CN102746260A - Method for preparing benzofuran-2-(3H)-one - Google Patents
Method for preparing benzofuran-2-(3H)-one Download PDFInfo
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- CN102746260A CN102746260A CN2012102102994A CN201210210299A CN102746260A CN 102746260 A CN102746260 A CN 102746260A CN 2012102102994 A CN2012102102994 A CN 2012102102994A CN 201210210299 A CN201210210299 A CN 201210210299A CN 102746260 A CN102746260 A CN 102746260A
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- ketone
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Abstract
The invention relates to an economical and environment-friendly method for preparing benzofuran-2-(3H)-one, which comprises the following steps: mixing 2-hydroxyphenylacetic acid, a water carrying agent and a catalyst of silica sulfonic acid, stirring, heating for reflux, taking water generated during reaction out of the reaction system through azeotropic distillation with the water carrying agent, cooling and filtering to recover the catalyst after the reaction, separating the water carrying agent to obtain the product; the weight ratio of the hydroxyphenylacetic acid and the water carrying agent is 0.2-1:1, and the water carrying agent is separated through distillation technology. The separation effect is ensured, and the pure and refined product is obtained. The beneficial effects of the invention are that: the catalyst using amount is low; the atom economy is good; the production cost is low; the discharge of three wastes is low; the conversion rate is up to above 97%; and the reaction post-treatment is simple.
Description
Technical field
The present invention relates to the preparation method of chemical substance, be specifically related to the preparation method of cumarone-2-(3H)-ketone.
Background technology
Cumarone-2-(3H)-ketone:
Be important organic synthesis intermediate, can be used for synthetic medicine, agricultural chemicals and novel antioxidant.Its common compound method mainly contains following several kinds:
1, is raw material with the o-hydroxy phenylacetic acid, forms for the catalyzer dehydration condensation with the dilute sulphuric acid; The shortcoming of this technology is: consume a large amount of an acidic catalysts, must add the alkali neutralization in the last handling process earlier and remove, also produce a large amount of saliferous when consuming alkali lye, contain toluene waste water, carry out subsequent reactions or purifying again and get difficulty of product.
2, with the o-hydroxy phenylacetic acid be raw material, with diacetyl oxide or excess acetyl chloride, cyclisation and getting; The shortcoming of this technology is: consume a large amount of diacetyl oxides and Acetyl Chloride 98Min., need to separate by-product acetate, cost is high.
3, be raw material hydrolysis synthesizing o-hydroxy acetate with the NSC 4613, do not separate that to add excess sulfuric acid directly synthetic; The shortcoming of this technology is: in need consume a large amount of acid with the sodium-chlor of by-product, produce a large amount of waste residue and waste water.
That is to say that all there is serious deficiency in synthesis technique of the prior art, the production capacity that has limited cumarone-2-(3H)-ketone enlarges and use range.
Summary of the invention
Main purpose of the present invention provides a kind of preparation method of cumarone-2-(3H)-ketone of economic environmental protection.
For realizing the foregoing invention purpose; The technical scheme that the present invention adopted is: the preparation method of a kind of cumarone-2-(3H)-ketone; Step comprises: o-hydroxy phenylacetic acid, band aqua and catalyzer silica gel sulfonic acid are mixed, and stirring heating refluxes, and the water that reaction generates is taken reaction system out of through band aqua component distillation; Reaction finishes the postcooling filtering recovering catalyst, and the decoupled band aqua obtains product.
Reaction equation:
Preferably, described band aqua is aromatic hydrocarbons or alkane or halohydrocarbon.Only otherwise bring side reaction and be convenient to and get final product with water sepn.Be more preferably described band aqua and be a kind of in toluene, YLENE, chlorobenzene, the hexane.Can the adaptive response system, do not produce by product, be convenient to azeotropic simultaneously again and anhydrate and follow-up oily water separation.
Preferably, described hydroxyl phenylacetic acid is 0.2～1:1 with the weight ratio of band aqua.Can guarantee that reaction effect is simultaneously more energy-conservation.
Preferably, described catalyst levels accounts for 0.5%～1% of hydroxyl phenylacetic acid quality.Like this can the save catalyst consumption, guarantee reaction efficiency simultaneously.
Preferably, described reaction end is that the massfraction that anhydrous generation of reaction system or o-hydroxy phenylacetic acid account for reaction system is lower than 1%.Not only guarantee the transformation efficiency of reaction and avoid follow-up system complicated component not easily separated, do not waste heating energy source simultaneously again.
Preferably, described decoupled band aqua adopts distillation or reduced pressure distillation process.Guarantee separating effect, obtain purified smart product.
Preferably; Described decoupled band aqua obtains thick product for distillation band aqua; Thick product directly uses as the midbody that is used for synthetic ICIA 5504, specifically is exactly: cumarone-2-(3H)-ketone is used for synthetic 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone, and product further obtains ICIA 5504 with reaction such as salt of wormwood; Be convenient to the subsequent technique of producing ICIA 5504 supporting like this; Because subsequent technique allows the residual existence of a small amount of band aqua, can reduce the isolating requirement of band aqua simultaneously, save production cost.
Useful technique effect of the present invention is:
1) catalyst levels is little, and the catalyzer that adds substrate quality 0.5%～1% can play good catalytic effect;
2) catalyzer can pass through simple filtration recovery set usefulness, saves production cost; Do not need simultaneously complicated aftertreatment, reduced the generation of the three wastes;
3) reaction times weak point, reaction yield is high, and transformation efficiency can reach more than 97%;
4) post-reaction treatment is simple;
5) entire reaction atom economy type is good, except that generating water, does not have other generation of waste materials.
Embodiment
Embodiment 1
In the reaction flask of 1000mL, add the 200g o-hydroxy phenylacetic acid, 500mL toluene and 2g silica gel sulfonic acid, stirring heating refluxes, and in water trap, collects the water that reaction generates, and the band aqua is back to reaction system.Content when o-hydroxy phenylacetic acid after about 4 hours is lower than 1%, cooling, and suction filtration reclaims silica gel sulfonic acid, and filtrating is reclaimed and is obtained cumarone-2-(3H)-ketone 175g, HPLC analysed preparation content 98.5%, yield 97.8% after toluene is reclaimed in underpressure distillation.
Embodiment 2
In the reaction flask of 1000mL, add the 200g o-hydroxy phenylacetic acid, 500mL YLENE and 2g silica gel sulfonic acid, stirring heating refluxes; In water trap, collect the water that reaction generates, when the content of o-hydroxy phenylacetic acid is lower than 1%, cooling; Suction filtration reclaims silica gel sulfonic acid; After reclaiming YLENE, the filtrating distillation obtains cumarone-2-(3H)-ketone 173g, HPLC analysed preparation content 99.0%, yield 97.1%.
Embodiment 3
In the reaction flask of 1000mL, add the 200g o-hydroxy phenylacetic acid, 700mL chlorobenzene and 2g silica gel sulfonic acid, stirring heating refluxes; In water trap, collect the water that reaction generates, when the anhydrous generation of reaction system, cooling; Suction filtration reclaims silica gel sulfonic acid; Filtrating obtains cumarone-2-(3H)-ketone 177g, HPLC analysed preparation content 97.9%, yield 98.3% after reclaiming chlorobenzene.
Embodiment 4
In the reaction flask of 1000mL, add the 200g o-hydroxy phenylacetic acid, 400mL normal hexane and 2g silica gel sulfonic acid, stirring heating refluxes; In water trap, collect the water that reaction generates, when the content of o-hydroxy phenylacetic acid is lower than 1%, cooling; Suction filtration reclaims silica gel sulfonic acid; Filtrating obtains cumarone-2-(3H)-ketone 176g, HPLC analysed preparation content 97.5%, yield 97.3% after reclaiming normal hexane.
Embodiment 5
In the reaction flask of 1000mL, add the 200g o-hydroxy phenylacetic acid, the silica gel sulfonic acid that reclaims among 500mL toluene and the embodiment 1, stirring heating refluxes; In water trap, collect the water that reaction generates, when the content of o-hydroxy phenylacetic acid is lower than 1%, cooling; Suction filtration reclaims silica gel sulfonic acid; After reclaiming toluene, the filtrating distillation obtains cumarone-2-(3H)-ketone 174g, HPLC analysed preparation content 98.7%, yield 97.4%.
Embodiment 6
In the reaction flask of 1500mL, add the 200g o-hydroxy phenylacetic acid, 900mL chlorobenzene and 1g silica gel sulfonic acid, stirring heating refluxes; In water trap, collect the water that reaction generates, when the anhydrous generation of reaction system, cooling; Suction filtration reclaims silica gel sulfonic acid; Filtrating obtains cumarone-2-(3H)-ketone 177g, HPLC analysed preparation content 96.9%, yield 97.1% after reclaiming chlorobenzene.
Claims (8)
1. the preparation method of a cumarone-2-(3H)-ketone; Step comprises: o-hydroxy phenylacetic acid, band aqua and catalyzer silica gel sulfonic acid are mixed; Stirring heating refluxes; The water that reaction generates is taken reaction system out of through band aqua component distillation, and reaction finishes the postcooling filtering recovering catalyst, and the decoupled band aqua obtains product.
2. the preparation method of cumarone-2-according to claim 1 (3H)-ketone is characterized in that: described band aqua is aromatic hydrocarbons or alkane or halohydrocarbon.
3. the preparation method of cumarone-2-according to claim 1 (3H)-ketone is characterized in that: described band aqua is a kind of in toluene, YLENE, chlorobenzene, the hexane.
4. the preparation method of cumarone-2-according to claim 1 (3H)-ketone is characterized in that: described hydroxyl phenylacetic acid is 0.2～1:1 with the weight ratio of band aqua.
5. the preparation method of cumarone-2-according to claim 1 (3H)-ketone is characterized in that: described catalyst levels accounts for 0.5%～1% of hydroxyl phenylacetic acid quality.
6. the preparation method of cumarone-2-according to claim 1 (3H)-ketone is characterized in that: described reaction end is that the massfraction that anhydrous generation of reaction system or o-hydroxy phenylacetic acid account for reaction system is lower than 1%.
7. according to the preparation method of any described cumarone-2-(3H)-ketone in the claim 1 to 6, it is characterized in that: described decoupled band aqua adopts distillation or reduced pressure distillation process.
8. according to the preparation method of any described cumarone-2-(3H)-ketone in the claim 1 to 6, it is characterized in that: described decoupled band aqua obtains thick product for distillation band aqua, and thick product directly uses as the midbody that is used for synthetic ICIA 5504.
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| CN2012102102994A CN102746260A (en) | 2012-06-25 | 2012-06-25 | Method for preparing benzofuran-2-(3H)-one |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336388A (en) * | 2016-07-27 | 2017-01-18 | 重庆紫光国际化工有限责任公司 | Synthetic method of benzofuran-2(3H)-one |
| CN109851600A (en) * | 2019-03-11 | 2019-06-07 | 上海凡生化学科技有限公司 | The preparation method of benzofuran -2- (3H) -one |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-06-25 CN CN2012102102994A patent/CN102746260A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336388A (en) * | 2016-07-27 | 2017-01-18 | 重庆紫光国际化工有限责任公司 | Synthetic method of benzofuran-2(3H)-one |
| CN106336388B (en) * | 2016-07-27 | 2019-07-05 | 重庆紫光国际化工有限责任公司 | The synthetic method of benzofuran -2- (3H) -one |
| CN109851600A (en) * | 2019-03-11 | 2019-06-07 | 上海凡生化学科技有限公司 | The preparation method of benzofuran -2- (3H) -one |
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Application publication date: 20121024 |