CN116283538A

CN116283538A - Preparation method of 9-phenanthrenecarboxylic acid

Info

Publication number: CN116283538A
Application number: CN202310206623.3A
Authority: CN
Inventors: 梅姜平; 张永飞; 陆金华
Original assignee: Wuxi Hailun Biotechnology Co ltd
Current assignee: Wuxi Hailun Biotechnology Co ltd
Priority date: 2023-03-06
Filing date: 2023-03-06
Publication date: 2023-06-23

Abstract

The invention relates to the technical field of organic chemistry, and discloses a preparation method of 9-phenanthrene formic acid, which comprises the following steps: taking phenanthrene as a main raw material, taking ferric bromide or zinc bromide as a catalyst, reacting with hydrobromic acid and hydrogen peroxide at 20-50 ℃ to generate 9-bromophenanthrene, reacting the 9-bromophenanthrene with cyanide under the catalyst to generate 9-nitrile phenanthrene, and hydrolyzing under alkaline conditions to obtain 9-phenanthrene formic acid. The method adopts the raw materials such as the phenanthrene, hydrobromic acid, hydrogen peroxide, sodium cyanide and the like which are cheap and easy to obtain to prepare the 9-phenanthrene formic acid, has low production cost, high conversion rate, good product quality, mild reaction conditions and low equipment requirements, and can be used for industrially preparing a large amount of 9-phenanthrene formic acid.

Description

Preparation method of 9-phenanthrenecarboxylic acid

Technical Field

The invention relates to the technical field of organic chemistry, in particular to a preparation method of 9-phenanthrene formic acid.

Background

The polycyclic aromatic hydrocarbon phenanthrene and the derivatives thereof have a larger pi system, and when the polycyclic aromatic hydrocarbon phenanthrene and the derivatives thereof coordinate with metal ions, the polycyclic aromatic hydrocarbon phenanthrene and the derivatives thereof can form a novel structure and generate unique functions due to the weak actions of pi … pi, C-H … pi, hydrogen bonds and the like, and particularly have wide potential application prospects in the aspects of optical, electrical, magnetic and other properties. At present, organic photoelectric materials containing polycyclic aromatic hydrocarbon structures are receiving a great deal of attention. Materials containing phenanthrene or phenanthryl derivatives increasingly exhibit their high application value with their high photo-thermal stability.

The synthetic routes reported in the literature for 9-phenanthrene carboxylic acid are summarized mainly as follows:

1. the preparation method comprises the steps of taking phenanthrene and carbon dioxide as starting materials, taking aluminum tribromide as a catalyst, and carrying out high-temperature and high-pressure reaction in benzene solvent to obtain 9-phenanthrenecarboxylic acid (Suzuki Y., hattori T., okuzawa T., miyano S.chemistry Letters,2002, 102-103).

2. 9-phenanthrene methyl sulfide and dichloro carbene are used as raw materials, and are subjected to substitution, oxidation and acidification to obtain 9-phenanthrene formic acid (Mueller, P., bernardinelli, G., pautex, N.tetrahedron Letters,1988,29,5877-5880).

3. 9-chloromethyl phenanthrene is used as a raw material, and 9-phenanthrene formic acid (Wu, G., ma, Y, li, Z, xu, J.Huaxue Xuebao,1987,45,875-880) is prepared through steps of substitution, oxidation and the like.

4. The preparation method of 9-phenanthrene formic acid (Wang Ligeng, chen Lu, zhang Hualong, and the like, a preparation method of 9-bromophenanthrene, CN107151197, bo Xianhe, wang Junjie, liu Chunsen, and the like, and a synthesis method of 9-phenanthrene acid, CN 101016243) is prepared from phenanthrene serving as a raw material through bromination, substitution, acidification and the like.

The synthesis method has various defects such as harsh reaction conditions, high reaction difficulty, low conversion rate and yield, high post-treatment difficulty, expensive and dangerous used reagents and the like, and can only be synthesized in a laboratory, thus being not beneficial to industrial production.

Disclosure of Invention

The invention aims to provide a preparation method of 9-phenanthrene formic acid, which aims to solve the problems of difficult operation, large pollution, high cost and the like in the production process of 9-phenanthrene formic acid in the background technology. The 9-phenanthrene formic acid synthesis process adopts conventional reaction, has mild conditions, low reagent cost, simple post-treatment and high yield, and is suitable for industrial mass production.

In order to achieve the above purpose, the present invention provides the following technical solutions: a method for preparing 9-phenanthrenecarboxylic acid, comprising the steps of:

1) Taking phenanthrene as a main raw material, taking ferric bromide or zinc bromide as a catalyst, reacting with hydrobromic acid and hydrogen peroxide for 3 hours at 20-50 ℃, filtering, and drying to obtain the 9-bromophenanthrene.

2) Reacting 9-bromophenanthrene with cyanide at 50-100 ℃ for 6h under the condition of a catalyst, concentrating, filtering and drying to obtain 9-nitrile phenanthrene.

3) Hydrolyzing 9-phenanthrene nitrile at 60-100 ℃ under alkaline condition, filtering to remove a small amount of insoluble impurities after the reaction is finished, adding hydrochloric acid into the filtrate to adjust the pH value to 2-3, filtering, adding methanol and active carbon into the filter cake, decoloring, recrystallizing and drying to obtain 9-phenanthrene formic acid. The reaction equation is as follows:

wherein:

cat is a catalyst;

OH ^- is a certain alkali.

The invention aims to provide a preparation method of 9-phenanthrene formic acid. The polycyclic aromatic hydrocarbon phenanthrene and the derivatives thereof have a larger pi system, and when the polycyclic aromatic hydrocarbon phenanthrene and the derivatives thereof coordinate with metal ions, the polycyclic aromatic hydrocarbon phenanthrene and the derivatives thereof can form a novel structure and generate unique functions due to the weak actions of pi … pi, C-H … pi, hydrogen bonds and the like, and particularly have wide potential application prospects in the aspects of optical, electrical, magnetic and other properties. At present, organic photoelectric materials containing polycyclic aromatic hydrocarbon structures are receiving a great deal of attention. Materials containing phenanthrene or phenanthryl derivatives increasingly exhibit their high application value with their high photo-thermal stability.

The 9-phenanthrene formic acid synthesis process adopts conventional reaction, has mild conditions, low reagent cost, simple post-treatment and high yield, and is suitable for industrial mass production.

Drawings

Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:

FIG. 1 is a schematic flow chart of a preparation method of 9-phenanthrene carboxylic acid.

FIG. 2 is 9-phenanthrenecarboxylic acid ¹ HNMR spectra.

FIG. 3 is 9-phenanthrenecarboxylic acid ¹³ CNMR spectra.

Detailed Description

For a better understanding of the objects, processes and results of the present invention, a method for preparing 9-phenanthrene carboxylic acid according to the present invention will be described in further detail with reference to the accompanying drawings, but the scope of the present invention is not limited thereto.

Example 1

Phenanthrene (17.8 g,0.100 mol) and hydrobromic acid solution (40.5 g,0.200 mol) are put into a reaction bottle, stirred, copper bromide (0.005 mol) is added, hydrogen peroxide (22.7 g,0.200 mol) is slowly added dropwise at 40 ℃, the addition is continued to keep the temperature for 2 hours, and TLC (thin layer chromatography) detects that no raw material phenanthrene exists. The reaction solution was cooled to 10℃and was filtered, washed with water and dried to give 22.5g of 9-bromophenanthrene.

9-bromophenanthrene (22.5 g,0.087 mol), ethylene glycol dimethyl ether (100 ml) and sodium cyanide solution (20 g,0.131 mol) were put into a reaction flask, stirred, and benzyl triethylammonium chloride (0.005 mol) was added thereto, followed by reaction at 85℃for 6 hours under thermal insulation, and TLC detection of the absence of starting material 9-bromophenanthrene. The reaction solution was concentrated under reduced pressure to remove ethylene glycol dimethyl ether, cooled to 20℃and filtered, washed with water and dried to give 15.3g of 9-phenanthrene nitrile.

9-phenanthroline (15.3 g,0.075 mol) sodium hydroxide (24.0 g,0.600 mol), 10ml absolute ethanol and 10ml water were put into a reaction flask, stirred and heated to reflux for 4h, and TLC detection of the absence of starting material 9-phenanthroline. Cooling to room temperature after the reaction is finished, filtering the reaction solution to remove a small amount of insoluble impurities, adding hydrochloric acid into the filtrate to adjust the pH value to 2-3, filtering, adding 60ml of methanol and 0.8g of activated carbon into the filter cake, heating, refluxing and decoloring for 1h, filtering while the filter cake is hot, refrigerating (4 ℃) the filtrate overnight, filtering and drying to obtain 15.4g of 9-phenanthrenecarboxylic acid. Total yield: 69.4%, HPLC (liquid chromatography): 99.3%.

Example 2

Phenanthrene (20 g,0.112 mol) and hydrobromic acid solution (45.4 g,0.224 mol) are put into a reaction bottle, stirred, zinc bromide (0.006 mol) is added, hydrogen peroxide (25.4 g,0.224 mol) is slowly added dropwise at 30 ℃, the addition is continued to keep the temperature for 4 hours, and TLC (thin layer chromatography) detects that no raw material phenanthrene exists. The reaction solution was cooled to 10℃and was filtered, washed with water and dried to give 23.6g of 9-bromophenanthrene.

9-bromophenanthrene (23.6 g,0.091 mol), ethylene glycol dimethyl ether (100 ml) and sodium cyanide solution (27.8 g,0.182 mol) were put into a reaction flask, stirred, tetrabutylammonium bromide (0.005 mol) was added thereto, the reaction was carried out at 75℃for 6 hours, and TLC detection was carried out for the absence of starting material 9-bromophenanthrene. The reaction solution was concentrated under reduced pressure to remove ethylene glycol dimethyl ether, cooled to 20℃and then filtered, washed with water and dried to give 16.6g of 9-phenanthrene nitrile.

9-phenanthroline (16.6 g,0.082 mol) potassium hydroxide (22.4 g,0.400 mol), 10ml of absolute ethyl alcohol and 10ml of water were put into a reaction flask, stirred and heated to reflux for 4 hours, and TLC detection of the absence of raw material 9-phenanthroline. Cooling to room temperature after the reaction is finished, filtering the reaction solution to remove a small amount of insoluble impurities, adding hydrochloric acid into the filtrate to adjust the pH value to 2-3, filtering, adding 60ml of methanol and 0.8g of activated carbon into the filter cake, heating, refluxing and decoloring for 1h, filtering while the filter cake is hot, refrigerating (4 ℃) the filtrate overnight, filtering and drying to obtain 16.1g of 9-phenanthrenecarboxylic acid. Total yield: 64.6%, HPLC (liquid chromatography): 99.0%.

It will be understood that the invention has been described in terms of several embodiments, and that various changes and equivalents may be made to these features and embodiments by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims

1. A preparation method of 9-phenanthrene formic acid is characterized by comprising the following steps:

taking phenanthrene as a main raw material, taking ferric bromide or zinc bromide as a catalyst, reacting with hydrobromic acid and hydrogen peroxide at 20-50 ℃ to generate 9-bromophenanthrene, reacting the 9-bromophenanthrene with cyanide under the catalyst to generate 9-nitrile phenanthrene, and hydrolyzing under alkaline conditions to obtain 9-phenanthrene formic acid. The reaction equation is as follows:

wherein:

cat is a catalyst;

OH ^- is a certain alkali.

2. The preparation method of 9-phenanthrene formic acid according to claim 1, wherein the brominating reagent is hydrobromic acid and hydrogen peroxide in a molar ratio of.

3. A process for the preparation of 9-phenanthrene carboxylic acid according to claim 2, wherein the bromination temperature is 20-50 ℃, preferably 30-40 ℃.

4. The method for preparing 9-phenanthrene carboxylic acid according to claim 1, wherein the catalyst is ferric bromide, zinc bromide or hydrobromide of transition metal.

5. A process for preparing 9-phenanthrenecarboxylic acid according to claim 4, wherein the catalyst is present in an amount of from 1 to 5% by weight of phenanthrene.

6. The method for preparing 9-phenanthrenecarboxylic acid according to claim 1, wherein the cyanidation reagent is sodium cyanide, potassium cyanide, cuprous cyanide, etc., and the reaction temperature is 50-100 ℃, preferably 75-85 ℃.

7. The method for preparing 9-phenanthrenecarboxylic acid according to claim 1, wherein the catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, 18 crown 6, 15 crown 5, etc.

8. The process for preparing 9-phenanthrene carboxylic acid according to claim 7, wherein the catalyst is present in an amount of 1 to 5% by weight of 9-bromophenanthrene.

9. The method for preparing 9-phenanthrene carboxylic acid according to claim 1, wherein the alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide or the like, and the molar ratio of the alkali to 9-phenanthrene nitrile is 3-6:1.

10. The process for the preparation of 9-phenanthrylic acid according to claim 9, wherein the hydrolysis temperature is 60-100 ℃, preferably 70-80 ℃.

11. The method for preparing 9-phenanthrene carboxylic acid according to claim 9, wherein the method for refining 9-phenanthrene carboxylic acid is as follows: after the reaction is finished, filtering to remove a small amount of insoluble impurities, adding hydrochloric acid into the filtrate to adjust the pH value to 2-3, filtering, adding methanol and active carbon into a filter cake, decoloring, recrystallizing and drying to obtain 9-phenanthrene formic acid.