One-step synthesis method of 1-benzoylpyrene

Abstract

The invention discloses a method for synthesizing an organic synthesis intermediate compound 1-benzoylpyrene having high yield and high selectivity through the catalytic Friedel-Crafts acylation reaction of condensed aromatic pyrene and benzoic anhydride by using cheap, accessible and hydrostable aluminum phosphotungstate and supported aluminum phosphotungstate as a catalyst and using non-polar solvent 1,2-dichloroethane as solvent. The 1-benzoylpyrene is widely used in multiple fields such as medicine, pesticide, dye and the like. The method is simple in reaction, convenient to operate, short in reaction time, low in reaction temperature, low in energy consumption and satisfactory in catalyst reusability, thus conforming to the requirements for greenness and environmental protection in the world at present.

Description

technical field [0001] The invention relates to a method for synthesizing 1-benzoylpyrene by using Friedel-Crafts acylation reaction, using aluminum phosphotungstate and loaded aluminum phosphotungstate as catalysts respectively. Background technique [0002] Aromatic ketones, as important organic synthesis intermediates, are widely used in the synthesis of medicines, pesticides, dyes, plastics, and cosmetics; 3 , FeCl 3 、TiCl 4 etc.) or Brfnsted acids (HF, H 2 SO 4 , HCl, etc.) catalyzed by the Friedel-Crafts acylation reaction of acylating reagents (mainly acyl halides) and aromatic hydrocarbons or the Fries rearrangement of aryl esters; in traditional acylation reactions, catalysts are often excessive, leading to industrial The more serious "three wastes" problem occurs in post-processing, and the equipment corrosion is serious during the production process; therefore, look for green catalysts with low catalytic content, environmental friendliness, cheap, easy recycli...

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Problems solved by technology

[0002] Aromatic ketones, as important organic synthesis intermediates, are widely used in the synthesis of medicines, pesticides, dyes, plastics, and cosmetics; 3 , FeCl 3 、TiCl 4 etc.) or Brfnsted acids (HF, H 2 SO 4 , HCl, etc.) catalyzed by the Friedel-Crafts acylation reaction of acylating reagents (mainly acyl halides) and aromatic hydrocarbons or the Fries rearrangement of aryl esters; in traditional acylation reactions, catalysts are often excessive, leading to industrial The more serious "three wastes" problem occurs in post-processing, and the equipment corrosion is serious during the production process; therefore, look for green catalysts with low catalytic content, environmental friendliness, cheap, easy recycling, and reusability, and use carboxylic acids or acid anhydrides instead of acid halides As an acylating reagent, it becomes the development trend of this reaction

[0003] As a new type of green and environment-friendly acid catalyst, heteropolyacid has the advantages of strong acidity and high activity, and has attracted the attention of extensive researchers. Difficult product separation, small specific surface area (l-10m 2 Inadequacies such as / g) have limited its application in acid-catalyzed reactions to a certain extent, thus it is difficult to bring into play its catalytic performance better; Immobilization on porous supports can improve its catalytic performance, separate and recover catalysts, and reduce production costs

[0004] The properties of Keggin-type heteropolyacids depend on the type of cations. Type A salts with relatively small cations have similar properties to bulk heteropolyacids: they are easily soluble in water and have a low specific surface area. On the contrary, B salts with larger cations Class B salts are not easily soluble in water, have a large specific surface area and relatively high thermal stability; in view of this, B class salts with larger cations have been widely studied and have been used in various catalytic reactions, while A class salts There are few studies. Habib Firouzabadi et al. (Tetrahedron Letters 44 (2003) 5343-5345) studied the acylation reaction of arenes and carboxylic acids catalyzed by aluminum phosphotungstate in the presence of trifluoroacetic anhydride, with mild reaction conditions, The reaction time is short and the yield of the product is high, but this process adds a relatively expensive reagent trifluoroacetic anhydride to remove the water generated during the reaction; in addition, the research team of this subject also studied phosphotungstic acid Aluminum catalyzes the acylation reaction of aromatic hydrocarbons and carboxylic acids. Although the yield of the product is high, the reaction temperature is high and the energy consumption is high (Tetrahedron 60 (2004) 10843-10850); It has similar properties to bulk phosphotungstic acid, and there must be certain defects in some acid-catalyzed reactions; some researchers have studied the loading of aluminum phosphotungstic acid on porous supports to improve its catalytic performance, Ch. Ramesh Kumar et al. ( Journal of Molecular Catalysis A: Chemical 350 (2011) 83- 90) studied the benzylation reaction of anisole and benzyl alcohol catalyzed by titanium dioxide-supported aluminum phosphotungstate. The experimental results showed that the catalyst showed good catalytic effect, and the reaction process No leaching of active ingredients occurs in

[0005] At present, the research on the Friedel-Crafts acylation reaction of aromatic hydrocarbons mainly focuses on benzene, naphthalene and their derivatives. There are also a small number of literature reports on condensed ring aromatic hydrocarbons such as anthracene, phenanthrene, pyrene, etc., but for aluminum phosphotungstate (AlPW 12 o 40 ) and supported aluminum phosphotungstate catalyzed the acylation reaction of pyrene and benzoic anhydride to synthesize 1-benzoylpyrene. After reviewing the literature, there is no report at home and abroad

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