Chapter 15: Radical Reactions
- Draw initiation, propagation and termination steps for radical halogenation reactions.
- Explain reactivity/selectivity principle applied to radical halogenation (chlorination vs. bromination).
- Draw products for radical addition to alkenes.
- Draw products for radical allyl addition to alkenes.
Chapter 16: Conjugation, Resonance and Dienes
- Explain stability of conjugated dienes using heats of hydrogenation
- Draw resonance hybrids.
- Draw mechanism for 1,2 and 1,4 addition to conjugated dienes.
- Explain kinetic vs. thermodynamic effects in reactions of conjugated dienes.
- Draw products of Diels-Alder reactions (including stereospecificity)
- Draw Diels-Alder mechanism.
- Explain reactivity of dienes for Diels-Alder reactions.
Chapter 18: Electrophilic Aromatic Substitution
- Draw EAS mechanism: halogenation, nitration, sulfonation, FC alkylation, and FC acylation.
- Draw mechanism for formation of electrophiles.
- Draw mechanism for Friedel-Crafts alkylation rearrangements.
- Explain direction effects for substituted benzenes – o,p directors and m-directors.
- Explain activation vs. deactivation of aromatic rings based on substituents.
- Determine products of EAS for mono-substituted aromatics.
- Determine products of EAS for di-substituted aromatics.
- Determine synthesis schemes for poly substituted aromatics.
- Draw products of benzylic halogenation reactions.
- Draw the products of oxidation and reduction reactions applied to aromatic side chains:
Permanganate oxidation, Wolff-Kishner reduction, Clemmensen reduction, Tin reduction
Chapter 19: Acidity of Carboxylic Acids
- Name carboxylic acids following IUPAC.
- Draw reactions and syntheses to form carboxylic acids.
- Apply carboxylic acids to fatty acids and pain relief topics.
- Determine relative acidity of carboxylic acids based on inductive effects.
- Determine acidity based on aromatic substituents.
- Determine structures of amino acids when neutral, acidic and basic.
Chapter 20: Introduction to Carbonyl Chemistry
- Explain general reactivity of carbonyl groups.
- Draw nucleophilic addition mechanism.
- Draw nucleophilic acyl substitution mechanism.
- Draw mechanism and products for reduction of carbonyls with lithium aluminum hydride and diisobutyl aluminum hydride.
- Rank reactivity of organometallic reagents copper, magnesium and lithium compounds.
- Draw mechanisms for reaction of organometallic compounds with aldehydes and ketones.
- Use acetals as protecting groups of aldehydes in synthesis problems.
- Draw mechanisms for reaction of organometallic compounds with various carboxylic acid derivatives.
- Draw products of reaction of organometallic reagents with carbon dioxide.
- Draw mechanism for addition of organometallic compounds to a, b unsaturated carbonyl compounds.
- Solve synthesis problems incorporating carbonyl chemistry.
Chapter 21: Nucleophilic Addition
- Explain relative reactivity of aldehydes and ketones.
- Name simple aldehydes and ketones using IUPAC nomenclature.
- Draw products of reactions that form aldehydes and ketones (previous material).
- Draw basic (or strong nucleophile) nucleophilic addition mechanism.
- Draw acid catalyzed nucleophilic addition mechanism.
- Draw mechanism and products of the Wittig reaction.
- Draw mechanism and products of nucleophilic addition of 1o and 2o amines (imine and enamine formation).
- Draw mechanism for formation of acetals and hemi-acetals.
- Apply hemi-acetal formation to pyranose and furanose forms of sugars.
- Apply acetal formation as protecting groups of carbonyls in synthesis problems.
Chapter 22: Nucleophilic Acyl Substitution
- Name simple carboxylic acid derivatives using IUPAC nomenclature.
- Draw generic nucleophilic acyl substitution reaction.
- Rank leaving groups/reactivity of carboxylic acid derivatives.
- Draw mechanisms for reaction of acid derivatives with hydride reducing agents and organometallics.
- Draw mechanism to form acid halides from carboxylic acids.
- Draw mechanisms to transform each carboxylic acid derivative into the less reactive derivatives.
- acid halide to anhydride, ester, amide, carboxylic acid
- anyhdride to ester, amide, carboxylic acid
- carboxylic acid to amides (DCC)
Chapter 23: Carbonyl Alpha Substitution Reactions
- Draw general alpha carbon reaction mechanisms incorporating enols for neutral/acidic reactions and enolates for basic reactions
- Draw basic and acidic tautomerizations.
- Determine if a kinetic or thermodynamic enolate will form, based on reaction conditions.
- Draw kinetic and thermodynamic enolate reaction mechanisms.
- Draw mechanisms for halogenation at alpha carbon.
- Draw mechanisms for direct enolate alkylation.
Chapter 24: Carbonyl Condensation Reactions
- Draw aldol reaction mechanisms (Single reactant, crossed, directed, and intramolecular).
- Draw Claisen condensation mechanism (Single reactant and Crossed)
- Draw Intramolecular Claisen mechanism (Dieckmann cyclization).
- Draw sulfur analogue of Claisen condensation (as in acetyl CoA).
- Determine products of Michael type reactions.
Chapter 25: Amines
- Draw reactions and syntheses used to form amines (reduction of nitro, amide, nitriles; reaction with alkyl halides).
- Determine relative basicity of amines based on availability of the lone pair electrons.
Chapter 26: Synthetic Polymers
- Draw addition polymerization reactions (including cationic and radical polymerization).
- Draw condensation polymerization reactions.