One-Step Synthesis of Picric Acid from Phenol

Full text of DOI:10.1080/00304948.2017.1291008

Organic Preparations and Procedures International
The New Journal for Organic Synthesis
ISSN: 0030-4948 (Print) 1945-5453 (Online) Journal homepage: http://www.tandfonline.com/loi/uopp20
One-Step Synthesis of Picric Acid from Phenol
Yuri G. Khabarov, Aleksandr A. Patrakeev, Viacheslav A. Veshnyakov, Dmitry
S. Kosyakov, Nikolay V. Ul'yanovskii & Anton Yu. Garkotin
To cite this article: Yuri G. Khabarov, Aleksandr A. Patrakeev, Viacheslav A. Veshnyakov, Dmitry
S. Kosyakov, Nikolay V. Ul'yanovskii & Anton Yu. Garkotin (2017) One-Step Synthesis of Picric
Acid from Phenol, Organic Preparations and Procedures International, 49:2, 178-181
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Date: 20 April 2017, At: 13:29

Organic Preparations and Procedures International, 49:178–181, 2017
Copyright Ó Taylor & Francis Group, LLC
ISSN: 0030-4948 print / 1945-5453 online
DOI: 10.1080/00304948.2017.1291008
OPPI BRIEF
One-Step Synthesis of Picric Acid from Phenol
Yuri G. Khabarov, Aleksandr A. Patrakeev, Viacheslav A.
Veshnyakov, Dmitry S. Kosyakov, Nikolay V. Ul’yanovskii,
and Anton Yu. Garkotin
Northern Arctic Federal University, Northern Dvina emb., 17, 163002,
Arkhangelsk, Russia
Picric acid (2,4,6-trinitrophenol) is widely used in industry. Picric acid is the starting
material for the synthesis of chloropicrin and picramic acid used in the synthesis of
1
dyes, medicines and other compounds and in studying the structure of metals. Picric
,2
3,4
5
6
acid exhibits relatively strong acidic properties (pK 0.42) and its salts (picrates) are
a
7
explosives.
Picric acid acts as an electron acceptor by electrostatic interactions. By hydrogen
bonding it forms molecular charge-transfer complexes with a number of electron-donor
8
–10
11–14
compounds such as aromatic hydrocarbons
and amines.
Complexes of picric acid
Picric acid is used to determine
reducing sugars. The application of picric acid for colorimetric determination of creati-
1
5,16
with aminophenols have antimicrobial properties.
1
7
1
8
19
20
nine, proteins and amino acids is based on the Jaffe reaction.
The synthesis of picric acid is carried out by several methods. Picric acid may be syn-
2
thesized by nitration of 2,4-dinitrophenol. As precursors in the synthesis of picric acid,
1
2
2
23,24
o- or p-nitrophenols and o- or p-phenolsulfonic acids
be prepared by the direct nitration of phenol in concentrated nitric acid. In this case, the
may be used. Picric acid can
2
5
high exothermic effect leads to phenol destruction and resinification and formation of
by-products. As a result, the yield of picric acid is low.
An increase in the yield and purity of the picric acid synthesized from phenol can be
achieved by changing the parameters of the medium. In this study, we report a simple one-
step synthesis of picric acid in an aqueous DMSO medium with high yield and high purity.
In preliminary studies, we were able to establish that the direct synthesis of picric
acid from phenol can be carried out by nitration with concentrated nitric acid in DMSO
with heating (Scheme 1). The conditions are so stringent that at the beginning of the reac-
tion, after 15 min of heating, phenol conversion is 100%, and mononitrophenols are
Received November 1, 2016; in final form December 14, 2016.
Address correspondence to Yuri G. Khabarov, Northern Arctic Federal University, Northern
Dvina emb., 17, 163002, Arkhangelsk, Russia. E-mail: khabarov.yu@mail.ru
178

One-Step Synthesis of Picric Acid from Phenol
179
detected in trace amounts. On the other hand nitration in aqueous DMSO avoids oxidation
reactions, so that the major products are only 2,4-dinitrophenol and picric acid. The quan-
tity of picric acid in the reaction mixture is gradually increased and after 4 h of heating
reaches 98.7%. Picric acid is precipitated (87%) from the reaction mixture by dilution
with ice-cold water. The isolated product was characterized by comparison of its IR spec-
tral data and melting point with those of an authentic sample. Elemental analysis of the
product conforms with its structure. The absence of sulfur in the product indicates that
the use of DMSO as reaction medium does not lead to contamination of the product dur-
ing isolation conditions. The mass spectrum of the isolated product has two monoisotopic
peaks corresponding to deprotonated molecules of picric acid and dinitrophenol (ESIMS:
m/z calculated for C H N O : 227.99; found: 227.99, m/z calculated for C H N O :
6
2
3
7
6 3 2 5
183.00; found: 183.00). Calculation of the relative intensities of their peaks shows that
the picric acid content is 99.97%.
Scheme 1
Experimental Section
In the research we used reagent grade commercial chemicals: phenol (freshly distilled,
ꢀ
boiling point 182 C), DMSO, concentrated nitric acid (63%), aqueous ammonia solution
(23%), ethanol (96%), picric acid and 2,4-dinitrophenol. Melting points were determined
on a Stuart melting point apparatus SMP30 using the standard open capillary method.
The IR spectrum was recorded on a Shimadzu FTIR-8400S spectrophotometer equipped
with a Pike Technologies MIRacle single reflection horizontal attenuated total reflection
accessory with a ZnSe crystal plate. Elemental analysis was performed on a EuroVector
EuroEA3000 CHNS-O elemental analyzer. ESI Mass spectra were recorded in negative
ion mode over the mass range of m/z 50–400 using an ABSciex TripleTOF 5600C hybrid
quadrupole time-of-flight mass spectrometer equipped with a DuoSpray ion source. For
the MS analysis of the reaction mixture, a 0.1 mL aliquot was neutralized with 1 mL of
aqueous ethanolic ammonia solution prepared by mixing equal volumes of aqueous
ammonia solution (23%) and ethanol (96%).
Picric Acid (2,4,6-Trinitrophenol). Safety warning: Picric acid (2,4,6-trinitrophenol)
is an explosive and may explode from heating, flame, friction or shocking. Adding concen-
trated nitric acid to a solution of phenol in DMSO is very exothermic and the mixture may
boil over. Therefore, the nitric acid should be added dropwise with careful cooling. Any
scale-up of this procedure would require diligent caution.
Phenol (0.5 g, 5.3 mmol) was dissolved in 1 mL of DMSO in a test tube and then
mL of 63% nitric acid (55.2 mmol) was slowly dropwise added to the solution with
4
cooling in ice-water bath. The mixture became brown. After gentle stirring, the dark
brown reaction mixture was heated under reflux in a boiling water bath for 4 h in the
hood. A deep brown gas was evolved and the color of the reaction mixture changed after

1
80
Khabarov et al.
1
.5–2 h heating from brown to yellow. The final reaction mixture was cooled in an
ice-water bath and diluted with a 4-fold volume of ice-cold water. The precipitate was
isolated by vacuum filtration, washed with ice-cold water and air dried to produce yellow
ꢀ
ꢀ
6
crystals, 1.059 g (87% yield), mp. 122 C (lit. mp. 122.5 C ). IR: 3105, 1630, 1607, 1526,
¡
1
429, 1339, 1312, 1177, 1148, 1087, 941, 918, 833, 783, 727, 702 cm . ESIMS: m/z
1
calculated for C H N O : 227.99; found: 227.99. Elemental analysis calculated for
6
2 3 7
C H N O : C, 31.45; H, 1.32; N, 18.34. Found: C, 31.39; H, 1.67; N, 18.16.
6 3 3 7
Acknowledgments
The study was performed using the equipment of the Core Facility Center “Arktika” of
Northern (Arctic) Federal University.
References
1
2
3
. Pat. 5383961 US, W. Bauer, G. Nagl, W. Steckelberg, J. Ritter and W. Mauelshagen, (1995).
. Pat. 5611818 US, M.J. Domingo, (1997).
. B.T. Fedoroff and O.E. Sheffield, “Encyclopedia of Explosives and Related Items”, Vol. 7,
p. 636, Picatinny Arsenal, Dover, NJ, 1975.
4. T. Urbanski, “Chemistry and technology of explosives”, Vol. 1, p. 647, Pergamon Press, New
York, NY, 1964.
5. D. Ferdian, M. Ariati and A. Norman, A. Met. Sci. Heat Treat., 55, 281 (2013).
6. D.R. Lide, “CRC Handbook of Chemistry and Physics”, p. 2661, CRC Press, Taylor & Francis,
Boca Raton, FL, 2007.
7. D. Srinivas, V.D. Ghuleb and K. Muralidharan, New J. Chem., 38, 3699 (2014).
8. A. Chandramohan, R. Bharathikannan, J. Chandrasekaran, P. Maadeswaran, R. Renganathan
and V. Kandavelu, J. Cryst. Growth., 310, 5409 (2008).
9. A. Chandramohan, R. Bharathikannan, M.A. Kandhaswamy, J. Chandrasekaran and Kandavelu
V, Cryst Res Technol., 43, 93 (2008).
1
1
1
0. A. Chandramohan, R. Bharathikannan, V. Kandavelu, J. Chandrasekaran and M.A. Kandhasw-
amy, Spectrochim. Acta A., 71, 755 (2008).
1. A. Chandramohan, R. Bharathikannan, M.A. Kandhaswamy, J. Chandrasekaran, R. Rengana-
than and V. Kandavelu, Cryst. Res. Technol., 43, 173 (2008).
2. R. Bharathikannan, A. Chandramohan, M.A. Kandhaswamy, J. Chandrasekaran, R. Rengana-
than and V. Kandavelu, Cryst. Res. Technol., 43, 683 (2008).
1
1
1
3. S. Anandhi, T.S. Shyju and R. Gopalakrishnan, J. Cryst. Growth., 312, 3292 (2010).
4. N. Singh and A. Ahmad, Can. J. Anal. Sci. Spectros., 54, 11 (2009).
5. A. Sheth, N. Doshi, D.J. Sen, R. Badmanaban and C.N. Patel, J. Chem. Pharm. Res., 2,
1
(2010).
16. T.S. Martins, A.A.S. Arauꢀjo, S.M. da Silva, J.R. Matos, P.C. Isolani and G. Vicentini, J. Solid
State Chem., 171, 212 (2003).
17. T.I.M.S. Lopes, A.O.S.S. Rangel, J.L.F.C. Lima and M.C.B.S.M. Montenegro, Anal. Chim.
Acta, 308, 122 (1995).

One-Step Synthesis of Picric Acid from Phenol
8. C. Slot, Scand J. Clin. Lab. Invest., 17, 381 (1965).
181
1
1
2
2
2
2
2
2
2
9. B.F. Gisin, Anal. Chim. Acta, 58, 248 (1972).
0. M. Jaffe, Zeitschrift f u€ r Analytische Chemie, 26, 121 (1887).
1. Pat. 82150 USSR, A.I. Titov and N.G. Laptev, (1949).
2. EP 0700894 A1, P. Metivier and L. Bernard, (1996).
3. Pat. RO 84186, R. Socolovschi, I. Duica and G. Pantau, (1984).
4. F. Olsen and J.C. Goldstein, Ind. Eng. Chem., 16, 66 (1924).
5. L. Ducry and D.M. Roberge, Angew. Chem., 117, 8186 (2005).
6. W.A. Schroeder, P.E. Wilcox, K.N. Trueblood and A.O. Dekker, Anal. Chem., 23, 1740 (1951).