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(Chapter 37)
Nitrogen containing
compound
T.N.T. CH3
Proteins
NO2 NO2
Enzymes
Drugs
NO2
Amines
Aliphatic R-NH2 R-N-R”
1o amine
R’
2o amine
R-N-H
3o amine
R’ R +
4o ammonium R-N-R” Br-
cpds
R’
Aromatic
NH2
IUPAC names
CH3NH2 Methanamine
(CH3)2NH N-methylmethanamine
(CH3)3N N,N-
dimethylmethanamine
C6H5NH2 Phenylamine (aniline)
Formation of amines
Alkylation of NH3
RX + NH3 → R-NH2 + R2-NH + R3N +
R4N+X-
(NH3 in large excess, 1o amine as main
product)
1o Amine from Amides and Nitriles
R-C≡N → RCH2NH2 (H2/Ni or LiAlH4)
RCONH2 → RCH2NH2(LiAlH4 /ether than
H+)
Formation of Amines
C6H5-NO2 → C6H5-NH2
Reducing agent:
H2/Ni
or
HCl,Fe (or Zn, Sn, SnCl2) then OH-
Basicity of Amines
NH3 pKb = 4.74
CH3NH2 3.36
CH3CH2NH2 3.25
CH3CH2CH2NH2 3.33
(CH3)2NH 3.28
(CH3)3N 4.30
C6H5NH2 9.4
Basicity of Amines
R H R +
H N: H O H N H OH-
H H
Order of basicity:
Why?
Explanation
Solvation of
protonated amine
R +
in water by
hydrogen bondingH2O H N H H2O
(more H, better H
solvation)
H2O
NH3>1o>2o>3o
Explanation
Effect of the
inductive electron R
push of the R R N:
groups R
Increase the
basicity
R +
Stabilize the
alkylammonium R N H
ion R
3o>2o>1o>NH3
Explanation
Lone pair e- partly
incorporated into ..
benzene ring NH2
Less ready for
protonation ..-
+
NH2
Reactions
Salt Formation
NH2 + HCl
NH3+ Cl-
NH2 + H2O
NaOH
+ NaCl
?
Reactions
Amide
Formation
O O
R-NH2 + CH3CCl → CH3CNHR + HCl
O O
R-NH2 + C6H5CCl → C6H5CNHR + HCl
High m.p.
Used in identification
Reaction with Nitrous acid
HNO2 prepared by NaNO2 + HCl
1o aliphatic amines
→ N+≡N Cl-
(stable at temp.<5oC, greater
stability by dispersing charge
into the benzene ring)
Mechanism
.. H+ -H2O ..
HO N O H N O N+ O N O
2 O +
.. .. + .. -H+
Ar NH2 + N+ O Ar NH2 N O
.. .. H+ +
Ar NH N O Ar N N OH Ar N N OH2
-H2O ..
+ +
Ar N N: Ar N N:
Stability of Ar-N+≡N
+
N N:
Benzenediazonium salt
C6H5-N2+ Cl-
C-N bond heavily polarized away
from benzene ring
C atom accept Nu: (against the
norm of aromatic chemistry)
Has considerable synthetic value
Benzenediazonium salt
Can be CuCl ArCl
replaced by a
CuBr
variety of ArBr
function
Ar-N2+ CuCN ArCN + N2
groups
I-
High yield ArI
No multiple H2O ArOH
substitution
Coupling reaction
..
N=N+: OH
1
O-
+ NaOH
(Napthalen-2-ol)
Ice cold