Organic Chemistry III Laboratory 10

Identification of Unknown N/Preparation of Dinitrobenzene

Purpose:
To identify unknown compound N nitrobenzene, and from it synthesize
dinitrobenzene.
Observations:
Upon the addition of sulphuric acid, significant heat was generated.
Throughout the reaction temp was maintained between 60-70C. Nitrogen dioxide
gas is noted evolving from the solution. After reaction was complete and the
water was added immediately precipitating a vibrant yellow solid
(dinitrobenzene).
Results:
O
+

HNO 3 + H2SO4

Density: 1.196g/cm3
Molar Mass: 123.11/mol
Mass Used:
Moles:

Density: 1.368g/cm3
Molar Mass: 168.11/mol
Final Mass: 5.27g
Moles:

Experimental Boiling Point (Nitrobenzene): 209-211C

Experimental Melting Point (Dinitrobenzene): 88-90C

TLC:
TLC was run in 1:1 pet. ether:ether and developed by UV
light.
All spots appeared readily under UV light. Rf value for the
product was calculated using the bottom spot, since it
appears the yellow colour associated with the target
product.
(
(

)
)

Discussion:
The unknown compound (N) was determined to be nitrobenzene. This was
determined to be the case since proton NMR revealed only aromatic peaks, and the C13
NMR contained only three peaks between 120 and 140 these facts seem to contradict
one another unless one takes into account that a nitro substituent greatly dampens the
carbon it is attached to. The IR spectrum confirmed mono-substitution. The IR spectrum
seems to indicate the presence of a nitro group and lack a strong peak in the 6001000cm-1 range that would be indicative of a halogen (the only other potential
substituent that would not produce a proton NMR peak outside of the aromatics).
Qualitative descriptions of nitrobenzene match the unknown liquid, and boiling point
confirms its identity.
A second nitro group was added to the meta position on the ring, resulting in
dinitrobenzene via the following mechanism:

As shown, the reaction proceeds according to electrophilic aromatic

substitution, with the nitro substituent acting as a strong electron withdrawing group
causing the majority of product to be m-dinitrobenzene. According to literature, the
experimental yield is typically about 93% meta product, with ortho and para products
occurring at 6% and 1% yields, respectively. i TLC revealed four distinct spots, one was
characterized by the yellow colour associated with the product, and one matched the Rf
value of the starting reagent, nitrobenzene. It follows logic that the remaining two spot
are the ortho and para products. The C13 NMR contains clear evidence of the presence
of ortho product. The para product is likely also present, but in too small quantities for
the NMR to resolve.
After the reaction had gone to completion, a colourless solution remained. The
distinct yellow colour of dinitrobenzene was not observed until the solution was

quenched in ice water. This, it must have existed as an ion in solution which was
deprotonated by water as detailed in the final step of the mechanism.
Yield was 108% crude product, indicating some level of contamination. The OH
bend on the IR scan of the product was significantly more pronounced than expected
according to the reference spectra. It stands to reason that the crude product is not
entirely dry.
UV spectra of the product reveals an absorption tail running past 400nm to
almost 500nm (well into the violet region). This absorption must be responsible for the
vibrant yellow colour we perceive. The relation between absorption and our perception
of colour is clearly more complicated than what a basic analysis of the visible spectrum
might lead us to believe.
The product contains two electron withdrawing groups as opposed to one, this property
pulls electron density away from the aromatic ring, causing the position meta to both
substituents to be significantly less reactive. As a result, the product can be said to be
less energetic than the starting reagent.

Joachim Buddrus (2003). Grundlagen der organischen Chemie (3 ed.). Berlin: de Gruyter. p. 360.