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Organic Chemistry

Organic Chemistry Chemistry

Author: Vollhardt and Schore
Publisher: LibreTexts Textmap
Source: LibreTexts
License: CC BY-NC-SA
Language: EN
Category: Basic Sciences

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Contents· 299 sections

01. 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)
02. 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
2.3: Acids and Bases Electrophiles and Nucleophiles
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)
03. Reactions of Alkanes: Bond-Dissociation Energies Radical Halogenation and Relative Reactivity
3-01 Strength of Alkane Bonds: Radicals
3-02Structure of Alkyl Radicals: Hyperconjugation
3-03 Conversion of Petroleum: Pyrolysis
3-04 Chlorination of Methane: The Radical Chain Mechanism
3-05 Other Radical Halogenations of Methane
3-06 Keys to Success: Using the Known Mechanism as a model for the Unknown
3-07 Chlorination of Higher Alkanes: Relative Reactivity and Selectivity
3-08 Selectivity in Radical Halogenation with Fluorine and Bromine
3-09 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)
04. 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)
05. 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)
06. Properties and Reactions of Haloalkanes: Bimolecular Nucleophilic Substitution
6-01 Physical Properties of Haloalkanes
6-02 Nucleophilic Substitution
6-03 Reaction Mechanisms Involving Polar Functional Groups: Using Electron-Pushing' Arrows
6-04 A Closer Look at the Nucleophilic Substitution Mechanism: Kinetics
6-05 Frontside or Backside Attack Stereochemistry of the SN2 Reaction
6-06 Consequences of Inversion in SN2 Reactions
6-07 Structure and SN2 Reactivity: The Leaving Group
6-08 Structure and SN2 Reactivity: The Nucleophile
6-09 Keys to Success: Choosing Among Multiple Mechanistic Pathways
6.03: Reaction Mechanisms Involving Polar Functional Groups: Using Electron-Pushing' Arrows
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)
07. Further Reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination
7.01: 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)
08. 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
09. Further Reactions of Alcohols and the Chemistry of Ethers
9.01: Reactions of Alcohols with Base: Preparation of Alkoxides
9.02: Reactions of Alcohols with Strong Acids: Alkyloxonium Ions in Substitution and Elimination Reactions of Alcohols
9.03: Carbocation Rearrangements
9.04: Organic and Inorganic Esters from Alcohols
9.05: Names and Physical Properties of Ethers
9.06: Williamson Ether Synthesis
9.07: Synthesis of Ethers: Alcohols and Mineral Acids
9.08: Reactions of Ethers
9.09: 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: Alkenes: Infrared Spectroscopy and Mass Spectrometry
11.01: Naming the Alkenes
11.02: Structure and Bonding in Ethene: The Pi Bond
11.03: Physical Properties of Alkenes
11.04: Nuclear Magnetic Resonance of Alkenes
11.05: Catalytic hydrogenatin of Alkenes: Relative Stability of Double Bonds
11.06: Preparation of Alkenes from Haloalkanes and Alkyl Sufonates: Bimolecular Elimination Revisited
11.07: Preparation of Alkenes by Dehydration of Alcohols
11.08: Infrared Spectroscopy
11.09: 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
12.01: Why Addition Reactions Proceed: Thermodynamic Feasibility
12.02: Catalytic Hydrogenation
12.03:Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides
12.04: Alcohol Synthesis by Electrophilic Hydration: Thermodynamic Control
12.05: Electrophilic Addition of Halogens to Alkenes
12.06: The Generality of Electrophilic Addition
12.07: Oxymncuration-Demercuration: A Special Elcctrophilic Addition
12.08: Hydroboration-Oxidation: A Stereospecific Anti-Markovnikov Hydration
12.09: 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
13-01 Naming the Alkynes
13-02 Properties and Bonding in the Alkynes
13-03 Spectroscopy of the Alkynes
13-04 Preparation of Alkynes by Double Elimination
13-05 Preparation of Alkynes from Alkynyl Anions
13-06 Reduction of Alkynes: The Relative Reactivity of the Two Pi Bonds
13-07 Electrophilic Addition Reactions of Alkynes
13-08 Anti-Markovnikov Additions to Triple Bonds
13-09 Chemistry of Alkenyl Halides
13.10: Ethyne as an Industrial Starting Material
13.11: Naturally Occurring and Physiologically Active Alkynes
14: Delocalized Pi Systems: Investigation by Ultraviolet and Visible Spectroscopy
14.01: Overlap of Three Adjacent p Orbitals: Electron Delocalization in the 2-Propenyl (Allyl) System
14.02: Radical Allylic Halogenation
14.03: Nucleophilic Substitution of Allylic Halides: SN1 and SN2
14.04: Allylic Organometallic Reagents: Useful Three-Carbon Nucleophiles
14.05: Two Neighboring Double Bonds: Conjugated Dienes
14.06: Electrophilic Attack on Conjugated Dienes: Kinetic and Thermodynamic Control
14.07:Delocalization among More than Two Pi Bonds: Extended Conjugation and Benzene
14.08: A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition
14.09: Electrocyclic Reactions
14.10: Polymerization of Conjugated Dienes: Rubber
14.11: Electronic Spectra: Ultraviolet and Visible Spectroscopy
15: Benzene and Aromaticity: Electrophilic Aromatic Substitution
15.01: Naming the Benzenes
15.02:Structure and Resonance Energy of Benzene: A First Look at Aromaticity
15.03: Pi Molecular Orbitals of Benzene
15.04: Spectral Characteristics of the Benzene Ring
15.05: Polycyclic Aromatic Hydrocarbons
15.06: Other Cyclic Polyenes: Huckel 's Rule
15.07: Huckel's Rule and Charged Molecules
15.08: Synthesis of Benzene Derivatives: Electrophilic Aromatic Substitution
15.09: 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)
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
17.01: Naming the Aldehydes and Ketones
17.02: Structure of the Carbonyl Group
17.03: Spectroscopic Properties of Aldehydes and Ketones
17.04: Preparation of Aldehydes and Ketones
17.05: Reactivity of the Carbonyl Group: Mechanisms of Addition
17.06: Addition of Water to Form Hydrates
17.07: Addition of Alcohols to Form Hemiacetals and Acetals
17.08: Acetals as Protecting Groups
17.09: 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
18.01: Acidity of Aldehydes and Ketones: Enolate Ions
18.02: Keto-Enol Equilibria
18.03: Halogenation of Aldehydes and Ketones
18.04: Alkylation of Aldehydes and Ketones
18.05: Attack by Enolates on the Carbonyl Function: Aldol Condensation
18.06: Crossed Aldol Condensation
18.07: Keys to Success: Competitive Rection Pathways and the Intramolecular Aldol Condensation
18.08: Properties of ab-Unsaturated Aldehydes and Ketones
18.09: 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
19.01: Naming the Carboxylic Acids
19.02: Structural and Physical Properties of Carboxylic Acids
19.03: Spectroscopy and Mass Spectrometry of Carboxylic Acids
19.04: Acidic and Basic Character of Carboxylic Acids
19.05: Carboxylic Acid Synthesis in Industry
19.06: Methods for Introducing the Carboxy Functional Group
19.07: Substitution at the Carboxy Carbon: The Addition-Elimination Mechanism
19.08: Carboxylic Acid Derivatives: Alkanoyl (Acyl) Halides and Anhydrides
19.09: 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
21: Amines and Their Derivatives
21.01: Naming the Amines
21.02: Structural and Physical Properties of Amines
21.03: Spectroscopy of the Amine Group
21.04: Acidity and Basicity of Amines
21.05: Synthesis of Amines by Alkylation
21.06: Synthesis of Amines by Reductive Amination
21.07: Synthesis of Amines from Carboxylic Amides
21.08: Quaternary Ammonium Salts: Hofmann Elimination
21.09: Mannich Reaction: Alkylation of Enols by Iminium Ions
21.10: Nitrosation of Amines
22: Chemistry of the Benzene Substituents: Alkylbenzenes Phenols and Benzenamines
22.01: Reactivity at the Phenylmethyl (Benzyl) Carbon: Benzylic Resonance Stabilization
22.02: Benzylic Oxidations and Reductions
22.03: Names and Properties of Phenols
22.04: Preparation of Phenols: Nucleophilic Aromatic Substitution
22.05: Alcohol Chemistry of Phenols
22.06: Electrophilic Substitution of Phenols
22.07: An Electrocyclic Reaction of the Benzene Ring: The Claisen Rearrangement
22.08: Oxidation of Phenols: Benzoquinones
22.09: 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
24.01: Names and Structures of Carbohydrates
24.02: Conformations and Cyclic Forms of Sugars
24.03: Anomers of Simple Sugars: Mutarotation of Glucose
24.04: Polyfunctional Chemistry of Sugars: Oxidation to Carboxylic Acids
24.05: Oxidative Cleavage of Sugars
24.06: Reduction of Monosaccharides to Alditols
24.07: Carbonyl Condensations with Amine Derivatives
24.08: Ester and Ether Formation: Glycosides
24.09: 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
25: Heterocycles: Heteroatoms in Cyclic Organic Compounds
25.1: Naming the Heterocycles
25.2: Nonaromatic Heterocycles
25.3: Structure and Properties of Aromatic Heterocyclopentadienes
25.4: Reactions of the Aromatic Heterocyclopentadienes
25.5: Structure and Preparation of Pyridine: An Azabenzene
25.6: Reactions of Pyridine
25.7: Quinoline and Isoquinoline: The Benzopyridines
25.8: Alkaloids: Physiologically Potent Nitrogen Heterocycles in Nature
26: Amino Acids Peptides Proteins and Nucleic Acids: Nitrogen-Containing Polymers in Nature
26.01: Structure and Properties of Amino Acids
26.02: Synthesis of Amino Acids: A Combination of Amine and Carboxylic Acid Chemistry
26.03: Synthesis of Enantiomerically Pure Amino Acids
26.04: Peptides and Proteins: Amino Acid Oligomers and Polymers
26.05: Determination of Primary Structure: Amino Acid Sequencing
26.06: Synthesis of Polypeptides: A Challenge in the Application of Protecting Groups
26.07: Merrifield Solid-Phase Peptide Synthesis
26.08: Polypeptides in Nature: Oxygen Transport by the Proteins Myoglobin and Hemoglobin
26.09: Biosynthesis of Proteins: Nucleic Acids
26.10: Protein Synthesis Through RNA
26.11: DNA Sequencing and Synthesis: Cornerstones of Gene Technology