Journal of Chemical Sciences

, Volume 129, Issue 10, pp 1587–1594 | Cite as

Iron(II) and copper(II) phthalocyanine-catalyzed synthesis of 2-nitro-4-methylsulfonylbenzoic acid under mild conditions

Regular Article



A novel method was developed to produce 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) by oxygen catalyzed by iron(II) phthalocyanine (FePc) and copper(II) phthalocyanine (CuPc). The order of activity for oxidation of NMST was found to be: FePc > CuPc. Meanwhile, major reaction parameters such as concentrations of catalyst and NaOH, reaction temperature and oxygen pressure have been investigated. Through optimization of the reaction parameters, the highest yield of NMSBA and conversion of NMST (up to 53%, 89.3%, respectively) were achieved with oxygen (2.0 MPa), FePc (\(1.0\times 10^{-4}\,\hbox {mol } \hbox {L}^{-1}\)), NaOH (\(0.6\,\hbox {mol } \hbox {L}^{-1}\)), in methanol at 55\(^{\circ }\hbox {C}\) for 8 h. A plausible mechanism for this catalytic process is proposed which involved deprotonation and radical pathways.

Graphical Abstract

A novel method to produce 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) by oxygen catalyzed by iron(II) phthalocyanine (FePc) and copper(II) phthalocyanine (CuPc) has been developed. The reaction parameters and mechanism were studied. The catalytic system will be readily applicable to large-scale production of NMSBA.


2-Nitro-4-methylsulfonyltoluene 2-nitro-4-methylsulfonylbenzoic acid aero oxidation metal phthalocyanines 



We greatly acknowledge the financial support in part by the National Key Research and Development Program of China (2016YFB0301703), National Natural Science Foundation of China (21602106), Natural Science Foundation of Jiangsu Province-Outstanding Youth Foundation (BK20170104) and Industry-Academy-Research Prospective Joint Project of Jiangsu Province (BY2016005-06).


  1. 1.
    Mitchell G, Bartlett D W, Fraser T E M, Hawkes T R, Holt D C, Townson J K and Wichert R A 2001 Mesotrione: a new selective herbicide for use in maize Pest. Manag. Sci. 57 120CrossRefGoogle Scholar
  2. 2.
    Bigelow L A 1919 Side-chain oxidations with potassium pennanganate J. Am. Chem. Soc. 41 1559CrossRefGoogle Scholar
  3. 3.
    Partenheimer W 1995 Methodology and scope of metal/bromide autoxidation of hydrocarbons Catal. Today 23 69CrossRefGoogle Scholar
  4. 4.
    Shaikh T M A and Sudalai A 2008 WO\(_{3}\)/70% TBHP/aqueous NaOH: an efficient catalytic combination for the selective oxidation of methylarenes and alkyl aryl ketones to benzoic acids Eur. J. Org. Chem. 2008 4877CrossRefGoogle Scholar
  5. 5.
    Hirai N, Kagayama T, Tatsukawa Y, Sakaguchi S and Ishii Y 2004 Development of an efficient method for preparation of 1,3,5-trihydroxyisocyanuric acid (THICA) and its use as aerobic oxidation catalyst Tetrahedron Lett. 45 8277Google Scholar
  6. 6.
    Yang G Y, Zheng L W, Wu G H, Lin X S and Song M P 2007 Manganese dioxide and \(N\)-hydroxyphthalimide: an effective catalytic system for oxidation of nitrotoluenes with molecular oxygen Adv. Synth. Catal. 349 2445CrossRefGoogle Scholar
  7. 7.
    Partenheimer W 2011 Chemistry of the oxidation of acetic acid during the homogeneous metal-catalyzed aerobic oxidation of alkylaromatic compounds Appl. Catal. A: Gen. 409 48Google Scholar
  8. 8.
    Sorokin A B 2013 Phthalocyanine metal complexes in catalysis Chem. Rev. 113 8152CrossRefGoogle Scholar
  9. 9.
    Wan Y, Liang Q, Cong T T, Wang X Y, Tao Y Y, Sun M Y, Li Z Y and Xu S 2015 Novel catalyst of zinc tetraamino-phthalocyanine supported by multi-walled carbon nanotubes with enhanced visible-light photocatalytic activity RSC Adv. 5 66286CrossRefGoogle Scholar
  10. 10.
    Bata P, Demjén A, Notheisz F and Zsigmond Á 2012 Comparative study of immobilized phthalocyanines in oxidative degradation Open Catal. J. 5 50CrossRefGoogle Scholar
  11. 11.
    Song X F, She Y B, Ji H B and Zhang Y H 2005 Highly efficient, mild, bromide-free and acetic acid-free dioxygen oxidation of \(p\)-nitrotoluene to \(p\)-nitrobenzoic acid with metal phthalocyanine catalysts Org. Process. Res. Dev. 9 297CrossRefGoogle Scholar
  12. 12.
    Zhao X H, Kong A G, Shan C C, Wang P, Zhang X H and Shan Y K 2009 Highly efficient and green oxidation of nitrotoluenes with dioxygen as oxidant in a novel homogeneous and recyclable catalytic system Catal. Lett. 131 526CrossRefGoogle Scholar
  13. 13.
    Brown R W 1990 Preparation of 2-(chloro,bromo or nitro)-4-(alkylsulfonyl) benzoic acids as intermediates for herbicides WO patent 9006301Google Scholar
  14. 14.
    Hagen H 1995 Preparation of methylsulfonylbenzoic acids US patent 5424481Google Scholar
  15. 15.
    Jary W, Poechlauer P and Lassnig M 2004 Method for producing optionally substitutedbenzoic acids WO patent 058698Google Scholar
  16. 16.
    Cheng C S, Wei Z Y and Ma X H 2015 Synthesis of 2-nitro-4-methylsulfonylbenzoic acid Asian J. Chem. 27 3559CrossRefGoogle Scholar
  17. 17.
    Jacobson S and Ely W 1996 In New Air Oxidation Route to Ortho-nitroaromatic Acids Chemical Industries (New York: Marcel Dekker) p. 87Google Scholar
  18. 18.
    Long X L, Zhang C, Zhu Y, Yang Z L, Yuan W K and Yuan W K 2016 Production of NMSBA from the oxidation of NMST with oxygen catalyzed by \(\text{ H }_{3}\text{ PW }_{12}\text{ O }_{40}\)/Co/Mn/Br homogeneous catalytic system Chem. Eng. J. 286 361CrossRefGoogle Scholar
  19. 19.
    Berkowitz J, Ellison G B and Gutman D 1994 Three methods to measure RH bond energies J. Phys. Chem. 98 2744CrossRefGoogle Scholar
  20. 20.
    Wang K, Zhou Z M, Song J H, Bi L X, Shen N, Wu Y K, Chen F X and Wen H L 2010 A metal-free aerobic oxidation of nitrotoluenes catalyzed by N,N\(^{\prime }\),N\(^{\prime \prime }\)-trihydroxyisocyanuric acid (THICA) and a novel approach to the catalyst J. Hazard. Mater. 184 400Google Scholar
  21. 21.
    Sorokin A B, Buisson P and Pierre A C 2001 Encapsulation of iron phthalocyanine in sol–gel materials Microporous Mesoporous Mater. 46 87Google Scholar
  22. 22.
    Neumann R and Sasson Y 1985 The autoxidation of alkylnitroaromatic compounds in base-catalysed phase-transfer catalysis by polythylene glycol under ultrasonic radiation Chem. Commun. 0 616Google Scholar
  23. 23.
    Nam W, Lee H J, Oh S Y, Kim C and Jang H G 2000 First success of catalytic epoxidation of olefins by an electron-rich iron(III) porphyrin complex and \(\text{ H }_{2}\text{ O }_{2}\): imidazole effect on the activation of \(\text{ H }_{2}\text{ O }_{2}\) by iron porphyrin complexes in aprotic solvent J. Inorg. Biochem. 80 219CrossRefGoogle Scholar
  24. 24.
    Sehlotho N and Nyokong T 2004 Catalytic activity of iron and cobalt phthalocyanine complexes towards the oxidation of cyclohexene using tert-butylhydroperoxide and chloroperoxybenzoic acid J. Mol. Catal. A: Chem. 209 51Google Scholar
  25. 25.
    Meunier B 1992 Metalloporphyrins as versatile catalysts for oxidation reactions andoxidative DNA cleavage Chem. Rev. 92 1411CrossRefGoogle Scholar
  26. 26.
    Hashimoto T, Hirose D and Taniguchi T 2015 Catalytic aerobic oxidation of arylhydrazides with iron phthalocyanine Adv. Synth. Catal. 357 3346CrossRefGoogle Scholar
  27. 27.
    Zhou X T and Ji H B 2014 Highly efficient selective oxidation of sulfides to sulfoxides by montmorillonite-immobilized metalloporphyrins in the presence of molecular oxygen Catal. Commun. 53 29Google Scholar
  28. 28.
    Aktaş A, Acar İ, Saka E T and Biyiklioglu Z 2016 Synthesis of polyfluoro substituted Co(II), Fe(II) phthalocyanines and their usage as catalysts for aerobic oxidation of benzyl alcohol J. Organomet. Chem. 815-816 1CrossRefGoogle Scholar
  29. 29.
    Shaabani A, Keshipour S and Hamidzad M 2014 Cobalt(II) phthalocyanine covalently anchored to cellulose as a recoverable and efficient catalyst for the aerobic oxidation of alkyl arenes and alcohols J. Mol. Catal. A: Chem. 395 494Google Scholar

Copyright information

© Indian Academy of Sciences 2017

Authors and Affiliations

  1. 1.Department of Applied Chemistry, College of Chemistry and Molecular EngineeringNanjing Tech UniversityNanjingChina

Personalised recommendations