Elsevier

Journal of Organometallic Chemistry

Volume 895, 1 September 2019, Pages 48-54
Journal of Organometallic Chemistry

(E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)Substituted Co(II) and Cu(II) phthalocyanines and their catalytic activities on the oxidation of phenols

https://doi.org/10.1016/j.jorganchem.2019.05.012Get rights and content

Highlights

  • Synthesis of (E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)Substituted Co(II) and Cu(II) Phthalocyanines.

  • Determination of catalytic activities of Co(II) and Cu(II) phthalocyanines on oxidation of phenols.

  • Different parameters influenced the oxidation process were determined.

Abstract

Phenols from various man-made activities pose threats to public health and aquatic ecosystems. A number of technologies (e.g., adsorption, oxidation, and biological methods) have been proposed and tested to remove phenolic compounds from different sources. Among these technologies, oxidation process is considered one of the most efficient tools for abating phenolic compounds because of low cost, easy scalability, and ecofriendly production. In this work, we aim to synthesize and characterize potential catalysts (Co(II) and Cu(II) phthalocyanines 6 and 7) for phenolic compounds oxidation. Different parameters influenced the oxidation process were determined and phenolic compounds oxidize to the less harmful products with high conversion and yield in the presence of Co(II) and Cu(II) phthalocyanine catalysts.

Introduction

Phenolic compounds are widely used in different industries including paints, fertilizers, surfactants, explosives, textiles, rubbers, plastics, curing agents, and antioxidants [1]. The exposure to phenols and its derivatives poses a serious problem to the human being as well as to the environment, due to which they are tagged as hazardous and top priority pollutants. Phenolic wastewater has carcinogenic, teratogenic and mutagenic influences on the growth and reproduction of aquatic organisms and contaminates drinking water sources [2,3]. Phenolic compounds are classified by the US Environmental Protection Agency as priority pollutants and negatively affect the taste and odor of water in concentrations as low as 0.5 mg/L. Additionally, they can be easily absorbed through skin contact, potentially acting as potent endocrine disruptors [4,5].

Metal phthalocyanines (MPcs) are very useful and versatile class of organic chromophores. Both unsubstituted and substituted phthalocyanines of transition metals are widely used as active layers of chemical sensors [[6], [7], [8]]. Introduction of electron donating or withdrawing substituents to phthalocyanine macrocycles has been shown to change the activity of MPcs to various substrates due to modification of both the electronic distribution in the aromatic macrocycle and the molecule energetic levels [[9], [10], [11], [12]]. Electron withdrawing fluorine substituents decrease the electron density of the aromatic macrocycle and increase the oxidation potential of the MPc molecule [[9], [10], [11], [12]]. This makes the fluorosubstituted phthalocyanines more active to the reducing different pheonls [13]. Cobalt phthalocyanine (CoPc), which is constituted by a cobalt atom located in the central cavity of a two-dimensional structure consisting of 18-π electron aromatic macrocycle, has attracted great interests as a catalyst because of its remarkable chemical properties and thermal stability [[14], [15], [16]]. Because of these reasons, we choosed fluorine groups to synthesize Co(II) and Cu(II) phthalocyanines.

Some previously reported catalysts are summarized in Table 1. Different peripherally groups substituted cobalt(II), iron(II), manganese(III), copper(II) phthalocyanines were investigated on 2,6-di-tert-buthylphenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, 2,3,6-trimethylphenol and p-nitrophenol oxidation [[17], [18], [19], [20], [21], [22], [23], [24]]. In Table 3, tetrasulfonated iron phthalocyanine was used in trichlorophenol oxidation reaction with H2O2 oxygen source. In the same work, 24% reaction conversion was obtained 24 h at 25 °C. According to Table 3, two oxidation works with H2O2 oxygen source were carried out tetrasulfonated cobalt phthalocyanine and octacationic iron phthalocyanine catalyst. The former employees 2,4,5 trichlorophenol oxidation reaction 24 h at 75 °C with 67% conversion and the latter was used trichlorophenol oxidation reaction 10 min at 25 °C with 6% conversion. By comparing the catalyst in these literatures, it is inferred that the compound 6 will be interesting catalyst in 2,3-dichlorophenol oxidation. In our previous work, tetrasubstituted Co(II) and Fe(II) phthalocyanine complexes were studied as catalyst in the oxidation of phenolic compounds [[25], [26], [27], [28], [29], [30], [31]]. In this work, firstly (2E)-3-[2-fluoro-5-(trifluoromethyl)phenyl]-1-(4-hydroxyphenyl)prop-2-en-1-one 3, (E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)phthalonitrile 5 and then cobalt(II) 6 and copper(II) 7 phthalocyanines have been synthesized and characterized with spectral data (IR, 1H NMR, 13C NMR, UV–Vis, mass spectroscopies). Secondly, oxidation of different phenolic compounds (4-nitrophenol, 3-chlorophenol, 2,3-dichlorophenol, 3-methoxyphenol) was chosen as the model reaction to study the catalytic activity of the synthesized Co(II) and Cu(II) phthalocyanines.

Section snippets

Experimental

The used materials, equipments and the general procedure for the oxidation of phenolic compounds were reported as supplementary information.

Synthesis and characterisation

All synthetic routes for (2E)-3-[2-fluoro-5-(trifluoromethyl)phenyl]-1-(4-hydroxyphenyl)prop-2-en-1-one (3), (E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy)phthalonitrile (5) and Co(II) and Cu(II) phthalocyanines (7 and 8) were shown in Fig. 1. At the first step of the work (2E)-3-[2-fluoro-5-(trifluoromethyl)phenyl]-1-(4-hydroxyphenyl)prop-2-en-1-one (chalcone) was prepared with the Claisen-Schmidt consendation of 4′-hydroxyacetophenone and

Conclusion

In conclusion, tetra substituted phthalocyanine complexes 6 and 7 bearing (E)-4-(4-(3-(2-fluoro-5-(trifluoromethyl)phenyl)acryloyl)phenoxy) units were designed and synthesized. In order to verify these novel products 35, a combination of spectral techniques such as MALDI–TOF mass spectral data, UV–Vis, FT–IR, 1H NMR and 13C NMR was used. MPcs 6–7 are highly soluble in most of the organic solvents and the catalytic activity of CoPc 6 was examined for the oxidation of 2,3-dichlorophenol using

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