MU Chemistry 210 WS97
Catalog of Things-to-Study
Preparation to Exam 3

---

Carbenium Ions - Stability and their Rearrangements

Knowledge of best leaving groups to make carbenium ions.
Stabilization of carbenium ions.

Stabilization due to alkyl groups (hyperconjugation)
Stabilization due to vinyl groups (conjugation)
Stabilization due to phenyl groups (conjugation)

Ability to recognize carbenium ions that might rearrange.

Is there a beta-H for a 1,2-H shift?
Is there a beta-alkyl group for a 1,2-alkyl shift?

Ability to judge whether the rearrangement will occur.

Secondary to tertiary carbenium ion.
Secondary to secondary.
Tertiary to tertiary.

Nucleophilic Substitution Reactions

Mechanisms of the uni- and bimolecular nucleophilic substitutions.

Knowledge of all steps.
Ability to draw potential energy diagrams.
Knowledge of stereochemical issues.
Knowledge of the rate equations and of reaction orders.
Ability to give specific examples.

Factors affecting the rates of the uni- and bimolecular reactions.

Head carbon type
Sterics
Nucleophilicity
Leaving group ability
Solvent (know the most important aprotic polar solvents)

Frontside bimolecular nucleophilic substitution (will not be tested)

Elimination Reactions

Mechanisms of E1, E2 and E1cB reactions.

Knowledge of all steps.
Ability to draw potential energy diagrams.
Knowledge of stereochemical issues

Sayzeff vs Hoffmann
Anti vs syn elimination

Knowledge of the rate equations and of reaction orders.
Ability to give specific examples for each type of reaction.

Use of kinetic isotope effects to distinguish among the mechanisms.
Ability to distinguish between S and E product formation.

Alkylhalides: Names, Preparations & Reactions

Ability to name alkylhalides.
Ability to differentiate between prim., sec. and tert. halides.
Preparations of alkylhalides (see other sections).

Alcohols: Names, Preparations & Reactions

Ability to name alcohols in the '-ol' and '-alcohol' systems.
Knowledge of the physical properties of alcohols

Solutibility and hydrophobic / hydrophilic interactions.
Hydrogen bonding ability.

Syntheses of alcohols in the laboratory.

Reaction of alkylhalides with hydroxide
Reaction of esters with hydroxide (ester cleavage, saponification)
Prim. alc.: Formaldehyde with organometallic reagents.
Sec. alc.: Aldehyde with organometallic reagent.
Tert. alc.: Ketone with organometallic reagent.
Reaction of esters with organomettalic reagents.
Reductions of aldehydes and ketones with hydride reagents

Oxidation of Alcohols.

Knowledge of oxidation bahaviours of prim., sec., and tert. alcohols.
Knowledge of Cr-based oxidizing reagents.
Knowledge of PCC.
Mechanism of oxidation with chromic acid.

Alcohols as Acids

Knowledge of strong bases for deprotonation of alcohols
Knowledge of reactions of alkalimetals with alcohols

How does it depend on the choice of the metal?
How does it depend on the type of alcohol?

Alcohols as Bases

Ability to recognize and name oxonium ions.
Knowledge of formation of oxonium ions by protonation of alcohols.
Use of oxonium ions as carbenium ion precursors.

Formation and Reaction of Esters

General schemes for preparation of organic and inorganic esters.

Condensation of acid and alcohol (eliminate water)
Condensation of acid halide and alcohol (eliminate HX)

Knowledge of the esterification mechanism.
Knowledge of the chloroalkane synthesis with thionyl chloride.
Knowledge of the bromoalkane synthesis with phosphorous tribromide.
Knowledge of the iodoalkane synthesis via sulfonates.

Formation and Reactions of Ethers

Ability to name acyclic and cyclic ethers (trivial names and IUPAC).
Ether synthesis via acid-catalyzed alcohol dimerization.
Williamson ether synthesis (inter- and intramolecular).
Acid-cat. ether cleavage of acyclic ethers
Base- & acid-cat. ether cleavage of cyclic ethers (regio- & stereochem.).

NMR Spectroscopy will NOT be part of this examination