GLu Chem 44.1 Exercise 1 Postlab

Discussion:
The synthesis of 2,4-dinitrophenylhydrazine started off with the preparation of the

hydrazine solution. This is done in order to have hydrazine available as a nucleophile
for the SNAr reaction. Dissolving hydrazine sulfate in water helps separate hydrazine
from sulfate in their ionic forms. The addition of sodium acetate and the subjection of
the solution under heat also allows the sulfate ions to react with sodium ions forming
water soluble sodium sulfates.
*Insert reaction here*
In order to precipitate the sodium sulfates and have them filtered out, the addition of
ethanol was done since ethanol practically makes sodium sulfate insoluble in water.
By this part, the filtrate should only contain hydrazine and acetate solution.
On a separate beaker, 1-chloro-2,4-dinitobenzene was dissolved with ethanol instead

of water due to it being more soluble in alcohols and only slightly soluble in water.
Supposedly, aromatic compounds act as a nucleophile due to the pi electrons present

in their rings but for this case, the electronegative withdrawing groups pull the
electrons towards them and therefore leaving the ring more electrophilic than normal.
As an electrophile, the 1-chloro-2,4-dinitobenzene is then acted upon by the hydrazine
in the hydrazine solution prepared a while ago. It is important to take note that this is
a better way to react the two reagents together instead of dissolving the hydrazine
sulfate directly on the 1-chloro-2,4-dinitobenzene solution since doing so might lead
to oversaturation of the solids in one part of the solution only and might not result to
hydrazine being available for the nucleophilic aromatic substitution to take place.
As the nucleophilic hydrazine attacks the electrophilic aromatic ring, the chlorine
atom gets to play its role as the good leaving group. After going through with possible
resonance, the leaving group’s place then gets replaced by the nucleophile and
therefore forming the product. This reaction all happens in a reflux set up where heat
hastens the reaction and the condenser condenses all the evaporated product and
remaining reagents back to the round bottom flask.
*Insert mechanism here*
It could be observed that during reflux, the color of the solution changes from bright
to dark yellow and then to a darker red-orange color. This was expected since as the
reflux proceeds, more of the product is being produced and based on textbook
descriptions, the 2,4-dinitrophenylhydrazine product is of red color. It was then
confirmed that the formed precipitates after the reflux was cooled down was red in
color after suction filtration was done.
To cleanse the product of possible impurities, it was first washed with warm ethanol,
to free it from unreacted 1-chloro-2,4-dinitobenzene, and then with cold water, to
remove any remaining sodium sulfate and possible unreacted hydrazine sulfate. After
filtration, the retrieved residue was dried up near a heat source to hasten the drying
process and evaporate both water and ethanol off the product.
Characterization of a synthesized compound is always necessary after every synthesis
in order to verify if the retrieved product is indeed the wanted product. For this
exercise, melting point determination was done first through the oil bath method.
However, a low melting point range was observed as compared to the textbook
melting point of 2,4-dinitrophenylhydrazine. This could be due to impurities still
present in the product since recrystallization, which is another method of purification,
was no longer done in this exercise.
With the second method of characterization on the other hand, positive results were
retrieved. This characterization involves the reaction of the product with certain
carbonyl compounds. Since, when mixed with acids, the product becomes a reagent
used for determination of aldehydes and ketones, benzaldehydes and acetone were
used as test compounds.
The result is expected to be positive for both test compounds with both are carbonyl
compounds however, precipiates were expected to be formed but wasn’t observed in
the exercise. Again, this could be due to impurities present on the product and/or the
reagents used for this characterization method. Either way, a change in color resulting
to orange for aldehydes and dark yellow for ketones were observed.
The reflux set-up allows heat to hasten the reaction without losing a lot of the
compound through evaporation, since their vapor easily gets condensed back through
the condenser.
This hydrazine solution then gets added to a solution of 1-chloro-2,4-dinitrobenzene

and ethanol.
Acetates are water soluble therefore washing the product with cold water should
supposedly remove any acetate impurities.
In order to do this, hydrazine sulfate must first be dissolved in water to separate
hydrazine and sulfate in their ionic forms. Hydrazine is wanted because it plays an
essential role as the nucleophile for this SNAr reaction.
The exercise started off with the preparation of the hydrazine solution. As mentioned,
this acts as a nucleophile for this SNAr reaction due to its but 1
has a very important role in this exercise since it acts as the nucleophile needed for the
SNAr reaction to take place.
Application:
References:
http://pediaa.com/difference-between-electrophilic-and-nucleophilic-aromatic-
substitution/
http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch12/ch12-8d.html
https://crab.rutgers.edu/~alroche/Ch17.pdf
Dugal M. 2005. Nitrobenzene and nitrotoluenes.

GLu Chem 44.1 Exercise 1 Postlab

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Discussion:

The synthesis of 2,4-dinitrophenylhydrazine started off with the preparation of the

Insert reaction here

On a separate beaker, 1-chloro-2,4-dinitobenzene was dissolved with ethanol instead

Supposedly, aromatic compounds act as a nucleophile due to the pi electrons present

Insert mechanism here

This hydrazine solution then gets added to a solution of 1-chloro-2,4-dinitrobenzene

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