WO2003101922A1 - Procede de decarbonylation d'un halogenure d'acide aromatique - Google Patents

Procede de decarbonylation d'un halogenure d'acide aromatique Download PDF

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Publication number
WO2003101922A1
WO2003101922A1 PCT/JP2003/005883 JP0305883W WO03101922A1 WO 2003101922 A1 WO2003101922 A1 WO 2003101922A1 JP 0305883 W JP0305883 W JP 0305883W WO 03101922 A1 WO03101922 A1 WO 03101922A1
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Prior art keywords
aromatic
phosphine
rhodium
acid chloride
acid
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PCT/JP2003/005883
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English (en)
Japanese (ja)
Inventor
Tetsuya Hirade
Kazuto Umezu
Yasuo Yoshida
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Ihara Chemical Industry Co., Ltd.
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Priority to JP2004509618A priority Critical patent/JP4320299B2/ja
Priority to AU2003235935A priority patent/AU2003235935A1/en
Publication of WO2003101922A1 publication Critical patent/WO2003101922A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
    • C07C63/70—Monocarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/62—Preparation of carboxylic acid halides by reactions not involving the carboxylic acid halide group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate

Definitions

  • the present invention relates to a method for decarbonylating an aromatic acid halide to obtain another core halogeno aromatic compound useful in the field of medicine and agrochemicals.
  • the present invention relates to a method for producing an aromatic compound and a catalyst therefor.
  • the method of obtaining a core halogeno aromatic compound by CO is known as a method of selectively obtaining an aromatic compound having a halogen atom bonded to a desired position on the surface.
  • 5-isophthalic acid chloride is unstable at high temperatures and decomposes at about 4-5% at 200 ° C to 230 ° C for 4 hours.
  • the decomposition rate after 4 hours at 50 ° C was about 10% or more, and a reaction at 230 ° C or lower was desired.
  • the present invention relates to an aromatic acid halide, which requires a long reaction time or a high temperature of 250 ° C. or more and special equipment and materials when the conventional technology is applied.
  • the purpose of the present invention is to carry out the weakening of the compound under milder conditions, and to obtain a product easily and in a short time in a good yield.
  • the present inventors have conducted intensive studies on the decarbonylation of aromatic acid halides.
  • a rhodium metal catalyst such as a rhodium complex
  • a hydrogenated aromatic phosphine for example, tris (aminofluorophenyl) phosphine as a ligand
  • the reaction proceeds more quickly at a lower temperature at a lower temperature.
  • the product is distilled off under rectification conditions, whereby the selectivity of the desired product can be improved.
  • the reaction can be continued continuously, or the reaction can be repeated, and the cost problem can be overcome, and the present invention has been completed. It came to that. ,
  • the present invention relates to a method for producing a corresponding core halogeno aromatic compound, which comprises decarbonylating an aromatic acid halide in the presence of a rhodium metal catalyst and a fluorinated aromatic phosphine. .
  • the present invention also relates to a catalyst for decarboxylation of an aromatic acid halide, comprising a rhodium metal catalyst and a fluorinated aromatic phosphine.
  • the present invention provides a method for producing a corresponding core halogeno aromatic compound, which comprises decarboxylating an aromatic acid halide at a relatively low temperature of about 200 ° C. And the use of a phosphine containing fluorine as a ligand.
  • triphenylphosphine has been used as a ligand.However, the reaction requires a high temperature and the reaction time is long, and when the reaction is performed at a relatively low temperature, for example, at 200 ° C, the conversion and the selectivity are high. The rates were not enough. However, they have found that these disadvantages can be solved by using a fluorine-containing phosphine as a ligand.
  • the “molar ratio to mo 1% * / ⁇ ” indicates a value based on the amount of the “catalytic metal”, As a result, the conversion rate was about 2 to 31% in the conventional method, but it was improved to about 73% in the method of the present invention, and the yield of the target product was about 72%, which was the conventional method. It was found to be more than doubled.
  • Table 2 shows the results of production examples of 3,5-dichlorobenzoic acid chloride using 5-chloroisofuroyl chloride as a raw material. Comparative Example 5 in Table 2 was reacted in the same manner as in Example 2 except that the ligand was changed.
  • the aromatic acid halide used as a raw material in the method of the present invention may be any one in which one or more acid halogen groups, that is, a carbonyl halide group is bonded to an aromatic group.
  • the group may have a substituent as long as it does not adversely affect the reaction.
  • Ar represents an aromatic group which may have a substituent
  • X represents a halogen atom
  • m represents an integer of 1 or 2 or more.
  • the halogen in the aromatic acid halide of the present invention may be a halogen such as chlorine, bromine or iodine, and preferably chlorine.
  • the aromatic group of the aromatic acid halide of the present invention is a monocyclic or polycyclic having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • Preferred aromatic groups include, for example, carbocyclic groups such as phenyl and naphthyl, but are not limited thereto.
  • the aromatic group in the aromatic acid halide of the present invention may have one or more substituents. Such a substituent is not particularly limited as long as it does not inhibit the decarbonylation reaction of the present invention.
  • Preferred substituents include, for example, an alkyl group, halogen and the like.
  • the alkyl group a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms is preferable, and more preferably An alkyl group having 1 to 6 carbon atoms is exemplified.
  • halogen examples include the above-mentioned chlorine and bromine.
  • M in the general formula (I) is an integer of 1 or more, and is an integer equal to or less than the number of hydrogen atoms that can be bonded to the aromatic group. Preferred m is 1, 2 or 3.
  • aromatic acid halide of the present invention include the following general formula (II):
  • X represents a halogen atom
  • Y represents a halogen atom or an alkyl group
  • m represents an integer from 1 to 6
  • n represents an integer from 0 to 5
  • m + n is 6 or less.
  • Xs may be of different types
  • Ys may be of different types.
  • halogen atom examples include those described above.
  • X and Y in the general formula (II) are 2 or more, they may be the same or different.
  • aromatic acid halides of the present invention include, for example, benzoyl chloride, benzoyl promide, benzoyl chloride, fluoric acid chloride, phthalic acid promide, and phthalic acid chloride.
  • Preferred aromatic acid halides in the method of the present invention include 5-chloroisophthalic acid chloride.
  • 5-chloroisophthalic acid chloride By using 5-chloroisophthalic acid chloride as a raw material compound, 3,5-dichloromethylbenzoic acid chloride, which is useful as an intermediate for agricultural chemicals, can be produced by the method of the present invention. It can be easily manufactured with a high selectivity.
  • rhodium metal catalysts include rhodium simple substance such as metal rhodium and rhodium chloride and rhodium compounds, but rhodium complexes, particularly rhodium organic complexes are preferred. .
  • Rhodium alone and rhodium compounds include rhodium powder (Rhodium, Powder), sponge-like rhodium (Rhodium, sponge), rhodium black (Rhodium black), rhodium chloride (III), and rhodium (III) chloride water.
  • rhodium complex examples include, for example, dodecacarbonyltetrarhodium (0), hexadecacarbonyl hexarhodium (0), dichloromethanetetracarbonylironlodium (I), and hydridotetracarbonylrhodium (0).
  • Inorganic complexes such as i-I), di-barchlorobis (cyclohexyl) dirhodium (I), dichloro-1-tetra (? 7-ethylene) dirhodium (1), dichloro-1-tetrakis (cyclo) Rhodium (I), dicarbonyl (7? -Cyclopentagenenyl) rhodium (I), (77-cyclopentenyl) (??-cyclooctadiene) rhodium
  • Examples of the fluorinated aromatic phosphine as a ligand in the catalyst of the present invention include aromatic phosphines containing at least one, and preferably two or more fluorine atoms in the molecule.
  • the fluorine-containing aromatic groups bonded to the phosphorus atom of the fluorinated aromatic phosphine may be the same or different. All three aromatic groups bonded to a phosphorus atom are preferably phosphine, which is a group containing a fluorine atom, but a fluorine atom is not necessarily bonded to all three aromatic groups. You do not have to.
  • the aromatic group in the fluorinated aromatic phosphine examples include the aromatic groups described above, and among them, a phenyl group is preferable.
  • the fluorine atom in the fluorinated aromatic phosphine of the present invention is preferably one which is directly bonded to an aromatic group, but it is not necessarily required to be directly bonded.
  • it may be an aromatic group having an alkyl group substituted by a fluorine atom such as a trifluoromethyl group.
  • fluorinated aromatic phosphine of the present invention examples include tris (4-fluorophenyl) phosphine, tris (difluorophenyl) phosphine, and tris (24,6-trifluoro). Phenyl) phosphine, tris (pentafluorophenyl) phosphine, tris (3,5-bis (trifluoromethyl) -phenyl) phosphine, etc. Phenyl) phosphine is preferred.
  • the addition of commonly used triphenylphosphine and the like is not sufficient in yield, and chlorotris (triphenylphosphine) rhodium, which is a complex of triphenylphosphine and rhodium, is not sufficient.
  • chlorotris (triphenylphosphine) rhodium which is a complex of triphenylphosphine and rhodium, is not sufficient.
  • the amount of the rhodium metal catalyst to be added in the present reaction may be 1 mol% or less based on the amount of the aromatic acid halide used as the raw material, and the range of the catalyst amount is from 0.001 to 1.0.
  • the reaction proceeds sufficiently in the range of 0 mol%, but is preferably in the range of 0.001 to 0.1 mol%.
  • the amount of the fluorinated aromatic phosphine to be added is 1 to 300 times, 3 to 300 times, preferably 10 to 10 times by mole ratio to the amount of the rhodium metal catalyst to be added. It is 0 times.
  • the fluorinated aromatic phosphine may be added as a rhodium complex, but in this case, it is necessary to add an excess amount of the fluorinated aromatic phosphine. preferable.
  • the fluorinated aromatic phosphine to be added in this case is preferably the same as the fluorinated aromatic phosphine forming the rhodium complex, but may be of a different type.
  • the reaction temperature for proceeding the decarbonylation reaction of the present invention is 130 to 300 ° C, preferably 150 to 250 ° C, more preferably 170 ° C. It is in the range of 2230 ° C.
  • the reaction can be carried out under normal pressure, increased pressure or reduced pressure, but it is usually preferably performed under reduced pressure or normal pressure, and more preferably under reduced pressure.
  • reaction of the present invention can be performed in a batch system or a continuous system.
  • the core halogeno aromatic compound represented by the general formula (IV) is a product in which 1 is 1 to 5 and m-1 is 1 or more.
  • a reactive distillation technique in which the reaction is carried out under reduced pressure and rectification and the reaction is carried out while distilling off the product.
  • the conditions of the reactive distillation such as the degree of reduced pressure can be arbitrarily set according to the physical properties (eg, vapor pressure) of the raw materials and the product.
  • this residue (including the active rhodium metal catalyst and ligand) is reused, and the raw materials are added again to react. Can be continued or repeated. Further, the reaction may be carried out by appropriately adding a rhodium metal catalyst and a ligand as needed.
  • the contents described in Japanese Patent Application No. 2002-15607779 are incorporated herein in their entirety.
  • Example 1 Production of 1,4-dichlorobenzene
  • 5-isophthalic chloride 3.0-0.0 g (0.01 26 mo 1) s di // mono-bis (cyclooctadiene) dirhodium (I) 0. 0.311 g (0.0000063 mol) and 0.21 g (0.0000378 mol) of tris (pentafluorophenyl) phosphine were charged. Subsequently, the temperature was slowly increased to 2 ° C and the mixture was aged at 200 ° C for 4 hours. After the acid chloride was treated with getylamine and analyzed by gas chromatography, the target 3,5-dichlorobenzoic acid chloride was found to be 55.2%, and further 3,5-dichlorobenzoic acid.
  • the tris (pentafluorophenyl) phosphine added as a ligand is gradually distilled out, and the tris (pentafluorophenyl) in the reactor is removed.
  • 3.16 g (0.0594 mole) of tris (pentafluorophenyl) phosphine was added dropwise to 5-chloroisophthalic acid chloride. Solution and add it to the reactor by dropping 5-chloroisophthalic acid chloride.
  • the concentration of tris (pentafluorofluorophenyl) phosphine in the reactor is more than a certain amount. Kept.
  • Tris (pentafluorophenyl) phosphine and 5-chloroisophthalic acid chloride in 408 g of the distillate are the target compounds by rectifying the distillate.
  • the residue in the reactor contained 1.81 g (0.0340 mol) of tris (pentafluorofluorophenyl) phosphine. This is 47% based on 3.83 g (0.0720 m01) of the total tris (pentafluorophenyl) phosphine used for the reaction.
  • Tris (pentafluorophenyl) phosphine present in the residue in the reactor at the end of this reaction can be used as a ligand in the next production. Therefore, 91% of the total tris (pentafluorophenyl) phosphine used in the reaction can be used for the next production without loss.
  • Example 4 Production of 3,5-dichloromouth benzoic acid chloride using the method of reactive distillation (production with a smaller amount of catalyst))
  • the tris (pentafluorophenyl) phosphine added as a ligand gradually distills out, and the concentration of tris (pentafluorophenyl) phosphine in the reactor decreases.
  • 1.48 g (0.0278 mol) of tris (pentafluorophenyl) phosphine was dissolved in the drop of 5-chloroisophthalic acid as needed.
  • the concentration of tris (pentafluorophenyl) phosphine in the reactor was kept above a certain level by adding dropwise into the reactor by dropping chloroisophthalic acid.
  • tris (pentafluorophenyl) phosphine 0.93 g was contained in 903 g of the distillate.
  • the tris (pentafluorofluorophenyl) phosphine and 5-chloroisofuroyl chloride are purified by distilling the distillate to obtain the target compound, 3,5-dichlorobenzoic acid chloride. After removing the benzene and by-produced 1,3,5-trichlorobenzene, it can be used repeatedly for the next production as a raw material in which the ligand is dissolved.
  • the solution in the anti-water reactor contains tris (pentafluorophenyl) phosphine and a rhodium metal catalyst, which can be used for the next production.
  • Example 5 Rhodium (III) chloride hydrate (R h C l 3, 3 H 2 0) as a ligand P (C eF 5) 3 3 was used, 5-dichloro port benzoic acid chloride Li de Manufacturing)
  • 5- black port isophthalic acid chloride Li de 7. 1 2 g (0. 0 3 0 m 0 1), rhodium (III) chloride hydrate (R h C l 3 '3 H 2 0) 0 0.079 g (0.0003 mol) and 1.596 g (0.0003 mol) of tris (pentafluorophenyl) phosphine were charged. Subsequently, the temperature was slowly raised to 200 ° C., and aging was performed at 200 ° C. for 4 hours. After the acid chloride was treated with getylamine and analyzed by gas chromatography, the desired 3,5-dichloromouth benzoic acid chloride was found to be 38.9%, and further 3,5%.
  • Example 3 A fraction of 61.9 g of the distillate obtained in Example 3 was rectified, and all 3,5-dichlorobenzoic acid chlorides and all 1,3,5-trichloromethane were obtained. After distilling off benzene and most of the 5-chloroisophthalic acid chloride, 0.18 g of tris (pentafluorophenyl) phosphine (0.0000 203 mol) and 5- A residue 5.01 consisting of 4.90 g (0.0206 mol) of isophthalic acid chloride was obtained (to this residue 5.01 under nitrogen atmosphere, dichloromethane).
  • Mouth bis (cyclooctadiene) dirhodium (I) 0.017 g (0.0068 mol) was added, followed by heating to 200 ° C and 200 ° C. Aged for 6 hours at C. After the acid chloride was treated with ethylamine and analyzed by gas chromatography, it was found that 3,7.8% of 3,5-dichloromethylbenzoic acid chloride was 47.8%, and that , 5-dichloro mouth benzoic acid mouth 1 de reacted decarbonylation, 3, 5-preparative land port benzene was produced 3% 5.
  • Example 10 tris (pentafluorofluorophenyl) phosphine contained in the residue obtained by reactive distillation and a rhodium metal catalyst were repeatedly used in the next production. Manufacturing
  • 1,3,5-trichloromouth benzene 5.54 g (0.0305 mol), where 3,1 mol) and 3,5-dicyclomouth benzoic acid chloride were further decarbonylated. It contained 5.49 g (0.023 1 m 0 1) of unreacted 5-chloroisofuroyl chloride.
  • Comparative Example 1 (Production of 1,4-dichlorobenzene using triphenylphosphine as a ligand) Under a nitrogen atmosphere, 4-1.3-chlorobenzoic acid chloride (1.36 g, 0.065 m 0 1), dichlorobis (cyclooctadiene) dirhodium (I) 0. 0 481 (0.0 000 975 mol) and 0.51 g of triphenylphosphine (0.0 195 mol) were charged. Then, 200. (The temperature was raised to 200 ° C, and the mixture was aged at 200 ° C for 6 hours and 30 minutes.
  • the core halogeno aromatic compound can be produced with good yield and purity and with simple operation by the decarbonylation reaction method of the aromatic acid halide. High utility value.
  • the reaction can be performed even at a low temperature at which the reaction does not proceed with the conventional catalyst, and special equipment and materials are not required, and at a low temperature that is advantageous in terms of energy cost, It is possible to obtain the product in a short time and with good yield.
  • the selectivity of the desired product can be improved.
  • the reaction can be continued continuously, or the reaction can be repeated, thereby overcoming cost problems. Furthermore, the molar ratio of the ligand to rhodium metal may be excessive, and the ligand can be produced by a simple operation.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

L'invention concerne un procédé de décarbonylation d'un halogénure d'acide aromatique, à l'aide duquel un produit de réaction peut être facilement obtenu en peu de temps et avec un grand rendement dans des conditions clémentes, et qui est adapté à une utilisation industrielle. Ce procédé consiste à soumettre un halogénure d'acide aromatique à la décarbonylation en présence d'un catalyseur métallique de rhodium et d'une phosphine aromatique fluorée pour produire le composé aromatique à noyau halogéné correspondant. L'invention concerne également un catalyseur permettant de mettre en oeuvre ce procédé. Des exemples préférés de phosphine aromatique fluorée comprennent de la tris(pentafluorophényl)phosphine.
PCT/JP2003/005883 2002-05-30 2003-05-12 Procede de decarbonylation d'un halogenure d'acide aromatique WO2003101922A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2004509618A JP4320299B2 (ja) 2002-05-30 2003-05-12 芳香族酸ハロゲン化物の脱カルボニル化法
AU2003235935A AU2003235935A1 (en) 2002-05-30 2003-05-12 Method for decarbonylation of aromatic acid halide

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JP2002-156779 2002-05-30
JP2002156779 2002-05-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114516780A (zh) * 2021-12-21 2022-05-20 宿迁市科莱博生物化学有限公司 3,4,5-三氟溴苯的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3869510A (en) * 1973-05-25 1975-03-04 Hooker Chemicals Plastics Corp Preparation of 3,5-dichlorobenzoyl chloride
GB1437899A (en) * 1973-12-17 1976-06-03 Dynamit Nobel Ag Preparation of chlorine-substituted aromatic carboxylic acid chlorides
JPS61260030A (ja) * 1985-05-14 1986-11-18 Sumitomo Chem Co Ltd 有機酸ハロゲン化物の脱カルボニル化方法
US4968852A (en) * 1986-04-01 1990-11-06 Central Glass Company, Limited Trifluoromethylbenzoyl bromide and conversion of same to bromobenzotrifluoride
JPH0748315A (ja) * 1993-08-04 1995-02-21 Kawaguchi Yakuhin Kk ハロゲン化ベンゾイルハライドの製造法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3869510A (en) * 1973-05-25 1975-03-04 Hooker Chemicals Plastics Corp Preparation of 3,5-dichlorobenzoyl chloride
GB1437899A (en) * 1973-12-17 1976-06-03 Dynamit Nobel Ag Preparation of chlorine-substituted aromatic carboxylic acid chlorides
JPS61260030A (ja) * 1985-05-14 1986-11-18 Sumitomo Chem Co Ltd 有機酸ハロゲン化物の脱カルボニル化方法
US4968852A (en) * 1986-04-01 1990-11-06 Central Glass Company, Limited Trifluoromethylbenzoyl bromide and conversion of same to bromobenzotrifluoride
JPH0748315A (ja) * 1993-08-04 1995-02-21 Kawaguchi Yakuhin Kk ハロゲン化ベンゾイルハライドの製造法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114516780A (zh) * 2021-12-21 2022-05-20 宿迁市科莱博生物化学有限公司 3,4,5-三氟溴苯的制备方法
CN114516780B (zh) * 2021-12-21 2024-03-29 科莱博(江苏)科技股份有限公司 3,4,5-三氟溴苯的制备方法

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JPWO2003101922A1 (ja) 2005-09-29
AU2003235935A1 (en) 2003-12-19
TW200307659A (en) 2003-12-16

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