CN102190640B - Method for preparing 3-(alpha-methoxy)methylenebenzofuran-2-(3H)-one from hydrocyanic acid in acrylonitrile waste gas - Google Patents
Method for preparing 3-(alpha-methoxy)methylenebenzofuran-2-(3H)-one from hydrocyanic acid in acrylonitrile waste gas Download PDFInfo
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Abstract
The invention relates to a method for preparing 3-(alpha-methoxy)methylenebenzofuran-2-(3H)-one from hydrocyanic acid in acrylonitrile waste gas. A ratio of (3H)-benzofuran-2-one to a catalyst to hydrocyanic acid to dimethyl sulfate is 1.0:(1.0-1.5):(1.0-1.5):(0.9-2.5), and the method comprises the following steps of: reacting the (3H)-benzofuran-2-one with the hydrocyanic acid to obtain an intermediate of 3-formoxylbenzofuran-2(3H)-one; and performing methoxylation by using the dimethyl sulfate to obtain the 3-(alpha-methoxy)-methylenebenzofuran-2(3H)-one. The method has the advantages of simple operation of reaction process, low cost of raw materials, a small quantity of three wastes, light environmental pollution and high yield.
Description
Technical field
The invention belongs to the organic synthesis field, particularly the synthetic method of a kind of 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone.
Background technology
3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, sterling is white crystals, 102～103 ℃ of fusing points.It is a kind of important organic chemical industry's intermediate, main synthesizing as the agricultural bactericide Azoxystrobin, Azoxystrobin methoxy acrylate (β-methoxyacrylates) sterilant or strobilurins analogue, have the characteristics such as efficient, wide spectrum, systemic activity are strong, nearly all Eumycetes germ evil all there is good activity, can be used for cereal, paddy rice, grape, potato, vegetables, fruit tree and other stem of plant foliar spray mists, seed treatment, also can carry out soil treatment.Azoxystrobin is used to crop safety, without poisoning under recommended dose, to underground water and environmental safety.
Document CN91110782.7, CN97118615.4, US5847138, US5760250 and Zhou Linfang etc. are at reports such as documents " the synthetic and optimization of 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone ", and the synthetic of 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone mainly is:
Cumarone-2 (3H)-ketone and trimethyl orthoformate react in the presence of diacetyl oxide, diacetyl oxide is namely made the catalyzer of reaction, while generates methyl acetate with the methyl alcohol of by-product again, reaction is proceeded, otherwise the reaction times is very long, and reaction yield is very low, cost is high, and a large amount of methyl acetate of by-product.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of new method for preparing 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone is provided, and technique is fairly simple, yield is high, and cost compare is low.
The present invention is the method for a kind of 3-of preparation (α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone; it is characterized in that at first by cumarone-2 (3H)-ketone in the presence of catalyzer; react with prussic acid; generate 3-formyl benzofuran-2 (3H)-ketone; the latter re-uses the methyl-sulfate methoxylation; obtain 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, wherein:
The reaction mass mol ratio is: cumarone-2 (3H)-ketone: catalyzer: prussic acid: methyl-sulfate=1.0: 1.0～1.5: 1.0～1.5: 0.9～2.5;
Formylation reaction temperature-10～25 ℃, 2～4 hours reaction times;
0～60 ℃ of methoxy temperature of reaction, 1～4 hour reaction times;
Described catalyzer is hydrogenchloride or hydrogen bromide.
The reaction principle contrast is as follows:
Concrete reaction formula is (catalyzer is take hydrogenchloride as example):
Advantage of the present invention:
The cost of material that reaction is used is low, and yield is high, and product cost is low.
Embodiment
Below in conjunction with embodiment the present invention is described, but does not limit the present invention.
Embodiment 1:
In the 500ml reaction flask, add dry toluene 200ml, prussic acid 5.5g; cumarone-2 (3H)-ketone 27g, stirring cools to below-10 ℃, passes into the hydrogen chloride gas of 7.5g drying; 0 ℃ of reaction of mixture 2 hours; then add in the 200g trash ice and be hydrolyzed, By Hydrolysis At Room Temperature 30 minutes is told toluene layer; water re-uses the extraction of 100ml toluene; the combining methylbenzene layer through anhydrous magnesium sulfate drying, reclaims toluene and obtains pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-ketone.
Above-mentioned oily matter is dissolved among the 150mlDMF, adds simultaneously salt of wormwood 42g powder, drips the 32g methyl-sulfate under the room temperature, after dripping end, continued insulation reaction 2 hours, add in the 200ml water, the 300ml ether divides the extraction hydrolyzed solution three times, and suitable quantity of water washing ether extracted liquid reclaims ether, add 30ml methyl alcohol, the cooling crystallization filters, and obtains the faint yellow crystallization 3-of 24.5g (α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, 100～101 ℃ of fusing points, yield 70%.
Embodiment 2:
In the 500ml reaction flask, add dry toluene 200ml, prussic acid 6.75g; cumarone-2 (3H)-ketone 27g, stirring cools to below 0 ℃, passes into the hydrogen chloride gas of 9.2g drying; 0 ℃ of reaction of mixture 2 hours; then add in the 200g trash ice and be hydrolyzed, By Hydrolysis At Room Temperature 30 minutes is told toluene layer; water re-uses the extraction of 100ml toluene; the combining methylbenzene layer through anhydrous magnesium sulfate drying, reclaims toluene and obtains pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-ketone.
Above-mentioned oily matter is dissolved among the 150mlDMF, adds simultaneously salt of wormwood 42g powder, drips the 32g methyl-sulfate under the room temperature, after dripping end, continued insulation reaction 2 hours, add in the 200ml water, the 300ml ether divides the extraction hydrolyzed solution three times, and suitable quantity of water washing ether extracted liquid reclaims ether, add 30ml methyl alcohol, the cooling crystallization filters, and obtains the faint yellow crystallization 3-of 28g (α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, 100～101 ℃ of fusing points, yield 79.5%.
Embodiment 3:
In the 500ml reaction flask, add dry toluene 200ml, prussic acid 6.0g; cumarone-2 (3H)-ketone 27g, stirring cools to below-10 ℃, passes into the hydrogen chloride gas of 8.2g drying; 0 ℃ of reaction of mixture 2 hours; then add in the 200g trash ice and be hydrolyzed, By Hydrolysis At Room Temperature 30 minutes is told toluene layer; water re-uses the extraction of 100ml toluene; the combining methylbenzene layer through anhydrous magnesium sulfate drying, reclaims toluene and obtains pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-ketone.
Above-mentioned oily matter is dissolved among the 150mlDMF, adds simultaneously salt of wormwood 35g powder, drips the 26g methyl-sulfate under the room temperature, after dripping end, continued insulation reaction 2 hours, add in the 200ml water, the 300ml ether divides the extraction hydrolyzed solution three times, and suitable quantity of water washing ether extracted liquid reclaims ether, add 30ml methyl alcohol, the cooling crystallization filters, and obtains the faint yellow crystallization 3-of 26.5g (α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, 100～101 ℃ of fusing points, yield 75%.
Claims (1)
1. method for preparing 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone; it is characterized in that at first by cumarone-2 (3H)-ketone and acrylonitrile waste gas prussic acid in the presence of catalyzer; reaction generates 3-formyl benzofuran-2 (3H)-ketone; the latter and methyl-sulfate reaction generate 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, wherein:
The reaction mass mol ratio is: cumarone-2 (3H)-ketone: catalyzer: prussic acid: methyl-sulfate=1.0:1.0～1.5:1.0～1.5:0.9～2.5;
Formylation reaction temperature-10～25 ℃, 2～4 hours reaction times;
0～60 ℃ of methoxy temperature of reaction, 1～4 hour reaction times;
Described catalyzer is hydrogenchloride.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010125440 CN102190640B (en) | 2010-03-17 | 2010-03-17 | Method for preparing 3-(alpha-methoxy)methylenebenzofuran-2-(3H)-one from hydrocyanic acid in acrylonitrile waste gas |
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| CN 201010125440 CN102190640B (en) | 2010-03-17 | 2010-03-17 | Method for preparing 3-(alpha-methoxy)methylenebenzofuran-2-(3H)-one from hydrocyanic acid in acrylonitrile waste gas |
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| CN102190640A CN102190640A (en) | 2011-09-21 |
| CN102190640B true CN102190640B (en) | 2013-03-27 |
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| CN113004234A (en) * | 2019-12-19 | 2021-06-22 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 3-hydroxymethylene benzofuran-2 (3H) -one and azoxystrobin intermediate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5847138A (en) * | 1990-11-16 | 1998-12-08 | Imperial Chemical Industries Plc | Chemical process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5847138A (en) * | 1990-11-16 | 1998-12-08 | Imperial Chemical Industries Plc | Chemical process |
| CN1219537A (en) * | 1990-11-16 | 1999-06-16 | 曾尼卡有限公司 | Process for preparing benzofuranone derivatives |
Non-Patent Citations (2)
| Title |
|---|
| J. A. ELIX，等.METHYLATION OF 3-ACYLBENZOFURAN-2(3H)-ONES.《Aust. J. Chem.》.1973,第26卷(第5期),1079-1091. * |
| 周林芳,等.3-(a-甲氧基)甲烯基苯并呋喃-2(3H)-酮的合成与优化.《农药》.2004,第43卷(第9期),第414-415页实验部分. * |
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