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Chemistry 231 and 232: Kenyon College

Chemistry

Author: Getzler, Hofferberth, and Hunsen
Publisher: Kenyon College
Source: LibreTexts
Language: EN
Category: Basic Sciences

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Contents· 269 sections

1: Structure and Bonding in Organic Molecules
1.1: The Scope of Organic Chemistry
1.2: Coulomb Forces - A Simplified View of Bonding
1.3: Ionic and Covalent Bonds - The Octet Rule
1.4: Electron-Dot Model of Bonding - Lewis Structures
1.5: Resonance Forms
1.6: Atomic Orbitals: A Quantum Mechanical Description of Electrons Around the Nucleus
1.7: Molecular Orbitals and Covalent Bonding
1.8: Hybrid Orbitals: Bonding in Complex Molecules and Practice Problems
1.9: Structures and Formulas of Organic Molecules
1.E: Structure and Bonding in Organic Molecules (Exercises)
2: Structure and Reactivity: Acids and Bases Polar and Nonpolar Molecules
2.1: Kinetics and Thermodynamics of Simple Chemical Processes
2.2: Keys to Success: Using Curved "Electron Pushing" Arrows to Describe Chemical Reactions
2.4: Functional Groups: Centers of Reactivity
2.5: Straight-Chain and Branched Alkanes
2.6: Naming the Alkanes
2.7: Structural and Physical Properties of Alkanes
2.8: Rotation about Single Bonds: Conformations
2.9: Rotation in Substituted Ethanes
2.E: Structure and Reactivity: Acids and Bases, Polar and Nonpolar Molecules (Exercises)
8.1 Brønsted Acidity and Basicity
8.2 Factors Affecting Brønsted Acidity
8.3: pKa Values
8.4 Solvent Effects
8.2 Factors Affecting Brønsted Acidity
8.3: pKa Values
8.4 Solvent Effects
3: Reactions of Alkanes: Bond-Dissociation Energies Radical Halogenation and Relative Reactivity
3.1: Strength of Alkane Bonds: Radicals
3.2: Structure of Alkyl Radicals: Hyperconjugation
3.3: Conversion of Petroleum: Pyrolysis
3.4: Chlorination of Methane: The Radical Chain Mechanism
3.5: Other Radical Halogenations of Methane
3.6: Keys to Success: Using the "Known" Mechanism as a model for the "Unknown"
3.7: Chlorination of Higher Alkanes: Relative Reactivity and Selectivity
3.8: Selectivity in Radical Halogenation with Fluorine and Bromine
3.9: Synthetic Radical Halogenation
3.10: Synthetic Chlorine Compounds and the Stratospheric Ozone Layer
3.11: Combustion and the Relative Stabilities of Alkanes
3.E: Reactions of Alkanes (Exercises)
4: Cycloalkanes
4.1: Names and Physical Properties of Cycloalkanes
4.2: Ring Strain and the Structure of Cycloalkanes
4.3: Cyclohexane: A Strain-Free Cycloalkane
4.4: Substituted Cyclohexanes
4.5: Larger Cycloalkanes
4.6: Polycyclic Alkanes
4.7: Carbocyclic Products in Nature
4.E: Cycloalkanes (Exercises)
5: Stereoisomers
5.1: Chiral Molecules
5.2: Optical Activity
5.3: Absolute Configuration: R-S Sequence Rules
5.4: Fischer Projections
5.5: Molecules Incorporating Several Stereocenters: Diastereomers
5.6: Meso Compounds
5.7: Stereochemistry in Chemical Reactions
5.8: Resolution: Separation of Enantiomers
5.E: Stereoisomers (Exercises)
6: Bimolecular Nucleophilic Substitution in Haloalkanes
6.1: Physical Properties of Haloalkanes
6.2: Nucleophilic Substitution
6.3: Reaction Mechanisms Involving Polar Functional Groups: Using "Electron-Pushing'" Arrows
6.3: Reaction Mechanisms Involving Polar Functional Groups: Using "Electron-Pushing\\'" Arrows
6.4: A Closer Look at the Nucleophilic Substitution Mechanism: Kinetics
6.5: Frontside or Backside Attack? Stereochemistry of the SN2 Reaction
6.6: Consequences of Inversion in SN2 Reactions
6.7: Structure and \(S N2\) Reactivity: The Leaving Group
6.8: Structure and SN2 Reactivity: The Nucleophile
6.9: Keys to Success: Choosing Among Multiple Mechanistic Pathways
6.10: Structure and SN2 Reactivity: The Substrate
6.11: The Sn2 Reaction at a Glance
6.E: Properties and Reactions of Haloalkanes: Bimolecular Nucleophilic Substitution (Exercises)
7: Further Reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination
7.1: Solvolysis of Tertiary and Secondary Haloalkanes
7.2: Unimolecular Nucleophilic Substitution
7.3: Stereochemical Consequences of SN1 Reactions
7.4: Effects of Solvent, Leaving Group, and Nucleophile on Unimolecular Substitution
7.5: Effect of the Alkyl Group on the SN 1 Reaction: Carbocation Stability
7.6: Unimolecular Elimination: E1
7.7: Bimolecular Elimination: E2
7.8: Keys to Success: Substitutin Versus Elimination-Structure Determines Function
7.9: Summary of Reactivity of Haloalkanes
7.E: Further Reactions of Haloalkanes: Unimolecular Substitution (Exercises)
8: Hydroxy of Functional Group: Alcohols: Properties Preparation and Strategy of Synthesis
8.1: Naming the Alcohols
8.2: Structural and Physical Properties of Alcohols
8.3: Alcohols as Acids and Bases
8.4: Industrial Sources of Alcohols: Carbon Monoxide and Ethene
8.5: Synthesis of Alcohols by Nucleophilic Substitution
8.6: Synthesis of Alcohols: Oxidation-Reduction Relation Between Alcohols and Carbonyl Compounds
8.7: Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis
8.8: Organometallic Reagents in the Synthesis of Alcohols
8.9: Keys to Success: An Introduction to Synthetic Strategy
9: Further Reactions of Alcohols and the Chemistry of Ethers
9.1: Reactions of Alcohols with Base: Preparation of Alkoxides
9.2: Reactions of Alcohols with Strong Acids: Alkyloxonium Ions in Substitution and Elimination Reactions of Alcohols
9.3: Carbocation Rearrangements
9.4: Organic and Inorganic Esters from Alcohols
9.5: Names and Physical Properties of Ethers
9.6: Williamson Ether Synthesis
9.7: Synthesis of Ethers: Alcohols and Mineral Acids
9.8: Reactions of Ethers
9.9: Reactions of Oxacyclopropanes
9.10: Sulfur Analogs of Alcohols and Ethers
9.11: Physiological Properties and Uses of Alcohols and Ethers
10: Using Nuclear Magnetic Resonance Spectroscopy to Deduce Structure
10.1: Physical and Chemical Tests
10.2: Defining Spectroscopy
10.3: Hydrogen Nuclear Magnetic Resonance
10.4: Using NMR Spectra to Analyze Molecular Structure: The Proton Chemical Shift
10.5: Tests for Chemical Equivalence
10.6: Integration
10.7: Spin-Spin Splitting: The Effect of Nonequivalent Neighboring Hydrogens
10.8: Spin-Spin Splitting: Some Complications
10.9: Carbon-13 Nuclear Magnetic Resonance
11.4: Nuclear Magnetic Resonance of Alkenes
11.8: Infrared Spectroscopy
11.9: Measuring the Molecular Mass of Organic Compounds: Mass Spectrometry
11.10: Fragmentation Patterns of Organic Molecules
11.11: Degree of Unsaturation: Another Aid to Identifying Molecular Structure
12: Reactions to Alkenes
11.1: Naming the Alkenes
11.2: Structure and Bonding in Ethene: The Pi Bond
11.3: Physical Properties of Alkenes
12.1: Why Addition Reactions Proceed: Thermodynamic Feasibility
12.2: Catalytic Hydrogenation
12.3: Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides
12.4: Alcohol Synthesis by Electrophilic Hydration: Thermodynamic Control
12.5: Electrophilic Addition of Halogens to Alkenes
12.6: The Generality of Electrophilic Addition
12.7: Oxymncuration-Demercuration: A Special Elcctrophilic Addition
12.8: Hydroboration-Oxidation: A Stereospecific Anti-Markovnikov Hydration
12.9: Diazomethane Carbenes and Cyclopropane Synthesis
12.10: Oxacyclopropane ( Epoxide) Synthesis: Epoxidation by Peroxycarboxylic Acids
12.11: Vicinal SYn Dihydroxylation with Osmium Tetroxide
12.12: Oxidative Cleavage: Ozonolysis
12.13:Radical Additions: Anti-Markovnikov Product Formation
12.14: Dimerization Oligomerization. and Polymerization of Alkenes
12.15: Synthesis of Polymers
12.16: Ethene: An Important Industrial Feedstock
12.17: Alkenes in Nature - Insect Pheromones
13: Alkynes: The Carbon
13.1: Naming the Alkynes
13.2: Properties and Bonding in the Alkynes
13.3: Spectroscopy of the Alkynes
13.4: Preparation of Alkynes by Double Elimination
13.5: Preparation of Alkynes from Alkynyl Anions
13.6: Reduction of Alkynes: The Relative Reactivity of the Two \(\pi\) Bonds
13.7: Electrophilic Addition Reactions of Alkynes
13.8: Anti-Markovnikov Additions to Triple Bonds
13.9: Chemistry of Alkenyl Halides
13.10: Ethyne as an Industrial Starting Material
13.11: Naturally Occurring and Physiologically Active Alkynes
15: Benzene and Aromaticity: Electrophilic Aromatic Substitution
15.1: Naming the Benzenes
15.2: Structure and Resonance Energy of Benzene: A First Look at Aromaticity
15.3: Pi Molecular Orbitals of Benzene
15.4: Spectral Characteristics of the Benzene Ring
15.5: Polycyclic Aromatic Hydrocarbons
15.6: Other Cyclic Polyenes: Huckel 's Rule
15.7: Huckel's Rule and Charged Molecules
15.8: Synthesis of Benzene Derivatives: Electrophilic Aromatic Substitution
15.9: Halogenation of Benzene: The Need for a Catalyst
15.10: Nitration and Sulfonation of Benzene
15.11: Friedel-Crafts Alkylation
15.12: Limitations of Friedel-Crafts Alkylations
15.13: Friedel-Crafts Alkanoylation (Acylation)
15: Delocalized Pi Systems: Investigation by Ultraviolet and Visible Spectroscopy
14.1: Overlap of Three Adjacent p Orbitals: Electron Delocalization in the 2-Propenyl (Allyl) System
14.2: Radical Allylic Halogenation
14.3: Nucleophilic Substitution of Allylic Halides: SN1 and SN2
14.4: Allylic Organometallic Reagents: Useful Three-Carbon Nucleophiles
14.5: Two Neighboring Double Bonds: Conjugated Dienes
14.6: Electrophilic Attack on Conjugated Dienes: Kinetic and Thermodynamic Control
14.7: Delocalization among More than Two Pi Bonds: Extended Conjugation and Benzene
14.8: A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition
14.9: Electrocyclic Reactions
14.10: Polymerization of Conjugated Dienes: Rubber
14.11: Electronic Spectra: Ultraviolet and Visible Spectroscopy
16: Electrophilic Attack on Derivatives of Benzene: Substituents Control Regioselectivity
16.1: Activation or Deactivation by Substituents on a Benzene Ring
16.2: Directing Inductive Effects of Alkyl Groups
16.3: Directing Effects of Substituents in Conjugation with the Benzene Ring
16.4: Electrophilic Attack on Disubstituted Benzenes
16.5: Synthetic Strategies Toward Substituted Benzenes
16.6: Reactivity of Polycyclic Benzenoid Hydrocarbons
16.7: Polycyclic Aromatic Hydrocarbons and Cancer
17: Aldehydes and Ketones - The Carbonyl Group
17.1: Naming the Aldehydes and Ketones
17.2: Structure of the Carbonyl Group
17.3: Spectroscopic Properties of Aldehydes and Ketones
17.4: Preparation of Aldehydes and Ketones
17.5: Reactivity of the Carbonyl Group: Mechanisms of Addition
17.6: Addition of Water to Form Hydrates
17.7: Addition of Alcohols to Form Hemiacetals and Acetals
17.8: Acetals as Protecting Groups
17.9: Nucleophilic Addition of Ammonia and Its Derivatives
17.10: Deoxygenation of the Carbonyl Group
17.11: Addition of Hydrogen Cyanide to Give Cyanohydrins
17.12: Addition of Phosphorus Ylides: The Wittig Reaction
17.13: Oxidation by Peroxycarboxylic Acids: The Baeyer- Villiger Oxidation
17.14: Oxidative Chemical Tests for Aldehydes
18: Enols Enolates and the Aldol Condensation: ab-Unsaturated Aldehydes and Ketones
18.1: Acidity of Aldehydes and Ketones: Enolate Ions
18.2: Keto-Enol Equilibria
18.3: Halogenation of Aldehydes and Ketones
18.4: Alkylation of Aldehydes and Ketones
18.5: Attack by Enolates on the Carbonyl Function: Aldol Condensation
18.6: Crossed Aldol Condensation
18.7: Keys to Success: Competitive Rection Pathways and the Intramolecular Aldol Condensation
18.8: Properties of ab-Unsaturated Aldehydes and Ketones
18.9: Conjugate Additions to ab-Unsaturated Aldehydes and Ketones
18.10: 12- and 14-Additions of Organometallic Reagents
18.11: Conjugate Additions of Enolate Ions: Michael Addition and Robinson Annulation
19: Carboxylic Acids
19.1: Naming the Carboxylic Acids
19.2: Structural and Physical Properties of Carboxylic Acids
19.3: Spectroscopy and Mass Spectrometry of Carboxylic Acids
19.4: Acidic and Basic Character of Carboxylic Acids
19.5: Carboxylic Acid Synthesis in Industry
19.6: Methods for Introducing the Carboxy Functional Group
19.7: Substitution at the Carboxy Carbon: The Addition-Elimination Mechanism
19.8: Carboxylic Acid Derivatives: Alkanoyl (Acyl) Halides and Anhydrides
19.9: Carboxylic Acid Derivatives: Esters
19.10: Carboxylic Acid Derivatives: Amides
19.11: Reduction of Carboxylic Acids by Lithium Aluminum Hydride
19.12: Bromination Next to the Carboxy Group: The Hell-Volhard-Zelinsky Reaction
19.13: Biological Activity of Carboxylic Acids
20: Carboxylic Acid Derivatives
20.1: Relative Reactivities, Structures, and Spectra of Carboxylic Acid Derivatives
20.2: Chemistry of Alkanoyl Halides
20.3: Chemistry of Carboxylic Anhydrides
20.4: Chemistry of Esters
20.5: Esters in Nature: Waxes, Fats, Oils, and Lipids
20.6: Amides: The Least Reactive Carboxylic Acid Derivatives
20.7: Amidates and Their Halogenation: The Hofmann Rearrangement
20.8: Alkanenitriles: A Special Class of Carboxylic
22: Chemistry of the Benzene Substituents: Alkylbenzenes Phenols and Benzenamines
22.1: Reactivity at the Phenylmethyl (Benzyl) Carbon: Benzylic Resonance Stabilization
22.2: Benzylic Oxidations and Reductions
22.3: Names and Properties of Phenols
22.4: Preparation of Phenols: Nucleophilic Aromatic Substitution
22.5: Alcohol Chemistry of Phenols
22.6: Electrophilic Substitution of Phenols
22.7: An Electrocyclic Reaction of the Benzene Ring: The Claisen Rearrangement
22.8: Oxidation of Phenols: Benzoquinones
22.9: Oxidation-Reduction Processes in Nature
22.10: Arenediazonium Salts
22.11: Electrophilic Substitution with Arenediazonium Salts: Diazo Coupling
23: Ester Enolates and the Claisen Condensation
23.1: B-Dicarbonyl Compounds: Claisen Condensations
23.2: B-Dicarbonyl Compounds as Synthetic Intermediates
23.3: B-Dicarbonyl Anion Chemistry: Michael Additions
23.4: Alkanoyl (Acyl) Anion Equivalents: Preparation of a-Hydroxyketones
24: Carbohydrates: Polyfunctional Compounds in Nature
24.1: Names and Structures of Carbohydrates
24.2: Conformations and Cyclic Forms of Sugars
24.3: Anomers of Simple Sugars - Mutarotation of Glucose
24.4: Polyfunctional Chemistry of Sugars: Oxidation to Carboxylic Acids
24.5: Oxidative Cleavage of Sugars
24.6: Reduction of Monosaccharides to Alditols
24.7: Carbonyl Condensations with Amine Derivatives
24.8: Ester and Ether Formation: Glycosides
24.9: Step-by-Step Buildup and Degradation of Sugars
24.10: Relative Configurations of the Aldoses: An Exercise in Structure Determination
24.11: Complex Sugars in Nature: Disaccharides
24.12: Polysaccharides and Other Sugars in Nature