阅读说明：本技术 一种合成苯并芴类化合物的方法 (Method for synthesizing benzfluorene compound ) 是由 刘运奎 陆露露 郑立孟 于 2018-08-28 设计创作，主要内容包括：本发明提供了一种合成苯并芴类化合物的合成方法,所述合成方法是：以式Ⅰ所示的邻炔基查尔酮类化合物和式Ⅱ所示的重氮盐为起始物,在路易斯酸、三氟乙醇存在条件下,于80℃～100℃温度下反应,反应完全得到反应混合液,经后处理制备得到式Ⅲ所示的苯并芴类化合物；所述式Ⅰ所示的邻炔基查尔酮类化合物与式Ⅱ所示的重氮盐、路易斯酸的物质的量之比为1：1～3：0.1～1；本发明的合成方法具有原料简单易得,对环境危害小,反应条件温和,操作简便,底物普适性好等特点。<Image he="231" wi="700" file="DDA0001780809060000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a synthetic method for synthesizing a benzfluorene compound, which comprises the following steps: taking an o-alkynyl chalcone compound shown in a formula I and a diazonium salt shown in a formula II as starting materials, reacting at the temperature of 80-100 ℃ in the presence of Lewis acid and trifluoroethanol to obtain a reaction mixed solution completely, and carrying out post-treatment to prepare a benzofluorene compound shown in a formula III; the quantity ratio of the o-alkynyl chalcone compound shown in the formula I to the substances of the diazonium salt and the Lewis acid shown in the formula II is 1: 1-3: 0.1 to 1; the synthesis method has the characteristics of simple and easily obtained raw materials, small environmental hazard, mild reaction conditions, simple and convenient operation, good substrate universality and the like.)

1. a method for synthesizing a benzfluorene compound is characterized by comprising the following steps: the method is specifically carried out according to the following steps:

taking an o-alkynyl chalcone compound shown in a formula I and a diazonium salt shown in a formula II as starting materials, reacting at the temperature of 80-100 ℃ in the presence of Lewis acid and trifluoroethanol to obtain a reaction mixed solution completely, and carrying out post-treatment to prepare a benzofluorene compound shown in a formula III; the quantity ratio of the o-alkynyl chalcone compound shown in the formula I to the substances of the diazonium salt and the Lewis acid shown in the formula II is 1: 1-3: 0.1 to 1;

in the formula I or the formula III,

R₁is H or methyl;

R₂is H, chloro, fluoro, methyl or methoxy;

R₃is H, isopropyl or acetyl;

in the formula II, R₄Is H or methyl.

2. The method for synthesizing a benzfluorene compound according to claim 1, wherein: the Lewis acid is one or a mixture of any more of ferric chloride, lithium trifluoromethanesulfonate and lithium tetrafluoroborate.

3. The method for synthesizing a benzfluorene compound according to claim 1, wherein: the Lewis acid is lithium trifluoromethanesulfonate.

4. The method for synthesizing a benzfluorene compound according to claim 1, wherein: the addition amount of the trifluoroethanol is 5-15 ml/mmol based on the amount of the compound shown in the formula I.

5. The method for synthesizing a benzfluorene compound according to claim 1, wherein: the reaction temperature was 90 ℃.

6. The method for synthesizing a benzfluorene compound according to claim 1, wherein: the post-treatment method of the reaction mixed liquid comprises the following steps: after the reaction is finished, cooling the reaction mixed solution to room temperature, adding 100-200-mesh column chromatography silica gel into the reaction solution, removing the solvent through reduced pressure distillation, then performing column chromatography separation, collecting eluent containing the target product by taking the mixed solution of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and removing the solvent through reduced pressure distillation to obtain the target product.

Technical Field

The invention relates to a method for synthesizing an organic compound, in particular to a method for synthesizing a benzfluorene compound.

Background

Fluorene and its derivatives are important compounds with rigid planar biphenyl structure, and the molecules contain a large conjugated system, and the special rigid fused ring structure makes the fluorene compounds exhibit many unique photoelectric properties and biological activities, and has potential wide application in photoelectric materials, medicine and other fields. As in the field of optoelectronics, fluorene derivative polymer material polyfluorene, which is an organic optoelectronics material, has become a blue light material that is very important and is considered by many scholars to be most promising for commercialization. The fluorene derivative has a large electron delocalization, a high fluorescence quantum yield and good photo-thermal stability, so that the fluorene derivative becomes a two-photon absorption material which is of great interest, and is gradually applied to the preparation of organic solar cell materials. In the biological field, many fluorene derivatives have been used as biosensing elements, and among them, water-soluble polyfluorene derivatives have been successfully used as fluorescent probes in gene detection, protein/enzyme concentration and activity determination, antigen-antibody recognition, bacterial detection and cell imaging, which have attracted great attention from chemists and biologists. More importantly, the fluorene compound is easy to carry out structural modification, various functional groups can be conveniently introduced into a fluorene ring, and the synthesis of the fluorene derivative and the development of potential new application of the fluorene compound become active research fields in recent years and develop rapidly.

In 2001, Sanz project group reported a method for rapidly synthesizing fluorene derivatives, which uses ortho-alkynyl styrene as raw material, gold salt and silver salt as catalyst, dichloromethane as solvent, ortho-alkynyl styrene under normal temperature to perform intramolecular cycloaddition reaction to synthesize dihydrobenzo [ a ] containing different substituents]The fluorene compounds (see org. Lett.,2012,14(18): 4778-. In 2006, the Hu project group reported that in the presence of catalytic amount of palladium acetate, tetrahydrofuran was used as a solvent, and 1-chloro-2-halogenobenzene and aryl Grignard reagent were reacted in one step to synthesize fluorene compounds with different substituents (see Org. Lett.,2006,8(22): 5057-one 5060). In 2010, the Hu subject group changed format reagents to phenylboronic acid and 1, 2-halobenzene over Pd (OAc) based on previous studies₂/Pcy₃The cross coupling and cyclization reactions are carried out in series under a catalytic system to generate the fluorene compound (see Angew. chem. int. Ed.,2010,49(16): 2909-2912).

In the methods for synthesizing fluorene compounds reported in the past, there are many defects, such as the use of transition metals, harsh reaction conditions and poor adaptability of reaction substrates.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a general, simple and efficient method for synthesizing the benzfluorene compounds.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for synthesizing a benzfluorene compound specifically comprises the following steps:

taking an o-alkynyl chalcone compound shown in a formula I and a diazonium salt shown in a formula II as starting materials, reacting at the temperature of 80-100 ℃ in the presence of Lewis acid and trifluoroethanol to obtain a reaction mixed solution completely, and carrying out post-treatment to prepare a benzofluorene compound shown in a formula III; the quantity ratio of the o-alkynyl chalcone compound shown in the formula I to the substances of the diazonium salt and the Lewis acid shown in the formula II is 1: 1-3: 0.1 to 1;

wherein, in the formula I or the formula III,

R₁is H or methyl;

R₂is H, chloro, fluoro, methyl or methoxy;

R₃is H, isopropyl or acetyl;

in the formula II, R₄Is H or methyl.

Further, the lewis acid is one or a mixture of any several of ferric chloride, lithium trifluoromethanesulfonate and lithium tetrafluoroborate, and is preferably lithium trifluoromethanesulfonate.

Furthermore, the addition amount of the trifluoroethanol is 5-15 ml/mmol based on the substance amount of the compound shown in the formula I.

In the reaction of the present invention, the reaction temperature is preferably 90 ℃.

The post-treatment method of the reaction mixed liquid comprises the following steps: after the reaction is finished, cooling the reaction mixed solution to room temperature, adding column chromatography silica gel (100-200 meshes) into the reaction solution, removing the solvent through reduced pressure distillation, separating through column chromatography, collecting eluent containing the target product by taking a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and removing the solvent through reduced pressure distillation to obtain the target product.

Compared with the prior art, the invention has the beneficial effects that:

(1) the method is safe and environment-friendly, and does not generate waste gas and waste water;

(2) the raw materials are easy to obtain, the substrate adaptability is good, and various substituent groups can realize aromatization;

(3) the reaction condition is mild;

(4) the reaction steps are simple, and the method is a new route for synthesizing various substituted benzfluorene compounds.

Detailed Description

The invention will be further illustrated by the following examples, without limiting the scope of the invention: