Instructor's Notes for Section 13

Mass Spectrometry, Mass Spectrometry (Mass Spec) Principles, A Normal Mass Spectrum

Importance of Determining the Molar Masses in Molecular Formula, Isotope Ratios, the M+1 and the M+2 Peaks

Analyze the atom isotopes given

Nitrogen Rule, Making the Molecular Ion (M+)

Four Types of Fragmentations 1) Loss of Water 2) Direct Hit on a σ Bond

Example of Direct Hit on a σ Bond (For Alkanes), Example of Direct Hit on a σ Bond (Benzylic Cleavage)

Four Types of Fragmentations cont. - 3) α-Cleavage

Alpha cleavage (with Aldehydes, Ketones and Carboxylic acids)

Mass Spec Fragmentation Examples

Predicting Fragmentation Patterns

Four Types of Fragmentations cont. – 4) McLafferty Rearrangment

Infrared Spectroscopy, Interaction of Electromagnetic Radiation(hν) with Molecules, Spectroscopy Theory, The Electromagnetic Spectrum,

IR Table

IR Spectrum Regions

Hydrogen Region (3550-2700 cm-1), Triple Bond Region (2300-2100 cm-1), Double Bond Region (1850-1350 cm-1), Specific Carbonyl Positions for Different Functional Groups, Fingerprint Region (1300-500 cm-1)

Interpreting IR Spectra by Functional Groups Part 1

Interpreting IR Spectra by Functional Groups Part 2

Interpreting IR Spectra by Functional Groups Part 3

Ultraviolet-Visible Spectroscopy, Definitions, Examples UV Spectrum, Lambert-Beer Law, Types of Electronic Transitions (from s, p, and NB orbitals)

Energy Diagram Examples, Probable Absorptions

Visible Region Colors, Determining Structure in the UV-Visible Spectroscopy Region

Practice Homework for Section 13

Practice Homework for Section 13 (Key)

Quiz for Section 13

Quiz for Section 13 (Key)

Instructor's Notes from Section 14

Nuclear Magnetic Resonance (NMR)

The Chemical Shift, The Chemical Shift , – Downfield Absorptions, – Inductive Effects, – pi Electron Effects

Chemically Equivalent H, Table with NMR Shifts

Assigning NMR Splittings – A Story of Balconies

Calculating Chemical Shifts – Part 1

Calculating Chemical Shifts – Part 2

Integration, Spin Coupling

Predicting Double Bond Proton Signals

Aromatic Coupling

Interpreting 1H NMR Spectra, Example 1

Interpreting 1H NMR Spectra, Example 2

13C (Carbon-13) NMR, 13C NMR Examples

DEPT 13C NMR - Distortional Enhancement by Polarization Transfer

Solving NMR Spectra - Example 1

Solving NMR Spectra - Example 2

Solving NMR Spectra - Example 3

Solving NMR Spectra - Example 4

Practice Homework for Section 14

Practice Homework for Section 14 (Key)

Quiz for Section 14

Quiz for Section 14 (Key)

Instructor's Notes for Section 15

Naming Carboxylic Acids and Esters

Naming Carboxylic Aldehydes and Ketones and Carbonyl Group Containing Molecules: When Attached to a Ring

Advanced Nomenclature, Multiple Functional Groups

Carboxylic Acid Derivatives, Benzoic Acid Derivatives

Practice: Multiple Functional Groups Part 1

Practice: Multiple Functional Groups Part 2

Substitution at Carbonyl Groups (C=O), Factors for Substitution Rate and Product Equilibrium, and Reactivity of Carbonyl Compounds

Preparation of Acyl Chlorides, and Reactions of Acyl Chlorides

Preparation of Anhydrides, Anhydride Synthesis

Preparation of Esters (3 ways)

Preparation of Carboxylic Acids

Saponification

Amide Hydrolysis, Nitrile Hydrolysis

Nitrile Hydrolysis and Saponification

Complete the Following Syntheses, Preparation of Amides

Reactions of LiAlH4 (with esters, anhydrides and acyl chlorides)

Reactions of LiAlH4 (c. acids, aldehyde, ketones, nitriles & amides)

Reactions of NaBH4

Reactions of LiAlH4, NaBH4 and H2/Ni (Recap)

Practice Homework for Section 15

Practice Homework for Section 15 (Key)

Quiz for Section 15

Quiz for Section 15 (Key)

Instructor's Notes for Section 16

Aldehydes and Ketones

Preparation of Aldehydes and Ketones

LiAlH(Ot-Bu)3 and DIBAL Reactions vs LiAlH4 and NaBH4, Catalytic Hydrogenation of Aldehydes and Ketones

Mechanisms of Attack – Basic, Mechanisms of Attack – Acidic, Addition of H2O (hydrate formation), Equlibrium

HCN Addition (Basic mechanism), Cyanide Reduction or Hydrolysis

Reactions of Carbonyl Compounds with Grignard Reagents

Wittig Reaction, Wittig Mechanism

Wittig Reactions, Retrosynthetic Analysis

Nitrogen Nucleophiles, Synthesis of Imines

Synthesis of Enamines

Imine Reductions

Addition of Alcohols

Acetal/Ketal Protection Chemistry

Conjugate Additions

Practice Homework for Section 16

Practice Homework for Section 16 (Key)

Quiz for Section 16

Quiz for Section 16 (Key)

Instructor's Notes for Section 17

Keto-Enol Tautomerism - Acidic and Basic Conditions

Reactivity of Enols: Alpha-Substitution Reactions, General Mechanism of Addition to Enols, Alpha Halogenation of Aldehydes and Ketones

Elimination Reactions of alpha-Bromoketones, Worked Example

Alpha Bromination of Carboxylic Acids - Hell–Volhard–Zelinskii reaction, Worked Example

Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation – Part 1

Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation – Part 2

Table - Acidity Constants for Some Organic Compounds

Alkylation of Enolate Ions, Constraints on Enolate Alkylation

Thermodynamic vs Kinetic Enolates

Malonic Ester Synthesis, Formation of Enolate and Alkylation, Dialkylation

Hydrolysis and Decarboxylation, Decarboxylation of beta-Ketoacids

Overall Conversion

Worked Example

Acetoacetic Ester Synthesis, Acetoacetic Ester (Ethyl Acetoacetate), Generalization: beta-Keto Esters

Direct Alkylation of Ketones, Esters, and Nitriles – Part 1

Direct Alkylation of Ketones, Esters, and Nitriles – Part 2

Alkylating and Acylating via an Enamine Intermediate

Aldol Reaction, Aldol Condensation

Characteristics of the Aldol Condensation

Ester Condensations, Dieckmann Condensation

Mixed Ester Condensations, Dianion Nucleophiles

Conjugate Additions of Enolates - aka Michael Reaction

Michael + Aldol = Robinson Annulation

Practice Homework for Section 17

Practice Homework for Section 17 (Key)

Quiz for Section 17

Quiz for Section 17 (Key)

Instructor's Notes for Section 18

Electrophilic Aromatic Substitution

Hammond Postulate, Electrophilic Aromatic Substitution: Nitration

Effect of Substituents

Effect of Substituents: EDG by Resonance, Effect of Substituents: EWG (Deactivation), Effect of Substituents: Halides (ortho-, para- Deactivating)

Table 1. Effect of Substituents on Electrophilic Aromatic Substitution, Steric Factors: ortho- vs para-, Multiple Substituents Effects

Nitration, Nitration Examples, Protecting Group Chemistry

Halogenation, Highly Activated Aromatic Rings

Friedel-Crafts Alkylation, Friedel-Crafts Alkylation Mechanism, Other Carbocation Forming Sources, Examples of Friedel-Crafts Alkylation

Friedel-Crafts Acylation, Mechanism, Examples of Friedel-Crafts Acylation

Nucleophilic Aromatic Substitution: Diazonium Ions

Additional Useful Reactions, Reduction Examples

More Useful Reactions

Summary of Reactions Known Up to this Point

Nucleophilic Aromatic Substitution: Addition-Elimination, Nucleophilic Aromatic Substitution: Addition-Elimination Examples

Nucleophilic Aromatic Substitution: Elimination - Addition, Nucleophilic Aromatic Substitution: Elimination – Addition Examples

EAS Total Synthesis Problems – Part 1

EAS Total Synthesis Problems – Part 2

For Activated Phenols and Anilines Use Protection Chemistry, EAS Total Synthesis Problems

Practice Homework for Section 18

Practice Homework for Section 18 (Key)

Quiz for Section 18

Quiz for Section 18 (Key)

Instructor's Notes for Section 19

Amines and Heterocyclic Compounds, Oxygen and Sulfur-Containing Saturated Heterocycles

pKa Values, Amines are Nucleophiles

The Resonance Contributors of Pyrrole, Electrophilic Aromatic Substitution Reactions

Why Substitution at the 2-Position? Relative Reactivites

Substitution Occurs at the 3-Position, Nucleophilic Substitution Occurs at the 2- and 4-Positions

Nucleophilic Aromatic Substitution Reactions, Forming Diazonium Ions

Reactions of the Side Chain

Practice Homework for Section 19

Practice Homework for Section 19 (Key)

Quiz for Section 19

Quiz for Section 19 (Key)

Instructor's Notes for Section 20

Carbohydrates, Stereochemistry

Fischer Projection Protocols, Structures - From 3D to Fischer Projections

Natural Carbohydrates

Memorizing aldose sugars with 3-6 carbons

Important Aldoses 3-5 carbons, Important Aldoses 6 carbons

Acetal and Ketal Formation

Acetal Formation Mechanism

Haworth Projections

From Fischer Projections to Chair Conformation

Anomeric Excess

Reactions of Monosaccharides – Part 1

Reactions of Monosaccharides – Part 2

Disaccharides, More Disaccharides

Polysaccharides, Glycogen

Practice Homework for Section 20

Practice Homework for Section 20 (Key)

Quiz for Section 20

Quiz for Section 20 (Key)

Instructor's Notes for Section 21

Amino Acids ‘R” Groups, Common Amino Acids

Stereochemistry, Zwitterions, and Properties

Table of pKa Values of Amino Acids, and Isoelectric Point (pI)

Amino Acids – Synthesis

Amino Acids – Reactions

Practice Homework for Section 21

Practice Homework for Section 21 (Key)

Quiz for Section 21

Quiz for Section 21 (Key)