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

Huang, Cheng Liang; Liu, Rui; Zhang, Caiting; Cheng, Qipeng

doi:10.1007/s12039-017-1373-4

Cited by 9 publications

(5 citation statements)

References 26 publications

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“…The authors stated that the catalytic system is suitable for oxidizing both electron-donating and electron-withdrawing substituted toluene derivatives and no significant loss of catalytic activity and selectivity was observed during the reusability and recyclability assays. The importance of developing sustainable conditions to obtain the 2-nitro-4-methylsulfonylbenzoic acid (NMSBA), a key intermediate in the synthesis of the cornfield herbicide mesotrione, prompted Liu and Zhu [78] to evaluate the efficiency of the Fe(II) and Cu(II) complexes of phthalocyanine, Fe(II)Pc and Cu(II)Pc (Figure 2) in the aerobic oxidation of the precursor 2-nitro-4-methylsulfonyltoluene (NMST) (Figure 29).…”

Section: Figure 24mentioning

confidence: 99%

“…A plausible mechanism for this catalytic process was proposed, which involved deprotonation and radical pathways. The importance of developing sustainable conditions to obtain the 2-nitro-4-methylsulf onylbenzoic acid (NMSBA), a key intermediate in the synthesis of the cornfield herbicide mesotrione, prompted Liu and Zhu [78] to evaluate the efficiency of the Fe(II) and Cu(II) complexes of phthalocyanine, Fe(II)Pc and Cu(II)Pc (Figure 2) in the aerobic oxidation of the precursor 2-nitro-4-methylsulfonyltoluene (NMST) (Figure 29).…”

Section: Figure 24mentioning

confidence: 99%

“…Epoxidation of different olefins using Co(II)Pc(SO3 − )4@-Zn2Al-LDH as catalyst[78] *. Reaction conditions: substrate 2 mmol; catalyst 6 mg; IBA 5 mmol; acetonitrile 8 mL; O2 15 mL/min; temperature 60 °C.…”

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Metallophthalocyanines as Catalysts in Aerobic Oxidation

et al. 2021

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The first remarkable property associated to metallophthalocyanines (MPcs) was their chemical “inertness”, which made and make them very attractive as stable and durable industrial dyes. Nevertheless, their rich redox chemistry was also explored in the last decades, making available a solid and detailed knowledge background for further studies on the suitability of MPcs as redox catalysts. An overlook of MPcs and their catalytic activity with dioxygen as oxidants will be discussed here with a special emphasis on the last decade. The mini-review begins with a short introduction to phthalocyanines, from their structure to their main features, going then through the redox chemistry of metallophthalocyanines and their catalytic activity in aerobic oxidation reactions. The most significant systems described in the literature comprise the oxidation of organosulfur compounds such as thiols and thiophenes, the functionalization of alkyl arenes, alcohols, olefins, among other substrates.

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Section: Figure 24mentioning

confidence: 99%

Section: Figure 24mentioning

confidence: 99%

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Metallophthalocyanines as Catalysts in Aerobic Oxidation

et al. 2021

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“…The low yield of NMSBA prevented that method from being applied commercially. Huang et al [ 7 ] used NMST as raw material, oxygen as oxidant, mixed reagent of methanol and sodium hydroxide as the solvent, and FePc or CuPc as catalyst to prepare NMSBA at 55°C and 2.0 MPa for 8 h. The NMST conversion was 89.3% and the NMSBA yield was only 53.0%. Methanol is expensive as a solvent and is liable to be oxidized in the reaction process.…”

Section: Introductionmentioning

confidence: 99%

Production of NMSBA from the oxidation of NMST in the homogeneous Co/Mn/Br/H₃PMo_xW_12−xO₄₀ catalytic system

et al. 2023

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2-nitro-4-methylsulphonylbenzoic acid (NMSBA) is an important intermediate for the preparation of the highly effective herbicide mesotrione. NMSBA is produced from the oxidation of 2-nitro-4-methylsulphonyltoluene (NMST) by nitric acid commercially, which suffers from the serious problems of low yield and heavy pollution. In this paper, a homogeneous system consisting of Co/Mn/Br/ Á H 3 PMo x W 12Àx O 40 has been applied to catalyze the production of NMSBA by oxidizing NMST with oxygen in acetic acid. The experiments indicate that the best value of x in the phosphomolybdenum tungsten heteropoly acid is 3. The optimum composition of this catalyst system is 1163 ppm H 3 Pmo 3 W 9 O 40 Á 12.17H 2 O, 247.5 ppm Co, 453.5 ppm Mn, and 1075 ppm Br. Such a catalytic system is able to achieve a NMST conversion of 94.93% and a NMSBA selectivity of 99.84%. H 3 PMo 3 W 9 O 40 exceeds both H 3 PMo 12 O 40 and H 3 PW 12 O 40 as a catalyst in the production of NMSBA from the oxidation of NMST by oxygen. K E Y W O R D S 2-nitro-4-methylsulphonylbenzoic acid, 2-nitro-4-methylsulphonyltoluene, catalytic oxidation, phosphomolybdenum tungsten heteropoly acid

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“…Jacobson 6 proposed preparing NMSBA with NMST as raw material, acetic acid as solvent, cobalt acetate (II) tetrahydrate as catalyst, acetaldehyde as accelerator, and oxygen as oxidant at 6.2 MPa. Huang et al 7 oxidized NMST to NMSBA by oxygen with methanol as solvent and metal phthalocyanine as catalyst. The metal phthalocyanine is unstable due to its poor antioxidant capacity and easy polymerization.…”

Section: Introductionmentioning

confidence: 99%

Production of NMSBA catalyzed by Co/Mn/Br together with the porous carbon made from coconut shell with ZnCl₂ as activator

Wang

Yang

Guo

et al. 2022

J of Chemical Tech & Biotech

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BACKGROUND 2‐nitro‐4‐methylsulfonylbenzoic acid (NMSBA) is commercially produced from the oxidation of 2‐nitro‐4‐methylsulfonyltoluene (NMST) with nitric acid as oxidant and V2O5 as catalyst in a strong acid solution; this process suffers from the following shortcomings: the discharge of large amounts of wastewater and waste gas, as along with the generation of polynitro compounds. It is necessary to develop a technology to avoid the pollution caused by oxidizing NMST with nitric acid. NMSBA can be synthesized by oxidizing NMST with air under the catalysis of the porous carbon made from coconut shell with ZnCl2 as an activator together with Co/Mn/Br. RESULTS The optimum conditions for the preparation of the porous carbon are as follows: impregnation temperature 60 °C, ZnCl2 concentration 0.50 mol L−1, impregnation duration 6 h, carbonization temperature 600 °C, and carbonization time 4 h. The surface characterization suggests that the carbon made in this study holds smaller surface area, acidic groups, and basic groups than the commercial carbon but owns more carboxyl. CONCLUSION The Co/Mn/Br/AC (AC,the porous carbon made in this study) catalytic system is superior to the Co/Mn/Br/H3PMo12O40@CAC(CAC,commercial activated carbon) catalytic system in the production of NMSBA from the oxidation of NMST. The NMSBA selectivity gained by the former is 93.40%, while that gained by the latter is 87.14%. The former can cut down the consumption of NMST and the expenditure of catalysts. The catalytic ability of the AC catalyst relies on its surface chemical characteristics and physical properties. More carboxyl on AC is the reason for the upgrade of NMSBA selectivity. © 2022 Society of Chemical Industry (SCI).

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

Cited by 9 publications

References 26 publications

Metallophthalocyanines as Catalysts in Aerobic Oxidation

Metallophthalocyanines as Catalysts in Aerobic Oxidation

Production of NMSBA from the oxidation of NMST in the homogeneous Co/Mn/Br/H₃PMo_xW_12−xO₄₀ catalytic system

Production of NMSBA catalyzed by Co/Mn/Br together with the porous carbon made from coconut shell with ZnCl₂ as activator

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

Cited by 9 publications

References 26 publications

Metallophthalocyanines as Catalysts in Aerobic Oxidation

Metallophthalocyanines as Catalysts in Aerobic Oxidation

Production of NMSBA from the oxidation of NMST in the homogeneous Co/Mn/Br/H3PMoxW12−xO40 catalytic system

Production of NMSBA catalyzed by Co/Mn/Br together with the porous carbon made from coconut shell with ZnCl2 as activator

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Production of NMSBA from the oxidation of NMST in the homogeneous Co/Mn/Br/H₃PMo_xW_12−xO₄₀ catalytic system

Production of NMSBA catalyzed by Co/Mn/Br together with the porous carbon made from coconut shell with ZnCl₂ as activator