EP1517876A1 - Procede de fabrication de composes organiques substitues et utilisation de catalyseurs pour des reactions de substitution - Google Patents

Procede de fabrication de composes organiques substitues et utilisation de catalyseurs pour des reactions de substitution

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Publication number
EP1517876A1
EP1517876A1 EP03732581A EP03732581A EP1517876A1 EP 1517876 A1 EP1517876 A1 EP 1517876A1 EP 03732581 A EP03732581 A EP 03732581A EP 03732581 A EP03732581 A EP 03732581A EP 1517876 A1 EP1517876 A1 EP 1517876A1
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EP
European Patent Office
Prior art keywords
group
formula
radicals
compound
integer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03732581A
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German (de)
English (en)
Inventor
Klaus KÜHLEIN
Peter Wasserscheid
Andreas Metlen
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Merck Patent GmbH
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Solvent Innovation GmbH
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Publication of EP1517876A1 publication Critical patent/EP1517876A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the present invention relates to improved substitution reactions on substituted organic compounds with metal salts which have anions which replace one or more substituents of the substituted organic compounds and, in particular, to a process for carrying out exchange reactions using a selected catalyst.
  • halogen atoms especially for the production of fluorinated halogen aromatics in the presence of alkali metal fluorides and a halogenated aromatic compound.
  • the components in these reactions are heated to very high temperatures in the absence of a solvent, e.g. to temperatures of up to 400 ° C, or the reaction is carried out at temperatures of about 200-230 ° C in an aprotic solvent such as sulfolane.
  • organic fluorine compounds can be prepared by reacting a corresponding chlorine or bromine substituted compound with a metal fluoride in benzonitrile as a solvent.
  • WO-A-97/32832 describes a process for the preparation of fluorine-containing aromatic compounds and fluorine-containing nitrogen-containing heteroaromatic compounds.
  • the process is characterized by reacting a halogen-containing aromatic starting compound with a fluoride, such as an alkali metal fluoride, in the presence of a specific phosphorus-containing catalyst.
  • a fluoride such as an alkali metal fluoride
  • WO-A-98/05610 discloses a process for the preparation of fluorine-containing compounds, which is carried out by reacting a halogen-containing aromatic compound with a fluoride, such as a
  • Alkali metal fluoride is characterized in the presence of a specific phosphonium catalyst.
  • the present invention relates to a method for producing a
  • Ri is an m-valent aliphatic, cycloaliphatic, aromatic or araliphatic radical, which is optionally substituted with inert organic or inorganic radicals and which can have heteroatoms within the chain or the core,
  • n 1 to 6
  • n an integer from 0 to 5
  • o is an integer from 1 to 6, with the proviso that for a given reaction the sum of n and o corresponds to the number m,
  • X is selected from the group consisting of a halogen atom, a nitro group, a carboxylic acid group, a carboxylic acid ester group and a carboxamide group
  • Y differs from X for a given reaction and is selected from the group consisting of a halogen atom, a nitro group, a cyano group, a thiocyanato group and an oxycarbonyl group, the process comprising the following steps:
  • Another aspect of the present invention relates to the use of catalysts of the formula IVa, IVb or IVc in substituent exchange reactions on organic compounds.
  • One aspect of the present invention is that the
  • Another aspect of the present invention is to be seen in the fact that the catalysts used according to the invention have only a low toxicity and therefore allow easy handling of the components.
  • Another aspect of the present invention is that the substituent exchange reaction without the use of additional Solvent can be carried out, whereby only the catalyst and the reactants have to be combined in a simple and efficient manner.
  • Another aspect of the present invention can be seen in the fact that the catalysts used can be recycled in a simple manner, as a result of which a high proportion of the catalyst is recovered and thus contributes to reducing the process costs.
  • This embodiment of the invention also includes the use of catalysts which are excluded in the process defined above.
  • the process according to the invention allows the production of defined target substances in high yield and high selectivity.
  • the new method is ideal for industrial use, leads to relatively low pollution of the environment and can be implemented with relatively low costs and simple means.
  • R ⁇ (X) m of the formula (II) can be organic compounds which have one to six substituents X, which are accessible to exchange reactions and which can be replaced by other substituents Y.
  • the result of these exchange reactions are compounds R ⁇ (X) n (Y) 0 of the formula (I), in which at least some or all of the substituents X have been replaced by substituent (s) Y.
  • Ri is an aliphatic, cycloaliphatic, aromatic or araliphatic radical of valence m, depending on the number of substituents X which for their part can additionally be substituted by inert organic or inorganic groups.
  • inert group is to be understood as a group that does not exchange or decompose under the reaction conditions used.
  • inert groups are aliphatic, cycloaliphatic, aromatic or araliphatic organic groups, the aldehyde group, the carboxylic acid group, the hydroxyl group, halogen atoms or the cyano group.
  • aliphatic groups or inert groups are straight-chain or branched hydrocarbon radicals which have between one and twenty carbon atoms.
  • Aliphatic groups can contain heteroatoms in the chain, for example oxygen, nitrogen or
  • Aliphatic groups can be saturated or can have one or more double bonds or triple bonds, which can be conjugated or isolated in the chain. However, the presence of such heteroatoms and / or unsaturated groups should not impair the stability of the starting materials under the respective reaction conditions.
  • aliphatic groups or inert groups are monovalent hydrocarbon groups which have one to six carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl or the corresponding divalent groups, such as methylene, ethylene, propylene and butylene.
  • Saturated aliphatic groups R 1 in particular saturated aliphatic hydrocarbons, which have one to ten carbon atoms, preferably one to six carbon atoms, are preferred.
  • cycloaliphatic groups or inert groups are cyclic hydrocarbon radicals which have between three and twenty carbon atoms.
  • Cycloaliphatic groups can contain ring heteroatoms, for example oxygen, nitrogen or sulfur atoms. Cycloaliphatic groups can be saturated or can have one or more double or triple bonds which can be conjugated or isolated in the ring.
  • Saturated cycloaliphatic groups R 1 are preferred, in particular saturated aliphatic hydrocarbons, the five to eight
  • Ring carbon atoms preferably five and six ring carbon atoms.
  • cycloaliphatic groups or inert groups are monovalent hydrocarbon radicals which have five to eight carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, or the corresponding divalent radicals, such as cyclohexylene.
  • Aromatic groups or inert groups can be carbocyclic aromatic groups or heterocyclic aromatic groups. Examples of aromatic groups are hydrocarbon residues between six and have twenty-two carbon atoms.
  • Aromatic groups may have heteroatoms in the core, e.g. Oxygen, nitrogen or sulfur atoms.
  • Heteroaromatic groups preferably have one or two heteroatoms.
  • Carbocyclic-aromatic hydrocarbon radicals or aromatic heterocyclic groups which have an oxygen, nitrogen or sulfur atom in the aromatic nucleus are preferred, particularly preferred aromatic carbocyclic groups having six, ten or fourteen
  • aromatic groups or of inert groups are monovalent aromatic hydrocarbon radicals, the six, ten or fourteen
  • Carbon atoms such as phenyl, naphthyl or anthracyl or the corresponding divalent radicals, such as phenylene or naphthylene.
  • aromatic groups or of inert groups are monovalent heteroaromatic groups which have four to nine ring carbon atoms and one and / or two ring oxygen, ring nitrogen or ring sulfur atoms, such as pyridine, furan, pyrrole, thiophene, imidazole, oxazole, thiazole, pyrazole , Pyrimidine, purine, quinoline and isoquinoline or the corresponding divalent radicals derived from these heteroaromatic groups.
  • Araliphatic groups or inert groups can be carbocyclic-aromatic groups or heterocyclic-aromatic groups which are bonded to or via an aliphatic chain. Examples of aromatic groups are listed above. These groups are connected to one another at or via an aliphatic hydrocarbon radical, which in turn contains heteroatoms in the chain, such as oxygen, nitrogen or Sulfur atoms can have.
  • An example of an araliphatic radical is benzyl.
  • Substituent X can be a halogen atom and / or a nitro group, a carboxylic acid group or a derivative of a carboxylic acid group, e.g. an ester group or an amide group.
  • halogen atoms are fluorine, chlorine, bromine and iodine. Chlorine is preferred.
  • substituent Y at least partially replaces substituent X.
  • substituent Y differs from substituent X and is selected from the group consisting of halogen atom, nitro group, cyano group, thiocyanato group and
  • Oxycarbonyl examples include fluorine, chlorine, bromine and iodine. Fluorine is preferred.
  • oxycarbonyl groups are radicals of the formula V.
  • Ris is a monovalent aliphatic, cycloaliphatic, aromatic or araliphatic radical which is optionally substituted with inert organic or inorganic radicals, for example an alkyl group or an aryl group. Examples of such monovalent radicals are given above listed.
  • R-is is preferably methyl or phenyl.
  • M (Y) P is a compound which carries the group Y to be introduced into the reaction product of the formula I.
  • M can be an alkali metal ion such as lithium, sodium, potassium, rubidium or cesium. M can also be an alkaline earth metal ion, such as magnesium, calcium or strontium. M can also be an ammonium ion, such as NH 4 + , NH 3 (R ⁇ 9 ) + , NH 2 (R ⁇ 9 ) 2 + , NH (R ⁇ 9 ) 3 + or N (R 19 ) 4 + ,
  • M can also be a phosphonium ion, preferably P (R- ⁇ 9 ) 4 + .
  • R 9 can be a monovalent organic group which has one of the meanings listed above.
  • R 9 is preferably alkyl having one to six carbon atoms.
  • M is preferably lithium, sodium, NH + and very particularly potassium.
  • the catalyst used in the process according to the invention is a pyridinium salt of the formula IVa, an imidazolium salt of the formula IVb or a pyrazolium salt of the formula IVc
  • radicals R 2 to R, R 8 to R 2 and R 13 to R ⁇ 7 within a molecule can differ within the given definition.
  • the radicals R 2 to R 1 are, independently of one another, hydrogen, aliphatic, cycloaliphatic, aromatic or araliphatic groups which are optionally substituted with inert organic or inorganic radicals and which can have heteroatoms within the chain or the core.
  • R2 to R ⁇ 7 are hydrogen, CrC 6 alkyl, phenyl and oligoether groups of the general formula - [(C X H2 X ) -O] y -R2o, where x is an integer between 1 and 6, preferably between 2 and 4 and y is an integer between 1 and 250, preferably between 1 and 30, in particular between 1 and 10 and R20 is hydrogen or a represents aliphatic, cycloaliphatic, aromatic or araliphatic group. Examples of aliphatic, cycloaliphatic, aromatic or araliphatic groups have already been listed above.
  • Preferred catalysts are compounds of the formulas IVa to IVc, in which all of the radicals R 2 to R 1 are hydrogen or some of the radicals, preferably one to three radicals R 2 to R, R 8 to R-
  • Further preferred catalysts are compounds of the formulas IVa to IVc, in which at least R 2 , one of the radicals R 9 or R- 12 or one of the radicals R- ⁇ 3 or R ⁇ CI-C ⁇ alkyl, phenyl and oligoether groups of the general formula defined above - [(C x H2 ⁇ ) -0] yR 2 o.
  • a q " is any mono-, di- or trivalent anion which is stable under the reaction conditions used.
  • the index q is preferably 1 or 2, particularly preferably 1.
  • a q are monovalent anions, such as halide anions, for example fluoride, chloride, bromide or iodide, pseudohalogen anions, for example thiocyanate, cyanate or cyanide, organic sulfonate anions, for example benzenesulfonate, trifluoromethylsulfonate, toluenesulfonate or bis-trifluoromethanesulfonate sulfanate sulfanate , e.g. octyl sulfate, lauryl sulfate or
  • Methoxyethylsulfat Carboxylate anions such as acetate or benzoate; mono- or divalent fluorine-containing complex anions of the general formula [M ' F x Z y ] n " , wherein M ' is selected from the group consisting of B, Al, Si, P, Ga, Sb, Sn, Fe, Co and Ni, x is an integer from 1 to 6, y is an integer from 0 to 5, x + y is an integer from 2 to 6 and n is 1 or 2, such as tetrafluoroborate, hexafluorophosphate or hexafluoroantimonate, or other monovalent anions, for example trifluoroacetate, nitrate, hydrogen sulfate, dihydrogen phosphate, trichlorostannate, trichloroferrate and tetrachloroaluminates; or divalent anions, e.g. B. hydrogen phosphate anions or sulfate an
  • a q are monovalent or polyvalent, fluorine-containing anions of the general formula [NFz] q" where N is an element from the group titanium, zirconium, zinc, boron, aluminum, silicon, gallium, phosphorus, arsenic, or antimony and z an Represents a number between 3 and 6.
  • Particularly suitable examples of A q " are the anions [BF 4 ] " and [PF 6 ] " .
  • a q are aliphatic or aromatic sulfate or sulfonate anions, such as alkyl sulfates, alkoxyalkyl sulfates, alkyl sulfonates, alkoxyalkyl sulfonates and aryl sulfonates, such as tosylate.
  • the process according to the invention can be carried out by combining the starting materials of the formulas II and III with a catalyst of the formulas IVa, IVb or IVc or else with mixtures of these catalysts.
  • Amounts are used or an excess of the compound of formula III is used, e.g. 1-5 moles of the compound of formula III to 1 mole of the compound of formula II.
  • the catalyst is generally used in an amount of 0.001 to 100% by weight, based on the amount of compound II in the composition, preferably in an amount of 0.01 to 50% by weight, particularly preferably 15 to 30% by weight. %.
  • the reactants and the catalyst are preferably used in finely divided form.
  • the compound of formula Hl should be in the form of Grains or preferably used as a powder.
  • the compound of formula III is preferably ground in a ball mill or is produced by a spray drying process. A large specific surface area of the particles of the compound of formula III generally increases the reaction rate. Preference is given to finely divided compounds of the formula III which have a specific surface area of 0.5 to 1.5 m 2 / g (determined by the BET method).
  • the reactants After the reactants have been mixed together, they can be heated to the desired reaction temperature to carry out the exchange reaction.
  • the exchange reaction can start at room temperature.
  • the reaction mixture is usually heated to temperatures at which at least one of the components melts.
  • the choice of reaction temperatures can depend on the nature of the catalyst and the starting materials.
  • the reaction can be carried out in a wide temperature range, for example in the range from 0 ° C. to 400 ° C.
  • Preferred reaction temperatures are in the range above 120 ° C., particularly preferably between 180 and 250 ° C.
  • temperatures above 180 ° C. are preferably used, particularly preferably temperatures between 280 and 350 ° C.
  • the reaction can be carried out in the presence of a solvent. Preferably no solvent is used.
  • solvents are liquids or solids Reaction temperature are liquid and inert and which promote the progress of the reaction.
  • solvents are aprotic solvents, preferably aprotic polar solvents.
  • solvents are acetone, carbon tetrachloride, dichloroethane, hexamethyl phosphoramide, N, N-dimethylpropyleneurea, nitrobenzoi, benzonitrile, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, sulfolane, N-methylpyrrolidone and dimethyl sulfone.
  • the solvent used is an oligoether of the general form
  • Me- (0-CH 2 -CH 2 ) v -0-Me where v is a number between 1 and 250, preferably 1 to 30, in particular 1 to 10.
  • a particularly preferred embodiment of the process according to the invention is the use of diethylene glycol dimethyl ether (diglyme) as a solvent.
  • These embodiments of the invention also include the use of
  • diglyme is used as the solvent and an aryl sulfonate, alkyl sulfonate, alkyl sulfate and / or alkoxyalkyl sulfate, very particularly preferably toluenesulfonate (tosylate) as the anion A q " .
  • Ri is an aromatic group and the radicals R 2 to R- ⁇ 7 are all hydrogen or one to three of these radicals are alkyl groups, in particular one to three oligoether groups, per compound of the formula IVa, IVb or IVc.
  • Y is selected from the group consisting of halogen atom and nitro group.
  • M is an alkali metal cation
  • p is 1
  • Y is selected from the group consisting of chloride, cyanide or nitro.
  • M (Y) P is used in a finely divided form.
  • a method is preferred in which m is 1 or 2, n is 0 or 1 and o is 1 or 2.
  • a process in which m is 1, n is 0 and o is 1 is very particularly preferred.
  • q is 1.
  • X is chloride and Y is fluoride or nitro.
  • diethylene glycol dimethyl ether diglyme
  • Ri is an aromatic radical and the radicals R 2 to R 1 are all hydrogen or hydrogen and one to three C 1 -C 6 alkyl groups, in particular methyl groups, and / or one to three oligoether groups of the formula defined above, per compound of the formula IVa, IVb or IVc
  • M is an alkali metal cation
  • Y is fluoride, nitro or cyanide
  • the reaction temperature is 180 ° C. or more.
  • diethylene glycol dimethyl ether (diglyme) is used as the solvent
  • m is 1 or 2
  • Ri is an m-valent phenyl group, an m-valent Naphthalene radical or an m-valent anthracenyl radical
  • the radicals R 2 to R- ⁇ are all hydrogen or hydrogen and one to three Ci-C ⁇ alkyl groups, especially methyl groups, and / or one to three oligoether groups of the formula defined above, per compound of formula IVa , IVb or IVc
  • M means a potassium or a sodium cation
  • X is chloride
  • Y is fluoride, nitro or cyanide
  • the reaction temperature is 180 ° C or more.
  • the reaction product formed can be obtained from the Reaction mixture are separated.
  • One method of isolating the reaction product is to extract the reaction mixture with an organic polar aprotic solvent, leaving the M (X) P formed during the reaction.
  • M, X and p have the meanings defined above.
  • the extracted components can be separated from one another by conventional techniques, for example by distillation. Unreacted starting material of the formula II, the product of the formula I and the catalyst of the formula IVa, IVb or IVc can be separated from one another and the catalyst can be used again in the next reaction sequence. In a distillation process, the compounds of the formulas I and II are removed and the catalyst IVa, IVb or IVc remains as a distillation residue.
  • reaction mixture is subjected to flash distillation and the distillation residue is treated with an organic polar aprotic solvent to extract the catalyst of the formula IV and to leave M (X) P as a residue , M, X and p have the meanings defined above.
  • Another embodiment of the present invention relates to the use of compounds of the formula IVa, IVb or IVc as a catalyst in the exchange process described above
  • , A and q have the meaning defined above.
  • the starting compounds of the formulas II and III and catalysts IVa to IVc used are compounds known per se or these can be prepared by processes known per se. Some of these compounds are commercially available.
  • TriMMlM 1-triethylene glycol methyl ether-2,3-dimethylimidazolium cation
  • TriMIM 1-triethylene glycol methyl ether-3-methylimidazolium cation
  • TriDecMIM 1-triethylene glycol methyl ether-2-decyl-3-methylimidazolium cation
  • BMIM 1-butyl-3-methylimidazolium cation
  • EtEGSO 4 ethoxyethyl sulfate
  • MeEGSO 4 ethoxymethyl sulfate
  • MeEG 2 SO 4 diethoxymethyl sulfate
  • EtEG 3 SO triethoxymethyl sulfate
  • BuEG 2 SO 4 diethoxybutyl sulfate
  • MeEGSO 3 ethoxymethyl sulfonate
  • EtSQ 4 ethyl sulfate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé d'échange de substituants dans des composés organiques, par exemple de chlore contre du fluor. Ledit procédé fait intervenir un catalyseur de formule (IVa), (IVb) ou (IVc), dans lesquelles les restes R2 à R17 sont indépendamment hydrogène, ou des groupes aliphatiques, cycloaliphatiques, aromatiques ou araliphatiques, Aq- est un anion de valence q, et q est un entier de 1 à 3.
EP03732581A 2002-06-18 2003-06-17 Procede de fabrication de composes organiques substitues et utilisation de catalyseurs pour des reactions de substitution Withdrawn EP1517876A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE2002127223 DE10227223A1 (de) 2002-06-18 2002-06-18 Verfahren zur Herstellung substituierter organischer Verbindungen und Verwendung von Katalysatoren für Substitutionsreaktionen
DE10227223 2002-06-18
PCT/EP2003/006379 WO2003106379A1 (fr) 2002-06-18 2003-06-17 Procede de fabrication de composes organiques substitues et utilisation de catalyseurs pour des reactions de substitution

Publications (1)

Publication Number Publication Date
EP1517876A1 true EP1517876A1 (fr) 2005-03-30

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EP03732581A Withdrawn EP1517876A1 (fr) 2002-06-18 2003-06-17 Procede de fabrication de composes organiques substitues et utilisation de catalyseurs pour des reactions de substitution

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Country Link
EP (1) EP1517876A1 (fr)
AU (1) AU2003238514A1 (fr)
DE (1) DE10227223A1 (fr)
WO (1) WO2003106379A1 (fr)

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WO2007106943A1 (fr) 2006-03-22 2007-09-27 Ultraclean Fuel Pty Ltd Procede d'elimination de soufre d'hydrocarbures liquides
US8013179B2 (en) 2008-05-23 2011-09-06 Protea Biosciences, Inc. Anionic acid-labile surfactants and methods of use
FR2956316A1 (fr) * 2010-02-17 2011-08-19 Oreal Composition cosmetique comprenant de l'acide ascorbique
US8791251B2 (en) 2011-06-03 2014-07-29 Protea Biosciences, Inc. Non-ionic acid-labile surfactants and methods of use
EP2768480A1 (fr) 2011-10-21 2014-08-27 Rigel Pharmaceuticals, Inc. Procédé et dispositif d'administration d'un sel xinafoate de n4-[(2,2-difluoro-4h-benzo[1,4]oxazin-3-one)-6-yl]-5-fluoro-n2-[3- (méthylaminocarbonylméthylèneoxy)phényl]-2,4-pyrimidinediamine
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
SG10201709956YA (en) 2013-03-15 2018-01-30 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
CN103539772B (zh) * 2013-10-31 2015-09-02 东莞市凯欣电池材料有限公司 一种氟代碳酸乙烯酯的制备方法
TW201609651A (zh) 2013-11-12 2016-03-16 陶氏農業科學公司 用於氟化化合物之過程（一）
TW201609652A (zh) 2013-11-12 2016-03-16 陶氏農業科學公司 用於氟化化合物之過程（三）
TW201524956A (zh) * 2013-11-12 2015-07-01 Dow Agrosciences Llc 用於氟化化合物之過程（二）
TWI726900B (zh) 2015-08-04 2021-05-11 美商陶氏農業科學公司 用於氟化化合物之過程

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WO2003106379A1 (fr) 2003-12-24
AU2003238514A1 (en) 2003-12-31
DE10227223A1 (de) 2004-01-08

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