CN111377892A - Process for preparing benzofuranones - Google Patents
Process for preparing benzofuranones Download PDFInfo
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- CN111377892A CN111377892A CN201811608065.9A CN201811608065A CN111377892A CN 111377892 A CN111377892 A CN 111377892A CN 201811608065 A CN201811608065 A CN 201811608065A CN 111377892 A CN111377892 A CN 111377892A
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- water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/83—Oxygen atoms
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Abstract
The invention relates to the field of synthesis of benzofuranone, and discloses a preparation method of benzofuranone. The preparation method of the benzofuranone comprises the following steps: in the absence of a catalyst, o-hydroxyphenylacetic acid and a water-containing solvent are subjected to a heat treatment so that o-hydroxyphenylacetic acid undergoes a ring closure reaction, and water is removed from the reaction system during the heat treatment, wherein the temperature of the heat treatment is 120 ℃ or higher. The preparation method of the benzofuranone has the advantages of low cost, high reaction speed, high yield and simple post-treatment.
Description
Technical Field
The invention relates to the field of synthesis of benzofuranone, and in particular relates to a preparation method of benzofuranone.
Background
The structure of the benzofuranone is shown as follows, the preparation method thereof is reported in many documents, and the representative method is to use o-hydroxyphenylacetic acid as a raw material and remove water in the presence of an acid catalyst to obtain the benzofuranone, such as: goncalo reported the synthesis of benzofuranones using p-toluenesulfonic acid as a catalyst (Journal of Nature,13(1),19-26,2001); Munoz-Muniz reported the preparation of benzofuranones by refluxing water in toluene over p-toluenesulfonic acid as catalyst (Tetrahedron,59(23), 4223-.
The above methods all use various acids as catalysts, after the reaction is finished, water is added for layering to remove the acid catalysts in general post-treatment, but the reaction is a reversible reaction, and a large amount of o-hydroxyphenylacetic acid is generated in the water washing process, so that the reaction yield is influenced. In addition, if the acid catalyst is not removed, the catalyst is removed by adopting a high-temperature product, more tar and polymer are formed in the process, and the reaction yield is obviously reduced.
Disclosure of Invention
The invention aims to overcome the problems of the prior art adopting an acid catalyst and provide a preparation method of benzofuranone, which has the advantages of low cost, high reaction speed, high yield and simple post-treatment.
The present inventors have unexpectedly found, during their studies, that the target product can be obtained in a higher yield by using a solvent with water, refluxing and dividing water under a high temperature condition, and without adding a catalyst, thereby completing the present invention.
That is, the present invention provides a method for preparing benzofuranone, comprising: in the absence of an acidic catalyst, o-hydroxyphenylacetic acid and a water-containing solvent are subjected to a heat treatment so that o-hydroxyphenylacetic acid undergoes a ring closure reaction, and water is removed from the reaction system during the heat treatment, wherein the temperature of the heat treatment is 120 ℃ or higher.
Preferably, the temperature of the heat treatment is preferably 120-180 ℃.
Preferably, the water-carrying solvent is one or more of chlorobenzene, m-xylene, o-xylene, p-xylene, trimethylbenzene, ethylbenzene, toluene, nitrobenzene, butyl acetate, isobutyl acetate, anisole, phenetole and phenylacetonitrile; more preferably, the water-carrying solvent is one or more of chlorobenzene, m-xylene, o-xylene, p-xylene and trimethylbenzene.
Preferably, the water-containing solvent is used in an amount of 0.5 to 10 parts by weight relative to 1 part by weight of o-hydroxyphenylacetic acid; more preferably, the water-containing solvent is used in an amount of 2 to 4 parts by weight relative to 1 part by weight of o-hydroxyphenylacetic acid.
Preferably, the pressure of the heat treatment is 0.1-10 Mpa; more preferably, the heat treatment is performed under normal pressure.
Preferably, the means for removing water from the reaction system during the heat treatment is reflux water diversion.
Preferably, the heat-treated product is purified by distillation to obtain benzofuranone.
Preferably, the conditions of the distillation include: the pressure of the distillation is 0 to 202kPa, more preferably 0 to 2 kPa.
Preferably, the heat-treated product is purified by crystallization to obtain benzofuranone.
Preferably, the crystallization is a cooling crystallization using a solvent selected from one or more of toluene, chlorobenzene, and xylene as a crystallization solvent.
According to the method of the present invention, it has the following advantageous effects.
1) The method of the invention has the advantages of no need of catalyst, low cost of raw materials, high reaction speed and short reaction time.
2) By adopting the method, only the solvent (namely the solvent with water) and the product exist in the reaction system, and the product can be directly crystallized after the reaction is finished or crystallized after the solvent is simply removed, so the operation is very simple and the yield is high.
3) Even if the purity of the o-hydroxyphenylacetic acid used as the raw material is not high and the reaction is finished without a catalyst, the reaction solvent can be distilled off, and then the benzofuranone with higher purity can be obtained by direct high-vacuum rectification or distillation.
4) The reaction is carried out under normal pressure, so that the reaction can be simplified, the equipment cost can be reduced, and the method is particularly suitable for industrial production.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, "pressure" means "absolute pressure".
The invention provides a preparation method of benzofuranone, which comprises the following steps: in the absence of an acidic catalyst, o-hydroxyphenylacetic acid and a water-containing solvent are subjected to a heat treatment so that o-hydroxyphenylacetic acid undergoes a ring closure reaction, and water is removed from the reaction system during the heat treatment, wherein the temperature of the heat treatment is 120 ℃ or higher.
According to the method of the present invention, benzofuranone can be obtained rapidly and in high yield by subjecting o-hydroxyphenylacetic acid and a water-containing solvent to a heat treatment at a temperature of 120 ℃ or higher and removing water from the reaction system during the heat treatment.
In the present invention, the specific temperature of the heat treatment may be appropriately adjusted depending on the water-containing solvent as long as the ring-closing reaction can be performed and water is removed from the reaction system during the heat treatment. Preferably, the temperature of the heat treatment is 120-. The heat treatment may be carried out for a time sufficient for the ring-closing reaction to proceed, and for example, the heat treatment may be stopped when no water is produced.
The temperature of the heat treatment may be, for example, 120 ℃, 122 ℃, 125 ℃, 128 ℃, 130 ℃, 132 ℃, 135 ℃, 138 ℃, 140 ℃, 142 ℃, 144 ℃, 145 ℃, 148 ℃, 150 ℃, 152 ℃, 155 ℃, 158 ℃, 160 ℃, 162 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃ or the like.
According to the method of the present invention, the above heat treatment is usually carried out under normal pressure, but in order to obtain a higher treatment temperature, the heat treatment may be carried out under pressure, preferably, the pressure of the heat treatment is 0.1 to 10MPa, more preferably 0.1 to 1.0 MPa. Particularly preferably, the heat treatment is carried out under normal pressure. The heat treatment is carried out under normal pressure, so that the target product can be obtained with high yield, the reaction can be simplified, the equipment cost can be reduced, and the method is particularly suitable for industrial production. In addition, when toluene is selected as the water-containing solvent, the pressure of the heat treatment is preferably 0.15 to 0.4 MPa.
According to the method of the present invention, the water-carrying solvent may be a solvent which can be generally azeotroped with water in the art, preferably, the water-carrying solvent is one or more of chlorobenzene, m-xylene, o-xylene, p-xylene, trimethylbenzene, ethylbenzene, toluene, nitrobenzene, butyl acetate, isobutyl acetate, anisole, phenetole and phenylacetonitrile; more preferably, the water-carrying solvent is one or more of chlorobenzene, m-xylene, o-xylene, p-xylene and trimethylbenzene.
According to the method of the present invention, the amount of the water-carrying solvent may be selected according to the amount of the o-hydroxyphenylacetic acid, and preferably, the amount of the water-carrying solvent is 0.5 to 10 parts by weight relative to 1 part by weight of the o-hydroxyphenylacetic acid; more preferably, the water-containing solvent is used in an amount of 2 to 4 parts by weight relative to 1 part by weight of o-hydroxyphenylacetic acid.
Specific examples of the amount of the water-containing solvent to be used relative to 1 part by weight of o-hydroxyphenylacetic acid include: 0.5 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3 parts by weight, 3.1 parts by weight, 3.2 parts by weight, 3.3 parts by weight, 3.4 parts by weight, 3.5 parts by weight, 3.6 parts by weight, 3.7 parts by weight, 3.8 parts by weight, 3.9 parts by weight, 4.5 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight and the like.
According to the method of the present invention, preferably, the manner of removing water from the reaction system during the heat treatment is to divide water under reflux.
According to the method of the present invention, only the solvent (i.e., the solvent with water) and the product are present in the reaction system, and therefore, the heat-treated product can be purified by distillation to obtain benzofuranone. Preferably, the conditions of the distillation include: the distillation pressure is 0-202kPa, and the distillation temperature is 20-300 ℃; more preferably, the conditions of the distillation include: the distillation pressure is 0-3kPa, and the distillation temperature is 50-120 ℃.
According to the method of the present invention, only the solvent (i.e., the solvent with water) and the product are present in the reaction system, and therefore, the heat-treated product can be refined by rectification to obtain benzofuranone.
According to the method of the present invention, since the reaction system contains only the solvent (i.e., the solvent with water) and the product, the heat-treated product can be purified by crystallization to obtain benzofuranone. For example, the heat-treated product may be crystallized directly after the reaction is completed, or may be crystallized after a simple solvent removal.
The method of the crystallization may employ various methods commonly used in the art, and preferably, the crystallization is a cooling crystallization using a solvent selected from one or more of toluene, chlorobenzene, and xylene as a crystallization solvent. In addition, the mother liquor after crystallization can be used as a solvent for the next crystallization. The mother liquor after crystallization is used as the solvent for the next crystallization, so that the yield can be improved, and the cost can be reduced.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
Example 1
A1000 ml reaction bottle with a reflux water separator is added with 153.68 (with the purity of 99 wt%, 1.0mol) of o-hydroxyphenylacetic acid and 500ml of chlorobenzene, the temperature is raised to about 140 ℃ for reflux, generated water is removed by reflux water separation, after reflux water separation for 3 hours, the temperature is reduced, all chlorobenzene is removed by decompression, 134.8g (the content is 97.5 wt%) of benzofuranone is obtained, and the yield is 98.0%.
NMR(CDCl3):3.92(s,2H),7.14-7.18(m,2H),7.30-7.33(t,1H),7.36-7.37(d,1H).
Example 2
153.68g of o-hydroxyphenylacetic acid (purity is 99 wt%, 1.0mol) and 500ml of o-xylene are added into a 1000ml reaction bottle with a reflux water separator, the reaction bottle is heated to about 144 ℃ for reflux, generated water is removed by reflux water separation, after reflux water separation for 3 hours, the reaction bottle is cooled, all xylene is removed by decompression, 133.1g of benzofuranone (content is 97.3 wt%) is evaporated by about 500Pa, and the yield is 96.5%. The product distilled out above was identified as benzofuranone by nuclear magnetic resonance.
Example 3
153.68g of o-hydroxyphenylacetic acid (with the purity of 99 weight percent and 1.0mol) and 500ml of toluene are added into a 1000ml pressure kettle with a reflux water separator, the temperature is raised to about 140 ℃, reflux water separation is carried out under pressure for 3 hours, the reflux water separation is finished, the temperature is reduced to below 50 ℃, a sample is taken for quantitative analysis of the content of the benzofuranone in toluene liquid, the benzofuranone is converted into 132.1g of the benzofuranone (with the yield of 98.5 percent), most of the toluene is removed under reduced pressure, the mixture is stirred and cooled to 0 ℃ for crystallization, the crystallization is carried out at low temperature, the granular benzofuranone is obtained by drying in a vacuum drying oven at 40 ℃, and the yield is 65 percent (toluene mother liquid can be used in. The granular product obtained above was identified as benzofuranone by nuclear magnetic analysis.
Comparative example 1
153.68g of o-hydroxyphenylacetic acid (with the purity of 99 weight percent and 1.0mol), 5g of concentrated sulfuric acid and 500ml of toluene are added into a 1000ml reaction bottle with a reflux water separator, the reaction bottle is heated to 108 ℃ and refluxed for 10 hours, generated water is removed by reflux water separation, when no water is generated, the reaction bottle is cooled to room temperature, water is added for stirring and layering, an organic phase is taken, then 5 weight percent of sodium carbonate aqueous solution is used for washing, finally, the reaction bottle is washed to be neutral by clear water, and a sample is taken to quantitatively analyze the content of the benzofuranone in the toluene solution and convert the benzofuranone into 112.1g of benzofuranone (the yield is 83.6%).
Comparative example 2
A1000 ml reaction bottle with a condenser tube and a receiver bottle was charged with 153.68 (purity 99 wt%, 1.0mol) (stirring was not started until most of the solvent was dissolved because of no stirring difficulty), heated to 140 ℃ and kept at the temperature for 5 hours, then cooled and charged with 1000ml of toluene to dissolve, a small amount of tarry insoluble substances were found, and a benzofuranone toluene solution was taken and quantitatively converted to yield 63.1%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A process for the preparation of a benzofuranone, the process comprising: in the absence of an acidic catalyst, o-hydroxyphenylacetic acid and a water-containing solvent are subjected to a heat treatment so that o-hydroxyphenylacetic acid undergoes a ring closure reaction, and water is removed from the reaction system during the heat treatment, wherein the temperature of the heat treatment is 120 ℃ or higher.
2. The method as claimed in claim 1, wherein the temperature of the heat treatment is 120-180 ℃.
3. The process of claim 1, wherein the water-laden solvent is one or more of chlorobenzene, m-xylene, o-xylene, p-xylene, trimethylbenzene, ethylbenzene, toluene, nitrobenzene, butyl acetate, isobutyl acetate, anisole, phenetole, and phenylacetonitrile.
4. The method of claim 3, wherein the water-laden solvent is one or more of chlorobenzene, m-xylene, o-xylene, p-xylene, and trimethylbenzene.
5. The process according to any one of claims 1 to 4, wherein the water-carrying solvent is used in an amount of 0.5 to 10 parts by weight, preferably 2 to 4 parts by weight, relative to 1 part by weight of o-hydroxyphenylacetic acid.
6. The method according to any one of claims 1 to 4, wherein the pressure of the heat treatment is 0.1 to 10 MPa;
preferably, the heat treatment is carried out under normal pressure.
7. The process according to any one of claims 1 to 4, wherein the water is removed from the reaction system during the heat treatment by refluxing water.
8. The method according to any one of claims 1 to 4, wherein the heat-treated product is purified by distillation to give benzofuranone;
preferably, the heat-treated product is refined by rectification to obtain benzofuranone.
9. The method of claim 8, wherein the conditions of the distillation comprise: the distillation pressure is 0-202 kPa.
10. The process according to any one of claims 1 to 4, wherein the heat-treated product is purified by crystallization to give benzofuranone;
preferably, the crystallization is a cooling crystallization using a solvent selected from one or more of toluene, chlorobenzene, and xylene as a crystallization solvent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685270A (en) * | 2020-12-28 | 2022-07-01 | 南通泰禾化工股份有限公司 | Treatment method of benzofuranone intermediate synthesis wastewater |
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| US4252817A (en) * | 1975-03-12 | 1981-02-24 | Sandoz Ltd. | Substituted-2,3-dihydrobenzofuran-2-ones |
| CN102002026A (en) * | 2010-10-20 | 2011-04-06 | 重庆紫光化工股份有限公司 | Preparation method of benzofuran-2-(3H)-ketone |
| CN102040572A (en) * | 2010-12-21 | 2011-05-04 | 江苏常隆化工有限公司 | Production method of benzofuranone |
| CN102241651A (en) * | 2011-05-25 | 2011-11-16 | 江苏七洲绿色化工股份有限公司 | Preparation method of azoxystrobin intermediate |
| CN102887879A (en) * | 2012-10-17 | 2013-01-23 | 江苏剑牌农化股份有限公司 | Method for synthesizing 2(3H)-benzofuranone by utilizing microwave |
-
2018
- 2018-12-27 CN CN201811608065.9A patent/CN111377892A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252817A (en) * | 1975-03-12 | 1981-02-24 | Sandoz Ltd. | Substituted-2,3-dihydrobenzofuran-2-ones |
| CN102002026A (en) * | 2010-10-20 | 2011-04-06 | 重庆紫光化工股份有限公司 | Preparation method of benzofuran-2-(3H)-ketone |
| CN102040572A (en) * | 2010-12-21 | 2011-05-04 | 江苏常隆化工有限公司 | Production method of benzofuranone |
| CN102241651A (en) * | 2011-05-25 | 2011-11-16 | 江苏七洲绿色化工股份有限公司 | Preparation method of azoxystrobin intermediate |
| CN102887879A (en) * | 2012-10-17 | 2013-01-23 | 江苏剑牌农化股份有限公司 | Method for synthesizing 2(3H)-benzofuranone by utilizing microwave |
Non-Patent Citations (1)
| Title |
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| 王宁 等: "《有机化学》", 31 January 2018, 江苏凤凰科学技术出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114685270A (en) * | 2020-12-28 | 2022-07-01 | 南通泰禾化工股份有限公司 | Treatment method of benzofuranone intermediate synthesis wastewater |
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