CN103435477A - Novel method for synthesizing para-ethoxybenzoic acid - Google Patents
Novel method for synthesizing para-ethoxybenzoic acid Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- SHSGDXCJYVZFTP-UHFFFAOYSA-N 4-ethoxybenzoic acid Chemical compound CCOC1=CC=C(C(O)=O)C=C1 SHSGDXCJYVZFTP-UHFFFAOYSA-N 0.000 title abstract description 8
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 12
- BRBLIIMKHOXZTN-UHFFFAOYSA-N (4-ethoxyphenyl)methyl-trimethylsilane Chemical compound C(C)OC1=CC=C(C[Si](C)(C)C)C=C1 BRBLIIMKHOXZTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 238000005286 illumination Methods 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000003749 cleanliness Effects 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000007445 Chromatographic isolation Methods 0.000 description 5
- 238000011097 chromatography purification Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- JRHHJNMASOIRDS-UHFFFAOYSA-N 4-ethoxybenzaldehyde Chemical compound CCOC1=CC=C(C=O)C=C1 JRHHJNMASOIRDS-UHFFFAOYSA-N 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- -1 silicane free radical Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YZNOHWUDLGWICS-UHFFFAOYSA-N (4-methoxyphenyl)methyl-trimethylsilane Chemical compound COC1=CC=C(C[Si](C)(C)C)C=C1 YZNOHWUDLGWICS-UHFFFAOYSA-N 0.000 description 1
- 235000014493 Crataegus Nutrition 0.000 description 1
- 241001092040 Crataegus Species 0.000 description 1
- 239000003416 antiarrhythmic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种合成对乙氧基苯甲酸的新方法，包括以下步骤：将(4-乙氧基苄基)三甲基硅烷加入反应器中；氧气氛中磁力搅拌反应；反应温度25℃；在300W Xe lamp光照条件下充分反应。本发明方法避免了传统合成方法中使用高毒，易制毒试剂，提高了工业合成反应的清洁性，降低了环境污染。本发明方法采用溴化氢溶液作为反应的催化剂催化剂，降低了成本。本发明方法一步完成，使用的原料种类单一，提高了工艺的经济性。The invention discloses a new method for synthesizing p-ethoxybenzoic acid, which comprises the following steps: adding (4-ethoxybenzyl) trimethylsilane into a reactor; magnetic stirring reaction in oxygen atmosphere; reaction temperature 25 ℃; Fully react under the light condition of 300W Xe lamp. The method of the invention avoids the use of highly toxic and precursor reagents in the traditional synthesis method, improves the cleanliness of industrial synthesis reactions, and reduces environmental pollution. The method of the invention adopts the hydrogen bromide solution as the catalyst catalyst of the reaction, which reduces the cost. The method of the invention is completed in one step, and the types of raw materials used are single, thereby improving the economical efficiency of the process.
Description
Technical field
The present invention relates to a kind of novel method of synthetic paraethoxybenxoic acid, especially a kind ofly take illumination as condition, catalyze and synthesize the method for anisic acid with aqueous solution of hydrogen bromide.
Background technology
Under (4-ethoxybenzoic acid) normal temperature, be white needle-like crystals, 197～199 ℃ of fusing points, be dissolved in ethanol, ether, chloroform, is slightly soluble in hot water, is insoluble in cold water.Paraethoxybenxoic acid is the intermediate of many medicines and spices, and for example it is new and effective, the intelligent intermediate that improves medicine mattress La Xitan of low toxicity, is also the important intermediate of antiarrhythmic drug SKF 33134A, also can be used for spices and sanitas.Its molecular formula is C
9h
100
3, relative molecular mass is 166.17.The structural formula of paraethoxybenxoic acid is:
The industrial process of paraethoxybenxoic acid is to adopt P-hydroxybenzoic acid under alkaline condition, with ethyl sulfate, ethylized, because P-hydroxybenzoic acid has carboxyl, consume more alkali while therefore ethylizing, also need to use acidifying after reaction, the P-hydroxybenzoic acid price is also more expensive, thereby has increased cost.Meng Xiangjun, Zhang Baofa, Ge Xin once reported that with p-cresol be raw material, by ethylization, dioxygen oxidation, prepared paraethoxybenxoic acid.But also to use ethyl sulfate while ethylizing in this technique, consume equally more alkali, and need two steps to complete; Also need to use CoBr in the process of dioxygen oxidation
2, MnBr
2make catalyzer Deng metal-salt.When having caused heavy metal contamination, also increased the cost of technique.
Along with the development of environmental economy, the drawback that does not have sustainable developability that traditional production method of paraethoxybenxoic acid comes out, need the method more friendly by environment badly and replace.
Photochemistry, as a new branch of science, has obtained the comparatively development of system in American-European countries.Wherein, the basic theory system of organic photochemistry has been set up.But, in China, the development of organic photochemistry is also relatively backward.Illumination and the free radical reaction that causes, often can at very low temperature, carry out, now a lot of side reactions can not occur, a lot of functional groups are not that activity is very high or do not participate in photoresponse under illumination in addition, therefore functional group's tolerance of this reaction will be fine, is more conducive to play a role in complete synthesis work.Photochemical method, for a lot of reactions, will no longer be needed to harsh anhydrous and oxygen-free condition, and operation is more prone to.In addition, luminous energy is more clean than heating, and save energy reduces costs, and can reduce the pollution that metal reagent brings simultaneously and reduce costs.
Summary of the invention
The invention provides a kind of (4-ethoxy benzyl) trimethyl silane and slough the trimethyl silicane free radical under illumination, generate corresponding benzyl radicals intermediate, benzyl radicals is oxidized to the 4-ethoxy-benzaldehyde under the oxygenizement of air subsequently, and the 4-ethoxy-benzaldehyde is oxidised with air to the 4-ethoxybenzoic acid under the catalysis of the hydrogen bromide solution of catalytic amount.It is a kind of under illumination condition that the present invention also provides, the method for the bond rupture of carbon silicon and high-selectivity oxidation.
For achieving the above object, a kind of method of synthetic paraethoxybenxoic acid comprises the following steps: (4-ethoxy benzyl) trimethyl silane is added in reactor; Magnetic agitation reaction in oxygen atmosphere; 25 ℃ of temperature of reaction; Fully reaction under 300W Xe lamp illumination condition.
The better technical scheme that realizes above-mentioned purpose is, reactor is quartz reactor, and reactor pressure is normal pressure.
The better technical scheme that realizes above-mentioned purpose is, also comprises spherical condensating tube is connected with quartz reactor, allows reaction carry out under the oxidation of air.
The better technical scheme that realizes above-mentioned purpose is to add catalyzer in reactor, the aqueous solution of hydrogen bromide that catalyzer used is 40 percent.Use catalyzer can improve speed of response, productive rate and selectivity.
The better technical scheme that realizes above-mentioned purpose is, also is included in reactor and adds solvent, and described solvent is selected in methylene dichloride, DMF, THF, benzene, acetonitrile, methyl alcohol, Nitromethane 99Min. the mixture of one or more.Wherein preferably anhydrous acetonitrile and dry-out benzene.
The better technical scheme that realizes above-mentioned purpose is, further comprising the steps of: pass into oxygen-containing gas in reactor, add catalyzer, add solvent, the aqueous solution of hydrogen bromide that catalyzer used is 40 percent, selected solvent is one or more mixtures in methylene dichloride, DMF, THF, benzene, acetonitrile, methyl alcohol, Nitromethane 99Min..
The better technical scheme that realizes above-mentioned purpose is, take the quartz reaction bottle as reaction vessel, and air is oxygenant, and temperature of reaction is room temperature, catalyzer is the hydrogen bromide solution of 40 percent aqueous solution of hydrogen bromide (20%moL) preferably, and solvent is selected anhydrous acetonitrile or dry-out benzene.
The inventive method has been compared significant advantage with traditional technology: it is energy derive that (1) novel method has adopted Xenon light shining, for the various fine chemicals of industrial preparation provide a kind of brand-new thinking.(2) the inventive method has been avoided in prior synthesizing method using high poison, easily makes malicious reagent, has improved the spatter property of industrial building-up reactions, has reduced environmental pollution.(3) the inventive method adopts the catalyst agent of hydrogen bromide solution as reaction, has reduced cost.(4) the inventive method one step completes, and the raw material type of use is single, has improved the economy of technique.(5) the inventive method can be chosen under normal temperature, normal pressure and complete reaction.Under normal temperature, normal pressure, reaction can reduce the requirement to conversion unit, reduces conversion unit manufacturing cost and reaction process cost, improves the security of reaction.(6) the present invention adopts air as oxidant source, has further saved cost.(7) the inventive method provides a kind of carbon silicon key efficiently to rupture, and the novel method of high-selectivity oxidation.
Reactor can be used quartz reactor, high-boron-silicon glass container in laboratory, during industrial production, can use with the tank reactor of quartz plate or tubular reactor etc.
Typical synthesis step is as follows: with organic solvent dissolution (4-ethoxy benzyl) trimethyl silane, then add proper catalyst, pass into air, under normal temperature, normal pressure under illumination condition stirring reaction.Through TLC and high performance liquid chromatography, determine, raw material (4-ethoxy benzyl) trimethyl silane reacts completely, rotary evaporation in vacuo, and column chromatographic isolation and purification, calculate aubepine and anisic acid component concentration separately.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
In 50mL quartz reaction bottle, add 42mg (4-ethoxy benzyl) trimethyl silane, the 10mL acetonitrile solvent, magnetic agitation in oxygen atmosphere, 25 ℃ of temperature, under Xe lamp (300W) illumination, reaction is 3 hours.Through TLC and efficient liquid phase chromatographic analysis, raw material (4-ethoxy benzyl) trimethyl silane reacts completely.Rotary evaporation in vacuo, column chromatographic isolation and purification, product p-ethoxybenzaldehyde quality is 3mg, productive rate is 9%[
1h NMR (400MHz, CDCl
3): δ 9.88 (s, 1H), 7.83 (d, J=8.8Hz, 2H), 6.99 (d, J=8.4Hz, 2H), 4.12 (q, J=6.8Hz, 2H), 1.46 (t, J=6.8,3H)]; The paraethoxybenxoic acid quality is 7mg, and productive rate is 21%[
1h NMR (400MHz, CDCl
3): δ 8.05 (d, J=9.2Hz, 2H), 6.93 (d, J=9.2Hz, 2H), 4.11 (q, J=6.8Hz, 2H), 1.45 (t, J=6.8,3H)].Keep other conditions constant, change the temperature of above-mentioned reaction, carry out at 0 ℃, 50 ℃ temperature respectively, temperature raises or reduces the productive rate that all makes this reaction and reduce.
Embodiment 2
In 50mL quartz reaction bottle, add 42mg (4-ethoxy benzyl) trimethyl silane, the 10mL solvent acetonitrile, 2.7 μ L hydrogen bromide solution (aq. mass content 40%), magnetic agitation in oxygen atmosphere, 25 ℃ of temperature, under Xe lamp (300W) illumination, reaction is 17 hours.After reaction times reaches, through TLC and efficient liquid phase chromatographic analysis, only have single product paraethoxybenxoic acid to generate.Rotary evaporation in vacuo, column chromatographic isolation and purification, product quality is 19mg, productive rate is 58%.Keep other conditions constant, change the temperature of above-mentioned reaction, carry out at 0 ℃, 50 ℃ temperature respectively, temperature raises or reduces the productive rate that all makes this reaction and reduce.
Embodiment 3
In 50mL quartz reaction bottle, add 42mg (4-ethoxy benzyl) trimethyl silane, the 10mL solvent acetonitrile, 5.4 μ L hydrogen bromide solution (aq. mass content 40%), magnetic agitation in oxygen atmosphere, 25 ℃ of temperature, under Xe lamp (300W) illumination, reaction is 9.5 hours.After reaction times reaches, through TLC and efficient liquid phase chromatographic analysis, only have single product paraethoxybenxoic acid to generate.Rotary evaporation in vacuo, column chromatographic isolation and purification, product quality is 25mg, productive rate is 75%.Keep other conditions constant, change the temperature of above-mentioned reaction, carry out at 0 ℃, 50 ℃ temperature respectively, temperature raises or reduces the productive rate that all makes this reaction and reduce.
Embodiment 4
In 50mL quartz reaction bottle, add 42mg (4-methoxy-benzyl) trimethyl silane, the 10mL solvent acetonitrile, 5.4 μ L hydrogen bromide solution (aq. mass content 40%), magnetic agitation in air atmosphere, 25 ℃ of temperature, under Xe lamp (300W) illumination, reaction is 4 hours.After reaction times reaches, through TLC and efficient liquid phase chromatographic analysis, only have single product anisic acid to generate.Rotary evaporation in vacuo, column chromatographic isolation and purification, product quality is 32mg, productive rate is 97%.Keep other conditions constant, change the temperature of above-mentioned reaction, carry out at 0 ℃, 50 ℃ temperature respectively, temperature raises or reduces the productive rate that all makes this reaction and reduce.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (5)
1. the novel method of a synthetic paraethoxybenxoic acid, is characterized in that, comprises the following steps: (4-ethoxy benzyl) trimethyl silane is added in reactor; Magnetic agitation reaction in oxygen atmosphere; 25 ℃ of temperature of reaction; Fully reaction under 300W Xe lamp illumination condition.
2. method according to claim 1, is characterized in that, reactor is quartz reactor, and reactor pressure is normal pressure.
3. method according to claim 2, is characterized in that, also comprises spherical condensating tube is connected with quartz reactor, allows reaction carry out under the oxidation of air.
4. method according to claim 1, is characterized in that, adds catalyzer in reactor, the aqueous solution of hydrogen bromide that catalyzer used is 40 percent.
5. method according to claim 1, is characterized in that, also is included in reactor and adds solvent, and described solvent is selected in methylene dichloride, DMF, THF, benzene, acetonitrile, methyl alcohol, Nitromethane 99Min. the mixture of one or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910623A (en) * | 2014-03-03 | 2014-07-09 | 复旦大学 | Preparation method for benzoic acid |
| CN104370736A (en) * | 2014-10-08 | 2015-02-25 | 郑州大学 | Synthesis method of 2-ethoxybenzoic acid compound |
| CN115420826A (en) * | 2022-08-30 | 2022-12-02 | 北京悦康科创医药科技股份有限公司 | Separation and detection method for impurities in starting material o-ethoxybenzoic acid in citric acid alidenafil raw material medicine |
-
2013
- 2013-08-28 CN CN201310379244.0A patent/CN103435477B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| LAURA CERMENATI, ET AL.: "TiO2-photocatalyzed reactions of some benzylic donors", 《CANADIAN JOURNAL OF CHEMISTRY》, vol. 81, 23 May 2003 (2003-05-23), pages 560 - 566 * |
| 张亚成: "光照条件下有机硅化合物C-Si键的高效裂解及高选择性氧化", 《南京理工大学硕士学位论文》, 1 January 2013 (2013-01-01), pages 34 - 61 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910623A (en) * | 2014-03-03 | 2014-07-09 | 复旦大学 | Preparation method for benzoic acid |
| CN104370736A (en) * | 2014-10-08 | 2015-02-25 | 郑州大学 | Synthesis method of 2-ethoxybenzoic acid compound |
| CN104370736B (en) * | 2014-10-08 | 2016-07-06 | 郑州大学 | A kind of synthetic method of 2-ethoxy benzonitrile acid compounds |
| CN115420826A (en) * | 2022-08-30 | 2022-12-02 | 北京悦康科创医药科技股份有限公司 | Separation and detection method for impurities in starting material o-ethoxybenzoic acid in citric acid alidenafil raw material medicine |
| CN115420826B (en) * | 2022-08-30 | 2023-05-30 | 北京悦康科创医药科技股份有限公司 | Separation detection method for impurities in o-ethoxybenzoic acid as starting material in sildenafil citrate bulk drug |
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