Economical Synthesis of Nitrophenols under Controlled Physical Parameters
Economical Synthesis of Nitrophenols under Controlled Physical Parameters
DOI:
https://doi.org/10.53560/PPASA(59-2)615Keywords:
Phenol, Nitration, Nitrophenols, o/p-selectivity, Yield, EconomicalAbstract
Current studies were performed to find an economical path for the synthesis of nitrophenols which are plant growth regulators (PGR) and are applied to crops for better agricultural production. The study discourages the involvement of costly surfactants such as CTAB, TBAB, H-β and γ-alumina catalysts in commercial production of nitrophenols. This synthesis requires the lower number of chemicals, less time and does not involve the advance instruments. Phenol and its derivatives were selectively nitrated into o/p nitrophenols economically by controlling only the physical parameters, i.e., dilution of nitric acid, reaction time and reaction temperature. The synthesised products were characterised by RP-HPLC and gas chromatography. The reaction between 98% phenol and 32.5% nitric acid at a temperature of 20°C (±2°C) required only 1 hour for optimum yield (91%) of nitrophenols with 77% ortho and 14% para selectivity and was found to have the most suitable route for economical production. The investigated synthetic path is relatively clean and environmentally friendly as it does not involve catalysts and solvents, like the conventional processes. This process may be adopted for commercialisation and industrial level production of nitrophenols for agricultural purposes.
References
L.G. Nickell, Plant Growth Regulators. Chemical and Engineering News. 56(41): 18-34 (1978).
G.A. Olah., R. Malhotra and S.C. Narang, Nitration: methods and mechanisms, in Across Conventional Lines: Selected Papers of George A Olah Volume 2. 2003, World Scientific. p. 975-979.
B.S. Furniss, Vogel’s textbook of practical organic chemistry. 1989: Pearson Education India.
V. Anuradha., P. Srinivas., P. Aparna and J.M. Rao, p-Toluenesulfonic acid catalysed regiospecific nitration of phenols with metal nitrates. Tetrahedron letters. 47(28): 4933-4935 (2006).
C. Braddock, Award. Novel recyclable catalysts for atom economic aromatic nitration. Green Chemistry. 3(2): G26-G32 (2001).
J.H. Clark, Chemistry of waste minimisation. 2012: Springer Science & Business Media.
K. Holmberg, Organic reactions in microemulsions. Current opinion in colloid & interface science. 8(2): 187-196 (2003).
K. Smith., K. Fry., M. Butters and B. Nay, Para- selective mononitration of alkylbenzenes under mild conditions by use of benzoyl nitrate in the presence of a zeolite catalyst. Tetrahedron letters. 30(39): 5333-5336 (1989).
Y.V. Geletii., A.J. Bailey., J.J. Cowan., I.A. Weinstock and C.L. Hill, Highly efficient and stable catalyst for peroxynitrite decomposition. Canadian Journal of Chemistry. 79(5-6): 792-794 (2001).
A.I. Vogel, A text-book of practical organic chemistry including qualitative organic analysis. 2013: Longmans Green And Co; London; New York; Toronto.
T. Lopez., J. Moreno., R. Gomez., X. Bokhimi., J. Wang., H. Yee-Madeira., G. Pecchi and P. Reyes, Characterisation of iron-doped titania sol–gel materials. Journal of Materials Chemistry. 12(3): 714-718 (2002).
Z. Helwani., M. Othman., N. Aziz., J. Kim and W. Fernando, Solid heterogeneous catalysts for transesterification of triglycerides with methanol: a review. Applied Catalysis A: General. 363(1-2): 1-10 (2009).
R.P. Cheng., S.H. Gellman and W.F. DeGrado, β-Peptides: from structure to function. Chemical reviews. 101(10): 3219-3232 (2001).
Z. Xinqiang., H. Yantao., S. Xiaolei and W. Yanji, Structure and catalytic performance of H3PW12O40/SiO2 prepared by several methods. Chinese journal of catalysis. 28(1): 91-95 (2007).
M.A. Zolfigol., F. Shirini and A.G. Chogamarani, Silica chloride/NaNO2 as a novel heterogeneous system for the nitration of phenols under mild conditions. Phosphorus, Sulfur, and Silicon. 178(9): 2019-2025 (2003).
A. Khder and A. Ahmed, Selective nitration of phenol over nanosized tungsten oxide supported on sulfated SnO2 as a solid acid catalyst. Applied Catalysis A: General. 354(1-2): 153-160 (2009).
G. Sharma., K.L. Reddy., P.S. Lakshmi and P.R. Krishna, ‘In situ’Generated ‘HCl’-An Efficient Catalyst for Solvent-Free Hantzsch Reaction at Room Temperature: Synthesis of New Dihydropyridine Glycoconjugates. Synthesis. 2006(01): 55-58 (2006).
M.A. Bigdeli., M.M. Heravi and G.H. Mahdavinia, Wet cyanuric chloride catalysed simple and efficient synthesis of 14-aryl or alkyl-14-H-dibenzo [a, j] xanthenes. Catalysis Communications. 8(11): 1595- 1598 (2007).
N. Lankaster, liopis-Mestre, V. Chem. Commun. 2812 (2003).
D. Džober., D. Lankaster., M. Ivanji and S. Topalović, Prodaja i upravljanje prodajom. 2006: Clio.
K. Amani and F. Maleki, Catalytic effects of some Keggin-type heteropoly acids and polyoxometalates on selective nitration of phenols. Journal of the Iranian Chemical Society. 4(2): 238-243 (2007).
M.M. Heravi., K. Bakhtiari and F.F. Bamoharram, An efficient and chemoselective synthesis of acylals from aromatic aldehydes and their regeneration, catalysed by 12-molybdophosphoric acid. Catalysis Communications. 7(7): 499-501 (2006).
D.P. Sawant and S. Halligudi, Alkylation of benzene with α-olefins over zirconia supported 12-silicotungstic acid. Journal of Molecular Catalysis A: Chemical. 237(1-2): 137-145 (2005).
D. Alberico., M.E. Scott and M. Lautens, Aryl− aryl bond formation by transition-metal-catalysed direct arylation. Chemical reviews. 107(1): 174-238 (2007).
P.B. Arockiam., C. Bruneau and P.H. Dixneuf, Ruthenium (II)-catalysed C–H bond activation and functionalisation. Chemical reviews. 112(11): 5879- 5918 (2012).
V.S. Thirunavukkarasu., S.I. Kozhushkov and L. Ackermann, C–H nitrogenation and oxygenation by ruthenium catalysis. Chemical Communications. 50(1): 29-39 (2014).
N. Schröder. Wencel⁃ Delord J, Glorius FJ Am. In Chem. Soc. 2012.
M. Anand., R.B. Sunoj and H.F. Schaefer III, Non- innocent additives in a palladium (II)-catalysed C–H bond activation reaction: insights into multimetallic active catalysts. Journal of the American Chemical Society. 136(15): 5535-5538 (2014).
K. Gao., P.-S. Lee., T. Fujita and N. Yoshikai, Cobalt-Catalyzed Hydroarylation of Alkynes through Chelation-Assisted C− H Bond Activation. Journal of the American Chemical Society. 132(35): 12249-12251 (2010).
M. Harrison., M. Heal and J. Cape, Evaluation of the pathways of tropospheric nitrophenol formation from benzene and phenol using a multiphase model. Atmospheric Chemistry and Physics. 5(6): 1679-1695 (2005).
M.R. Heal., M.A. Harrison and N. Cape, Evaluation of the pathways of tropospheric nitrophenol formation from benzene and phenol using a multiphase model. (2005).
T. Umschlag., R. Zellner and H. Herrmann, Laser- based studies of NO 3 radical reactions with selected aromatic compounds in aqueous solution. Physical Chemistry Chemical Physics. 4(13): 2975-2982 (2002).
B. Barletta., E. Bolzacchini., S. Meinardi., M. Orlandi and B. Rindone, The NO3 radical-mediated liquid phase nitration of phenols with nitrogen dioxide. Environmental science & technology. 34(11): 2224-2230 (2000).
D. Vione., S. Belmondo and L. Carnino, A kinetic study of phenol nitration and nitrosation with nitrous acid in the dark. Environmental chemistry letters. 2(3): 135-139 (2004).
D. Vione., V. Maurino., C. Minero., M. Vincenti and E. Pelizzetti, Aromatic photonitration in homogeneous and heterogeneous aqueous systems. Environmental Science and Pollution Research. 10(5): 321-324 (2003).
B. Yuan., J. Liggio., J. Wentzell., S.-M. Li., H. Stark., J.M. Roberts., J. Gilman., B. Lerner., C. Warneke and R. Li, Secondary formation of nitrated phenols: insights from observations during the Uintah Basin Winter Ozone Study (UBWOS) 2014. Atmospheric Chemistry and Physics. 16(4): 2139-2153 (2016).
C.B. McPake., C.B. Murray and G. Sandford, Sequential Continuous Flow Processes for the Oxidation of Amines and Azides by using HOF MeCN. ChemSusChem. 5(2): 312-319 (2012).
J. Jacoway., G.N. Kumar and K.K. Laali, Aromatic nitration with bismuth nitrate in ionic liquids and in molecular solvents: a comparative study of Bi (NO3) 3• 5H2O/[bmim][PF6] and Bi (NO3) 3• 5H2O/1, 2-DCE systems. Tetrahedron Letters. 53(50): 6782-6785 (2012).
L. Ji., Z. Lin., M. Alcoutlabi and X. Zhang, Recent developments in nanostructured anode materials for rechargeable lithium-ion batteries. Energy & Environmental Science. 4(8): 2682-2699 (2011).
A. Lalitha and K. Sivakumar, Zeolite H‐Y– Supported Copper (II) Nitrate: A simple and effective solid‐supported reagent for nitration of phenols and their derivatives. Synthetic Communications. 38(11): 1745-1752 (2008).
A. Chhatre., R. Joshi and B. Kulkarni, Microemulsions as media for organic synthesis: selective nitration of phenol to ortho-nitrophenol using dilute nitric acid. Journal of colloid and interface science. 158(1): 183-187 (1993).
