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Radicals

Homolytic and Heterolytic Bond Cleavage

by Dr. S. Gevorg
an example of a radical reaction

Chemical reactions are rearrangements of atoms as the bonds between them are broken and new ones are formed. For example, in the following reaction, the C-Br bond is broken, and the C-Cl bond is formed:     Let’s now compare … Read more

Categories Energy Changes In Organic Chemistry, Radical Reactions Tags Radicals Leave a comment
Organic Chemistry Study Guides
Chemistry Steps Membership Benefits Organic Chemistry

Structure and Bonding

  • Lewis Structures in Organic Chemistry
  • Valency and Formal Charges in Organic Chemistry
  • How to Determine the Number of Lone Pairs
  • Bonding Patterns in Organic Chemistry
  • sp3, sp2, and sp Hybridization in Organic Chemistry with Practice Problems
  • How to Quickly Determine The sp3, sp2, and sp Hybridization
  • Bond Lengths and Bond Strengths
  • VSEPR Theory – Molecular and Electron Geometry of Organic Molecules
  • Dipole-dipole, London Dispersion and Hydrogen Bonding Interactions
  • Dipole Moment and Molecular Polarity
  • Boiling Point and Melting Point in Organic Chemistry
  • Boiling Point and Melting Point Practice Problems
  • Solubility of Organic Compounds
  • General Chemistry Overview Quiz

Molecular Representations

  • Bond-Line or Skeletal Structures
  • Functional Groups in Organic Chemistry with Practice Problems
  • Bond-line, Lewis, and Condensed Structures with Practice Problems
  • Curved Arrows with Practice Problems
  • Resonance Structures in Organic Chemistry with Practice Problems
  • Rules for Drawing Resonance Structures
  • Major and Minor Resonance Contributor
  • How to Choose the More Stable Resonance Structure
  • Drawing Complex Patterns in Resonance Structures
  • Localized and Delocalized Lone Pairs with Practice Problems
  • Molecular Representations Quiz

Acids and Bases

  • Acids and Bases – General Chemistry
  • Organic Acids and Bases
  • Organic Acid-Base Mechanisms
  • Acid Strength and pKa
  • How to Determine the Position of Equilibrium for an Acid-Base Reaction
  • Inductive and Resonance (Mesomeric) Effects
  • Factors That Determine the pKa and Acid Strength
  • How to Choose an Acid or a Base to Protonate or Deprotonate a Given Compound
  • Lewis Acids and Bases
  • Basicity of Amines
  • Organic Acids and Bases Practice Problems
  • Organic Acids and Bases Quiz

Alkanes and Cycloalkanes

  • Naming Alkanes by IUPAC Nomenclature Rules Practice Problems
  • Naming Bicyclic Compounds
  • Naming Bicyclic Compounds-Practice Problems
  • How to Name a Compound with Multiple Functional Groups
  • Primary, Secondary, and Tertiary Carbon Atoms in Organic Chemistry
  • Constitutional or Structural Isomers with Practice Problems
  • Degrees of Unsaturation or Index of Hydrogen Deficiency
  • The Wedge and Dash Representation
  • Sawhorse Projections
  • Newman Projections with Practice Problems
  • Staggered and Eclipsed Conformations
  • Conformational Isomers of Propane
  • Newman Projection and Conformational Analysis of Butane
  • Newman Projection of Chair Conformation
  • Gauche Conformation
  • Gauche Conformation, Steric, Torsional Strain Energy Practice Problems
  • Ring Strain
  • Steric vs Torsional Strain
  • Conformational Analysis
  • Drawing the Chair Conformation of Cyclohexane
  • Ring Flip: Drawing Both Chair Conformations with Practice Problems
  • 1,3-Diaxial Interactions and A value for Cyclohexanes
  • Ring-Flip: Comparing the Stability of Chair Conformations with Practice Problems
  • Cis and Trans Decalin
  • IUPAC Nomenclature Practice Problems
  • IUPAC Nomenclature Summary Quiz
  • Alkanes and Cycloalkanes Practice Quiz

Stereochemistry

  • How to Determine the R and S Configuration
  • The R and S Configuration Practice Problems
  • What is Nonsuperimposable in Organic Chemistry
  • Chirality and Enantiomers
  • Diastereomers-Introduction and Practice Problems
  • Enantiomers vs Diastereomers
  • Cis and Trans Isomers
  • E and Z Alkene Configuration with Practice Problems
  • Enantiomers, Diastereomers, the Same or Constitutional Isomers with Practice Problems
  • Configurational Isomers
  • Optical Activity
  • Specific Rotation
  • Racemic Mixtures
  • Enantiomeric Excess (ee): Percentage of Enantiomers from Specific Rotation with Practice Problems
  • Symmetry and Chirality. Meso Compounds
  • Fischer Projections with Practice Problems
  • R and S Configuration in the Fischer Projection
  • R and S configuration on Newman projections
  • R and S Configuration of Allenes
  • Converting Bond-Line, Newman Projection, and Fischer Projections
  • Resolution of Enantiomers: Separate Enantiomers by Converting to Diastereomers
  • Stereochemistry Practice Problems
  • Stereochemistry Practice Quiz

Energy Changes In Organic Chemistry

  • Energy and Organic Chemistry Reactions
  • Bond Lengths and Bond Strengths
  • Homolytic and Heterolytic Bond Cleavage
  • The Heat of Reaction from Bond Dissociation Energies

Nucleophilic Substitution Reactions

  • Introduction to Alkyl Halides
  • Nomenclature of Alkyl Halides
  • Substitution and Elimination Reactions
  • Nucleophilic Substitution Reactions – An Introduction
  • All You Need to Know About the SN2 Reaction Mechanism
  • The SN2 Mechanism: Kinetics, Thermodynamics, Curved Arrows, and Stereochemistry with Practice Problems
  • The Stereochemistry of SN2 Reactions
  • Stability of Carbocations
  • The SN1 Nucleophilic Substitution Reaction
  • Reactions of Alkyl Halides with Water
  • The Stereochemistry of the SN1 Reaction Mechanism
  • The SN1 Mechanism: Kinetics, Thermodynamics, Curved Arrows, and Stereochemistry with Practice Problems
  • Steric Hindrance in SN2 and SN1 Reactions
  • Carbocation Rearrangements in SN1 Reactions with Practice Problems
  • Ring Expansion Rearrangements
  • Ring Contraction Rearrangements
  • When Is the Mechanism SN1 or SN2?
  • Reactions of Alcohols with HCl, HBr, and HI Acids
  • SOCl2 and PBr3 for Conversion of Alcohols to Alkyl Halides
  • Alcohols in SN1 and SN2 Reactions
  • How to Choose Molecules for Doing SN2 and SN1 Synthesis-Practice Problems
  • Exceptions in SN2 and SN1 Reactions
  • Nucleophilic Substitution and Elimination Practice Quiz
  • Reactions Map of Alkyl Halides

Alkenes: Structure, Stability, and Nomenclature

  • Alkenes: Structure and Stability
  • Naming Alkenes by IUPAC Nomenclature Rules
  • Cis and Trans Isomers
  • E and Z Alkene Configuration with Practice Problems

Elimination Reactions

  • Substitution and Elimination Reactions
  • The E2 Mechanism
  • E2 Elimination Practice Problems
  • Zaitsev's Rule - Regioselectivity of E2 Elimination Reactions
  • The Hofmann Elimination of Amines and Alkyl Fluorides
  • Stereoselectivity of E2 Elimination Reactions
  • Stereospecificity of E2 Elimination Reactions
  • SN2 and E2 Rates of Cyclohexanes
  • Elimination Reactions of Cyclohexanes with Practice Problems
  • POCl3 for Dehydration of Alcohols
  • The E1 Mechanism with Practice Problems
  • Regioselectivity of E1 Reactions
  • Stereoselectivity of E1 Reactions
  • How to tell if it is E2 or E1 Mechanism
  • SN1 vs E1 Reactions
  • SN2 vs E2 Reactions
  • Dehydration of Alcohols by E1 and E2 Elimination
  • Mesylates and Tosylates as Good Leaving Groups
  • Mitsunobu Reaction
  • SN1 SN2 E1 E2 – How to Choose the Mechanism
  • Polar Protic and Polar Aprotic Solvents
  • SN1 SN2 E1 or E2 - the Largest Collection of Practice Problems
  • The Hammond Postulate
  • The E1cB Elimination Mechanism
  • Nucleophilic Substitution and Elimination Practice Quiz
  • Reactions Map of Alkyl Halides

Addition Reactions of Alkenes

  • Electrophilic Addition Reactions to Alkenes
  • Markovnikov's Rule
  • Markovnikov's Rule with Practice Problems
  • Addition of Water to Alkenes
  • Acid-Catalyzed Hydration of Alkenes with Practice Problems
  • Rearrangements in Alkene Addition Reactions
  • Oxymercuration-Demercuration
  • Addition of Alcohols to Alkenes
  • Free-Radical Addition of HBr: Anti-Markovnikov Addition
  • Hydroboration-Oxidation: The Mechanism
  • Hydroboration-Oxidation of Alkenes: Regiochemistry and Stereochemistry with Practice Problems
  • Halogenation of Alkenes and Halohydrin Formation
  • The Regiochemistry of Alkene Addition Reactions
  • The Stereochemistry of Alkene Addition Reactions
  • Cis product in an anti-Addition Reaction of Alkenes
  • Ozonolysis of Alkenes with Practice Problems
  • Syn Dihydroxylation of Alkenes with KMnO4 and OsO4
  • Anti-Dihydroxylation of Alkenes with MCPBA and Other Peroxides with Practice Problems
  • Oxidative Cleavage of Alkenes with KMno4 and O3
  • Alkene Reactions Practice Problems
  • Changing the Position of a Double Bond
  • Changing the Position of a Leaving Group
  • Alkenes Multi-Step Synthesis Practice Problems
  • Alkene Addition Reactions Practice Quiz
  • Reactions Map of Alkenes

Alkynes

  • Introduction to Alkynes
  • Naming Alkynes by IUPAC Nomenclature Rules - Practice Problems
  • Preparation of Alkynes by Elimination Reactions
  • Hydrohalogenation of Alkynes
  • Addition of Water to Alkynes
  • Acid-Catalyzed Hydration of Alkynes with Practice Problems
  • Reduction of Alkynes
  • Halogenation of Alkynes
  • Hydroboration-Oxidation of Alkynes with Practice Problems
  • Ozonolysis of Alkynes with Practice Problems
  • Alkylation of Terminal Alkynes in Organic Synthesis with Practice Problems
  • Reactions of Acetylide Ions
  • Alkyne reactions summary practice problems
  • Alkyne Synthesis Reactions Practice Problems
  • Alkyne Naming and Reactions Practice Quiz
  • Reactions Map of Alkynes

Nuclear Magnetic Resonance (NMR) Spectroscopy

  • NMR Spectroscopy – An Easy Introduction
  • NMR Chemical Shift
  • NMR Chemical Shift Range and Value Table
  • NMR Number of Signals and Equivalent Protons
  • Homotopic, Enantiotopic, Diastereotopic, and Heterotopic
  • Homotopic Enantiotopic Diastereotopic Practice Problems
  • Integration in NMR Spectroscopy
  • Splitting and Multiplicity (N+1 rule) in NMR Spectroscopy
  • NMR Signal Splitting N+1 Rule Multiplicity Practice Problems
  • 13C Carbon NMR
  • DEPT NMR: Signals and Problem Solving
  • NMR Spectroscopy-Carbon-Dept-IR Practice Problems

Organic Structure Determination

  • NMR Spectroscopy-Carbon-Dept-IR Practice Problems
  • Infrared (IR) Spectroscopy Practice Problems
  • Solving Mass Spectrometry Practice Problems

Radical Reactions

  • Free-Radical Addition of HBr: Anti-Markovnikov Addition
  • Initiation, Propagation, Termination in Radical Reactions
  • Selectivity in Radical Halogenation
  • Stability of Radicals
  • Resonance Structures of Radicals
  • Stereochemistry of Radical Halogenation with Practice Problems
  • Allylic Bromination by NBS with Practice Problems
  • Radical Halogenation in Organic Synthesis

Reactions of Alcohols

  • Nomenclature of Alcohols: Naming Alcohols based on IUPAC Rules with Practice Problems
  • Preparation of Alcohols via Substitution or Addition Reactions
  • Reaction of Alcohols with HCl, HBr, and HI Acids
  • Mesylates and Tosylates as Good Leaving Groups
  • SOCl2 and PBr3 for Conversion of Alcohols to Alkyl Halides
  • Alcohols in Substitution Reactions  Practice Problems
  • POCl3 for Dehydration of Alcohols
  • Dehydration of Alcohols by E1 and E2 Elimination
  • The Oxidation States of Organic Compounds
  • LiAlH4 and NaBH4 Carbonyl Reduction Mechanism
  • Alcohols from Carbonyl Reductions - Practice Problems
  • Grignard Reaction in Preparing Alcohols with Practice Problems
  • Grignard Reaction in Organic Synthesis with Practice Problems
  • Protecting Groups For Alcohols in Organic Synthesis
  • Oxidation of Alcohols: PCC, PDC, CrO3, DMP, Swern, and All of That
  • Diols: Nomenclature, Preparation, and Reactions
  • NaIO4 Oxidative Cleavage of Diols
  • The Pinacol Rearrangement
  • The Williamson Ether Synthesis
  • Alcohol Reactions Practice Problems
  • Naming Thiols and Sulfides
  • Reactions of Thiols
  • Alcohols Quiz – Naming, Preparation, and Reactions
  • Reactions Map of Alcohols

Ethers and Epoxides

  • Preparation of Epoxides
  • Ring-Opening Reactions of Epoxides
  • Reactions of Epoxides under Acidic and Basic Conditions
  • Reactions of Epoxides Practice Problems
  • The Grignard Reaction of Epoxides
  • Naming Ethers
  • The Williamson Ether Synthesis
  • Reactions of Ethers-Ether Cleavage

Conjugated Systems

  • Resonance and Conjugated Dienes
  • Allylic Carbocations
  • 1,2 and 1,4 Electrophilic Addition to Dienes
  • Kinetic vs Thermodynamic Control of Electrophilic Addition to Dienes

The Diels-Alder Reaction

  • Diels-Alder Reaction: Dienes and Dienophiles
  • Predict the Products of the Diels-Alder Reaction with Practice Problems
  • Endo and Exo Products of Diels-Alder Reaction with Practice Problems
  • Regiochemistry of the Diels–Alder Reaction with Practice Problems
  • Identify the Diene and Dienophile of the Diels-Alder reaction with Practice Problems
  • Diels-Alder Reaction in Organic Synthesis Practice Problems

Aromatic Compounds

  • Naming Aromatic Compounds
  • Introduction to Aromatic Compounds
  • Benzene – Aromatic Structure and Stability
  • Aromaticity and Huckel's Rule
  • The 4n+2 Rule
  • Identify Aromatic, Antiaromatic, or Nonaromatic Compounds
  • Frost Circle
  • Annulenes

Electrophilic Aromatic Substitution

  • Electrophilic Aromatic Substitution – The Mechanism
  • The Halogenation of Benzene
  • The Nitration of Benzene
  • The Sulfonation of Benzene
  • Activating and Deactivating Groups
  • Friedel-Crafts Alkylation with Practice Problems
  • Friedel-Crafts Acylation with Practice Problems
  • Vilsmeier-Haack Reaction
  • The Alkylation of Benzene by Acylation-Reduction
  • Ortho, Para, Meta in EAS with Practice Problems
  • Ortho, Para, and Meta in Disubstituted Benzenes
  • Why Are Halogens Ortho-, Para- Directors yet Deactivators?
  • Is Phenyl an Ortho/Para or Meta Director?
  • Limitations of Electrophilic Aromatic Substitution Reactions
  • Orientation in Benzene Rings With More Than One Substituent
  • Synthesis of Aromatic Compounds From Benzene
  • Arenediazonium Salts in Electrophilic Aromatic Substitution
  • Reactions at the Benzylic Position
  • Benzylic Bromination
  • Nucleophilic Aromatic Substitution
  • Nucleophilic Aromatic Substitution Practice Problems
  • Reactions of Phenols
  • Reactions of Aniline
  • Meta Substitution on Activated Aromatic Ring
  • Electrophilic Aromatic Substitution Practice Problems
  • Aromatic Compounds Quiz
  • Reactions Map of Aromatic Compounds

Aldehydes and Ketones

  • Nomenclature of Aldehydes and Ketones
  • How to Name a Compound with Multiple Functional Groups
  • Preparation of Aldehydes and Ketones
  • Nucleophilic Addition to Carbonyl Groups
  • Reduction of Aldehydes and Ketones
  • Reactions of Aldehydes and Ketones with Water
  • Reactions of Aldehydes and Ketones with Alcohols: Acetals and Hemiacetals
  • Acetals as Protecting Groups for Aldehydes and Ketones
  • Formation and Reactions of Imines and Enamines
  • Reductive Amination
  • Acetal Hydrolysis Mechanism
  • Imine and Enamine Hydrolysis Mechanism
  • Hydrolysis of Acetals, Imines, and Enamines-Practice Problems
  • Reaction of Aldehydes and Ketones with CN, Cyanohydrin Formation
  • The Wittig Reaction: Examples and Mechanism
  • The Wittig Reaction: Practice Problems
  • Aldehydes and Ketones to Carboxylic Acids
  • Reactions of Aldehydes and Ketones - Practice Problems
  • Aldehydes and Ketones Reactions Practice Quiz
  • Reactions Map of Aldehydes
  • Reactions Map of Ketones

Carboxylic Acids and Their Derivatives-Nucleophilic Acyl Substitution

  • Preparation of Carboxylic Acids
  • Naming Carboxylic Acids
  • Naming Nitriles
  • Naming Esters
  • Naming Carboxylic Acid Derivatives – Practice Problems
  • The Addition-Elimination Mechanism
  • Fischer Esterification
  • Ester Hydrolysis by Acid and Base-Catalyzed Hydrolysis
  • What is Transesterification?
  • Esters Reaction with Amines – The Aminolysis Mechanism
  • Ester Reactions Summary and Practice Problems
  • Preparation of Acyl (Acid) Chlorides (ROCl)
  • Reactions of Acid Chlorides (ROCl) with Nucleophiles
  • R2CuLi Organocuprates - Gilman Reagent
  • Reaction of Acyl Chlorides with Grignard and Gilman (Organocuprate) Reagents
  • Reduction of Acyl Chlorides by LiAlH4, NaBH4, and LiAl(OtBu)3H
  • Reduction of Carboxylic Acids and Their Derivatives
  • Preparation and Reaction Mechanism of Carboxylic Anhydrides
  • Amides - Structure and Reactivity
  • Naming Amides
  • Amides Hydrolysis: Acid and Base-Catalyzed Mechanism
  • Amide Dehydration Mechanism by SOCl2, POCl3, and P2O5
  • Amide Reduction Mechanism by LiAlH4
  • Reduction of Amides to Amines and Aldehydes
  • Amides Preparation and Reactions Summary
  • Amides from Carboxylic Acids-DCC and EDC Coupling
  • The Mechanism of Nitrile Hydrolysis To Carboxylic Acid
  • Nitrile Reduction Mechanism with LiAlH4 and DIBAL to Amine or Aldehyde
  • The Mechanism of Grignard and Organolithium Reactions with Nitriles
  • The Reactions of Nitriles
  • Converting Nitriles to Amides
  • Carboxylic Acids to Ketones
  • Esters to Ketones
  • Carboxylic Acids and Their Derivatives Practice Problems
  • Carboxylic Acids and Their Derivatives Quiz
  • Reactions Map of Carboxylic Acid Derivatives

Alpha Carbon Chemistry: Enols and Enolates

  • Keto-Enol Tautomerization
  • Alpha Halogenation of Enols and Enolates
  • The Haloform and Iodoform Reactions
  • Alpha Halogenation of Carboxylic Acids
  • Alpha Halogenation of Enols and Enolates Practice Problems
  • The E1cB Elimination Mechanism
  • Aldol Reaction – Principles and Mechanism
  • Aldol Condensation – Dehydration of Aldol Addition Product
  • Intramolecular Aldol Reactions
  • Aldol Addition and Condensation Reactions – Practice Problems
  • Crossed Aldol And Directed Aldol Reactions
  • Crossed Aldol Condensation Practice Problems
  • The Cannizzaro reaction
  • Alkylation of Enolates Alpha Position
  • Enolate Alkylation Practice Problems
  • Acetoacetic Ester Synthesis
  • Acetoacetic Ester Enolates Practice Problems
  • Malonic Ester Synthesis
  • Decarboxylation
  • Michael Reaction: The Conjugate Addition of Enolates
  • Robinson Annulation, Shortcut, and Retrosynthesis
  • Claisen Condensation
  • Dieckmann condensation – An Intramolecular Claisen Reaction
  • Crossed Claisen and Claisen Variation Reactions
  • Claisen Condensation Practice Problems
  • Stork Enamine Synthesis
  • Mannich Reaction
  • Enolates in Organic Synthesis – a Comprehensive Practice Problem

Amines

  • Naming Amines: Systematic and Common Nomenclature
  • Preparation of Amines
  • The Gabriel Synthesis of Primary Amines
  • Imines from Aldehydes and Ketones with Primary Amines
  • Enamines from Aldehydes and Ketones with Secondary Amines
  • The Hofmann Elimination of Amines and Alkyl Fluorides
  • The Reaction of Amines with Nitrous Acid
  • Reactions of Amines Practice Problems
  • The Cope elimination
  • Basicity of Amines
  • Boc Protecting Group for Amines

Organic Synthesis Problems

  • Organic Chemistry Multistep Synthesis Practice Problems
  • Organic Synthesis Puzzles
  • Acetals as Protecting Groups for Aldehydes and Ketones
  • How to Choose Molecules for Doing SN2 and SN1 Synthesis-Practice Problems
  • Alkene Reactions Practice Problems
  • Changing the Position of a Double Bond
  • Changing the Position of a Leaving Group
  • Alkenes Multi-Step Synthesis Practice Problems
  • Alkyne Synthesis Reactions Practice Problems
  • Radical Halogenation in Organic Synthesis
  • Grignard Reaction in Organic Synthesis with Practice Problems
  • Ortho Para Meta in EAS with Practice Problems
  • Orientation in Benzene Rings With More Than One Substituent

Carbohydrates

  • Carbohydrates – Structure and Classification
  • Erythro and Threo
  • R and S Configuration on Fischer Projections
  • D and L Sugars
  • Aldoses and Ketoses: Classification and Stereochemistry
  • Epimers and Anomers
  • Converting Fischer, Haworth, and Chair forms of Carbohydrates
  • Mutarotation
  • Glycosides
  • Isomerization of Carbohydrates
  • Ether and Ester Derivatives of Carbohydrates
  • Oxidation of Monosaccharides
  • Reduction of Monosaccharides
  • Kiliani–Fischer Synthesis
  • Wohl Degradation
  • Carbohydrates Practice Problem Quiz

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