Synthesis of Amine Flashcards
xReagents for Reduction of Amine
Reagent
1. LiAlH4, ether
2. H2O
replace nitrile and carbonyl group with hydrogens
Reduction of Nitrile
Reagent
1. LiAlH4, ether
2. H2O
Nitrile -> R-CH2-> NH2
Reduction of Amides
Reagent
1. LiAlH4, ether
2. H2O
Replace carbonyl to hydrogen. Oxygen turns into Hydrogens
Reduction of Nitro Groups
Reagents
1. H2/ Pd
Turns NO2 into NH2
Gabriel Synthesis
Preparing a primary amine from an alkyl halide using an phthalimide
Reagent
1. KOH, EtOH
2. R-CH2-X
3. KOH, H2O
Reduction of Azide
A two step reactions where an amine can be prepped by reacting an alkyl halide with an azide (N3) and with LiAlH4/H2O
- R-X react with N3
- R-N3 react with LiAlH4 to form R-NH2
Hoffman Rearrangement
treating a primary amide with an aqueous
alkaline solution of bromine to form an amine
- Protonation of Nitrogen
- Electrophilic Attack on Br2
- Protonation of Nitrogen
- Electrophilic Attack on Br2
- Nucleophilic Attack on Central Carbon by OH-
- Electrophilic Attack on H2O by Nitrogen
- Protonation of OH on Carbon
- Rearrangement
- R-NH2 attack water to form R-NH3
Curtis Rearrangment
migration of an R group from the C=O carbon atom to the neighboring nitrogen with simultaneous loss of a leaving group.
Reagent
NaN3 / Et2O
Amide turns into NH2
What’s the condition for curtis rearrangement
Carbonyl group with halide react with NaN3/ EtOH to form amine
What’s the condition for Hoffman rearrangement
PRIMARY amide react with Br2 in alkaline solution to form amine
Hoffman Elimination
Treating a secondary amine to an alkene
Reagent
Ch3-I / EtOH
Ag2O / heat
What is the condition for Hoffman Elimination
NH2 is a poor leaving group thus, Amine must be methylated to a salt in order to become a good electrophile.
Sandmeyer Reaction
Primary arylamines react with
HNO2/ H2SO4 to yield stable arenediazonium salts, (N2)
If arlamine with arenediazonium salt react with nucleophile, the nucleophile will replace the N2
