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TRANSCRIPT
AminesAmines NomenclatureNomenclature PropertiesProperties Preparation reactionsPreparation reactions Characteristic reactionsCharacteristic reactions SpectroscopySpectroscopy
Nomenclature Nomenclature and Properties and Properties
of Aminesof Amines
Preparation Reactions of Preparation Reactions of AminesAmines
Reduction reactionsReduction reactions RearrangementsRearrangements Nucleophilic substitution reactionsNucleophilic substitution reactions
Amines via ReductionAmines via Reduction
Reduction of nitro compoundsReduction of nitro compounds Reduction of nitrilesReduction of nitriles Reduction of amidesReduction of amides
Reduction of imines/enaminesReduction of imines/enamines Reductive amination of Reductive amination of
aldehydes/ketonesaldehydes/ketones
Amines via Reduction: A SummaryAmines via Reduction: A Summary
R NO2 R NH2
R CN RCH2NH2
R C NH2
O
RCH2NH2
R C
O
NHR' RCH2NHR'
R C
O
NR'2 RCH2NR'2
R' C
R''
NH R' C
R''
H
NH2
R' C
R''
NR R' C
R''
H
NHR
C CH NR2 C
H
CH2NR2
R' C
R''
ONH3
or
R' C
R''
ORNH2
H2 / Pt or LiAlH 4
H2 / Pt or LiAlH 4
LiAlH 4
LiAlH 4
LiAlH 4
H2 / Pt
LiAlH 4
orH2 / Pt
LiAlH 4
H2 / Pt or LiAlH 4
H2 / Pt
H2 / Pt
or Sn / H+
Amines via Amines via RearrangementRearrangement Hofmann rearrangement (degradation)Hofmann rearrangement (degradation)
Curtius rearrangementCurtius rearrangement
R C
O
NH2X2
OH-/H2ORNH2 CO2+
∆Primary amide
R C
O
N N N+
Acyl azide
∆ H2ORNH2 CO2+ +N2
Amines via Bimolecular Amines via Bimolecular Nucleophilic SubstitutionNucleophilic Substitution
C
O
C
O
N HKOH
C
O
C
O
N K+ RCH2XC
O
C
O
N CH2R
C
O
C
O
N CH2ROH-/H2O
RCH2NH2 +
C
O
C
O
O
O
RCH2X + NH3 RCH2NH2
RCH2NH2RCH2X
RCH2NHCH2R
RCH2NHCH2RRCH2X
(RCH2)3N
(RCH2)3NRCH2X
(RCH2)4N+
X
GabrielSynthesis
Alkylation
Δ
Amine ReactionsAmine Reactions Reaction as Bases: Salt FormationReaction as Bases: Salt Formation Amide FormationAmide Formation AlkylationAlkylation Reaction with Nitrous AcidReaction with Nitrous Acid
Amine Reactions with Nitrous AcidAmine Reactions with Nitrous Acid Primary amines: DiazotizationPrimary amines: Diazotization Secondary Amines: Nitrosamine formationSecondary Amines: Nitrosamine formation Tertiary Amines: C-nitroso compoundsTertiary Amines: C-nitroso compounds
RNH2HONO
oC0
R N N+
alkyl diazonium saltunstable
N2 + R+
ArNH2HONO
oC0
+Ar NN
aryl diazonium salt
Nu N2 + Ar Nu
R2NHor
ArNHR
HONO o
C0
RN
R
NO
NR
NO
Ar
or
Nitrosamines
NR2HONO
oC0
NR2NO
Aromatic C-nitroso compound
stable at low temp.
Mechanism of Diazonium salt formationMechanism of Diazonium salt formation
H O N O + H+
H2O
+
nitrosoniumion
R NH2
N O++
R N
H
H
N O+
N-nitrosoammoniumion
R N
H
H
N O+
+ H2O R N
H
N O + H3O+
N-nitrosamine
R N
H
N Otautomerization
R N N OH
a diazenol
R N N OH + H+ R N N OH
H
R N N OH
HR N N + H2O
+
a diazoniumion
N OOH
H
+
N OOH
H
+
+
+
N O+
Diazonium Salt ReactionsDiazonium Salt Reactions
N N+
Phenol
HO N N
an azo dye
H3PO2
H
OH
H2O
heatKI
I
CN
CuCN
Cl
CuCl
CuBrBr F
1. HBF4
2. heat
Reactions of PhenolsReactions of Phenols Salt formation via strong base or active metalSalt formation via strong base or active metal
Williamson ether synthesisWilliamson ether synthesis Ester formationEster formation
Friedel-Crafts acylation: Fries rearrangementFriedel-Crafts acylation: Fries rearrangement HalogenationHalogenation
Coupling with diazonium saltsCoupling with diazonium salts Kolbe-Schmitt CarboxylationKolbe-Schmitt Carboxylation
Reimer-Tiemann reactionReimer-Tiemann reaction
Phenol Reactions: A Phenol Reactions: A SummarySummary
OH
NaOH
or
Na
O- Na+ 1. NaOH
2.RX (primary)
OR
RCOCl
or
(RCO)2O
OC
O
R
AlCl3
OH
C
O
RArN2
+
OH
N
NAr
CO24-7 atmheat
OH
C
O
O-Na+
CHCl3
O-
C
O
H
NaOH
Na+
Halogenation of Halogenation of PhenolsPhenols
OH OH
Br
OH
Cl
Br2CS2
low temp.
Cl2
no solventhigh temp.
majorproduct
majorproduct
No Lewis acid is required
OH OH
Br
Br Br
OH
Cl
ClClBr2Cl2
H2O H2O
No Lewis acid is required
Reimer-Tiemann Reaction MechanismReimer-Tiemann Reaction Mechanism
OH
CHCl3
NaOH/H2Oheat
C
O
H
OH
salicylaldehyde
CHCl3 + OH- CCl3- + H2O
CCl3- CCl2 + Cl-
a carbene
+ OH-
OOH O
H
O
H CCl2+
O
H
CCl2 CHCl2
O-
CHCl2
O-
H2O
heat
OHC
O
H+ HCl2
Overall: