WO2020132792A1 - Composé de 2-benzoyle malonate, procédé de préparation correspondant et utilisation associée - Google Patents

Composé de 2-benzoyle malonate, procédé de préparation correspondant et utilisation associée Download PDF

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WO2020132792A1
WO2020132792A1 PCT/CN2018/123070 CN2018123070W WO2020132792A1 WO 2020132792 A1 WO2020132792 A1 WO 2020132792A1 CN 2018123070 W CN2018123070 W CN 2018123070W WO 2020132792 A1 WO2020132792 A1 WO 2020132792A1
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compound
formula
reaction
benzoylmalonate
acid
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PCT/CN2018/123070
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English (en)
Chinese (zh)
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樊小彬
徐晓明
林行军
黄超
陈宇
沈启富
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江苏联化科技有限公司
联化科技(盐城)有限公司
联化科技（德州）有限公司
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Priority to PCT/CN2018/123070 priority Critical patent/WO2020132792A1/fr
Publication of WO2020132792A1 publication Critical patent/WO2020132792A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids

Definitions

  • the invention relates to a 2-benzoylmalonate compound, its preparation method and application.
  • 4-halo-2-trifluoromethylacetophenone is an important intermediate for the synthesis of fungicidal triazole compounds, such as clofluconazole (English common name mefentrifluconazole; trade name Revysol) is the latest BASF exclusive patent Triazole fungicide.
  • clofluconazole is also a sterol demethylation inhibitor, its mechanism of action is to prevent the biosynthesis of ergosterol, inhibit cell growth and eventually lead to the collapse of cell membranes. It is the largest listed product in BASF's history. Revysol will be listed in more than 50 countries around the world and used on more than 60 crops. There is a market of about 1 billion euros in the world.
  • a raw material is easy to obtain, avoids the Grignardization reaction with greater risk, and is easy to operate, and is more suitable for the preparation method of industrial mass production, which is still the research focus of those skilled in the art.
  • the technical problem to be solved by the present invention is to overcome the defects of the existing 4-halo-2-trifluoromethyl acetophenone preparation method that the raw materials are rare, the cost is high, the operation is cumbersome, the risk is high, and it is not conducive to industrial production.
  • a 2-benzoylmalonate compound, its preparation method and application are provided.
  • 4-halo-2-trifluoromethylacetophenone can be prepared in one step reaction, and the operation is simple.
  • the present invention solves the above technical problems through the following technical solutions.
  • the present invention provides a method for preparing an acetophenone compound represented by formula III, which includes the steps of: in an organic solvent, in the presence of acid and water, the 2-benzoyl propionate represented by formula I
  • the diacid compounds and/or their tautomers can be subjected to the deesterification reaction as shown below to obtain the acetophenone compounds represented by formula III,
  • X is F, Cl, Br or I; R 1 and R 2 are each independently C 1 to C 4 alkyl.
  • the tautomers of the 2-benzoylmalonate compounds represented by Formula I include, but are not limited to, compounds represented by Formula Ia, Formula Ib, or Formula Ic:
  • X is preferably F or Cl.
  • the C 1 -C 4 alkyl groups are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; Preferably, it is methyl or ethyl.
  • the organic solvent may be a conventional organic solvent in this type of reaction in the art, such as an aromatic solvent, and preferably is halogenated benzene (such as chlorobenzene, bromobenzene, and o-dichlorobenzene) in the present invention.
  • halogenated benzene such as chlorobenzene, bromobenzene, and o-dichlorobenzene
  • benzene such as chlorobenzene, bromobenzene, and o-dichlorobenzene
  • halogenated benzene such as chlorobenzene, bromobenzene, and o-dichlorobenzene
  • halogenated benzene such as chlorobenzene, bromobenzene, and o-dichlorobenzene
  • alkylbenzene such as toluene and/or xylene
  • chlorobenzene and/or bromobenzene are, for example, chlor
  • the amount of the organic solvent can be the amount conventionally used in this type of reaction in the art, so as not to affect the reaction; the organic solvent described in the present invention and the 2-benzoylpropanediol represented by Formula I
  • the mass of the ester compound and/or its tautomer is preferably 1:1 to 5:1, more preferably 2:1 to 2.5:1.
  • the acid may be a conventional acid in this type of reaction in the art, such as an inorganic acid, preferably sulfuric acid and/or phosphoric acid.
  • the molar ratio of the acid to the 2-benzoylmalonate compound represented by Formula I and/or its tautomer is preferably 0.9:1 to 3.5:1 , More preferably from 1:1 to 2:1 (eg 1.4:1, 1.6:1).
  • the molar ratio of the water to the 2-benzoylmalonate compound represented by Formula I and/or its tautomer is preferably 0.9:1 to 10:1 , More preferably from 1:1 to 7:1 (eg 2.5:1).
  • the acid and the water are preferably a mixture, and the mass concentration of the acid in the mixture is preferably 50% to 90% (for example, 75%).
  • the temperature of the deesterification reaction may be a conventional temperature in this type of reaction in the art, for example, 100°C to 140°C (eg, 105°C, 110°C, 115°C, 120°C, 130°C, 135°C, 140°C), preferably 120°C to 130°C.
  • the progress of the reaction can be monitored using conventional monitoring methods in the art (such as TLC, HPLC, or NMR).
  • monitoring methods such as TLC, HPLC, or NMR.
  • the 2-benzoyl group represented by Formula I is used The end point of the reaction is when the malonate compound and/or its tautomers disappear or no longer react.
  • the preparation method may further include the steps of: in an organic solvent, a mixture of compound IV and a basic reagent is subjected to an acylation reaction with compound V as shown below, to obtain 2 of the formula I -The benzoyl malonate compounds and/or tautomers thereof are sufficient;
  • the operation and conditions of the acylation reaction may be conventional operations and conditions in this type of reaction in the art.
  • the organic solvent may be a conventional organic solvent in this type of reaction in the art, such as ether solvents, organic sulfoxide solvents, amide solvents, ketone solvents, ester solvents, nitriles Solvents, halogenated benzenes (such as one or more of chlorobenzene, bromobenzene and o-dichlorobenzene, and also such as chlorobenzene and/or bromobenzene) and alkylbenzenes (such as toluene and/or xylene)
  • halogenated benzenes such as one or more of chlorobenzene, bromobenzene and o-dichlorobenzene, and also such as chlorobenzene and/or bromobenzene
  • alkylbenzenes such as toluene and/or xylene
  • One or more of; in the present invention is preferably one or more of chlorobenzene, bromobenzen
  • the amount of the organic solvent may not be limited so as not to affect the reaction; in the present invention, the quality of the organic solvent and the compound V is preferably 1:1 to 5:1, more preferably 2.5:1 ⁇ 3.5:1.
  • the alkaline reagent may be a common alkaline reagent in this type of reaction in the art, such as magnesium salt (eg magnesium chloride), magnesium alkoxide (eg magnesium ethoxide and/or magnesium methoxide), sodium alkoxide (eg sodium ethoxide and/or One or more of sodium methoxide), sodium hydride and triethylamine, preferably magnesium ethoxide and/or sodium methoxide in the present invention.
  • magnesium salt eg magnesium chloride
  • magnesium alkoxide eg magnesium ethoxide and/or magnesium methoxide
  • sodium alkoxide eg sodium ethoxide and/or One or more of sodium methoxide
  • sodium hydride and triethylamine preferably magnesium ethoxide and/or sodium methoxide in the present invention.
  • the molar ratio of the compound V to the compound IV may be a conventional molar ratio in this type of reaction in the art.
  • the molar ratio of the compound V to the compound IV in the present invention is preferably 1.2:1 ⁇ 1:1.2 (for example 1:1).
  • the molar ratio of the basic reagent to the compound IV may be a conventional molar ratio in this type of reaction in the art.
  • the molar ratio of the basic reagent to the compound IV in the present invention is preferably 1.2 : 1 to 1: 1.2 (for example, 1:1).
  • the preparation method preferably includes the steps of reacting the compound IV and the alkaline reagent at a temperature of 100°C to 110°C in the organic solvent to obtain The mixture; at a temperature of 0 °C ⁇ 30 °C, the compound V is added dropwise to the mixture, the acylation reaction is carried out to obtain the 2-benzoyl represented by the formula I
  • the malonate compounds and/or tautomers thereof may be sufficient.
  • the progress of the reaction can be monitored using conventional monitoring methods in the art (such as TLC, HPLC, or NMR). Generally, the end point of the reaction is when the compound III disappears or no longer reacts .
  • the preparation method may further include the following post-processing steps. After the acylation reaction is completed, acid is added to neutralize, extract, concentrate, and crystallize to obtain the 2-benzoylpropionate represented by Formula I The diacid compound and/or its tautomer is sufficient.
  • the preparation method may further include the following steps: in the presence of a catalyst, the compound VI and Cl 2 are subjected to the following chlorination reaction to prepare the compound V, as needed;
  • the catalyst may be a conventional catalyst in this type of reaction in the art, such as azobisisobutyronitrile.
  • the amount of the catalyst may be a conventional amount used in this type of reaction in the art.
  • the molar ratio of the catalyst in the present invention to the compound VI is preferably 0.5:100 to 1:100 (eg 0.6:100) .
  • the temperature of the chlorination reaction may be a conventional temperature in this type of reaction in the art, for example, 50°C to 65°C (again, for example, 55°C to 60°C).
  • the progress of the reaction can be monitored using conventional monitoring methods in the art (such as TLC, HPLC, or NMR).
  • TLC TLC
  • HPLC HPLC
  • NMR NMR
  • the preparation method may further include the following steps: in the presence of a catalyst, the compound VII and water are subjected to a hydrolysis reaction as described below to obtain the compound VI;
  • the catalyst may be a conventional catalyst in this type of reaction in the art, such as Lewis acid.
  • it is preferably one or more of ferric chloride, aluminum trichloride, zinc chloride, and tin chloride. Species, more preferably ferric chloride.
  • the amount of the catalyst may be a conventional amount used in this type of reaction in the art.
  • the molar ratio of the catalyst in the present invention to the compound VII is preferably 0.5:100 to 10:100 (eg 2.5:100) .
  • the amount of the water may be a conventional amount used in this type of reaction in the art.
  • the molar ratio of the water to the compound VII in the present invention is preferably 0.5:1 to 2:1 (for example, 1:1) .
  • the temperature of the hydrolysis reaction may be a conventional temperature in this type of reaction in the art, for example, 100°C to 140°C (also for example, 110°C to 115°C).
  • the progress of the reaction can be monitored by conventional monitoring methods in the art (such as TLC, HPLC, or NMR).
  • TLC TLC
  • HPLC HPLC
  • NMR NMR
  • the end point of the reaction is when the compound VII disappears or no longer reacts, for example HPLC detection showed that the content of the compound VII was ⁇ 1%.
  • the present invention provides a 2-benzoylmalonate compound represented by Formula I, or a tautomer thereof:
  • X is F, Cl, Br or I; R 1 and R 2 are independently C 1 to C 4 alkyl.
  • the tautomers of the 2-benzoylmalonate compounds represented by Formula I include, but are not limited to, compounds represented by Formula Ia, Formula Ib, or Formula Ic:
  • X is preferably F or Cl.
  • the C 1 ⁇ C 4 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; preferably a Methyl or ethyl.
  • the 2-benzoylmalonate compounds represented by formula I or tautomers thereof, wherein the 2-benzoylmalonate compounds represented by formula I
  • the compound can have any of the following structures:
  • the present invention provides a method for preparing a 2-benzoylmalonate compound represented by Formula I, or a tautomer thereof, which includes the steps of combining Compound IV and a base in an organic solvent
  • the mixture of sex reagents may be acylated with Compound V as shown below to obtain the 2-benzoylmalonate compound represented by Formula I or tautomers thereof;
  • the operation and conditions of the acylation reaction may be conventional operations and conditions in this type of reaction in the art.
  • the organic solvent may be a conventional organic solvent in this type of reaction in the art, such as ether solvents, organic sulfoxide solvents, amide solvents, ketone solvents, ester solvents, nitrile solvents, halogenated benzene (For example, one or more of chlorobenzene, bromobenzene, and o-dichlorobenzene, and for example, chlorobenzene and/or bromobenzene) and one or more of alkylbenzenes (such as toluene and/or xylene) In the present invention, it is preferably one or more of chlorobenzene, bromobenzene and toluene.
  • the amount of the organic solvent may not be limited as long as it does not affect the reaction; in the present invention, the mass of the organic solvent and the compound V is preferably 1:1 to 5:1, more preferably 2.5:1 ⁇ 3.5:1.
  • the alkaline reagent may be a common alkaline reagent in this type of reaction in the art, such as magnesium salt (eg magnesium chloride), magnesium alkoxide (eg magnesium ethoxide and/or magnesium methoxide), sodium alkoxide (eg sodium ethoxide and/or One or more of sodium methoxide), sodium hydride and triethylamine, preferably magnesium ethoxide and/or sodium methoxide in the present invention.
  • magnesium salt eg magnesium chloride
  • magnesium alkoxide eg magnesium ethoxide and/or magnesium methoxide
  • sodium alkoxide eg sodium ethoxide and/or One or more of sodium methoxide
  • sodium hydride and triethylamine preferably magnesium ethoxide and/or sodium methoxide in the present invention.
  • the molar ratio of the compound V to the compound IV may be a conventional molar ratio in this type of reaction in the art.
  • the molar ratio of the compound V to the compound IV in the present invention is preferably 1.2:1 ⁇ 1:1.2 (for example 1:1).
  • the molar ratio of the basic reagent to the compound IV may be a conventional molar ratio in this type of reaction in the art.
  • the molar ratio of the basic reagent to the compound IV in the present invention is preferably 1.2 : 1 to 1: 1.2 (for example, 1:1).
  • the preparation method preferably includes the steps of reacting the compound IV and the alkaline reagent at a temperature of 100°C to 110°C in the organic solvent to obtain The mixture; at a temperature of 0 °C ⁇ 30 °C, the compound V is added dropwise to the mixture, the acylation reaction is carried out to obtain the 2-benzoyl represented by the formula I
  • the malonate compounds and/or tautomers thereof may be sufficient.
  • the progress of the reaction can be monitored using conventional monitoring methods in the art (such as TLC, HPLC, or NMR). Generally, the end point of the reaction is when the compound V disappears or no longer reacts .
  • the preparation method may further include the following post-processing steps. After the acylation reaction is completed, acid is added to neutralize, extract, concentrate, and crystallize to obtain the 2-benzoylpropionate represented by Formula I The diacid compound or its tautomer is sufficient.
  • the method for preparing the 2-benzoylmalonate compound represented by formula I, or a tautomer thereof, may further include the steps of: performing compound VI and Cl 2 in the presence of a catalyst
  • the following chlorination reaction can be used to prepare the compound V,
  • the catalyst may be a conventional catalyst in this type of reaction in the art, such as azobisisobutyronitrile.
  • the amount of the catalyst may be a conventional amount used in this type of reaction in the art.
  • the molar ratio of the catalyst in the present invention to the compound VI is preferably 0.5:100 to 1:100 (eg 0.6:100) .
  • the temperature of the chlorination reaction may be a conventional temperature in this type of reaction in the art, for example, 50°C to 65°C (again, for example, 55°C to 60°C).
  • the progress of the reaction can be monitored using conventional monitoring methods in the art (such as TLC, HPLC, or NMR).
  • TLC TLC
  • HPLC HPLC
  • NMR NMR
  • the method for preparing the 2-benzoylmalonate compound represented by the formula I may further include the following steps. In the presence of a catalyst, the compound VII and water are subjected to the following hydrolysis reaction to obtain The compound VI mentioned is sufficient;
  • the catalyst may be a conventional catalyst in this type of reaction in the art, such as Lewis acid.
  • it is preferably one or more of ferric chloride, aluminum trichloride, zinc chloride, and tin chloride. Species, more preferably ferric chloride.
  • the amount of the catalyst may be a conventional amount used in this type of reaction in the art.
  • the molar ratio of the catalyst in the present invention to the compound VII is preferably 0.5:100 to 10:100 (eg 2.5:100) .
  • the amount of the water may be a conventional amount used in this type of reaction in the art.
  • the molar ratio of the water to the compound VII in the present invention is preferably 0.5:1 to 2:1 (for example, 1:1) .
  • the temperature of the hydrolysis reaction may be a conventional temperature in this type of reaction in the art, for example, 100°C to 140°C (also for example, 110°C to 115°C).
  • the progress of the reaction can be monitored by conventional monitoring methods in the art (such as TLC, HPLC, or NMR).
  • TLC TLC
  • HPLC HPLC
  • NMR NMR
  • the end point of the reaction is when the compound VII disappears or no longer reacts, for example HPLC detection showed that the content of the compound VII was ⁇ 1%.
  • the reagents and raw materials used in the present invention are commercially available.
  • the positive progress effect of the present invention is that the present invention provides a method for synthesizing 2-(4-halo-2-tris with malonate diester using 4-halo-2-trifluoromethylbenzoyl chloride as raw material Fluoromethylbenzoyl) malonate diester; the 2-benzoylmalonate compound is hydrolyzed and decarboxylated to obtain the corresponding 4-halo-2-trifluoromethylacetophenone new synthetic route .
  • the raw material readily available, the process is simple and safe, the Grignardization reaction with greater risk is avoided, but also the yield is high, which is more suitable for large-scale industrial production.
  • the purity is detected by HPLC, and the specific conditions are as follows: HPLC column: HSS T3 1.8um, 2.1*100mm, eluent: 0.05% formic acid aqueous solution + 0.05 formic acid acetonitrile (in 30min at 30 °C, the gradient from 95:5 ⁇ 5:95, flow rate 0.4ml/min).
  • step 1
  • step 1
  • reaction solution was added to dilute hydrochloric acid to separate layers, and the aqueous layer was separated.
  • 40g of 75% sulfuric acid solution was added to the organic layer, and the temperature was raised to 135°C-140°C, and the temperature was kept for 2 hours. After cooling to room temperature, the aqueous layer was separated and then washed with 5% sodium bicarbonate solution. The layers were separated, the organic layer was desolvated to recover bromobenzene, and then rectified to obtain 4-bromo-2-trifluoromethylacetophenone 56.6g, yield 91.8%, purity 99.5%.
  • reaction solution was added to dilute hydrochloric acid to separate layers, and the aqueous layer was separated.
  • 40g of 75% sulfuric acid solution was added to the organic layer, and the temperature was raised to 110°C to 115°C, and the temperature was kept for 2 hours. After cooling to room temperature, the aqueous layer was separated and then washed with 5% sodium bicarbonate solution. The layers were separated, the organic layer was desolvated to recover bromobenzene, and then rectified to obtain 4-bromo-2-trifluoromethylacetophenone 50g, yield 81%, purity 99.5%.
  • reaction solution was then added to Divide in dilute hydrochloric acid, separate the water layer, add 40g of 75% sulfuric acid solution to the organic layer, heat up to 120°C ⁇ 130°C, keep warm for 2h, and the reaction is over when no gas is generated.
  • the aqueous layer was separated, then washed with 5% sodium bicarbonate solution, separated into layers, the organic layer was desolvated to recover chlorobenzene, and then rectified to obtain 4-iodo-2-trifluoromethylacetophenone 68.7g, yield 93% (calculated based on 4-chloro-2-trifluoromethylbenzoyl chloride), purity 99.5%.

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Abstract

La présente invention concerne un composé de 2-benzoyle malonate, un procédé de préparation correspondant et une utilisation associée. L'invention concerne un procédé de préparation d'un composé d'acétylbenzène représenté par la formule III, comprenant l'étape suivante consistant à : soumettre, dans un solvant organique en présence d'acide et de l'eau, un composé de 2-benzoyle malonate représenté par la formule I et/ou un tautomère de celui-ci à une réaction de dé-estérification telle que présentée ci-dessous pour obtenir un composé d'acétylbenzène représenté par la formule III, dans laquelle X représente F, Cl, Br ou I et R1 et R2 représentent indépendamment des groupes alkyle en C1-C4. Le composé de 2-benzoyle malonate selon la présente invention peut être utilisé pour une réaction afin d'obtenir en outre du 4-halogéno-2-trifluorométhyl-acétophénone ; le mode opératoire étant facile et simple.
PCT/CN2018/123070 2018-12-24 2018-12-24 Composé de 2-benzoyle malonate, procédé de préparation correspondant et utilisation associée WO2020132792A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020040158A1 (en) * 2000-07-26 2002-04-04 Clariant Gmbh Process for preparing substituted benzoyl chlorides
WO2011021492A1 (fr) * 2009-08-18 2011-02-24 セントラル硝子株式会社 Procédé de production de composés aromatiques substitués par un formyle
CN102249921A (zh) * 2010-05-17 2011-11-23 上海升华医药科技有限公司 2-(2,3-二甲基苯基)丙二酸二酯,其制备方法和用途
CN102356056A (zh) * 2009-03-17 2012-02-15 帝人芳纶有限公司 芳族醛转化成芳族酰基卤的方法
CN104016840A (zh) * 2014-06-16 2014-09-03 辽宁天予化工有限公司 一种邻三氟甲基苯甲醛的制备方法
CN105967986A (zh) * 2016-05-30 2016-09-28 北京旭阳科技有限公司 3-羟基苯乙酮的合成方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020040158A1 (en) * 2000-07-26 2002-04-04 Clariant Gmbh Process for preparing substituted benzoyl chlorides
CN102356056A (zh) * 2009-03-17 2012-02-15 帝人芳纶有限公司 芳族醛转化成芳族酰基卤的方法
WO2011021492A1 (fr) * 2009-08-18 2011-02-24 セントラル硝子株式会社 Procédé de production de composés aromatiques substitués par un formyle
CN102249921A (zh) * 2010-05-17 2011-11-23 上海升华医药科技有限公司 2-(2,3-二甲基苯基)丙二酸二酯,其制备方法和用途
CN104016840A (zh) * 2014-06-16 2014-09-03 辽宁天予化工有限公司 一种邻三氟甲基苯甲醛的制备方法
CN105967986A (zh) * 2016-05-30 2016-09-28 北京旭阳科技有限公司 3-羟基苯乙酮的合成方法

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