CN102887879A - Method for synthesizing 2(3H)-benzofuranone by utilizing microwave - Google Patents
Method for synthesizing 2(3H)-benzofuranone by utilizing microwave Download PDFInfo
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- CN102887879A CN102887879A CN2012103935384A CN201210393538A CN102887879A CN 102887879 A CN102887879 A CN 102887879A CN 2012103935384 A CN2012103935384 A CN 2012103935384A CN 201210393538 A CN201210393538 A CN 201210393538A CN 102887879 A CN102887879 A CN 102887879A
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Abstract
The invention discloses a method for synthesizing 2(3H)-benzofuranone by utilizing microwave, which comprises the following steps: after making o-chloro or o-bromo, o-iodophenylacetic acid react at a high temperature or a high temperature and a high pressure, acidifying the material, extracting the raw material without any solvent, and then directly dehydrating the material under a negative pressure, directly transferring the material into a microwave reactor with a stirrer, setting power; after monitoring the reaction completely with HPLC (high-performance liquid chromatography), changing a dehydration device into an external negative-pressure microwave condensing device, setting distilling power, collecting fractions and cooling to obtain a light yellow crystalline solid that is 2(3H)-benzofuranone. The method provided by the invention is a process for synthesizing 2(3H)-benzofuranone, which has the advantages of simple operation, short production period, low energy consumption, no solvent and high yield, and being green and pollution-free.
Description
Technical field
This paper relates to the field of chemical synthesis, relates in particular to a kind of method of utilizing synthetic 2 (the 3H)-benzofuranones of microwave.
Background technology
Azoxystrobin is a kind of methoxy acrylic acid series bactericidal agent of Syngenta Co.,Ltd's exploitation, sells at present and comes the sterilant first place, and 2(3H)-benzofuranone is the key intermediate of sterilant Azoxystrobin.Domestic and international main synthetic method is with adjacent chloro toluylic acid or adjacent bromo toluylic acid at present, adjacent iodo toluylic acid is starting raw material, behind high-temperature high-voltage reaction, acidifying, through solvent extraction, crystallization makes o-hydroxy phenylacetic acid, yield is about 60%, with o-hydroxy phenylacetic acid after 3～4 times of toluene dissolvings, add again dehydration catalyst sulfuric acid or tosic acid, 110 ℃～120 ℃ reactions of high temperature 8h～12h reflux dewatering, piptonychia benzene after washing, with obtaining 2(3H after the another kind of solvent recrystallization)-benzofuranone, the single step yield is about 88%, this method begins to be approximately 40h to the o-hydroxy phenylacetic acid cycle from adjacent chloro toluylic acid, cycle is long, need extraction, the recrystallization crystallization yield is on the low side, relatively good to the sour water solvability mainly due to o-hydroxy phenylacetic acid, extraction has brought difficulty, causes the whole preparation process need be with three kinds of solvents and a large amount of dehydration catalysts, although partial solvent can reclaim, but cost recovery is larger, and Environmental costs increase, and dehydration is at high temperature carried out, time is longer, cause product partially carbonized, polymerization and produce tar obtains 2(3H and make)-jaundice of benzofuranone color, about content 97%, two step total recoverys only have 52.8%.How under condition gentleness, eco-friendly, to solve efficiently 2(3H)-the synthetic of benzofuranone is the major issue that faces at present.
Summary of the invention
The present invention seeks to the problem that exists for above-mentioned prior art, provide a kind of simple to operate, with short production cycle, energy consumption is low, the synthetic 2(3H of solvent-free, green non-pollution, high yield)-technique of benzofuranone.
The problem that exists for solving above-mentioned prior art, the present invention is achieved through the following technical solutions: a kind of method of utilizing synthetic 2 (the 3H)-benzofuranones of microwave comprises the steps:
A. with weight ratio be adjacent halobenzene acetic acid, sodium hydroxide and the water of 505:504:1500 behind high temperature or high-temperature high-voltage reaction, acidifying PH≤1 forms o-hydroxy phenylacetic acid, most moisture is taken off in distillation;
B. the material after the dehydration changes in the microwave reactor with agitator, and reaction power is 400w～900w, reaction times 20-35min;
C. the HPLC monitoring reaction fully after, material changes the negative-pressure microwave water distilling apparatus over to, distillation pressure is-0.01～-0.09Mpa, distillation power is 600w～900w, distillation time is 20min～40min, collects the cut cooling and obtains faint yellow crystalloid solid, i.e. 2(3H)-benzofuranone.
Adjacent halobenzene acetic acid described in the steps A is adjacent chloro toluylic acid, adjacent bromo toluylic acid or adjacent iodo toluylic acid.
The pressure of distillation described in the step C is-0.04～-0.08Mpa.
The method of the invention is compared with existing Technology, has the following advantages and effect:
1. the reaction of this product is intramolecular dehydration, utilize microwave heating so that the compound microwave energy absorbing, and so that intramolecular reaction, reach dehydrating effect, and because the production water molecules is energy transmission medium best in the microwave reaction, removing of water molecules is conducive to be reversed to positive reaction, the generation of accelerated reaction, so that dehydration is more complete, reaction yield is higher, and the time is shorter; Microwave heating power used in the present invention can effectively be controlled temperature of reaction, reacts under this condition, can greatly reduce the generation of side reaction, reduces the polymerization of compound, and is conducive to shorten dewatering time, reduces dehydration temperaturre.
2. the present invention and existing comparison of processes, with adjacent chlorine or adjacent bromine, adjacent iodo toluylic acid behind high temperature or high-temperature high-voltage reaction, need not extraction after the acidifying, several steps such as crystallization, dissolving high temperature dehydration, directly adopt microwave dehydration to need not catalysts and solvents, improve speed of reaction, greatly reduce cost, green non-pollution easy and simple to handle, solvent-free.
3. have processing method now from extraction, crystallization, dissolving, high temperature dehydration, the 2(3H of preparation)-benzofuranone 40h consuming time, and adopt microwave reaction and vacuum distillation dehydration total time≤1h, shortened preparation cycle, raise the efficiency, reduce power consumption.
4. the present invention is prepared into 2(3H)-benzofuranone purity content is more than 99%, need not to carry out the silicagel column purifying, need not recrystallization, and two step total recoverys are up to more than 95%.
Embodiment
The invention will be further described below in conjunction with embodiment.But the present invention should not only limit to these examples.
Embodiment 1
A kind of method of utilizing synthetic 2 (the 3H)-benzofuranones of microwave comprises the steps:
A. with purity be 99.0% adjacent chloro toluylic acid 101.0g, sodium hydroxide 100.8g and water 300.0g after pyroreaction, acidifying PH≤1 forms o-hydroxy phenylacetic acid, most moisture is taken off in distillation;
B. the material after the dehydration changes in the microwave reactor with agitator, and reaction power is 400w, reaction times 30min;
C. the HPLC monitoring reaction fully after, material changes the negative-pressure microwave water distilling apparatus over to, distillation pressure is-0.04Mpa, distillation power is 600w, distillation time is 40min, it is 2(3H that the cooling of collection cut obtains faint yellow crystalloid solid)-benzofuranone 75.1g, purity is 99.0%, yield is 95.6%.
Embodiment 2
A. with purity be 99.0% adjacent chloro toluylic acid 101.0g, sodium hydroxide 100.8g and water 300.0g behind high-temperature high-voltage reaction, acidifying PH≤1 forms o-hydroxy phenylacetic acid, most moisture is taken off in distillation;
B. the material after the dehydration changes in the microwave reactor with agitator, and reaction power is 900w, reaction times 25min;
C. the HPLC monitoring reaction fully after, change dewatering unit into the negative-pressure microwave condensing works, material changes the negative-pressure microwave water distilling apparatus over to, distillation pressure is-0.01Mpa, distillation power is 600w, and distillation time is 30min, and it is 2(3H that the cooling of collection cut obtains faint yellow crystalloid solid)-benzofuranone 73.5g, purity is 99.0%, and yield is 93.6%.
Embodiment 3
A. with purity be 99.0% adjacent chloro toluylic acid 101.0g, sodium hydroxide 100.8g and water 300.0g behind high-temperature high-voltage reaction, acidifying PH≤1 forms o-hydroxy phenylacetic acid, most moisture is taken off in distillation;
B. the material after the dehydration changes in the microwave reactor with agitator, and reaction power is 800w, reaction times 35min;
C. the HPLC monitoring reaction fully after, change dewatering unit into the negative-pressure microwave condensing works, material changes the negative-pressure microwave water distilling apparatus over to, distillation pressure is-0.09Mpa, distillation power is 600w, and distillation time is 25min, and it is 2(3H that the cooling of collection cut obtains faint yellow crystalloid solid)-benzofuranone 74.5g, purity is 99.4%, and yield is 94.8%.
Embodiment 4
A. with purity be 99.0% adjacent chloro toluylic acid 101.0g, sodium hydroxide 100.8g and water 300.0g behind high-temperature high-voltage reaction, acidifying PH≤1 forms o-hydroxy phenylacetic acid, most moisture is taken off in distillation;
B. the material after the dehydration changes in the microwave reactor with agitator, and reaction power is 800w, reaction times 20min;
C. the HPLC monitoring reaction fully after, change dewatering unit into the negative-pressure microwave condensing works, material changes the negative-pressure microwave water distilling apparatus over to, distillation pressure is-0.08Mpa, distillation power is 600w, and distillation time is 20min, and it is 2(3H that the cooling of collection cut obtains faint yellow crystalloid solid)-benzofuranone 77.5g, purity is 99.3%, and yield is 98.6%.
Claims (3)
1. a method of utilizing synthetic 2 (the 3H)-benzofuranones of microwave comprises the steps:
A. with weight ratio be adjacent halobenzene acetic acid, sodium hydroxide and the water of 505:504:1500 behind high temperature or high-temperature high-voltage reaction, acidifying PH≤1 forms o-hydroxy phenylacetic acid, most moisture is taken off in distillation;
B. the material after the dehydration changes in the microwave reactor with agitator, and reaction power is 400w～900w, reaction times 20-35min;
The C.HPLC monitoring reaction fully after, material changes the negative-pressure microwave water distilling apparatus over to, distillation pressure is-0.01～-0.09Mpa, distillation power is 600w～900w, distillation time is 20min～40min, collects the cut cooling and obtains faint yellow crystalloid solid, i.e. 2(3H)-benzofuranone.
2. the described method of utilizing synthetic 2 (the 3H)-benzofuranones of microwave according to claim 1, it is characterized in that: adjacent halobenzene acetic acid described in the steps A is adjacent chloro toluylic acid, adjacent bromo toluylic acid or adjacent iodo toluylic acid.
3. each described method of utilizing synthetic 2 (the 3H)-benzofuranones of microwave according to claim 1 and 2 is characterized in that: the pressure of distillation described in the step C is-0.04～-0.08Mpa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541767A (en) * | 2016-01-08 | 2016-05-04 | 中山大学 | Method for preparing isosinensetin compound through intramolecular cyclization reaction |
| CN111170971A (en) * | 2019-12-28 | 2020-05-19 | 安徽中羰碳一工业技术有限责任公司 | Method for synthesizing benzofuranone by taking o-chlorotoluene as raw material |
| CN111377892A (en) * | 2018-12-27 | 2020-07-07 | 北京颖泰嘉和生物科技股份有限公司 | Process for preparing benzofuranones |
| 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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| 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 |
| CN102417498A (en) * | 2011-08-24 | 2012-04-18 | 重庆紫光化工股份有限公司 | Synthetic method of 3-(alpha-methoxy)methylene benzofuran-2(3H)-one |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102417498A (en) * | 2011-08-24 | 2012-04-18 | 重庆紫光化工股份有限公司 | Synthetic method of 3-(alpha-methoxy)methylene benzofuran-2(3H)-one |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541767A (en) * | 2016-01-08 | 2016-05-04 | 中山大学 | Method for preparing isosinensetin compound through intramolecular cyclization reaction |
| CN105541767B (en) * | 2016-01-08 | 2018-01-12 | 中山大学 | A kind of method that different Aurone compound is prepared through Intra-molecular condensation |
| CN111377892A (en) * | 2018-12-27 | 2020-07-07 | 北京颖泰嘉和生物科技股份有限公司 | Process for preparing benzofuranones |
| CN111170971A (en) * | 2019-12-28 | 2020-05-19 | 安徽中羰碳一工业技术有限责任公司 | Method for synthesizing benzofuranone by taking o-chlorotoluene as raw material |
| CN111170971B (en) * | 2019-12-28 | 2023-07-25 | 安徽中羰碳一工业技术有限责任公司 | Method for synthesizing benzofuranone by taking o-chlorotoluene as raw material |
| 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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