Nucleophilic aromatic substitution also known as SnAr is less common than electrophilic

substitution due to the abundant pi electron density of the aromatic rings (McMurry, 2011)
.However, aromatic compounds such as aryl halides with electron withdrawing groups undergo
SnAr because the electron withdrawing groups pull electron density from the ring enough to
make it susceptible to reactions with nucleophiles; it also helps that halides are good leaving
groups because of their weak basicity. Electron withdrawing groups are therefore considered as
activators towards SnAr and they are most effective at the ortho and para positions rather than
the meta position (relative to the carbon bearing the leaving group) because if the E.W.G is
meta relative to the leaving group, the E.W.G won’t be able to temporarily hold electron density
(resonance) to stabilize the ring after the addition of the nucleophile; the opposite is true for
electron withdrawing groups which are ortho and/or para relative to the ipso carbon (carbon
containing the halide and the nucleophile).

Fig. 1.1 Resonance Structures of Meisenheimer Complex at different E.W.G positions relative to
ipso carbon

The main component of Brady’s reagent, 2,4 – dinitrophenylhydrazine (2,4 – DNP), can be
synthesized by the reaction of hydrazine sulfate and 2,4 –dinitrochlorobenzene (Org.
Synth. 1933, 13, 36)

Fig. 1.2 Reaction of Hydrazine sulfate and 2,4 – dinitrochlorobenzene

The mechanism for this reaction involves a two-step, SnAr reaction, the first step being an addition
reaction and the second step being an elimination reaction. The first step involves the attack of the
nucleophile (hydrazine) to the carbon bearing the chlorine atom forming a Meisenheimer complex; the
activation energy for this step is higher due to the removal of the aromaticity of the ring.
(show reaction)

Fig.1.3 Formation of Meisenheimer complex

The second step involves the removal of one of the substituents in the ipso carbon, in this case the
carbon containing the chlorine atom and hydrazine. The nucleophile can be ejected forming the original
substrate (2,4 – dinitrochlorobenzene) or the halide can be ejected forming a new product; in this case,
if the chlorine is ejected, 2,4 – DNP is formed.

(show reaction)

Fig.1.4 Formation of 2,4 – DNP and 2,4 – dinitrochlorobenzene

To test if the product obtained is 2,4 – DNP, it’s melting point can be determined , the melting
point of pure 2,4 – DNP is 194 C although the melting point is not sharp because the sample
shrinks in the capillary tube 10 C below the melting point (Org. Synth. 1933, 13, 36). The
reaction of 2,4 – DNP with carbonyl compounds can also be exploited to test the
product obtained, in the experiment, benzaldehyde and acetone will be used as test
compounds. Yellow, orange or orange -red precipitates indicate a positive result, this
colored precipitate is 2,4-dinitrophenylhydrazone - the product of the reaction
between 2,4 –DNP and carbonyl containing compounds.

Fig.1.5 Formation of 2,4 – dinitrophenylhydrazone from benzaldehyde and ketone reactions

with 2,4 - DNP

LIST OF NECESSARY CHEMICALS