Nitrogen compounds

(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:

2o > 1o > 3o > NH3 > C6H5NH2

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

RNH2 + NaNO2 + HCl → [R←N+≡N]Cl-

Aliphatic
ROH H O
2 Diazonium salt
-H+ R+ + N2 (unstable)
C=C
X- (evolution of N2 serves
R-X as a test for 1o amine)
Reaction with Nitrous acid
 1o aromatic amine

NH2 + NaNO2 + HCl

→ 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

Orange II, Azo dye (1876)

1
N+= N- Also serve as a test
for 1o aromatic amine
HO