0 1 2 NaN UI Springfield CHE 269 Organic Chemistry II Spring 2016: Morsch Reading Assignments Homework Problems Homework Solutions Quizzes Template:HideTOC 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.