Umich Chem 215 - Final Exam

Final Exam of Umich Chem 215 - Chapters 11-17 + 19.5/.6

Oxidation

• Increase in the amount of oxygen in a molecule

• Loss of electrons

• OIL RIG

Reduction

• Decrease in the amount of oxygen in a molecules

• Gain of electrons

• OIL RIG

Making Hydroxyl a Leaving Group

• Protonate the hydroxyl

• Sulfonate ester

• Convert alcohol into an acid halide

  • PCl₅, PBr₃,PI₃,SOCl₂

  • All invert the stereochemistry at the alcohol besides SOCl₂ without pyridine

Jones Reagent & Products of Reaction

• CrO₃/H₂O, H₂SO₄

• Primary alcohol becomes a carboxylic acid

• Secondary alcohol becomes a ketone

• Tertiary alcohol does not react

Swern Oxidation Reagent & Product

• Oxalyl chloride, DMSO, & TEA

• Primary alcohol becomes an aldehyde

• Secondary alcohol becomes a ketone

Anhydrous Oxidizing Reagents & Products

• Collins Reagent - CrO₃ & 2 py

• ClCrO₃ & py+

• Cr₂O₇ & 2 py+

• Primary alcohol becomes an aldehyde

• Secondary alcohol becomes a ketone

Oxidation Mechanism of Secondary Alcohols

• Attack of ROH onto oxidant

• Deprotonation of former hydroxyl

• Elimination via deprotonation at the hydroxyl carbon

Oxidation Mechanism of Primary Alcohols

• Attack of ROH onto oxidant

• Deprotonation of former hydroxyl

• Elimination via deprotonation at the hydroxyl carbon

• Acid catalyzed addition of H₂O (if aqueous)

• Steps 1-3 repeat if hydrate is formed.

Formation of Epoxide Rings Mechanism

• Forming an epoxide ring from an alkene & then breaking it can be used to both keep & invert stereochemistry based on the conditions used to break it.

• Acidic - Sn1 - retention

• Basic - Sn2 - inversion

Resultants of Epoxide Opening Reactions

• Products of an epoxide opening reaction have the connectivity of HO-C-C-Nuc

Alkene - 1) O₃ 2)H₂O₂ —- H₂O₂

Reagents used for the formation of carboxylic acids from alkenes.

Primary alcohol - CrO₃, H₂O, H₂SO₄

Reagents used for the oxidation of primary alcohols to carboxylic acids.

Aldehyde - Ag₂O, NaOH, H₂O

Reagents used for the oxidation of aldehydes to carboxylic acids.

Aldehyde - CuSO₄/citric acid

Reagents used for the oxidation of aldehyde to form carboxylic acids.

Aldehyde - (CH₃)₃COOH/(CH₃)₃COH, (CH₃)₃COK

Reagents used for the oxidation of aldehyde to form carboxylic acids.

Aldehyde - AgNO₃/NH₃

Reagents used for the oxidation of aldehyde to form carboxylic acids.

Aldehyde - NaClO₂/H₂O₂

Reagents used for the oxidation of aldehyde to form carboxylic acids.

Aldehyde - SO₂OKOOH

Reagents used for the oxidation of aldehyde to form carboxylic acids.

Hydrolysis of carboxylic acid derivatives results in:

Carboxylic acids (after acidification/protonation)

Conditions to open lactones

Strong acid, typically TsOH

Reagents to form a carboxylic acid from a benzene ring with a Bromine

1) Mg 2) CO₂ 3) H₂SO₄/H₂O

Preparation of acid chlorides

Reacting a carboxylic acid with SOCl₂

Acylation of a carboxylic acid using a carboxylic only requires these conditions:

Heat >100 degrees C

An inter/intramolecular condensation of two carboxylic acids results in this:

An anhydride