Chapter 13 Conjugated p-Systems.ppt

Chapter 13: Conjugated p-Systems Allylic Substitution Allylic Chlorination Allylic Chlorination: Mechanism Allylic Bromination: NBS Allylic Radical: MO Description p Molecular Orbitals: General Rules Allylic Radical: MO Description Resonance: The Carbonate Ion Rules for Drawing Resonance Structures Rules for Drawing Resonance Structures Alkadienes (Polyunsaturated HCs) Alkadienes: 1,3-Butadiene Alkadienes: 1,3-Butadiene MOs UV-Vis Spectroscopy UV-Vis Absorption Spectrum 1,4 Addition in Conjugated Dienes 1,4 Addition in Conjugated Dienes Diels-Alder Reactions: 1,4 Cycloadditions Diels-Alder Reactions: 1,4 Cycloadditions Diels-Alder Reactions: 1,4 Cycloadditions * Allylic Substitution—Allyl Radicals (Section 13.2) Allyl Radical Stability (Section 13.3) Allyl Cation/Anion (Section 13.4) Resonance Structures Revisited (Section 13.5) Alkadienes, Polyunsaturated Hydrocarbons (Section 13.6) 1,3 Butadiene (Section 13.7 – 13.8) UV-Vis Spectroscopy (Section 13.9) Electrophilic Attack: 1,4 Addition (Section 13.10) Diels-Alder Reactions (Section 13.11) First Reaction ? Addition of Br2 to Alkene Second Reaction ? Allylic Substitution Illustrates Reaction’s Dependence Upon Conditions Allyl Choride Synthesis Known as “Shell Process” Radical Substitution Mechanism (Multi-Step) Initiation Propagation Termination Allylic C—H Bonds Relatively Ease to Dissociate Termination Arises from Any Combination of Radicals NBS: N-Bromosuccinimide (Low Br2 Concentration) Nonpolar Solvent, Dilute Conditions Primarily Get Allylic Substitution Product Three p Orbitals Combine to Form 3 p Molecular Orbitals One Unpaired Electron (Radical) p Molecular Orbitals are Symmetric Nodes Are Through Atoms or Bonds Nodes Represent an Orbital Phase Change (+/-) In Allyl Radical, Unpaired Electron on C1 and C3 (NOT C2) p Molecular Orbitals Explain Resonance in Allyl Radical Same Orbital Picture for Same Carbon Scaffold (O