Eco-friendly procedure for the synthesis of 4-(Phenylamino)pent-3-en-2-one using an heterogeneous catalyst – ZnCl2/Natural phosphate

https://doi.org/10.1016/j.matpr.2021.01.018Get rights and content

Highlights

  • A novel pathway for the synthesis of 4-(Phenylamino)pent-3-en-2-one (PAPO).

  • ZnCl2/Natural Phosphate a promising available, cheap, non-toxic, and reusable catalyst.

  • Mild conditions, high yield.

  • The reaction showed a good environmental profile.

Abstract

A new environmentally friendly synthesis of 4-(Phenylamino)pent-3-en-2-one has been developed by condensing aniline with acetylacetone using ZnCl2/Natural Phosphate. The effect of catalyst nature and mass, solvents, reaction time, and temperature on the yield were conducted. The results showed that the condensation reaction was carried out efficiently during 2 h at 35 °C in ethanol. The catalyst could be reused during two cycles without a significant loss in its activity.

To investigate the environmental performance of this synthesis, a set of green chemistry metrics has been determined such as atom economy (AE), reaction mass efficiency (RME), stoichiometric factor (SF), and material recovery parameter (MRP). At the same time, we considered the Green Star Metric including simultaneously all of the principles of green chemistry. It appeared from the results that the environmental performance has been significantly improved when recycling catalyst and solvent, however, the use of less hazardous reagents us well us a renewable raw material is highly recommended to further improve the safety and the greenness of the developed synthesis.

Introduction

4-(Phenylamino)pent-3-en-2-one (PAPO) or 4-Anilinopent-3-en-2-one (APO) belongs to β-enaminones known also as β-ketoenamines a very useful and widely used synthons in organic synthesis of aromatic and heterocyclic compounds [1]. Their broad fields of application are mainly due to their promising structural features, they combine the ambident nucleophilicity of enamines with the ambident electrophilicity of enones, indeed, PAPO can coordinate numerous metal ions to produce powerful catalysts widely used in organic synthesis [2], [3], [4]. PAPO can be also considered as versatile building blocks particularly in heterocyclic chemistry to produce diverse molecules designed for specific applications, such as phosphorus ylides compounds, widely used as precursors in many reactions to provide heterocyclic compounds, alkenes, and drugs [5], or to provide isothiazole derivatives with various biological and pharmacological properties [6], and for the synthesis of Pyrrole-4-one, an important structural skeleton widely present in biologically active substances and natural products [7].

Several methods have been reported for the synthesis of PAPO, but the condensation of aniline with acetylacetone in the presence of catalyst is one of the most preferred synthesis routes which is usually catalyzed by Bi(TFA)3 [8], SiO2-Cl [9], HClO4-SiO2 [10], Nano SiO2 [11], Cu(NO3)2·3H2O [12], Cu nanoparticles [13], Ag nanoparticles [14], CuO nanoparticles [15], Ag-Cu nanoparticles [16], Amberlyst-15 [17], montmorillonite K-10 [18], NbCl5, Fe(NO3)3·9H2O [19], Laccase [20], NbOPO4 [21], Onion Extract [22], Industrial-Quality Graphene Oxide (IQGO) [23], CoFe2O4 NPs [24], Diphenylammonium triflates (DPAT) [25], [(PPh3)AuCl]/AgOTf [26], Ag/γ-Fe2O3@meso-TiO2 [27], silica gel [28], P2O4/SiO2 [29], ZnO Nps [30], SbCl3/Al2O3 [31], Fe(OTf)3 [32], NiO [33], etc. These catalysts have shown their efficiency despite, in some cases, the high reaction time or the low yield recorded.

Due to the importance of this reaction, the need to develop other catalysts taking into consideration the availability of the raw material and the catalyst cost in addition to the catalytic performance is essential for possible industrial application [34]. Therefore, developing economically viable, eco-friendly heterogeneous catalysts is very attractive.

We report herein the use of natural phosphate (NP) as a solid catalyst for the synthesis of PAPO under heterogeneous conditions. NP represents an interesting material for a wide variety of catalytic applications due to its stability and its favorable intrinsic characteristics. The use of a very abundant natural resources as NP becomes particularly interesting because it is a non-toxic, inexpensive, mild, and environmentally benign catalyst.

To show the advantages and limitations of the developed procedure, we conducted an environmental assessment using two complementary tools, Green Chemistry metrics, and Green Star to quantify all twelve principles of green chemistry.

Section snippets

Preparation of catalyst (ZnCl2/NP)

Natural phosphate (NP) was prepared from a phosphate rock mined from khouribga deposit located in Morocco. NP is carried out by quartering, washing, and granulometric separation. The detailed procedure is described in our previous work [35]. The fraction of particle size 100–400 μm was isolated, calcined at 900 °C for 2 h and washed with water, recalcined again at 900 °C for 30 min, and finally crushed and sieved to <63 μm.

Supported ZnCl2 on natural phosphate was prepared by wet impregnation

FTIR spectrum analysis

The FTIR spectra of NP and ZnCl2/NP showed some changes due to the addition of ZnCl2 (Fig. 1), nevertheless, the general appearance of the NP spectrum has remained the same, this shows that the impregnation of NP with ZnCl2 did not modify the apatitic structure of NP. Nearly the same results were observed by Bazi et al. [36] who used ZnCl2/NP for the transesterification reaction, and also by Khatab et al. when comparing the IR spectrum of hydroxyapatite pure and doped with ZnCl2 [37].

The main

Conclusion

In this work, we have presented a novel pathway for the synthesis of 4-(Phenylamino)pent-3-en-2-one using zinc chloride supported on natural phosphate as heterogeneous catalyst. Reaction conditions have been optimized and showed that a maximum product yield of 88% was obtained by using 0.08 g of catalyst, ethanol as solvent, under 35 °C and during 2 h. The catalyst can be reused two times without significant loss in activity.

The Andraos algorithm was used to assess the environmental performance

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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