldaric Acid) Monosaccharides - Oxidative Cleavage Monosaccharides - Osazones Monosaccharides - Kiliani-Fischer Monosaccharides - Wohl Degradation Monosaccharides - Ruff Degradation Disaccharide Polysaccharide Proteins and Amino Acids L and D Amino Acids Polar Amino Acids Amino Acid Chart Peptide Bond Acid-Base Properties of Amino Acids Isoelectric Point