Lecture 6 NO2 NH2

o Br Br
CN
H2/Pt
Br

ortho, para HNO3

+ NaNO2/HCl
H2SO4
N≡N
Br Br
FeBr3 ?
Br2

Br first as it is o, p directing
Hint: diazonium chemistry +
NH2 N≡N Nu

NaNO2/HCl Weak nucleophile

(ROH, RSH, -CN, etc)

Go back and look at resonance

Basicity
..

..
..
..

Pyridine Pyrrole Imidazole

Which of these are/is basic?

Base → proton acceptor or electron pair donor

..

Pyrrole → basic?
Not basic as lone pair is delocalised as used for aromaticity
→ lone pair is in a p orbital
 Aromatic: Yes
Basic: Yes
Lone pair is in sp2 orbital C C

..
N C

..
sp2 hybridised
Pyridine

C C

Lone pair not delocalised → basic

.. in sp2 orbital

Aromatic: Yes
Basic: Yes due to lone pair in sp2 orbital
..

Imidazole

Basicity continued O

..
..
.. ..
NH2 HN CH3

A B C

Rank the compounds in order of basicity

most least

B C A
 + + +
NH2 NH2 NH2
.. - -
B

..
↔ ↔

..
-
-
O O
..
..
.. +
HN CH3 HN CH3

C
↔

O
-lone pair is delocalised into
so not as available CH3

.. .. ..
NH2 NH2 NH2

NO2 O
.. – CH3
..

aniline p-nitro aniline p-methoxy aniline

Rank them

.. + + +
NH2 NH2 NH2 NH2

- -
↔ ↔ ↔

-
- -
O–N=O O=N=O O=N=O O–N=O
+ + + +
 ..
NH2
-will make ring electron rich, making the lone pair
on nitrogen less likely to be delocalised into the
ring

O
.. – CH3
..

-most basic will have the electrons concentrated in a single place

.. .. ..
NH2 NH2 NH2

NO2 O
.. – CH3

delocalisation? Delocalised Excellent ..

Rubbish
↓
OK e- goes into Because methoxy group will
nitro group be trying to push its own
electrons into ring

.. .. ..
NH2 NH2 NH2

> >

O
.. – CH3 NO2
..

Most Least
 .. ..
NH2 NH2

Which is more basic?

NO2
NO2

More basic

..
NH2 +
NH2 +
NH2

↔ - ↔

+ - + - + -
N O N O - N O

O O O

Acidity
OH OH OH

NO2 O
.. – CH3
..

Rank them

What makes a strong acid?

O
..
..

.. ..
Strong acid H O S O H
.. .. Weak acid CH3CH2OH

O
..
..

+H2O +H2O

O
..
..

CH3CH2O- + H3O+
- .. .. Strong base
Weak base O S O H + H3O+
..

.. ..

O
..
..
 .. - .. - .. -
O O O

..

..

..
..
..

..
NO2 O
.. – CH3

..
A B C

Base strength: B<A<C

Acid strength : B>A>C
..
..