Chapter 14: Alpha Substitution Reactions of Carbonyls

Ch. 14 – Alpha Substitution Reactions of Carbonyls

DAT Organic Chemistry Outline

Chapter 14: Alpha Substitution Reactions of Carbonyls Lesson 14.1 – Alpha Substitution Reactions Enolates and Enols

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Enolates are better nucleophiles because they have a negative charge

Keto-enol tautomerization

How to deprotonate -hydrogen More substituted -hydrogen gets deprotonated with typical base Less substituted -hydrogen gets deprotonated with LDA

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Ch. 14 – Alpha Substitution Reactions of Carbonyls

DAT Organic Chemistry Outline

Lesson 14.2 – Alpha Halogenation and Haloform Reaction Base-promoted Alpha Halogenation (all alpha hydrogens replaced with halogen)

Acid-catalyzed Alpha Halogenation (only one alpha hydrogen replaced with halogen)

Alpha-Deuteration (all alpha hydrogens replaced with D atom regardless of acidic or basic)

Haloform Reaction (need a CH3)

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Produces a yellow precipitate if methyl ketone is present – useful lab test

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Ch. 14 – Alpha Substitution Reactions of Carbonyls

DAT Organic Chemistry Outline

Lesson 14.3 – Aldol Condensation

Aldol Shortcut

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Ch. 14 – Alpha Substitution Reactions of Carbonyls

DAT Organic Chemistry Outline

Lesson 14.4 – Claisen Condensation • Just like Aldol Condensation, except with esters. Enolate adds to an ester.

Claisen Shortcut

Beta-Decarboxylation

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Ch. 14 – Alpha Substitution Reactions of Carbonyls

DAT Organic Chemistry Outline

Lesson 14.5 – Acetoacetic Ester Synthesis

Lesson 14.6 – Malonic Ester Synthesis

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