Chemistry 331: Outline for Final Exam Chapter 4: Alcohols and Alkyl Halides Nomenclature Alkyl halides Alcohols Structure-Property Relationships Reactions of Alcohols with Hydrogen Halides The acid-catalyzed SN1 mechanism Reaction rate: relative stabilities of carbocations The acid-catalyzed SN2 mechanism Halogenation of alkanes Free-radical chain mechanism: initiation, propagation and termination Relative stability of free radicals Higher alkanes: regioselectivity (no calculations!) Chapter 5: Structure and Preparation of Alkenes. Elimination Reactions Nomenclature Geometric isomers: cis and trans E-Z notation Structure-Property Relationships Preparation of Alkenes: Elimination Reactions Dehydration of alcohols Zaitsev rule and stereoselectivity The acid-catalyzed E1 mechanism Rearrangements Dehydrohalogenation of alkyl halides The E2 mechanism; one step (concerted) Anti elimination The E1 mechanism (minor) Chapter 6: Reactions of Alkenes. Addition Reactions Hydrogenation of Alkenes Heats of hydrogenation; pecking order Stereochemistry of hydrogenation; syn addition Electrophilic additions Addition of hydrogen halides Markovnikov's rule Mechanism; usually two steps via carbocation intermediates Carbocation rearrangements; usually secondary to teriary Free-radical addition of HBr; use HBr and peroxides Sulfuric acid-catalyzed hydration; sulfuric acid and water; oxymercuration-demercuration Addition of halogens; X2 Formation of halohydrins: X2 and water Other Reaction of Alkenes Hydroboration-oxidation; first use B2H6 then H2O2 and OH- Epoxidation; use peracetic acid Ozonolysis; use O3, then Zn and water Polymerization (minor) Introduction to Organic Synthesis   Chapter 7: Stereochemistry Enantiomers Chirality Optical activity Absolute configuration: R and S Fischer projections Reactions that create a chiral center Compounds Containing Two or More Chiral Centers Diastereomers and enantiomers Meso compounds Stereoisomers in substituted cyclohexanes Reactions that produce diastereomers Chapter 8: Nucleophilic Substitution Nucleophilic Substitution Functional group transformation Ranking of leaving groups; stable ones are best Two mechanisms: SN1 and SN2 SN2 Mechanism Kinetics: bimolecular (second order) Stereochemistry; inversion at the reaction center Mechanism; curved arrows in a single step Steric effects; can be a or b Nucleophiles and nucleophilicity; large, neutral nucleophiles best SN1 Mechanism Kinetics; unimolecular (first order) Carbocation stability; tertiary better than secondary Stereochemistry; racemization Solvent effects; polar protic solvents are best Substitution vs Elimination: predominant SN1, SN2, E1 or E2 mechanisms? Substitutions/eliminations of Alcohols Sulfonate esters Reaction with HX Chapter 9: Alkynes Nomenclature Structure/Properties Structure Acidity of terminal alkynes Preparation of Alkynes Alkylation of terminal alkynes Elimination of dihalides Reactions of Alkynes Hydrogenation to give cis-alkenes; to give alkanes Metal-ammonia reduction to give trans-alkenes Hydration to give ketones Addition of halogens Ozonolysis to give carboxylic acids Chapter 10: Conjugation in Dienes and Allylic Systems Allyl and Allylic Systems Allyl cations; HX and X2 reactions Allylic radicals; NBS reaction Dienes Conjugated dienes Electrophilic additions to conjugated dienes Pericyclic Reactions The Diels-Alder reaction Molecular orbital theory p molecular orbitals of alkenes and polyenes p frontier molecular orbital analysis of cycloadditions   Chapter 11: Arenes and Aromaticity Benzene Structure Stability Nomenclature of Substituted Benzenes One group Two groups More than two groups As a group Common names used by the IUPAC Polycyclic aromatic hydrocarbons Reactions of Arenes Reduction catalytic hydrogenation Birch reduction (not the mechanism) Benzylic reactions free radical halogenation oxidation of arenes nucleophilic substitution preparation of alkenylbenzenes additions to alkenylbenzenes Aromaticity Hückel 4n + 2 rule Aromatic ions Heterocyclic aromatic compounds Chapter 12 Reactions of Arenes. Electrophilic Aromatic Substitution Electrophilic Aromatic Substitution General Mechanism Nitration Sulfonation Halogenation Friedel-Crafts alkylation Friedel-Crafts acylation Acylation-reduction Reactivity and Orientation in Electrophilic Aromatic Substitution Substituent effects activating/o,p-directing substituents deactivating/m-directing substituents halogen substituents Effect of multiple substituents Regioselective synthesis Regioselective synthesis     © Copyright 2008, University of Colorado at Colorado Springs