RXNS: For each chemical reaction listed below it is anticipated that a student will be able to recall

• the reagents necessary to accomplish the transformation,
• the reaction stereochemistry, and
• the reaction regiochemistry.

The student should be able to apply this knowledge to

• predict the product of a specific reaction,
• suggest a suitable reactant to yield a specific product, and
• utilize the reaction in a synthetic scheme.

* Students should be able to provide a detailed mechanism for the chemical reactions marked with *.

Chapter 16: The Chemistry of Alcohols Summarized and Extended: Glycols, Ethers, and Related Sulfur Compounds

Objectives

• RXNS: (mostly review, new reactions are italicized)
  • Synthesis of alcohols via hydration or hydroboration of alkenes, substitution of alkyl halides, and reduction of carbonyl compounds.*
  • Synthesis of glycols from oxidation of alkenes and from reactions of epoxides*.
  • Synthesis of ethers from substitution reactions*.
  • Reactions of alcohols in substitution and elimination reactions*, protection as THP ethers*, and oxidation to aldehydes and carboxylic acids.
  • Reactions of glycols as carbonyl protecting groups*, (in oxidative cleavage), in the pinacol rearrangement.*
  • Formation and use of alkoxide ions and thiolate and their use as nucleophiles.
  • Cleavage of ethers by strong acids.*
  • Formation and use of thioalkoxide ions and sulfonium ions.*
  • Formation of thioacetals and their use for alkylation and reduction at carbonyl carbons.*
  • Oxidation and reduction of thiols.
• Know the IUPAC nomenclature for alcohols, ethers, thiols, and sulfides.
• Know the physical properties and understand the acid/base reactions of alcohols, ethers, and thiols.

Assigned Problems (Jones): 37, 43*, 45-47, 49-53, 55, 57-60.
[*Hint for problem 43: THF is a red herring.]

Chapter 17: Carbonyl Chemistry at the α Position

Objectives

• RXNS:
  • Acid and base catalyzed racemization and deuterium exchange at the α position.*
  • Halogenation at the α position.*
  • Haloform reaction.
  • Aldol condensations* (including intramolecular, crossed aldol, and Knoevenagel).
  • Alkylation at the α C.
  • Michael additions.*
• Understand the factors that stabilize enolates and their action as bases and nucleophiles.
• Recognize the chemical consequences of enolization.

Assigned Problems (Jones): 33, 34, 36, 37, 40-42, 44, 46, 47, 50, 52, 53, 57*, 62
[*for problem 57, also determine the structure of E, which is not shown]

Chapter 18: Carboxylic Acids

Objectives

• RXNS:
  • Formation of esters*, amides*, acid halides*, and acid anhydrides*.
  • Reactions with metal hydrides.
  • Reactions with organolithium reagents*.
  • Hunsdieker reaction.
  • Reactions at the α C: bromination*, alkylation*, HVZ
  • Synthesis of carboxylic acids from oxidation of alcohols, aldehydes, and aromatic compounds; from alkenes: from the haloform reaction; from additions to CO₂.
• Know the IUPAC nomenclature for carboxylic acids.
• Be able to predict the relative acidity of different carboxylic acids and rationalize them.

Assigned Problems (Jones): 24-27, 29-35, 39-42

Chapter 19: Carboxylic Acids Derivatives

Objectives

• RXNS:
  • Formation of carboxylic acids*, acid anhydrides*, acid halides*, amides*, and esters*.
  • Reactions of acid derivatives with metal hydrides.*
  • Reactions of acid derivatives with organometallic reagents*.
  • Recuctions of acid halides (Rosenmund).
  • Friedel-Crafts acylation.*
  • Transesterification.*
  • N-alkylation of amides.*
  • Reactions of ester enolates including the Claisen condensation*, its variants*, and alkylation*.
  • Alkylation* and decarboxylative hydrolysis* of malonic esters.
• Know the IUPAC nomenclature for acid halides, acid anhydrides, esters, lactones, amides, lactams, nitriles, and ketenes.
• Understand the relative reactivity of the functional groups toward nucleophilic attack.

Assigned Problems (Jones): 35-38, 41-43, 45, 47a-d, 51, 52, 55, 56, 58

Chapter 20: Nitrogen Containing Compounds

Objectives

• RXNS:
  • Synthesis of amines via nucleophilic substitution* or reduction of amides*/azides/imines/nitriles*/nitro-groups.
  • Reactions of amines as nucleophiles for alkylation*, imine*, enamine*, and amide formation*.
  • Conversion of amines to diazonium ions and their subsequent reactions.
  • Use of amines in Hofmann and Cope eliminations.
• Know the IUPAC nomenclature for amines.
• Recognize the effects of the physical and structural properties of amines.
• Be able to rank the acidity and basicity of various nitrogen containing compounds.
• Recognize the varied biological importance of alkaloids and amino acids.

Assigned Problems (Jones): 30-33, 36, 38-41, 43, 49* (*Even if you can't determine the structures try to show a mechanism for transformation of A-B, B-C, and C-D.)

Chapter 21: Orbital Symmetry Control: Pericyclic Reactions

Objectives

• RXNS:
  • Electrocyclic ring opennings and closings.
  • Cycloadditions (inc. Diels-Alder, 1,3-dipolar cycloadditions, and 1,3-dipolar cycloreversions).
  • Sigmatropic Shifts (inc. sigmatropic H shifts, sigmatropic C shifts, and Cope rearrangements).
• Be able to apply a molecular orbital explanation to a rationale of the above reactions.
• Understand the Woodward-Hoffmann rules and be able to apply them to determine whether
  • an electrocycic reaction is conrotatory or disrotatory under thermal or photochemical conditions
  • what types of molecules undergo thermal cycloadditions and what type require photochemical conditions
  • what types of sigmatropic shifts are allowed

Assigned Problems (Jones): 24-29, 31-33, 38