Chapter 22: Condensations and Alpha Substitutions of Carbonyl Compounds

Start with: Use: Product: Notes

Enolate Alkylation ketone/aldehyde 1) LDA 2) R-X ketone/aldehyde alpha substitution

1) R2NH/H+ 2) E+ 3)
Enamine ketone/aldehyde ketone/aldehyde alpha substitution
+
H3O

alpha halogenated trihalogenation, aka

carbonyl compound X2, -OH
carbonyl "haloform"
Alpha
Halogenation as many halogenations as
alpha halogenated
carbonyl compound X2, CH3COOH
carbonyl X2's supplied

Hell-Volhard- alpha brominated goes through acid bromide

carboxylic acid 1) Br2/PBr3 2) H2O
Zelinsky carboxylic acid intermediate
Aldol 1) H+ or -OH conjugated double dehydration drives the
two carbonyls
Condensation bond carbonyl completion of the reaction
2) heat, H+ or -OH
Claisen "base promoted" then re-
two esters 1) NaOR 2) H3O+ diketone
Condensation protonated in dilute acid
1) -OCH2CH3 2)
Malonic Ester substituted acetic
diethyl malonate R-X 3)
Synthesis acid
heat, H3O+
1) -OCH2CH3 2)
Acetoacetic Ester substituted
ethyl acetoacetate R-X 3)
Synthesis acetone
heat, H3O+