CN113880698B

CN113880698B - Preparation method of 9, 10-dibutoxyanthracene

Info

Publication number: CN113880698B
Application number: CN202111294141.5A
Authority: CN
Inventors: 张雷雷; 杨波勇; 张伟; 郇利刚
Original assignee: Jinan Zhouxing Pharmaceutical Technology Co ltd
Current assignee: Jinan Zhouxing Pharmaceutical Technology Co ltd
Priority date: 2021-11-03
Filing date: 2021-11-03
Publication date: 2022-03-25
Anticipated expiration: 2041-11-03
Also published as: CN113880698A

Abstract

The invention discloses a preparation method of 9, 10-dibutoxyanthracene. In the method, anthraquinone reacts with n-butyryl chloride in the presence of sodium hydroxide and sodium hydrosulfite to obtain an intermediate M1, and the intermediate M1 is reduced by triethylsilane to prepare 9, 10-dibutoxyanthracene. Anthraquinone and n-butyl chloride are subjected to acylation reaction at a low temperature, impurities are controllable, a metal reducing agent for generating hydrogen is avoided, safety is guaranteed, and a target product of high-purity 9, 10-dibutoxyanthracene can be obtained by reduction with triethylsilane. The synthesis method of the invention has the advantages of simple operation, easily obtained raw materials, high product purity and high yield, and is suitable for industrial production.

Description

Preparation method of 9, 10-dibutoxyanthracene

Technical Field

The invention relates to a preparation method of 9, 10-dibutoxyanthracene, belonging to the technical field of medicines.

Background

The anthracene diether compound is an organic optical material, wherein 9, 10-dibutoxyanthracene is a representative compound and is used as a photoresist initiator. 9, 10-dibutoxyanthracene of the formula C₂₂H₂₆O₂Molecular weight: 322.44, the structural formula is as follows.

The presently disclosed synthetic methods, such as Seitz, Ulrich et al, disclose general methods for the preparation of anthracene diethers (Seitz, Ulrich; Daub,

synthesis 686-688 (1986)). The method takes anthracene diketone compounds as raw materials, adopts sodium hydrosulfite to reduce and prepare a sodium phenolate intermediate, and then carries out etherification reaction with halogenated hydrocarbon to prepare the anthracene diether compounds, and the halogenated hydrocarbon of the processThe etherification reaction is carried out with a modest conversion and yield, and the use of higher cost halides (e.g., methyl iodide).

CN 112939758A discloses a method for preparing 9, 10-dibutoxyanthracene, which is an organic optical material, by metal reduction, wherein anthraquinone or substituted anthraquinone, mixed metal powder, phase transfer catalyst, water, alkali solution and alkyl halide (bromobutane) are prepared into 9, 10-dibutoxyanthracene by a one-pot method, and the mixed metal powder adopted by the method for reduction is: zinc powder and other metal powders (tin powder, iron powder, aluminum powder or nickel powder). In the route, zinc powder and other metal powder are used for reduction, so that the safety is poor; the use of bromobutane is costly and results in a high target cost.

Disclosure of Invention

In order to solve the problems, the invention provides a novel preparation method of 9, 10-dibutoxyanthracene, which comprises the steps of reacting anthraquinone with n-butyryl chloride in the presence of sodium hydroxide and sodium hydrosulfite to obtain an intermediate M1, and reducing the intermediate M1 with triethylsilane to obtain the 9, 10-dibutoxyanthracene. Anthraquinone and n-butyl chloride are subjected to acylation reaction at a low temperature, impurities are controllable, a metal reducing agent for generating hydrogen is avoided, safety is guaranteed, and a target product of high-purity 9, 10-dibutoxyanthracene can be obtained by reduction with triethylsilane.

The technical scheme of the invention is as follows: a preparation method of 9, 10-dibutoxyanthracene is characterized in that anthraquinone (SM1) is used as a starting material, dichloromethane is used as a solvent, under the condition that sodium hydroxide aqueous solution and sodium hydrosulfite exist, butyryl chloride is dropwise added, the temperature is kept at 20-40 ℃ after dropwise adding for reaction, standing is carried out for layering after the reaction is finished, a water phase is removed, triethylsilane is dropwise added for reduction, the temperature is kept at 20-40 ℃ after dropwise adding for reaction, and the temperature is reduced for crystallization after the reaction is finished, so that 9, 10-dibutoxyanthracene (PP) is obtained.

The synthetic route is shown below.

Further, in the method, indium tribromide is used for catalyzing triethylsilane for reduction, and the using amount of the indium tribromide is 0.1-1.0% of the mass of the triethylsilane.

The molar ratio of the anthraquinone to the sodium dithionite to the butyryl chloride to the triethylsilane is 1 (1.5-2.5) to 2-3): (3-4), preferably the molar ratio is 1:2:2.5: 3.5.

Adding tetrabutyl ammonium bromide before adding sodium dithionite, wherein the dosage of tetrabutyl ammonium bromide is 0.1-1.0% of the molar weight of anthraquinone. The using amount of the sodium hydroxide is 5-10 times, preferably 8-9 times of the molar weight of the anthraquinone.

Preferably, after the butyryl chloride is added dropwise, the reaction is carried out for 1-3 h at the temperature of 30-35 ℃. And (3) after the triethylsilane is dripped, carrying out heat preservation reaction at 30-35 ℃ for 1-5 h, preferably 2-3 h.

The invention has the beneficial effects that:

1. anthraquinone and n-butyryl chloride are subjected to acylation reaction at low temperature, and impurities are controllable; the use of a metal reducing agent for generating hydrogen is avoided, and the safety is ensured. The target product of the 9, 10-dibutoxyanthracene with high purity can be obtained by reduction with triethylsilane.

2. The synthesis method is simple and convenient to operate, the used raw materials are easy to obtain, the product purity is high (more than or equal to 99.90%), the yield is high (about 90%), and the method is suitable for industrial production.

Drawings

FIG. 1 is a diagram of 9, 10-dibutoxyanthracene prepared in example 1¹H NMR chart;

FIG. 2 is a diagram of 9, 10-dibutoxyanthracene prepared in example 1¹³C NMR chart;

FIG. 3 is a mass spectrum of 9, 10-dibutoxyanthracene prepared in example 1.

Detailed Description

Example 1

Adding 20g of anthraquinone, 80g of dichloromethane, 110g of 30% sodium hydroxide solution and 0.2g of tetrabutylammonium bromide into a 500ml four-neck bottle, adding 32.9g of sodium dithionite into the system for 10 times for reaction, then controlling the temperature to be minus 5-5 ℃, starting to dropwise add 25.4g of butyryl chloride, after the dropwise addition is finished, preserving the temperature for reaction at 30-35 ℃ for 2 hours, standing for layering after the reaction is finished, removing an aqueous phase, and drying sodium sulfate. Then adding 0.34g of indium tribromide into the feed liquid, dropwise adding 40g of triethylsilane, carrying out heat preservation reaction at 30-35 ℃ for 3 hours, cooling to 5-15 ℃ after the reaction is finished, carrying out crystallization for 1-1.5 hours, carrying out suction filtration to obtain a wet product, carrying out forced air drying at 40-45 ℃ for 2-3 hours to obtain a finished product 28.2g, and obtaining the yield: 91.10% and the purity is 99.92%.

H NMR of the product,¹³The C NMR and mass spectra are shown in FIGS. 1 to 3, respectively.

MS⁺/M＝322。

¹H NMR(400MHz,CDCl₃,300K):δ(ppm)＝8.37-8.34(m,4H),7.53-7.50(m,4H),4.22(t,J＝6.6Hz,4H),2.12-2.05(m,4H),1.80-1.71(m,4H),1.13(t,J＝7.5,6H)。

¹³C NMR(101MHz,CDCl₃,300K):δ(ppm)＝147.5,125.1,125.1,122.7,75.8,32.7,19.5,14.1。

Example 2

Adding 20g of anthraquinone, 100g of dichloromethane, 100g of 30% sodium hydroxide solution and 0.15g of tetrabutylammonium bromide into a 500ml four-neck bottle, adding 32g of sodium dithionite into the system for 10 times for reaction, then controlling the temperature to be minus 5-5 ℃, starting dropwise adding 30.5g of butyryl chloride, after dropwise adding, preserving the temperature for 30-35 ℃ for reaction for 1.5h, after the reaction is finished, standing for layering, removing a water phase, and drying sodium sulfate. Then adding 0.30g of indium tribromide into the feed liquid, dropwise adding 39g of triethylsilane, carrying out heat preservation reaction at 30-35 ℃ for 2.5h, cooling to 5-15 ℃ after the reaction is finished, carrying out crystallization for 1-1.5 h, carrying out suction filtration to obtain a wet product, and carrying out forced air drying at 40-45 ℃ for 2-3 h to obtain a finished product 27.6g, wherein the yield is as follows: 89.14 percent and the purity is 99.95 percent.

Example 3

Adding 20g of anthraquinone, 90g of dichloromethane, 100g of 30% sodium hydroxide solution and 0.25g of tetrabutylammonium bromide into a 500ml four-neck bottle, adding 33g of sodium dithionite into the system for 10 times for reaction, then controlling the temperature to be minus 5-5 ℃, starting to dropwise add 23.4g of butyryl chloride, keeping the temperature at 30-35 ℃ after dropwise adding is finished, reacting for 2 hours, standing for layering after the reaction is finished, removing a water phase, and drying sodium sulfate. Then adding 0.32g of indium tribromide into the feed liquid, dropwise adding 41g of triethylsilane, carrying out heat preservation reaction at 30-35 ℃ for 2 hours, cooling to 5-15 ℃ after the reaction is finished, carrying out crystallization for 1-1.5 hours, carrying out suction filtration to obtain a wet product, and carrying out forced air drying at 40-45 ℃ for 2-3 hours to obtain a finished product 27.3g, wherein the yield is as follows: 88.32% and the purity is 99.92%.

Claims

1. A preparation method of 9, 10-dibutoxyanthracene is characterized in that anthraquinone is used as a starting material, dichloromethane is used as a solvent, under the condition that sodium hydroxide aqueous solution and sodium hydrosulfite exist, butyryl chloride is dripped, the temperature preservation reaction is carried out at 20-40 ℃ after the dripping is finished, standing and layering are carried out after the reaction is finished, a water phase is removed, triethylsilane is dripped for reduction, the temperature preservation reaction is carried out at 20-40 ℃ after the dripping is finished, and the temperature is reduced and crystallization is carried out after the reaction is finished, so that 9, 10-dibutoxyanthracene is obtained;

indium tribromide is adopted to catalyze triethylsilane for reduction, and the usage amount of the indium tribromide is 0.1-1.0% of the mass of the triethylsilane;

adding tetrabutyl ammonium bromide before adding sodium dithionite, wherein the dosage of the tetrabutyl ammonium bromide is 0.1-1.0% of the molar weight of the anthraquinone.

2. The method for preparing 9, 10-dibutoxyanthracene according to claim 1, wherein the molar ratio of anthraquinone, sodium dithionite, butyryl chloride and triethylsilane is 1 (1.5-2.5) to (2-3): (3-4).

3. The method for preparing 9, 10-dibutoxyanthracene according to claim 1, wherein the amount of sodium hydroxide is 5 to 10 times the molar amount of anthraquinone.

4. The method for preparing 9, 10-dibutoxyanthracene according to claim 1, wherein the reaction is carried out at 30-35 ℃ for 1-3 hours after the addition of butyryl chloride.

5. The method for preparing 9, 10-dibutoxyanthracene according to any one of claims 1 to 4, wherein the reaction is carried out with an incubation at 30 to 35 ℃ for 1 to 5 hours after the addition of triethylsilane.