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WO2011021492A1 - Procédé de production de composés aromatiques substitués par un formyle - Google Patents

Procédé de production de composés aromatiques substitués par un formyle Download PDF

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Publication number
WO2011021492A1
WO2011021492A1 PCT/JP2010/062879 JP2010062879W WO2011021492A1 WO 2011021492 A1 WO2011021492 A1 WO 2011021492A1 JP 2010062879 W JP2010062879 W JP 2010062879W WO 2011021492 A1 WO2011021492 A1 WO 2011021492A1
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group
substituted aromatic
dihalomethyl
aromatic compound
reaction
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Japanese (ja)
Inventor
剛 近藤
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Central Glass Co Ltd
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Central Glass Co Ltd
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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
    • C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
    • C07C45/43—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis of >CX2 groups, X being halogen

Definitions

  • the present invention is a method for producing a formyl group-substituted aromatic compound having a trifluoromethyl group (sometimes referred to as “aromatic aldehyde”) useful as a raw material for synthesizing dyes, fragrances, medicines, agricultural chemicals and other organic compounds. More particularly, the present invention relates to a method for producing a corresponding aromatic aldehyde by hydrolyzing a dihalomethyl group-substituted aromatic compound in which a ring hydrogen atom is substituted with a trifluoromethyl group.
  • benzal chlorides which are dihalomethyl group-substituted aromatic compounds, are slow to hydrolyze into benzaldehydes simply by mixing with water and heating. Therefore, benzal chlorides are conventionally hydrolyzed using various catalysts. Methods for producing benzaldehydes that decompose are known.
  • Non-Patent Documents 1 and 2 A method for producing benzaldehydes by hydrolyzing benzal chlorides using an acid or alkaline aqueous solution (Non-Patent Documents 1 and 2), (2) Presence of cuprous chloride or cupric chloride Below, benzal chlorides are hydrolyzed to produce benzaldehyde (Patent Document 1, Patent Document 2), (3) An aqueous solution of iron salt is added to benzal chlorides and hydrolyzed to produce benzaldehydes (Patent Document 3), (4) A method of hydrolyzing benzal chlorides in the presence of anhydrous zinc chloride to produce benzaldehydes (Patent Document 4), (5) In the presence of zinc oxide, There exist methods, such as the method (patent document 5) etc. which hydrolyze a salchloride and manufacture benzaldehyde.
  • An object of the present invention is to provide a method for producing a corresponding aromatic aldehyde by hydrolyzing a dihalomethyl group of a dihalomethyl group-substituted aromatic compound substituted with a trifluoromethyl group in a short time.
  • the present inventors examined a method for hydrolyzing a dihalomethyl group of a dihalomethyl group-substituted aromatic compound substituted with a trifluoromethyl group by catalyzing an iron salt. By preliminarily presenting an aldehyde compound and an iron salt in the aromatic compound, it was found that the selectivity of the target aromatic aldehyde was high and the reaction was completed in a very short time, and the present invention was completed. .
  • the hydrolysis of the dihalomethyl group of the aromatic compound substituted with the dihalomethyl group substituted by the trifluoromethyl group is the substitution of the dihalomethyl group not substituted by the trifluoromethyl group.
  • the reaction rate is predicted to be slower than that of the aromatic compound, and the remarkable difference in the reaction time in the case of using an iron salt as a catalyst is the difference between each of the examples of JP-B-48-693 and JP-A-2006-160635. It can be easily seen from the comparison.
  • Japanese Patent Publication No. 48-693 describes that when an anhydrous iron salt is added to benzal chloride having no trifluoromethyl group, a resin is formed immediately.
  • the present invention is as follows.
  • invention 1 A method for producing a formyl group-substituted aromatic compound represented by the general formula (2) by hydrolyzing a dihalomethyl group-substituted aromatic compound represented by the general formula (1) in the presence of an iron salt, Dissolving the aldehyde compound and iron salt in the dihalomethyl group-substituted aromatic compound before the hydrolysis reaction occurs, and the rate at which water is not exceeded after reaching the reaction temperature sufficient for the hydrolysis reaction to occur.
  • the method for producing the above-mentioned formyl group-substituted aromatic compound which comprises adding the compound into the reaction system in Step 1.
  • Ar represents an aromatic ring
  • X represents a halogen atom
  • R represents a monovalent organic group which may be different from each other
  • l is 1 to 3
  • m is 1 to 5
  • n is 0 to Represents an integer of 5 and 1 ⁇ l + m + n ⁇ 6.
  • Ar, R, l, m and n are the same as those in the general formula (1).
  • Invention 2 The production method of Invention 1, wherein the aldehyde compound is a formyl group-substituted aromatic compound to be obtained by the production method.
  • the method of the present invention can obtain a desired aromatic aldehyde with high selectivity from a dihalomethyl group-substituted aromatic compound substituted with a trifluoromethyl group, and can complete the reaction in a very short time. Since the catalyst can be used repeatedly, it is an industrially suitable method.
  • a dihalomethyl group-substituted aromatic compound of the general formula (1) having a trifluoromethyl group is hydrolyzed in the presence of an iron salt to produce a corresponding formyl group-substituted aromatic compound of the general formula (2).
  • the aldehyde compound and the iron salt are dissolved in the dihalomethyl group-substituted aromatic compound, and after the reaction temperature is sufficient for the hydrolysis reaction to occur, the water is removed at a rate of disappearance. Add into the reaction system at a rate not exceeding.
  • Ar represents an aromatic ring
  • X represents a halogen atom
  • R represents a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group
  • l is 1 to 3
  • m is 1 ⁇ 5
  • n represents an integer of 0 ⁇ 5
  • Ar, R, l, m, and n are the same as those in the general formula (1).
  • Ar is an aromatic ring having 4 to 8 ring carbon atoms or a condensed ring in which 2 to 10 of them are condensed, and a heterocycle in which any carbon atom is substituted with an oxygen atom, a nitrogen atom, or a sulfur atom, Also good.
  • benzene ring examples include benzene ring, naphthalene ring, anthracene ring, pyrene ring, phenanthrene ring, perylene ring, coronene ring, pyridine ring, quinoline ring, thiophene ring, pyrrole ring, furan ring, etc., but benzene ring, naphthalene A ring and a pyridine ring are preferable, and a benzene ring is more preferable.
  • the halogen atom of X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably chlorine.
  • the number l of dihalomethyl groups is 1 to 3, and is preferably 1.
  • the number m of the substituted trifluoromethyl groups is 1 to 5, preferably 1 or 2, more preferably 1, and the number n of substituents R other than the trifluoromethyl group is 1 to 5, and 0 to 2 is 0 or 1 is more preferable.
  • the aromatic compound having a dihalomethyl group is preferably an aromatic compound in which a trifluoromethyl group and a dihalomethyl group are substituted on the adjacent ring carbon, and an aromatic compound in which a chlorine atom or a fluorine atom is further substituted on the ring carbon.
  • a group compound is preferable, and as the aromatic, a benzene ring, a naphthalene ring or a pyridine ring is preferable, and a benzene ring is particularly preferable.
  • R since it is an object to improve the hydrolysis reactivity of a formyl group bonded to an aromatic ring substituted with an electron-withdrawing trifluoromethyl group, it is represented by R other than the trifluoromethyl group.
  • the valent organic group is not particularly limited, and the reaction proceeds more easily with a substituent that is inherently electron donating.
  • a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a hydroxyl group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group , Alkoxy group, aryl group, aralkyl group, aryloxy group, carboalkoxy group, nitro group, sulfochloride group, alkylsulfonyl group, sulfonic acid alkyl ester group, sulfonic acid aryl ester group, substituted or unsubstituted sulfonic acid amide group , A methylenedioxy group.
  • the alkyl group, alkenyl group and alkynyl group contained in the structure are each a linear, branched or cyclic alkyl group, alkenyl group and alkynyl group having 1 to 20 carbon atoms.
  • the aryl group is a so-called broad aryl group in which one hydrogen atom is eliminated from an aromatic compound, and an aryl group having 4 to 20 carbon atoms.
  • these alkyl groups, alkenyl groups, alkynyl groups, and aryl groups can further have a substituent.
  • a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom
  • hydroxyl group cyano group
  • alkyl group alkenyl group, alkynyl group, alkoxy group, aryl group, aralkyl group, aryloxy group
  • examples thereof include a carboalkoxy group, a nitro group, a sulfochloride group, an alkylsulfonyl group, a sulfonic acid alkyl ester group, a sulfonic acid aryl ester group, a substituted or unsubstituted sulfonic acid amide group, and a methylenedioxy group.
  • Any carbon atom contained in the structure can be substituted with an oxygen atom, a sulfur atom, a nitrogen atom or a carbonyl group.
  • R is preferably a halogen atom, hydroxyl group, cyano group, methyl group, ethyl group, n-propyl group, iso-propyl group, phenyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group or the like.
  • the halogen atom is more preferably a fluorine atom or a chlorine atom.
  • dihalomethyl group-substituted aromatic compound used in the present invention examples include compounds exemplified in JP 59-21637 A, and specifically, for example, 1-trifluoromethyl-2-di Halomethylbenzene, 1-trifluoromethyl-3-dihalomethylbenzene, 1-trifluoromethyl-4-dihalomethylbenzene, 3-dihalomethyl-4-trifluoromethylhalobenzene, 2-trifluoromethyl-3- Dihalomethylhalobenzene, 3-trifluoromethyl-4-dihalomethylhalobenzene, 2-trifluoromethyl-6-dihalomethylhalobenzene, 2-dihalomethyl-4-trifluoromethylhalobenzene, 3-trifluoro Methyl-5-dihalomethylhalobenzene, 2-trifluoromethyl-4-dihalomethylhalo , 2-trifluoromethyl-5-dihalomethylhalobenzene, 2-dihalomethyl-5-d
  • halo of the dihalomethyl group is read as “chloro” or “bromo”, and “halo” of the halo group (halogen atom substituted on the aromatic ring) is read as “chloro” or “fluoro”.
  • the dihalomethyl group is preferably a dichloromethyl group.
  • aromatic compounds having a dihalomethyl group can be obtained by halogenating the methyl group of the corresponding compound with a halogenating agent by a known method. For example, it can be obtained together with a compound having a trichloromethyl group and a compound having a dichloromethyl group by chlorinating with a chlorinating agent such as phosphorus trichloride.
  • the dihalomethyl group of the dihalomethyl group-substituted aromatic compound represented by the general formula (1) used as a raw material is a formyl group. It is a converted compound and other partial structures do not change.
  • the iron salt used in the present invention is an iron halide, and examples thereof include ferric chloride, ferrous chloride, ferric bromide, and ferrous bromide, and ferric chloride is most preferable. Hydrates of these iron salts can also be used. Further, the iron salt can be prepared in advance as a complex and used.
  • the amount of the iron salt used is 0.1 to 30% by mass, preferably 0.5 to 20% by mass of the dihalomethyl group-substituted aromatic compound represented by the general formula (1) of the raw material, and 1 to 10% by mass. Is more preferable. If it is less than 0.1% by mass, sufficient activity cannot be obtained, and if it exceeds 30% by mass, there is no problem in terms of reaction, but the post-treatment becomes complicated, which is not preferable.
  • the aldehyde compound added to the dihalomethyl group-substituted aromatic compound represented by the general formula (1) used as a raw material before hydrolysis reaction occurs may be an aldehyde compound in which a formyl group is bonded to a ring.
  • aldehyde compounds include aldehyde compounds represented by the general formula (3).
  • Ar ′ represents an aromatic ring
  • R ′ each independently represents a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group.
  • the aromatic ring represented by Ar ′ may be the same aromatic ring as Ar.
  • the monovalent organic group in R ′ is the same monovalent organic group or trifluoromethyl group as R. Since this aldehyde compound needs to be dissolved in the dihalomethyl group-substituted aromatic compound according to the present invention, it must have a benzene ring and a formyl group in order to dissolve the iron salt.
  • Can be exemplified formyl group-substituted aromatic compound represented by the general formula is a product corresponding to each of the compounds exemplified as dihalomethyl-substituted aromatic compound represented by the formula (1) (2).
  • These aldehyde compounds are the desired products of the reaction, and are most preferred because they can be easily purified by distillation or the like.
  • the amount of the aldehyde compound added is 0.001 to 100 parts by mass, and 0.005 to 1 part by mass with respect to 1 part by mass of the trifluoromethyl group-containing aromatic compound represented by the general formula (1) of the raw material.
  • 0.01 to 0.1 part by mass is more preferable.
  • an appropriate solvent may be added to the reaction system.
  • the solvent used is a liquid that is inert under the reaction conditions of the present invention, and examples thereof include halogenated hydrocarbons such as tetrachloroethylene and 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene, and mesitylene, and chlorobenzene.
  • halogenated hydrocarbons such as tetrachloroethylene and 1,2-dichloroethane
  • aromatic hydrocarbons such as toluene, xylene, and mesitylene, and chlorobenzene.
  • a halogenated aromatic compound etc. can be illustrated.
  • the rate of water addition is kept slower than that consumed in the hydrolysis reaction so that liquid water does not stay in the reaction system. Therefore, the rate of water addition is determined by the type of reaction substrate, the amount of iron salt as a catalyst, and the reaction temperature.
  • the total amount of water added is dihalomethyl represented by the general formula (1), which is a raw material for the reaction, because the hydrogen halide produced as a by-product in the hydrolysis reaction is sometimes accompanied by water vapor. Although it is used slightly more than 1 mol per 1 mol of the group-substituted aromatic compound, it may be 1 to 2 mol, and is usually about 1.1 mol. If the amount is less than 1 mole, hydrolysis is not completed, and excessively used water is not preferable because it forms a water layer and does not contribute to the reaction, and the hydrolysis rate is significantly reduced.
  • the reaction temperature is 40 ° C. or higher and below the boiling point of the reaction solution, but it can be usually 40 to 200 ° C., preferably 80 to 160 ° C., more preferably 90 to 140 ° C. Below 40 ° C, the reaction is slow and impractical. Moreover, when the reaction temperature exceeds 200 ° C., a polymerization reaction may occur, which is not preferable.
  • the reaction pressure is not particularly limited, but may be 0.05 to 1 MPa.
  • the container used for the reaction can be a glass container, a glass lining container, a fluororesin container or the like, but is not limited to these materials.
  • the reaction can be carried out in any form such as batch, semi-flow, and flow.
  • the reaction vessel is charged with a dihalomethyl group-substituted aromatic compound and a predetermined amount of aldehyde compound as raw materials, and an iron salt is added thereto.
  • the dihalomethyl group-substituted aromatic compound represented by the general formula (1) usually does not substantially dissolve inorganic iron salts such as ferric chloride, it is also preferable to dissolve in advance in the aldehyde compound. In many cases, the iron salt dissolves and the contents of the reactor are colored reddish brown. When this solution is heated to reach the reaction temperature, water is gradually added at the hydrolysis rate so that water droplets do not stay in the reaction system, and hydrogen chloride is generated, indicating the progress of the hydrolysis reaction. .
  • the completion of the reaction can be known also by adding a predetermined amount of water, confirming the generation of a predetermined amount of hydrogen chloride, or changing the color tone of the reaction solution. It can also be confirmed by high-performance liquid chromatography (HPLC) or gas chromatography (GC) by disappearance of raw materials or maximization of products.
  • HPLC high-performance liquid chromatography
  • GC gas chromatography
  • the formyl group-substituted aromatic compound represented by the general formula (2) can be obtained by heating and / or reducing the pressure in the reaction vessel and distilling the product.
  • the iron salt remaining in the reactor after distilling off the product does not lose its catalytic activity as shown in the examples, so that it can be used repeatedly in the same reaction. At this time, it is preferable to leave a predetermined amount of the product necessary for the next reaction.
  • Example 2 Into a 100 ml Erlenmeyer flask equipped with a Dimroth condenser, put 50 g of OTFBAC with a purity of 99.2%, 5 g of OTFBAD with a purity of 99.0%, and 0.25 g of anhydrous ferric chloride (powder): Heat with stirring with a tic stirrer. When the liquid temperature reached about 130 ° C., 4.2 g of pure water was successively added dropwise over about 10 minutes with a Pasteur pipette (1 ml). After the dropwise addition, the reaction was completed by stirring at 126 to 134 ° C. for about 10 minutes.
  • Examples 3 to 11 50 g of OTFBAC was newly added to the OTFBAD residue containing iron chloride obtained in Example 2, and the same test as in Example 2 was performed. The reaction temperature, the addition time of pure water, the amount of added water and the yield of OTFBAD are shown in Table 1 (Example 3). Further, the same test was repeated (Examples 4 to 11). Table 1 shows the specifications at that time. During these tests, no anhydrous ferric chloride was added.
  • Example 12 A 100 ml Erlenmeyer flask equipped with a Dimroth condenser was charged with 98.4% 2-trifluoromethyl-5-fluorobenzal chloride (abbreviated as “2TF5FBAC”): 50 g, 99.8% purity 2-trifluoro.
  • Methyl-5-fluorobenzaldehyde (abbreviated as “2TF5FBAD”): 5 g
  • anhydrous / ferric chloride (powder) 0.25 g were added and heated with stirring with a magnetic stirrer. When the liquid temperature reached about 130 ° C., 4.5 g of pure water was successively added dropwise over about 10 minutes with a Pasteur pipette (1 ml).
  • Examples 13 to 21 50 g of 2TF5FBAC was newly added to the 2TF5FBAD residue containing iron chloride obtained in Example 12, and the same test as in Example 12 was performed. Table 2 shows the reaction temperature, the addition time of pure water, the amount of added water, and the yield of 2TF5FBAD. Further, the same test was repeated (Examples 14 to 21). Table 2 shows the specifications at that time. During these tests, no anhydrous ferric chloride was added.
  • Example 22 A 100 ml Erlenmeyer flask equipped with a Dimroth condenser was charged with 99.1% purity 4-chloro-2-trifluoromethylbenzal chloride (abbreviated as 4C2TFBAC): 50 g, 99.9% purity 4-chloro-2-tri Fluoromethylbenzaldehyde (abbreviated as 4C2TFBAD): 5 g and anhydrous / ferric chloride (powder): 0.25 g were added and heated while stirring with a magnetic stirrer. When the liquid temperature reached about 135 ° C., 4.8 g of pure water was successively dropped over about 10 minutes with a Pasteur pipette (1 ml).
  • 4C2TFBAC 4-chloro-2-trifluoromethylbenzal chloride
  • 4C2TFBAD anhydrous / ferric chloride
  • Example 23 The same test as in Example 22 was performed by newly charging 50 g of 4C2TFBAC into the 4C2TFBAD residue containing iron chloride obtained in Example 22.
  • the reaction temperature, the addition time of pure water, the amount of added water and the yield of 4C2TFBAD are shown in Table 3 (Example 23). Further, the same test was repeated (Examples 24 to 31). Table 3 shows the specifications at that time. During these tests, no anhydrous ferric chloride was added.
  • the desired aromatic aldehyde can be obtained from the dihalomethyl group-substituted aromatic compound substituted with a trifluoromethyl group in a very short time with high selectivity.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention a pour objet un procédé pour la production de composés aromatiques substitués par un formyle qui comprend les étapes consistant à hydrolyser un composé aromatique substitué par un dihalométhyle représenté par la formule générale (1) en le composé aromatique substitué par un formyle correspondant en présence d'un sel de fer, un aldéhyde et un sel de fer étant dissous dans le composé aromatique substitué par un dihalométhyle avant la survenue de l'hydrolyse, et après que le système réactionnel résultant atteint une température de réaction suffisante pour provoquer l'hydrolyse, de l'eau étant ajoutée au système réactionnel à une vitesse qui ne dépasse pas la vitesse de consommation de l'eau. Dans la formule générale (1), Ar est un cycle aromatique ; X est un atome d'halogène ; les R sont chacun indépendamment un groupe organique monovalent ; et l est un nombre entier de 1 à 3, m est un nombre entier de 1 à 5, et n est un nombre entier de 0 à 5, l, m et n satisfaisant à la relation : 1 = l + m + n = 6. Par l'utilisation de ce procédé, le groupe dihalométhyle d'un composé aromatique substitué par un dihalométhyle ayant un groupe trifluorométhyle en tant qu'autre substituant peut être hydrolysé en un temps court.
PCT/JP2010/062879 2009-08-18 2010-07-30 Procédé de production de composés aromatiques substitués par un formyle Ceased WO2011021492A1 (fr)

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JP2009189346A JP2011037803A (ja) 2009-08-18 2009-08-18 ホルミル基置換芳香族化合物の製造方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516047A (zh) * 2011-12-13 2012-06-27 联化科技股份有限公司 一种邻三氟甲基苯甲醛及其中间体的制备方法
CN106278837A (zh) * 2015-05-28 2017-01-04 联化科技（台州）有限公司 邻三氟甲基-4-卤代苯甲醛的制备方法及其中间体
WO2019052440A1 (fr) 2017-09-12 2019-03-21 江苏恒瑞医药股份有限公司 Dérivé d'indole-formamide substitué par un atome de deutérium, son procédé de préparation et ses applications médicales
CN111348996A (zh) * 2018-12-24 2020-06-30 江苏联化科技有限公司 一种2-苯甲酰丙二酸酯类化合物、其制备方法及应用
WO2020132792A1 (fr) * 2018-12-24 2020-07-02 江苏联化科技有限公司 Composé de 2-benzoyle malonate, procédé de préparation correspondant et utilisation associée

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EP0077853A1 (fr) * 1980-10-10 1983-05-04 Occidental Chemical Corporation Chlorure de trifluorméthylbenzylidène et procédé pour sa préparation
JPH0748307A (ja) * 1992-11-26 1995-02-21 Hoechst Ag 芳香族アルデヒドの製造方法
JP2005272324A (ja) * 2004-03-23 2005-10-06 Central Glass Co Ltd ３−ホルミル−５−トリフルオロメチルベンゾニトリル誘導体とその製造方法
JP2006045095A (ja) * 2004-08-03 2006-02-16 Central Glass Co Ltd ３−ホルミル−５−トリフルオロメチルベンゾニトリル誘導体とその製造方法
JP2006160635A (ja) * 2004-12-03 2006-06-22 Central Glass Co Ltd ２−トリフルオロメチル−５−フルオロベンズアルデヒドおよびその誘導体の製造方法
JP2006213630A (ja) * 2005-02-03 2006-08-17 Central Glass Co Ltd ２−トリフルオロメチル−６−フルオロベンズアルデヒドおよびその誘導体の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0077853A1 (fr) * 1980-10-10 1983-05-04 Occidental Chemical Corporation Chlorure de trifluorméthylbenzylidène et procédé pour sa préparation
JPH0748307A (ja) * 1992-11-26 1995-02-21 Hoechst Ag 芳香族アルデヒドの製造方法
JP2005272324A (ja) * 2004-03-23 2005-10-06 Central Glass Co Ltd ３−ホルミル−５−トリフルオロメチルベンゾニトリル誘導体とその製造方法
JP2006045095A (ja) * 2004-08-03 2006-02-16 Central Glass Co Ltd ３−ホルミル−５−トリフルオロメチルベンゾニトリル誘導体とその製造方法
JP2006160635A (ja) * 2004-12-03 2006-06-22 Central Glass Co Ltd ２−トリフルオロメチル−５−フルオロベンズアルデヒドおよびその誘導体の製造方法
JP2006213630A (ja) * 2005-02-03 2006-08-17 Central Glass Co Ltd ２−トリフルオロメチル−６−フルオロベンズアルデヒドおよびその誘導体の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516047A (zh) * 2011-12-13 2012-06-27 联化科技股份有限公司 一种邻三氟甲基苯甲醛及其中间体的制备方法
CN106278837A (zh) * 2015-05-28 2017-01-04 联化科技（台州）有限公司 邻三氟甲基-4-卤代苯甲醛的制备方法及其中间体
WO2019052440A1 (fr) 2017-09-12 2019-03-21 江苏恒瑞医药股份有限公司 Dérivé d'indole-formamide substitué par un atome de deutérium, son procédé de préparation et ses applications médicales
CN111348996A (zh) * 2018-12-24 2020-06-30 江苏联化科技有限公司 一种2-苯甲酰丙二酸酯类化合物、其制备方法及应用
WO2020132792A1 (fr) * 2018-12-24 2020-07-02 江苏联化科技有限公司 Composé de 2-benzoyle malonate, procédé de préparation correspondant et utilisation associée
CN111348996B (zh) * 2018-12-24 2023-09-08 江苏联化科技有限公司 一种2-苯甲酰丙二酸酯类化合物、其制备方法及应用

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