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Attempted Organic Synthesis of Two Nitrated Benzene Com-

Saylor E. Jessop; Langdon Martin, PhD

ABSTRACT: Synthesis of two benzene compounds to air dry overnight on a watch glass.
was attempted with bromobenzene as the starting
material. The initial intended product, 2-(para-nitro-
phenyl)-1-propene, was to be synthesized via nitra-
tion of bromobenzene followed by a Grignard reac-
tion with acetone and reaction with sulfuric acid to conc. Acid
produce the alkene. Upon multiple failed attempts at
getting the Grignard reaction to start, the intended
product was altered. The nitro group of para-
bromonitrobenzene was reduced using Sn-Cl2. 0.498
g of para-bromoaniline were isolated and confirmed Figure 1. Reaction of bromobenzene with concentrated
with NMR results after a purification. sulfuric acid and concentrated nitric acid to produce para-

Following successful synthesis of para-bromonitroben-

zene, the product was dissolved in approximately 20 mL
Synthesis has long played a significant role in the study of anhydrous ether and placed in a 250 mL RB flask along
of organic chemistry and can also be an economic and with 1.5 equivalents of magnesium turnings and an iodine
medical benefit. In this study, a synthesis of 2-para-nitro- crystal. Following the procedure from Reference 2, the
phenyl-1-propene was attempted using bromobenzene as mixture was stirred for several minutes and refluxed, with
the starting reagent. Bromobenzene underwent nitration no indication that the reaction was starting. A few drops
using concentrated sulfuric acid and nitric acid, followed of 1,2-dibromoethane were added in the hopes that the
by several attempts at a Grignard reaction with acetone. reaction would progress, with no success. Two more
The resulting intermediate was then going to be reacted Grignard reactions were attempted in similar conditions,
with sulfuric acid to remove the alcohol group and form altering magnesium concentrations and presence of io-
the alkene. When the Grignard reaction wouldnt start, the dine. The ether was also switched to a more anhydrous
target molecule was eventually altered. supply and the synthesized para-bromonitrobenzene was
The new target was started from para-bromonitroben- switched to a commercial supply. However, despite multi-
zene and the goal was to reduce the nitro group using a ple attempts, the reaction would not start. The scheme of
procedure with Sn-Cl2, followed by a reductive amination the attempted reaction can be seen in Figure 2.
with acetone to produce an isopropylamine group para to
the bromine on the benzene ring.
The first synthetic attempt was initiated using 2 mL of Mg Acetone
bromobenzene (19 mmol). The reagent was combined
with 4.0 mL (76 mmol) of concentrated sulfuric acid in a
25 mL round-bottom flask, following the procedure in Ref-
erence 1. The mixture was stirred and cooled in an ice
bath as 2 mL (31.2 mmol) of concentrated nitric acid was
Figure 2. Reaction of para-bromonitrobenzene with mag-
slowly added in a hood. The reaction was allowed to
nesium to form a Grignard reagent. Grignard reaction with
progress in the ice bath for ten minutes, followed by re-
acetone to produce intermediate.
moval and warming to room temperature. During this time,
a yellow solid formed in the RB flask that was isolated via
vacuum suction through a Hirsch funnel. The reaction
scheme for this procedure can be found in Figure 1. The
product was then recrystallized in methanol and allowed
Upon the third unsuccessful attempt at carrying out a RESULTS AND DISCUSSION
Grignard reaction, the target product was switched to
include a reductive amination instead of a Grignard reac- The initial nitration of bromobenzene yielded a total
tion. Approximately 3.0 g (14.85 mmol) of commercial mass of 0.403 g (1.995 mmol) of a whitish-yellow solid,
para-bromonitrobenzene was massed and dissolved in making for a percent yield of 10.5%. While this yield was
100 mL ethyl acetate following the procedure outlined in relatively low, there was still enough of the product to carry
Reference 3. This was combined with 5.6 g (24.82 mmol) out further reactions. However, the Grignard reaction that
of SnCl2-2H2O in a RB flask and allowed to react at ap- was attempted as the next step was not successful in
proximately 50C. The reaction scheme for the reductive starting and therefore yielded no product. During one at-
amination can be found in Figure 3. An 1H NMR was taken tempt, the nitration of bromobenzene was redone at a
of this product and can be found in Figure 4. Due to the higher scale and yielded 2.828 g of para-bromonitroben-
dissimilarity between the produced 1H NMR and the litera- zene (14 mmol), although this was still a relatively low per-
ture 1H NMR of para-bromoaniline, displayed in Figure 5, a cent yield at 9.2%. Even with a higher concentration of
purification process was undertaken. The purification in- alkyl bromide, the Grignard could not be initiated.
volved redissolving the product in ethyl acetate and ex- In the reduction of a nitro group using commercial para-
tracting it with two portions of 40 mL of 1 M HCl. This bromonitrobenzene as a starting material, 0.498 g (2.90
caused the Sn to precipitate out of the solution and an mmol) of product was isolated, making for a 19.5% yield.
additional extraction with 1M NaOH was performed to The product was a brown solid with a slightly sweet smell
remove the para-bromoaniline from the organic ethyl ac- and was determined to be the impure form of para-bro-
etate layer. During this process, the solution changed to a moaniline after a comparison of 1H NMR spectra. Follow-
bright pink and then a vibrant yellow, but only very small ing purification via extraction and another concentration
particles of a brown solid precipitated out of the solution with the rotovap, the mass of the product was 0.197 g
despite a highly basic pH. Finally, the solution was evapo- (1.15 mmol), for a final yield of 7.74%. The 1H NMR on this
rated off and an 1H NMR was performed on the final prod- purified product looked to be much closer to the literature
uct, which can be found in Figure 6. No further procedures 1H NMR for this compound, containing a downfield peak
were conducted due to time restraints. around 2 ppm that was absent in the 1H NMR of the un-
purified product.
Due to time constraints, only two reactions were suc-
cessfully carried out during the course of this synthesis
project: the nitration of bromobenzene and the reduction
of the nitro group in commercial para-bromonitrobenzene.

Figure 3. Reduction of nitro group in para-bromonitroben-

zene to para-bromoaniline.

Figure 4. 1H NMR spectra of unpurified product from the reduction of the nitro group in
Figure 5. Literature 1H NMR spectra of para-bromoaniline

Figure 6. 1H NMR spectra of purified para-bromoaniline from the reduction of the nitro
group in para-bromonitrobenzene
Despite several attempts, the intended products were not
successfully synthesized. Reaching the original product, 2-
(para-nitrophenyl)-1-propene, was obstructed by the failure of
the Grignard reaction to start. Future attempts at synthesizing
this molecule would perhaps include maintaining greater at-
tention to keeping the ether anhydrous and using a pure
para-bromonitrobenzene for the formation of the Grignard
reagent. It was also suggested that this molecule may just not
make an efficient substrate for this type of reaction.
The new target was also not fully completed, although the
nitro group on the para-bromonitrobenzene was successfully
reduced to form para-bromoaniline of a reasonable purity.
However, time constraints disallowed doing a melting point
analysis and the synthesis procedure could not be continued
to add an isopropyl group to the amine group of para-bro-
moaniline, which would have been carried out with acetone.
While disappointing that these synthetic targets could not be
fully reached, the experience was still a rewarding one and
involved a high level of independence, quick thinking, and
perseverance. A greater comfort level with standard organic
reactions and methodologies was also achieved.

I would like to thank Langdon Martin for his unending pa-
tience during this entire project. With every roadblock he was
there to provide answers and he juggled a dozen students at
once with grace. Thanks for an awesome year full of learning!

1. L. Martin. Electrophilic Aromatic Substitution: Synthesis
of a Bromonitrobenzene Isomer. 2015.
2. L. Martin. The Grignard Reaction: Synthesis of a Ter-
tiary Alcohol. 2016.

3. Common Organic Chemistry. Nitro Reduction: SnCl2.