EP1370506A1 - Production of fluorine compounds - Google Patents

Production of fluorine compounds

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Publication number
EP1370506A1
EP1370506A1 EP02708176A EP02708176A EP1370506A1 EP 1370506 A1 EP1370506 A1 EP 1370506A1 EP 02708176 A EP02708176 A EP 02708176A EP 02708176 A EP02708176 A EP 02708176A EP 1370506 A1 EP1370506 A1 EP 1370506A1
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EP
European Patent Office
Prior art keywords
fluorine
adducts
compounds
produces
mono
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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EP02708176A
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German (de)
French (fr)
Inventor
Max Braun
Carsten Brosch
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Solvay Fluor GmbH
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Solvay Fluor und Derivate GmbH
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Publication of EP1370506A1 publication Critical patent/EP1370506A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
    • C01B17/4561—Compounds containing sulfur, halogen and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
    • C01B17/4561—Compounds containing sulfur, halogen and oxygen only
    • C01B17/4576—Sulfuryl fluoride (SO2F2)
    • 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
    • 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
    • C07C17/206—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 HX
    • 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
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the invention relates to a process for the preparation of fluorine-substituted compounds from chlorine-substituted compounds with chlorine-fluorine exchange or by HF addition to C-C multiple bonds.
  • Inorganic and organic fluorine compounds are very important in chemistry and technology.
  • Inorganic acid fluorides for example sulfuryl fluoride or sulfuryl chlorofluoride, are products for use per se and also intermediates.
  • Sulfuryl fluoride has been proposed, for example, as a catalyst for the production of fluorocarbon compounds.
  • Sulfurylchlorofluorid is an intermediate for the production of Sulfuryl luorid.
  • Sulfuryl fluoride can be attached to unsaturated hydrocarbons; the sulfonyl fluoride formed is useful as a catalyst.
  • Fluorine-containing carbon compounds and hydrocarbon compounds can be used in many ways, for example as blowing agents for the production of plastics, as refrigerants or as solvents.
  • Carboxylic acids and carboxylic acid derivatives (for example carboxylic acid esters or dicarboxylic acid esters) which have a carbon-fluorine bond are in turn useful as such or intermediates in chemical synthesis.
  • Trifluoroacetic acid esters are useful, for example, as solvents and as intermediates in the manufacture of trifluoroethanol.
  • -Fluoro-ß-dicarbonyl compounds are important intermediates, for example in the production of ⁇ -fluoroacrylic acid esters, see EP-A-0 597 329.
  • EP-A-0 597 329 and DE-OS 199 42 374 disclose that HF Adducts of amines as Catalyst can be used in fluorination reactions or as a fluorinating agent.
  • the object of the present invention is to provide new HF adducts of nitrogen compounds with improved properties and their use in fluorination. These tasks are solved by the new RF adducts and the application method according to the invention.
  • the process according to the invention for the preparation of fluorine-containing compounds from halogen-containing, preferably chlorine-containing compounds with halogen-fluorine exchange or by HF addition from CC multiple bonds is carried out in the presence of the HF adduct of a mono- or bicyclic compound with at least 2 nitrogen atoms, at least 1 Nitrogen atom is built into the ring system, carried out as a catalyst or fluorinating agent.
  • Gaseous or liquid compounds are preferably produced under normal conditions.
  • monocyclic compounds are used. It is then a matter of saturated or unsaturated 5-ring, 6-ring or 7-ring compounds. At least 1 nitrogen atom is built into the ring. Another nitrogen atom can also be built into the ring system. Alternatively or additionally, the ring can be substituted by one or more amino groups. Preferred are dialkylamino groups in which the alkyl groups can be the same or different and comprise 1 to 4 carbon atoms. The amino group can also represent a saturated ring system, for example a piperidino group. Representatives of monocyclic ring systems that can be used are dialkylaminopyridine, dialkylaminopiperidine and dialkylaminopiperazine. In another embodiment, they are bicyclic compounds.
  • 1, 2 or more nitrogen atoms can be integrated into the ring system.
  • the compounds can be substituted by one or more amino groups.
  • Dialkylamino groups are again preferred, where the alkyl groups can be the same or different and comprise 1 to 4 carbon atoms or together with the nitrogen atom form a saturated ring system, such as the piperidinyl group.
  • Bicyclic amidines are particularly preferred, in particular 1,5-diaza-bicyclo [4.3.0] non-5-ene (DBN) and 1,8-diazabicyclo [5.4.0] undec-7-cene (DBU).
  • the above-mentioned compounds with at least 2 nitrogen atoms are used in the form of the HF adducts. They can either be prepared beforehand by reacting the amines with hydrogen fluoride. Alternatively, they can also be prepared in situ if hydrogen fluoride is introduced into the reaction mixture accordingly.
  • inorganic or organic acid fluorides are produced from corresponding acid chlorides.
  • Preferred acid fluorides are sulfuryl chlorofluoride and sulfuryl fluoride. Both can be made from sulfuryl chloride or a mixture of chlorine and sulfur dioxide.
  • Alkyl and aryl fluorosulfonates can also be prepared from the corresponding chlorosulfonates.
  • Chlorophosgene can be fluorinated to fluorophosgene.
  • Carboxylic acid fluorides can also be prepared from carboxylic acid chlorides. Carboxylic acid fluorides are preferably used or dicarboxylic acid fluorides from the corresponding carboxylic acid chlorides or dicarboxylic acid chlorides with a chain length of up to 12 carbon atoms in total. Aliphatic and aromatic carboxylic acid fluorides can be produced. These can also be substituted by halogen atoms, for example fluorine and / or chlorine atoms. Aliphatic acid fluorides with a total of 2 to 7, in particular 2 to 4, carbon atoms are preferably prepared.
  • Acetyl fluoride, difluoroacetyl fluoride, chlorodifluoroacetyl fluoride or trifluoroacetyl fluoride are preferably prepared.
  • Propionyl fluoride and propionyl fluoride substituted with 1 to 5 fluorine atoms are also very easy to produce.
  • the method according to the invention can also be used to produce fluorine-containing compounds with a CF bond from chlorine-containing compounds with a C-Cl bond.
  • the transfer of C (O) Cl groups to C (0) F groups has already been mentioned above.
  • chloroalkanes with 1 to 5 carbon atoms can be converted into alkanes substituted by fluorine and optionally chlorine.
  • the process is also very suitable for chlorine-fluorine exchange on activated carbon atoms, for example on those carbon atoms which are ⁇ -permanent to C (0) groups.
  • chlorine-substituted ketones or diketones, chlorine-substituted aliphatic carboxylic acid compounds or chlorine-substituted dicarboxylic acid compounds can be fluorinated.
  • Fluorine-containing carboxylic acid derivatives such as fluorinated carboxylic acid fluorides, carboxylic acid esters or carboxylic acid amides are preferably prepared.
  • alkylene-bridged dicarboxylic acid derivatives or diketones which are substituted by at least 1 fluorine atom in the alkylene bridge, which is preferably 1 to 2 carbon atoms long.
  • the two radicals A can be the same or different and each represent alkyl, aryl, alkoxy, aryloxy or an amino group and R represents hydrogen, fluorine, alkyl or aryl.
  • the starting material is compounds of the formula (II).
  • X represents chlorine, bromine or iodine
  • R 1 has the meaning given for formula (I) for R and can additionally also represent chlorine, bromine or iodine.
  • reaction is expediently carried out at from 20 ° C. to 100 ° C. If R 1 in the feed product of the formula (II) is chlorine, bromine or iodine, an ⁇ , ⁇ -di-fluorine- ⁇ -dicarbonyl compound is obtained, that is to say a compound of the formula (I) in which R is fluorine.
  • A can be, for example, for straight-chain or branched, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, straight-chain or branched, unsubstituted or substituted alkoxy, unsubstituted or substituted aryloxy or an unsubstituted or substituted amino group of the formulas ( III) to (V) NH 2 , (III)
  • R 1 , R 2 and R 3 are alkyl, preferably C -C 6 alkyl, or aryl, preferably phenyl.
  • R 2 and R 3 can be the same or different.
  • the substituents optionally present in the alkyl and alkoxy groups can be, for example, halogen atoms, preferably fluorine, chlorine and / or bromine or nitro groups.
  • aryl and aryloxy groups can be, for example, C 1 -C 6 -alkyl groups, preferably methyl or ethyl, halogen atoms, preferably fluorine, chlorine and / or bromine, or nitro groups.
  • A preferably contains 1 to 6 C atoms, in particular 1 to 2 C atoms, and in the meaning of aryl and aryloxy, A preferably represents phenyl.
  • R and R 1 can represent , for example, hydrogen, straight-chain or branched, unsubstituted or substituted C 1 -C 12 -alkyl or unsubstituted or substituted phenyl.
  • suitable substituents for alkyl groups are halogen atoms or nitro groups
  • substituents for aryl groups are, for example, C 1 -C 6 -alkyl groups, halogen atoms or nitro groups.
  • R 'can additionally represent chlorine, bromine or iodine, in particular chlorine or bromine.
  • R and R 1 are preferably hydrogen, or R 'is chlorine and R is fluorine.
  • X preferably represents chlorine or bromine. It is preferred to prepare dialkyl fluoromalonate and dialkyl difluoronate.
  • Alkyl here means C 1 -C 4 .
  • 2,2-difluoropropionic acid and its derivatives such as esters, for example C1-C4-alkyl or aryl esters, can also be prepared from the corresponding 2,2-dichloropropionic acid compounds.
  • the hydrofluoride adduct can be used as a fluorinating agent. It should then be used in such an amount, or the reaction is carried out so long that the hydrofluoride adduct is not dehydrated so far that HCl adducts are formed. Otherwise, regeneration with hydrogen fluoride is recommended.
  • the hydrofluoride adduct it is also possible to use the hydrofluoride adduct as a catalyst. HF is then introduced into the reaction as a fluorinating agent. The amount of HF is advantageously at least 1 mol HF / gram atom of chlorine to be exchanged. Used HF adduct can be regenerated using HF.
  • hydrofluoride adduct acts as a catalyst here, a continuous procedure is possible.
  • HF can be used on hexafluoropropene Production of 1, 1, 1, 2, 3, 3, 3-heptafluoropropane can be added or also on tetrafluoroethylene for the production of pentafluoroetha.
  • the process according to the invention can preferably be carried out without a solvent. This can be advantageous since the workup is easier and there are no interactions such as side reactions with the solvent to be feared.
  • the process can also be carried out by adding a solvent during or preferably after the reaction, which causes the formation of two liquid phases, one phase being the solvent and the organic compound and the other phase being the amine HF Adduct contains, so that the separation of organic compounds from their mixtures with amine HF adducts is possible in a simple manner.
  • a solvent during or preferably after the reaction, which causes the formation of two liquid phases, one phase being the solvent and the organic compound and the other phase being the amine HF Adduct contains, so that the separation of organic compounds from their mixtures with amine HF adducts is possible in a simple manner.
  • the process also works to separate mixtures that contain two or more organic compounds. This phase formation embodiment will now be further described.
  • the process with 2-phase formation is preferably used for the separation of those organic compounds which are substituted by at least one fluorine atom ' .
  • examples for example, hydrocarbons substituted by at least one fluorine atom, cycloaliphatic hydrocarbons, aromatic hydrocarbons, esters, thioesters or ketones can be separated off.
  • the process is particularly advantageous when used on organic compounds which cannot be separated, or only with difficulty, using conventional methods such as distillation directly from the mixture with amine HF adducts or by aqueous workup. These are, for example, with compounds with a boiling point which is higher than 50 ° C, or thermolabile compounds which do not survive temperatures, for example above 50 ° C, without decomposition.
  • the process is advantageous in any case, since according to the invention the amine-HF adduct is not hydrolyzed during workup.
  • Another object of the invention are new hydrofluoride adducts of 1,5-diaza-bicyclo [4.3.0] non-5-ene (DBN) and 1,8-diaza-bicyclo [5.4.0] undec-7 -en (DBU). They prefer the formulas:
  • the invention also HF adducts of N-dialkylaminopyridine, wherein alkyl is C- j _-C4 means, in particular adducts, wherein the mole ratio of HF to the amine is greater than 1: 1, is preferably equal to or less than 9; very particularly HF adducts, in which alkyl is methyl.
  • the method according to the invention allows the fluorine-chlorine exchange to be carried out with a high yield, particularly in the case of diketones and diesters.
  • the amine complex was placed in a 100 ml PFA flask with a reflux condenser (water cooling), then the diethyl chloromalonate was added and the mixture was heated in an oil bath at 80 ° C. with stirring. Samples were taken from the solution after 1, 3, 6 and 12 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 12 hours, 91.23% of the starting material had been converted to diethyl fluoromalonate. The selectivity was quantitative.
  • the amine complex was placed in a 100 ml PFA flask with a reflux condenser (water cooling), then the diethyl chloromalonate was added and the mixture was heated in an oil bath at 80 ° C. with stirring. Samples were taken from the solution after 1, 3, 6, 12, 18 and 24 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 24 hours, 72.5% of the starting material had been converted to diethyl fluoromalonate. The selectivity was quantitative.
  • the amine complex was placed in a 100 ml PFA flask with a reflux condenser (water cooling), then the diethyl chloromalonate was added and the mixture was heated in an oil bath at 80 ° C. with stirring. During the reaction, the solution darkened from orange to dark red. Samples were taken from the solution after 1, 3, 6, 12 and 18 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 18 hours, 21.8% of the starting material had been converted to diethyl fluoromalonate with quantitative selectivity.
  • the diethyl chloromalonate was placed in a 100 ml multi-necked flask with a reflux condenser (water cooling), then the triethylamine complex was added dropwise with stirring.
  • the solution was tempered at 100 ° C. in an oil bath. Samples were taken from the solution after 3 and 6 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 6 hours, 3.3% of the starting material had been converted to diethyl fluoromalonate.
  • the amine complex was placed in a 100 ml PFA flask with a reflux condenser (water cooling) and the acetonitrile was added, then the chloromonic acid diethyl ester was added and the mixture was heated at 80 ° C. in an oil bath with stirring. Samples were taken from the solution after 1, 3, 6, 12, 18 and 24 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 24 hours, 66.02% of the starting material had been converted to diethyl fluoromalonate.
  • the amine complex was placed in a 100 ml PFA flask with reflux condenser and dropping funnel.
  • the reflux condenser was fed through a cryomat with -30 ° C cold brine.
  • a steel cylinder (with a volume of approx. 300 ml) with dip tube and gas outlet was switched after the cooler, which was heated to -78 ° C in a Dewar with CO / methanol.
  • S0 2 C1 2 was slowly introduced into the oily, light yellow solution with vigorous stirring. A short time after the start of the introduction, gas evolution was observed.
  • an oil bath at 100 ° C. was placed under the flask and heated for a further 1 h with cooling and 1 h without cooling in order to completely drive off the S0 2 F 2 formed .
  • Example 2 As in Example 1, 0.6 mol of 1,8-diazabicyclo- [5.4.0] - undec-7-ene-1 HF was reacted with 0.15 mol of the dichloromone ester. After adding trifluoroacetic acid ethyl ester, the phases formed were separated and the product isolated.
  • phase separation could also be achieved with isopropyl trifluoroacetate, trifluorotrichloroethane, hexane and cyclohexane.
  • the extractant could then be separated off by flash distillation and the product could be finely distilled.

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

Abstract

Inorganic and organic compounds containing fluorine can, for example, be produced from corresponding compounds containing chlorine by exchanging chlorine and fluorine using fluorinating agents. It was found that monocylic or bicyclic compounds having at least two nitrogen atoms, at least one of said nitrogen atoms being incorporated into the ring system, can be used as a catalyst or fluorinating agent for chlorine-fluorine exchange reactions. As a result sulphurylchlorofluoride, sulphurylfluoride or carboxylic acid fluoride can be produced. It is also possible to achieve HF addition to C-C multiple bonds and chlorine-fluorine exchange with respect to carbon atoms. Mono or dichloromalonic acid esters can, for instance, be converted into difluoromalonic acid esters. Preparation is simplified by using suitable solvents in order to force the reaction mixtures into a 2-phase zone.

Description

Herstellung von Fluorverbindungen Production of fluorine compounds
Beschreibungdescription
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von fluorsubstituierten Verbindungen aus chlorsubstituierten Verbindungen unter Chlor-Fluor-Austausch oder durch HF-Anlagerung an C-C-Mehrfachbindungen.The invention relates to a process for the preparation of fluorine-substituted compounds from chlorine-substituted compounds with chlorine-fluorine exchange or by HF addition to C-C multiple bonds.
Anorganische und organische Fluorverbindungen haben einen hohen Stellenwert in Chemie und Technik. Anorganische Säurefluoride, beispielsweise Sulfurylfluorid oder Sulfuryl- chlorfluorid, sind Produkte zur Verwendung per se und auch Zwischenprodukte. Sulfurylfluorid ist beispielsweise als Katalysator für die Herstellung von Fluorkohlenwasserstoff- verbindungen vorgeschlagen worden. Sulfurylchlorfluorid ist ein Zwischenprodukt zur Herstellung von Sulfuryl luorid. Sulfurylfluorid kann an ungesättigte Kohlenwasserstoffe angelagert werden; das gebildete Sulfonylfluorid ist als Katalysator brauchbar. Fluor enthaltende KohlenstoffVerbindungen und KohlenwasserstoffVerbindungen sind vielfältig anwendbar, beispielsweise als Treibmittel für die Herstellung von Kunststoffen, als Kältemittel oder als Lösemittel. Carbonsäuren und Carbonsäurederivate (beispielsweise Carbonsäureester oder Dicarbonsäureester) , die eine Kohlenstoff-Fluor-Bindung aufweisen, sind wiederum als solche brauchbar oder Zwischenprodukte in der chemischen Synthese. Trifluoressigsäureester sind beispielsweise als Lösungsmittel und als Zwischenprodukt bei der Herstellung von Trifluorethanol brauchbar. -Fluor-ß- dicarbonylVerbindungen sind wichtige Zwischenprodukte, beispielsweise bei der Herstellung von α-Fluoracrylsäureestern, siehe EP-A-0 597 329. Aus der EP-A-0 597 329 und der DE-OS 199 42 374 ist bekannt, daß HF-Addukte von Aminen als Katalysator bei Fluorierungsreaktionen oder auch als Fluorie- rungsmittel verwendet werden können.Inorganic and organic fluorine compounds are very important in chemistry and technology. Inorganic acid fluorides, for example sulfuryl fluoride or sulfuryl chlorofluoride, are products for use per se and also intermediates. Sulfuryl fluoride has been proposed, for example, as a catalyst for the production of fluorocarbon compounds. Sulfurylchlorofluorid is an intermediate for the production of Sulfuryl luorid. Sulfuryl fluoride can be attached to unsaturated hydrocarbons; the sulfonyl fluoride formed is useful as a catalyst. Fluorine-containing carbon compounds and hydrocarbon compounds can be used in many ways, for example as blowing agents for the production of plastics, as refrigerants or as solvents. Carboxylic acids and carboxylic acid derivatives (for example carboxylic acid esters or dicarboxylic acid esters) which have a carbon-fluorine bond are in turn useful as such or intermediates in chemical synthesis. Trifluoroacetic acid esters are useful, for example, as solvents and as intermediates in the manufacture of trifluoroethanol. -Fluoro-ß-dicarbonyl compounds are important intermediates, for example in the production of α-fluoroacrylic acid esters, see EP-A-0 597 329. EP-A-0 597 329 and DE-OS 199 42 374 disclose that HF Adducts of amines as Catalyst can be used in fluorination reactions or as a fluorinating agent.
Aufgabe der vorliegenden Erfindung ist es, neue HF- Addukte von Stickstoffverbindungen mit verbesserten Eigenschaften und ihre Anwendung bei der Fluorierung anzugeben. Diese Aufgaben werden durch die neuen HF-Addukte und das erfindungsgemäße Anwendungsverfahren gelöst.The object of the present invention is to provide new HF adducts of nitrogen compounds with improved properties and their use in fluorination. These tasks are solved by the new RF adducts and the application method according to the invention.
Das erfindungsgemäße Verfahren zur Herstellung von fluorhaltigen Verbindungen aus halogenhaltigen, vorzugsweise chlorhaltigen Verbindungen unter Halogen-Fluor-Austausch oder durch HF-Anlagerung aus C-C-Mehrfachbindungen wird in Anwesenheit des HF-Addukts einer mono- oder bicyclischen Verbindung mit mindestens 2 Stickstoffatomen, wobei mindestens 1 Stickstoffato in das Ringsystem eingebaut ist, als Katalysator oder Fluorierungsmittel durchgeführt.The process according to the invention for the preparation of fluorine-containing compounds from halogen-containing, preferably chlorine-containing compounds with halogen-fluorine exchange or by HF addition from CC multiple bonds is carried out in the presence of the HF adduct of a mono- or bicyclic compound with at least 2 nitrogen atoms, at least 1 Nitrogen atom is built into the ring system, carried out as a catalyst or fluorinating agent.
Bevorzugt werden bei Normalbedingungen gasförmige oder flüssige Verbindungen hergestellt.Gaseous or liquid compounds are preferably produced under normal conditions.
Gemäß einer Ausführungsform setzt man monocyclische Verbindungen ein. Es handelt sich dann um gesättigte oder ungesättigte 5-Ring-, 6-Ring- oder 7-Ring-Verbindungen. Mindestens 1 Stickstoffatom ist in den Ring eingebaut. Es kann auch noch ein weiteres Stickstoffatom in das Ringsystem eingebaut sein. Alternativ oder zusätzlich kann der Ring durch eine oder mehrere A inogruppen substituiert sein. Bevorzugt sind Dialkylaminogruppen, in denen die Alkylgruppen gleich oder verschieden sein können und 1 bis 4 Kohlenstoffatome umfassen. Die Aminogruppe kann auch ein gesättigtes Ringsystem, beispielsweise eine Piperidinogruppe, darstellen. Gut brauchbare Vertreter von monocyclischen Ringsystemen sind Dialkyl- aminopyridin, Dialkylaminopiperidin und Dialkylaminopipera- zin. Gemäß einer anderen Ausführungsform handelt es sich um bicyclische Verbindungen. Auch hier können 1, 2 oder mehr Stickstoffatome in das Ringsystem integriert sein. Die Verbindungen können durch eine oder mehr Aminogruppen substituiert sein. Bevorzugt sind wieder Dialkylaminogruppen, wobei die Alkylgruppen gleich oder verschieden sein können und 1 bis 4 C-Atome umfassen oder zusammen mit dem Stickstoffatom ein gesättigtes Ringsystem bilden, wie beispielsweise die Piperidinyl-Gruppe .According to one embodiment, monocyclic compounds are used. It is then a matter of saturated or unsaturated 5-ring, 6-ring or 7-ring compounds. At least 1 nitrogen atom is built into the ring. Another nitrogen atom can also be built into the ring system. Alternatively or additionally, the ring can be substituted by one or more amino groups. Preferred are dialkylamino groups in which the alkyl groups can be the same or different and comprise 1 to 4 carbon atoms. The amino group can also represent a saturated ring system, for example a piperidino group. Representatives of monocyclic ring systems that can be used are dialkylaminopyridine, dialkylaminopiperidine and dialkylaminopiperazine. In another embodiment, they are bicyclic compounds. Here too, 1, 2 or more nitrogen atoms can be integrated into the ring system. The compounds can be substituted by one or more amino groups. Dialkylamino groups are again preferred, where the alkyl groups can be the same or different and comprise 1 to 4 carbon atoms or together with the nitrogen atom form a saturated ring system, such as the piperidinyl group.
Ganz besonders bevorzugt sind bicyclische Amidine, insbesondere 1, 5-Diaza-bicyclo [4.3.0]non-5-en (DBN) und 1,8-Di- azabicyclo [5.4.0] undec-7-cen (DBU) .Bicyclic amidines are particularly preferred, in particular 1,5-diaza-bicyclo [4.3.0] non-5-ene (DBN) and 1,8-diazabicyclo [5.4.0] undec-7-cene (DBU).
Aus dem vorstehend gesagten wird klar, daß mindestens 2 Stickstoffatome in den brauchbaren Verbindungen basische Eigenschaften aufweisen müssen und, je nach Art der Bindungen, an 2 oder 3 Kohlenstoffatome gebunden sind.From the above it is clear that at least 2 nitrogen atoms in the useful compounds must have basic properties and, depending on the type of bonds, are bound to 2 or 3 carbon atoms.
Die vorstehend genannten Verbindungen mit mindestens 2 Stickstoffatomen werden in Form der HF-Addukte eingesetzt. Dabei kann man sie entweder vorab herstellen, indem man die Amine mit Fluorwasserstoff umsetzt. Alternativ kann man sie auch in situ herstellen, wenn man entsprechend Fluorwasserstoff in das Reaktionsgemisch einleitet.The above-mentioned compounds with at least 2 nitrogen atoms are used in the form of the HF adducts. They can either be prepared beforehand by reacting the amines with hydrogen fluoride. Alternatively, they can also be prepared in situ if hydrogen fluoride is introduced into the reaction mixture accordingly.
Gemäß einer Ausführungsform werden anorganische oder organische Säurefluoride aus entsprechenden Säurechloriden hergestellt. Bevorzugte Säurefluoride sind Sulfurylchlorfluorid und Sulfurylfluorid. Beide können aus Sulfurylchlorid oder einem Gemisch aus Chlor und Schwefeldioxid hergestellt werden. Auch lassen sich Alkyl- und Arylfluorsulfonate aus den entsprechenden Chlorsulfonaten herstellen. Chlorphosgen kann zu Fluorphosgen fluoriert werden.According to one embodiment, inorganic or organic acid fluorides are produced from corresponding acid chlorides. Preferred acid fluorides are sulfuryl chlorofluoride and sulfuryl fluoride. Both can be made from sulfuryl chloride or a mixture of chlorine and sulfur dioxide. Alkyl and aryl fluorosulfonates can also be prepared from the corresponding chlorosulfonates. Chlorophosgene can be fluorinated to fluorophosgene.
Auch Carbonsaurefluoride können aus Carbonsäurechloriden hergestellt werden. Bevorzugt stellt man Carbonsaurefluoride oder Dicarbonsäurefluoride aus den entsprechenden Carbonsäurechloriden bzw. Dicarbonsäurechloriden mit einer Kettenlänge von insgesamt bis zu 12 C-Atomen her. Dabei sind aliphatische und aromatische Carbonsaurefluoride herstellbar. Diese können auch durch Halogenatome, beispielsweise Fluor- und/oder Chloratome substituiert sein. Bevorzugt stellt man aliphatische Säurefluoride mit insgesamt 2 bis 7, insbesondere 2 bis 4 Kohlenstoffatomen her. Bevorzugt stellt man Acetylfluorid, Difluoracetylfluorid, Chlordifluoracetylfluorid oder Trifluoracetylfluorid her. Weiterhin sehr gut herstellbar sind Propionylfluorid sowie mit 1 bis 5 Fluoratomen substituiertes Propionylfluorid.Carboxylic acid fluorides can also be prepared from carboxylic acid chlorides. Carboxylic acid fluorides are preferably used or dicarboxylic acid fluorides from the corresponding carboxylic acid chlorides or dicarboxylic acid chlorides with a chain length of up to 12 carbon atoms in total. Aliphatic and aromatic carboxylic acid fluorides can be produced. These can also be substituted by halogen atoms, for example fluorine and / or chlorine atoms. Aliphatic acid fluorides with a total of 2 to 7, in particular 2 to 4, carbon atoms are preferably prepared. Acetyl fluoride, difluoroacetyl fluoride, chlorodifluoroacetyl fluoride or trifluoroacetyl fluoride are preferably prepared. Propionyl fluoride and propionyl fluoride substituted with 1 to 5 fluorine atoms are also very easy to produce.
Das erfindungsgemäße Verfahren kann auch angewendet werden, um fluorhaltige Verbindungen mit CF-Bindung aus chlorhaltigen Verbindungen mit C-Cl-Bindung herzustellen. Die Überführung von C (O) Cl-Gruppen C (0) F-Gruppen wurde vorstehend schon erwähnt . Beispielsweise kann man Chloralkane mit 1 bis 5 Kohlenstoffatomen in durch Fluor und gegebenenfalls Chlor substituierte Alkane überführen.The method according to the invention can also be used to produce fluorine-containing compounds with a CF bond from chlorine-containing compounds with a C-Cl bond. The transfer of C (O) Cl groups to C (0) F groups has already been mentioned above. For example, chloroalkanes with 1 to 5 carbon atoms can be converted into alkanes substituted by fluorine and optionally chlorine.
Gut geeignet ist das Verfahren auch zum Chlor-Fluor-Austausch an aktivierten Kohlenstoffatomen, beispielsweise an solchen Kohlenstoffatomen, die α-ständig zu C(0) -Gruppen stehen. Beispielsweise kann man durch Chlor substituierte Ketone oder Diketone, chlorsubstituierte aliphatische Carbonsäureverbindungen oder an der Kohlenstoffbrücke durch Chlor substituierte Dicarbonsäureverbindungen fluorieren. Bevorzugt stellt man Fluor enthaltende Carbonsäurederivate wie fluorierte Carbonsaurefluoride, Carbonsäureester oder Carbonsäu- reamide her. Gleichermaßen bevorzugt stellt man alkylenver- brückte Dicarbonsäurederivate oder Diketone her, die in der Alkylenbrücke, die vorzugsweise 1 bis 2 Kohlenstoffatome lang ist, durch mindestens 1 Fluoratom substituiert sind. Dabei kann man von den Chlorverbindungen oder auch Bromverbindungen ausgehen. Das Verfahren kann sehr gut zur Herstellung der in der EP-A 597 329 beschriebenen Verbindungen hergestellt werden. Dieses sind Verbindungen der Formel (I)The process is also very suitable for chlorine-fluorine exchange on activated carbon atoms, for example on those carbon atoms which are α-permanent to C (0) groups. For example, chlorine-substituted ketones or diketones, chlorine-substituted aliphatic carboxylic acid compounds or chlorine-substituted dicarboxylic acid compounds can be fluorinated. Fluorine-containing carboxylic acid derivatives such as fluorinated carboxylic acid fluorides, carboxylic acid esters or carboxylic acid amides are preferably prepared. Likewise, preference is given to producing alkylene-bridged dicarboxylic acid derivatives or diketones which are substituted by at least 1 fluorine atom in the alkylene bridge, which is preferably 1 to 2 carbon atoms long. You can start from the chlorine compounds or bromine compounds. The process can be very good for making the in of the compounds described in EP-A 597 329. These are compounds of formula (I)
A-C(0)-C(R) (F)-C(0)-AA-C (0) -C (R) (F) -C (0) -A
in der die beiden Reste A gleich oder verschieden sein können und jeweils für Alkyl, Aryl, Alkoxy, Aryloxy oder eine Aminogruppe und R für Wasserstoff, Fluor, Alkyl oder Aryl stehen.in which the two radicals A can be the same or different and each represent alkyl, aryl, alkoxy, aryloxy or an amino group and R represents hydrogen, fluorine, alkyl or aryl.
Ausgangsmaterial sind Verbindungen der Formel (IIThe starting material is compounds of the formula (II
A-C(0)C(X(R' )-C(0)-AA-C (0) C (X (R ') -C (0) -A
in derin the
X für Chlor, Brom oder Jod steht,X represents chlorine, bromine or iodine,
A die bei Formel (I) angegebene Bedeutung hat und R1 die bei Formel (I) für R angegebene Bedeutung hat und zusätzlich noch für Chlor, Brom oder Jod stehen kann.A has the meaning given for formula (I) and R 1 has the meaning given for formula (I) for R and can additionally also represent chlorine, bromine or iodine.
Man führt die Umsetzung zweckmäßig bei Temperaturen von 20 °C bis 100 °C durch. Falls im Einsatzprodukt der Formel (II) R1 für Chlor, Brom oder Jod steht, wird eine α,α-Di- fluor-ß -dicarbonylverbindung erhalten, das heißt eine Verbindung der Formel (I), in der R für Fluor steht.The reaction is expediently carried out at from 20 ° C. to 100 ° C. If R 1 in the feed product of the formula (II) is chlorine, bromine or iodine, an α, α-di-fluorine-β-dicarbonyl compound is obtained, that is to say a compound of the formula (I) in which R is fluorine.
In den Formeln (I) und (II) kann A beispielsweise für geradkettiges oder verzweigtes, unsubstituiertes oder substituiertes Alkyl, unsubstituiertes oder substituiertes Aryl, geradkettiges oder verzweigtes, unsubstituiertes oder substituiertes Alkoxy, unsubstituiertes oder substituiertes Aryloxy oder eine unsubstituierte oder substituiertes Aminogruppe der Formeln (III) bis (V) stehen NH2, (III)In the formulas (I) and (II), A can be, for example, for straight-chain or branched, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, straight-chain or branched, unsubstituted or substituted alkoxy, unsubstituted or substituted aryloxy or an unsubstituted or substituted amino group of the formulas ( III) to (V) NH 2 , (III)
NHR1 (IV) ' undNHR 1 (IV) ' and
NR2R3 (V) ,NR 2 R 3 (V),
in denenin which
R1, R2 und R3 Alkyl, vorzugsweise C -C6-Alkyl, oder Aryl, vorzugsweise Phenyl, bedeuten. R2 und R3 können dabei gleich oder verschieden sein.R 1 , R 2 and R 3 are alkyl, preferably C -C 6 alkyl, or aryl, preferably phenyl. R 2 and R 3 can be the same or different.
Bei den gegebenenfalls in den Alkyl- und Alkoxygruppen vorhandenen Substituenten kann es sich beispielsweise um Halogenatome, vorzugsweise Fluor, Chlor und/oder Brom oder Nitrogruppen handeln.The substituents optionally present in the alkyl and alkoxy groups can be, for example, halogen atoms, preferably fluorine, chlorine and / or bromine or nitro groups.
Bei den gegebenenfalls an Aryl- und Aryloxygruppen vorhanden Substituenten kann es sich beispielsweise um C^-Cg- Alkylgruppen, vorzugsweise Methyl oder Ethyl, Halogenatome, vorzugsweise Fluor, Chlor und/oder Brom, oder Nitrogruppen handeln .The substituents optionally present on aryl and aryloxy groups can be, for example, C 1 -C 6 -alkyl groups, preferably methyl or ethyl, halogen atoms, preferably fluorine, chlorine and / or bromine, or nitro groups.
In der Bedeutung von Alkyl und Alkoxy enthält A vorzugsweise 1 bis 6 C-Atome, insbesondere 1 bis 2 C-Atome, und in der Bedeutung von Aryl und Aryloxy steht A vorzugsweise für Phenyl .In the meaning of alkyl and alkoxy, A preferably contains 1 to 6 C atoms, in particular 1 to 2 C atoms, and in the meaning of aryl and aryloxy, A preferably represents phenyl.
In den Formeln (I) und (II) können R und R1 beispielsweise für Wasserstoff, geradkettiges oder verzweigtes, unsubstituiertes oder substituiertes C1-C12~Alkyl oder unsubstituiertes oder substituiertes Phenyl stehen. Als Substituenten für Alkylgruppen kommen beispielsweise Halogenatome oder Nitrogruppen in Frage, als Substituenten für Arylgruppen beispielsweise C1-C6-Alkylgruppen, Halogenatome oder Nitrogruppen. In Formel (II) kann R' zusätzlich für Chlor, Brom oder Jod, insbesondere für Chlor oder Brom, stehen. Vorzugsweise stehen R und R1 für Wasserstoff, oder R' steht für Chlor und R für Fluor.In the formulas (I) and (II), R and R 1 can represent , for example, hydrogen, straight-chain or branched, unsubstituted or substituted C 1 -C 12 -alkyl or unsubstituted or substituted phenyl. Examples of suitable substituents for alkyl groups are halogen atoms or nitro groups, and substituents for aryl groups are, for example, C 1 -C 6 -alkyl groups, halogen atoms or nitro groups. In formula (II), R 'can additionally represent chlorine, bromine or iodine, in particular chlorine or bromine. R and R 1 are preferably hydrogen, or R 'is chlorine and R is fluorine.
In der Formel (II) steht X vorzugsweise für Chlor oder Brom. Bevorzugt stellt man Fluormalonsäuredialkylester und Difluormalonsäuredialkylester her. Alkyl bedeutet hier C1-C4. Herstellbar sind z.B. auch 2 , 2-Difluorpropionsäure und deren Derivate wie Ester, beispielsweise Cl-C4-Alkyl- oder Aryle- ster, aus den entsprechenden 2 , 2-Dichlorpropionsäure- verbindungen.In formula (II), X preferably represents chlorine or bromine. It is preferred to prepare dialkyl fluoromalonate and dialkyl difluoronate. Alkyl here means C 1 -C 4 . For example, 2,2-difluoropropionic acid and its derivatives such as esters, for example C1-C4-alkyl or aryl esters, can also be prepared from the corresponding 2,2-dichloropropionic acid compounds.
Wie schon in der deutschen Offenlegungsschrift 199 42 374 beschrieben, kann das Hydrofluoridaddukt als Fluo- rierungsmittel eingesetzt werden. Es soll dann in einer solchen Menge eingesetzt werden, oder die Umsetzung wird solange durchgeführt, daß das Hydrofluoridaddukt nicht soweit dehy- drofluoriert wird, daß sich HCl-Addukte bilden. Anderenfalls empfiehlt sich eine Regenerierung mit Fluorwasserstoff. Es ist, wie in der DE-OS 199 42 374 bereits beschrieben, auch möglich, das Hydrofluoridaddukt als Katalysator einzusetzen. Als Fluorierungsmittel wird dann HF in die Reaktion eingebracht. Die Menge an HF beträgt vorteilhaft mindestens 1 Mol HF/Grammatom an auszutauschendem Chlor. Verbrauchtes HF- Addukt kann mittels HF regeneriert werden.As already described in German Offenlegungsschrift 199 42 374, the hydrofluoride adduct can be used as a fluorinating agent. It should then be used in such an amount, or the reaction is carried out so long that the hydrofluoride adduct is not dehydrated so far that HCl adducts are formed. Otherwise, regeneration with hydrogen fluoride is recommended. As already described in DE-OS 199 42 374, it is also possible to use the hydrofluoride adduct as a catalyst. HF is then introduced into the reaction as a fluorinating agent. The amount of HF is advantageously at least 1 mol HF / gram atom of chlorine to be exchanged. Used HF adduct can be regenerated using HF.
Da hier das Hydrofluoridaddukt als Katalysator wirkt, ist eine kontinuierliche Verfahrensweise möglich.Since the hydrofluoride adduct acts as a catalyst here, a continuous procedure is possible.
Eine andere Ausführungsform umfaßt die Anlagerung von HF an nucleophile oder elektrophile C-C-Doppel- oder Dreifachbindungen. Bevorzugtes Ausgangsmaterial sind ungesättigte aliphatische KohlenwasserstoffVerbindungen, die durch 1 oder mehrere Halogenatome substituiert sein können. Bevorzugte Verbindungen sind solche mit einer C2-C4-Kette. Besonders bevorzugt sind diese durch mindestens 1 Chlor- oder Fluoratom substituiert. Beipielsweise kann HF an Hexafluorpropen zur Herstellung von 1, 1, 1, 2, 3 , 3 , 3-Heptafluorpropan angelagert werden oder auch an Tetrafluorethylen zwecks Herstellung von Pentafluoretha .Another embodiment involves the attachment of HF to nucleophilic or electrophilic CC double or triple bonds. Preferred starting materials are unsaturated aliphatic hydrocarbon compounds, which can be substituted by 1 or more halogen atoms. Preferred compounds are those with a C 2 -C 4 chain. These are particularly preferably substituted by at least 1 chlorine or fluorine atom. For example, HF can be used on hexafluoropropene Production of 1, 1, 1, 2, 3, 3, 3-heptafluoropropane can be added or also on tetrafluoroethylene for the production of pentafluoroetha.
Das erfindungsgemäße Verfahren kann bevorzugt ohne Lösungsmittel .durchgeführt werden. Dies kann von Vorteil sein, da die Aufarbeitung einfacher ist und keine Wechselwirkungen wie Nebenreaktionen mit dem Lösungsmittel zu befürchten sind.The process according to the invention can preferably be carried out without a solvent. This can be advantageous since the workup is easier and there are no interactions such as side reactions with the solvent to be feared.
Das Verfahren kann alternativ aber auch so durchgeführt werden, dass man während oder bevorzugt nach der Umsetzung ein Lösungsmittel zusetzt, welches die Bildung zweier flüssiger Phasen bewirkt, wobei die eine Phase das Lösungsmittel und die organische Verbindung und wobei die andere Phase das Amin-HF-Addukt enthält, so dass die Abtrennung organischer Verbindungen aus ihren Gemischen mit Amin-HF-Addukten auf einfache Weise möglich ist. Natürlich funktioniert das Verfahren auch zur Abtrennung von Gemischen, die zwei oder mehr organische Verbindungen enthalten. Diese Ausführungsform unter Phasenbildung wird nun weiter beschrieben.Alternatively, the process can also be carried out by adding a solvent during or preferably after the reaction, which causes the formation of two liquid phases, one phase being the solvent and the organic compound and the other phase being the amine HF Adduct contains, so that the separation of organic compounds from their mixtures with amine HF adducts is possible in a simple manner. Of course, the process also works to separate mixtures that contain two or more organic compounds. This phase formation embodiment will now be further described.
Gemische von Amin-HF-Addukten und organischen Verbindungen resultieren beispielsweise bei Fluorierungsreaktionen, wenn man während der Fluorierungsreaktion Fluorwasserstoff einspeist und/oder das Amin-HF-Addukt nicht soweit als Fluo- rierungsmittel ausnutzt, dass nach der Reaktion kein Amin-HF- Addukt mehr vorliegt, sondern Amin-HCl-Addukt, wenn es sich um eine Chlor-Fluor-Austauschreaktion handelt. Entsprechende Vorgehensweisen werden beispielsweise in der deutschen Offen- legungsschrift 199 42 374 sowie in der noch nicht vorveröffentlichten deutschen Anmeldung ... (101 04 663.4) beschrieben.Mixtures of amine-HF adducts and organic compounds result, for example, in fluorination reactions if hydrogen fluoride is fed in during the fluorination reaction and / or the amine-HF adduct is not used as a fluorinating agent to such an extent that no amine-HF adduct is left after the reaction is present, but amine-HCl adduct if it is a chlorine-fluorine exchange reaction. Appropriate procedures are described, for example, in German Offenlegungsschrift 199 42 374 and in the as yet unpublished German application ... (101 04 663.4).
Bevorzugt wird das Verfahren mit 2-Phasenbildung zur Abtrennung von solchen organischen Verbindungen angewandt, welche durch mindestens ein Fluoratom' substituiert sind. Bei- spielsweise kann man durch mindestens ein Fluoratom substituierter Kohlenwasserstoffe, cycloaliphatische Kohlenwasserstoffe, aromatische Kohlenwasserstoffe, Ester, Thioester oder Ketone abtrennen.The process with 2-phase formation is preferably used for the separation of those organic compounds which are substituted by at least one fluorine atom ' . examples for example, hydrocarbons substituted by at least one fluorine atom, cycloaliphatic hydrocarbons, aromatic hydrocarbons, esters, thioesters or ketones can be separated off.
Besonders vorteilhaft ist das Verfahren natürlich bei der Anwendung auf organische Verbindungen, die' nicht oder schlecht mit üblichen Methoden wie Destillation direkt aus dem Gemisch mit Amin-HF-Addukten oder durch wässrige Aufarbeitung getrennt werden können. Dies sind beispielsweise mit Verbindungen mit einem Siedepunkt, der höher als 50 °C ist, oder thermolabile Verbindungen, die Temperaturen beispielsweise oberhalb von 50 °C nicht unzersetzt überstehen. Das Verfahren ist aber in jedem Fall vorteilhaft, da erfindungsgemäß das Amin-HF-Addukt bei der Aufarbeitung nicht hydroly- siert wird.Of course, the process is particularly advantageous when used on organic compounds which cannot be separated, or only with difficulty, using conventional methods such as distillation directly from the mixture with amine HF adducts or by aqueous workup. These are, for example, with compounds with a boiling point which is higher than 50 ° C, or thermolabile compounds which do not survive temperatures, for example above 50 ° C, without decomposition. However, the process is advantageous in any case, since according to the invention the amine-HF adduct is not hydrolyzed during workup.
Ein weiterer Gegenstand der Erfindung sind neue Hydro- fluorid-Addukte von 1, 5-Diaza-bicyclo [4.3.0] -non-5-en (DBN) und 1, 8-Diaza-bicyclo [5.4.0]undec-7-en (DBU) . Sie haben bevorzugt die Formeln:Another object of the invention are new hydrofluoride adducts of 1,5-diaza-bicyclo [4.3.0] non-5-ene (DBN) and 1,8-diaza-bicyclo [5.4.0] undec-7 -en (DBU). They prefer the formulas:
DBN- (HF)X,DBN- (HF) X ,
worin x gleich 1 ist oder für l<x< 9 steht undwhere x is 1 or stands for l <x <9 and
DBU- (HF)y,DBU- (HF) y ,
worin y gleich 1 ist oder für l<y<9 steht.where y is 1 or stands for l <y <9.
Gegenstand der Erfindung sind auch HF-Addukte von N-Dialkylaminopyridin, wobei Alkyl C-j_-C4 bedeutet, insbesondere Addukte, worin das Mol-Verhältnis von HF zum Amin größer als 1:1 ist, vorzugsweise gleich oder kleiner 9 ist; ganz besonders HF-Addukte, worin Alkyl für Methyl steht. Das erfindungsgemäße Verfahren gestattet, den Fluor- Chlor-Austausch mit hoher Ausbeute durchzuführen, besonders bei Diketonen und Diestern.The invention also HF adducts of N-dialkylaminopyridine, wherein alkyl is C- j _-C4 means, in particular adducts, wherein the mole ratio of HF to the amine is greater than 1: 1, is preferably equal to or less than 9; very particularly HF adducts, in which alkyl is methyl. The method according to the invention allows the fluorine-chlorine exchange to be carried out with a high yield, particularly in the case of diketones and diesters.
Die folgenden Beispiele sollen die Erfindung weiter erläutern, ohne sie in ihrem Umfang einzuschränken. The following examples are intended to illustrate the invention without restricting its scope.
Beispiele 1 bis 6;Examples 1 to 6;
Chlor-Fluoraustausch an DiesternChlorine-fluorine exchange on diesters
Allgemeine Reaktionsgleichung:General reaction equation:
CH3-CH2-COO-CHCl-COO-CH2-CH3 + Amin x HF → CH3-CH2-COO-CHF-COO-CH2-CH3 + Amin x HClCH 3 -CH 2 -COO-CHCl-COO-CH 2 -CH 3 + amine x HF → CH 3 -CH 2 -COO-CHF-COO-CH 2 -CH 3 + amine x HCl
Fluorierungsversuche mit DBU und DBM-HF/Aminko pleaeen. in Abwesenheit eines Lösungsmittels:Fluorination experiments with DBU and DBM-HF / Aminko pleaeen. in the absence of a solvent:
Beispiel 1 ;Example 1 ;
Ansatz :Approach:
0,15 mol 2-Chlormalonsäurediethylester 29,3 g0.15 mol of diethyl 2-chloromalonate 29.3 g
0,3 mol 1, 5-Diazabicyclo[4.3.0]non-5-en x 1,73 HF 54,4 g0.3 mol 1, 5-diazabicyclo [4.3.0] non-5-ene x 1.73 HF 54.4 g
Aufbau u. Durchführung :Construction u. Execution :
In einem 100 ml PFA-Kolben mit Rückflußkühler (Wasserkühlung) wurde der Aminkomplex vorgelegt, dann wurde der Chlormalon- säurediethylester dazugegeben und die Mischung unter Rühren bei 80 °C im Ölbad temperiert. Nach 1, 3, 6 und 12 Stunden wurden Proben aus der Lösung entnommen. Diese wurden hydroly- siert und mit Natriumsulfat getrocknet und zur GC Analyse gegeben. Nach 12 Stunden waren 91,23 % des Eduktes zu Fluorma- lonsäurediethylester umgesetzt. Die Selektivität war quantitativ.The amine complex was placed in a 100 ml PFA flask with a reflux condenser (water cooling), then the diethyl chloromalonate was added and the mixture was heated in an oil bath at 80 ° C. with stirring. Samples were taken from the solution after 1, 3, 6 and 12 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 12 hours, 91.23% of the starting material had been converted to diethyl fluoromalonate. The selectivity was quantitative.
Beispiel 2;Example 2;
Ansatz :Approach:
0,15 mol 2-Chlormalonsäurediethylester 29,3 g0.15 mol of diethyl 2-chloromalonate 29.3 g
0,3 mol 1, 8-Diazabicyclo [5.4.0 ]undec-7-en x 1,37 HF 56,5 g Aufbau u. Durchführung :0.3 mol 1, 8-diazabicyclo [5.4.0] undec-7-ene x 1.37 HF 56.5 g Construction u. Execution :
In einem 100 ml PFA-Kolben mit Rückflußkühler (Wasserkühlung) wurde der Aminkomplex vorgelegt, dann wurde der Chlormalon- säurediethylester dazugegeben und die Mischung unter Rühren bei 80 °C im Ölbad temperiert. Nach 1, 3, 6 ,12, 18 und 24 Stunden wurden Proben aus der Lösung entnommen. Diese wurden hydrolysiert und mit Natriumsulfat getrocknet und zur GC Analyse gegeben. Nach 24 Stunden waren 72,5 % des Eduktes zu Fluormalonsäurediethylester umgesetzt. Die Selektivität war quantitativ.The amine complex was placed in a 100 ml PFA flask with a reflux condenser (water cooling), then the diethyl chloromalonate was added and the mixture was heated in an oil bath at 80 ° C. with stirring. Samples were taken from the solution after 1, 3, 6, 12, 18 and 24 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 24 hours, 72.5% of the starting material had been converted to diethyl fluoromalonate. The selectivity was quantitative.
Beispiel 3;Example 3;
Ansatz :Approach:
0,10 mol 2-Chlormalonsäurediethylester 19,5 g0.10 mol of diethyl 2-chloromalonate 19.5 g
0,05 mol 1, 5-Diazabicyclo[4.3.0]non-5-en x 2,93 HF 8,8 g0.05 mol 1, 5-diazabicyclo [4.3.0] non-5-ene x 2.93 HF 8.8 g
Aufbau u. Durchführung :Construction u. Execution :
In einem 100 ml PFA-Kolben mit Rückflußkühler (Wasserkühlung) wurde der Aminkomplex vorgelegt, dann wurde der Chlormalon- säurediethylester dazugegeben und die Mischung unter Rühren bei 80 °C im Ölbad temperiert. Während der Reaktion verdunkelte sich die Lösung von Orange nach Dunkelrot. Nach 1, 3, 6, 12 und 18 Stunden wurden Proben aus der Lösung entnommen. Diese wurden hydrolysiert und mit Natriumsulfat getrocknet und zur GC Analyse gegeben. Nach 18 Stunden waren 21,8 % des Eduktes zu Fluormalonsäurediethylester bei quantitativer Selektivität umgesetzt.The amine complex was placed in a 100 ml PFA flask with a reflux condenser (water cooling), then the diethyl chloromalonate was added and the mixture was heated in an oil bath at 80 ° C. with stirring. During the reaction, the solution darkened from orange to dark red. Samples were taken from the solution after 1, 3, 6, 12 and 18 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 18 hours, 21.8% of the starting material had been converted to diethyl fluoromalonate with quantitative selectivity.
Beispiel 4:Example 4:
Ansatz:Approach:
0,10 mol 2-Chlormalonsäurediethylester 19 , 5 g0.10 mol of diethyl 2-chloromalonate 19.5 g
0,05 mol l,8-Diazabicyclo[5.4.0]undec-7-en x 3,09 HF 10,7 g Aufbau u. Durchführung:0.05 mol l, 8-diazabicyclo [5.4.0] undec-7-ene x 3.09 HF 10.7 g Construction u. Execution:
In einem 100 ml PFA-Kolben mit Rückflußkühler (Wasserkühlung) wurde der Aminkomplex vorgelegt, dan "wurde der Chlormalon- säurediethylester dazugegeben und die Mischung unter Rühren bei 80 °C im Ölbad temperiert. Nach 1, 3 und 6 Stunden wurden Proben aus der Lösung entnommen. Diese wurden hydrolysiert und mit Natriumsulfat getrocknet und zur GC Analyse gegeben. Nach 6 Stunden waren 4,1 % des Eduktes zu Fluormalonsäurediethylester umgesetzt.In a 100 ml PFA flask equipped with a reflux condenser (water cooling) was submitted to the amine complex, dan "was the Chlormalon- acid diethyl ester was added thereto and the mixture with stirring at 80 ° C temperature-controlled oil bath. After 1, 3 and 6 hours, samples from the solution These were hydrolyzed and dried with sodium sulfate and added for GC analysis After 4.1 hours, 4.1% of the starting material had been converted to diethyl fluoromalonate.
Beispiel 51 (Vergleichsbeispiel) ohne LösungsmittelExample 51 (comparative example) without solvent
Ansatz :Approach:
0,23 mol 2-Chlormalonsäurediethylester 53,1 g0.23 mol of diethyl 2-chloromalonate 53.1 g
0,16 mol Triethylamin x 2,72 HF 24,6 g0.16 mol triethylamine x 2.72 HF 24.6 g
Aufbau u . Durchführung :Construction u. Execution :
In einem 100 ml Mehrhalskolben mit Rückflußkühler (Wasserkühlung) wurde der Chlormalonsäurediethylester vorgelegt, dann wurde der Triethylaminkomplex unter Rühren zugetropft . Die Lösung wurde bei 100 °C im Ölbad temperiert. Nach 3 und 6 Stunden wurden Proben aus der Lösung entnommen. Diese wurden hydrolysiert und mit Natriumsulfat getrocknet und zur GC Analyse gegeben. Nach 6 Stunden waren 3,3 % des Eduktes zu Fluormalonsäurediethylester umgesetzt .The diethyl chloromalonate was placed in a 100 ml multi-necked flask with a reflux condenser (water cooling), then the triethylamine complex was added dropwise with stirring. The solution was tempered at 100 ° C. in an oil bath. Samples were taken from the solution after 3 and 6 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 6 hours, 3.3% of the starting material had been converted to diethyl fluoromalonate.
Beispiel 6 ;Example 6;
Vergleichsversuch in Gegenwart von Lösungsmittel mit Triethylamin x HF-KomplexComparative experiment in the presence of solvent with triethylamine x HF complex
Ansatz :Approach:
0,375 mol 2-Chlormalonsäurediethylester 73,125 g0.375 mol of diethyl 2-chloromalonate 73.125 g
0,5 mol Triethylamin x 2,72 HF0.5 mol triethylamine x 2.72 HF
0,25 mol Triethylamin0.25 mol triethylamine
125 ml Acetonitril Aufbau u. Durchführung:125 ml acetonitrile Construction u. Execution:
In einem 100 ml PFA-Kolben mit Rückflüßkühler (Wasserkühlung) wurde der Aminkomplex vorgelegt und das Acetonitril zugegeben, dann wurde der Chlormalonsäurediethylester dazugegeben und die Mischung unter Rühren bei 80 °C im Ölbad temperiert. Nach 1, 3, 6 ,12, 18 und 24 Stunden wurden Proben aus der Lösung entnommen. Diese wurden hydrolysiert und mit Natriumsulfat getrocknet und zur GC Analyse gegeben. Nach 24 Stunden waren 66,02 % des Eduktes zu Fluormalonsäurediethylester umgesetzt.The amine complex was placed in a 100 ml PFA flask with a reflux condenser (water cooling) and the acetonitrile was added, then the chloromonic acid diethyl ester was added and the mixture was heated at 80 ° C. in an oil bath with stirring. Samples were taken from the solution after 1, 3, 6, 12, 18 and 24 hours. These were hydrolyzed and dried with sodium sulfate and added for GC analysis. After 24 hours, 66.02% of the starting material had been converted to diethyl fluoromalonate.
Beispiele 7 bis 11:Examples 7 to 11
Herstellung von Säurefluoriden:Production of acid fluorides:
S02C12 + Amin x HF → S02F2 + HClS0 2 C1 2 + amine x HF → S0 2 F 2 + HCl
Aufbau und Durchführung: (gilt für alle Beispiele zur Herstellung von Säurefluoriden)Structure and implementation: (applies to all examples for the production of acid fluorides)
In einem 100 ml PFA-Kolben mit Rückflußkühler und Tropftrichter wurde der Aminkomplex vorgelegt . Der Rückflußkühler wurde über einen Kryomaten mit -30 °C kalter Sole gespeist. Um das Reaktionsprodukt aufzufangen war nach dem Kühler ein Stahlzy- linder (mit ca. 300 ml Volumen ) mit Tauchrohr und Gasausgang geschaltet, der in einem Dewar mit CO /Methanol auf -78 °C temperiert worden ist. Bei Raumtemperatur wurde langsam und unter starkem Rühren S02C12 in die ölige, hellgelbe Lösung eingeleitet. Kurze Zeit nach Beginn der Einleitung war eine Gasentwicklung zu beobachten. Nach Beendigung des Zutropfens wurde ein Ölbad mit 100 °C unter den Kolben gestellt und noch 1 h mit Kühlung und 1 h ohne Kühlung nachtemperiert, um das entstandene S02F2 vollständig auszutreiben.The amine complex was placed in a 100 ml PFA flask with reflux condenser and dropping funnel. The reflux condenser was fed through a cryomat with -30 ° C cold brine. In order to collect the reaction product, a steel cylinder (with a volume of approx. 300 ml) with dip tube and gas outlet was switched after the cooler, which was heated to -78 ° C in a Dewar with CO / methanol. At room temperature, S0 2 C1 2 was slowly introduced into the oily, light yellow solution with vigorous stirring. A short time after the start of the introduction, gas evolution was observed. After the dropping had ended, an oil bath at 100 ° C. was placed under the flask and heated for a further 1 h with cooling and 1 h without cooling in order to completely drive off the S0 2 F 2 formed .
Beispiel 7: Ansatz :Example 7: Approach:
0,20 mol Sulfurylchlorid S02C12 26,99 g0.20 mol sulfuryl chloride S0 2 C1 2 26.99 g
0,24 mol l,5-Diazabicyclo[4.3.0]non-5-en x 2,67 HF 42,50 g0.24 mol l, 5-diazabicyclo [4.3.0] non-5-ene x 2.67 HF 42.50 g
Auswertung:Evaluation:
Nach Durchführung obengenannter allgemeiner Versuchsvorschrift konnten somit 57,70 % S02F2 und 35,27 % S02FC1 bezogen auf die eingesetzte Eduktmenge isoliert werden.After carrying out the above general test instructions, it was possible to isolate 57.70% S0 2 F 2 and 35.27% S0 2 FC1 based on the amount of starting material used.
Beispiel 8;Example 8;
Ansatz :Approach:
0,20 mol Sulfurylchlorid S02C12 26,99 g0.20 mol sulfuryl chloride S0 2 C1 2 26.99 g
0,127 mol l,5-Diazabicyclo[4.3.0]non-5-en x 7,19 HF 42,50 g0.127 mol l, 5-diazabicyclo [4.3.0] non-5-ene x 7.19 HF 42.50 g
Auswertung:Evaluation:
Nach Durchführung oben genannter allgemeiner Versuchsvorschrift konnten somit 90,65 % S02F2 und 0,34 % S02FC1 bezogen auf die eingesetzte Eduktmenge isoliert werden.After carrying out the above-mentioned general test instructions, 90.65% S0 2 F 2 and 0.34% S0 2 FC1 based on the amount of starting material used could be isolated.
Beispiel 9:Example 9:
Ansatz :Approach:
0,20 mol Sulfurylchlorid S02Cl2 26,99 g0.20 mol sulfuryl chloride S0 2 Cl 2 26.99 g
0,253 mol 1,8 Diazabicyclo [5.4.0]undec-7-en x 5,58 HF 40,90 g0.253 mole 1.8 diazabicyclo [5.4.0] undec-7-en x 5.58 HF 40.90 g
Auswertung :Evaluation:
Nach Durchführung oben genannter allgemeiner Versuchsvorschrift konnten somit 0,04 % S02F2 und 69,87 % S02FC1 bezogen auf die eingesetzte Edukte enge isoliert werden. Beispiel 10; (Vergleichsbeispiel)After carrying out the above-mentioned general test instructions, 0.04% S0 2 F 2 and 69.87% S0 2 FC1 could thus be closely isolated based on the starting materials used. Example 10; (Comparative Example)
Ansatz :Approach:
0,20 mol Sulfurylchlorid S02C12 26,99 g0.20 mol sulfuryl chloride S0 2 C1 2 26.99 g
0,21 mol Pyridin x 2,93 HF 28,50 g0.21 mol pyridine x 2.93 HF 28.50 g
Auswertung :Evaluation:
Nach Durchführung oben genannter allgemeiner Versuchsvorschrift konnten somit 5,03 % S02F2 und 28,12 % S02FC1 bezogen auf die eingesetzte Eduktemenge isoliert werden.After carrying out the above-mentioned general test instructions, 5.03% S0 2 F 2 and 28.12% S0 2 FC1 could be isolated based on the amount of starting material used.
Beispiel 11;Example 11;
Ansatz :Approach:
0,15 mol Sulfurylchlorid S02C12 20,25 g0.15 mol sulfuryl chloride S0 2 C1 2 20.25 g
0,16 mol 4-Dimethylaminopyridin x 2,93 HF 28,90 g0.16 mol of 4-dimethylaminopyridine x 2.93 HF 28.90 g
Auswertung :Evaluation:
Nach Durchführung oben genannter allgemeiner Versuchsvorschrift konnten somit 16,40 % S02F2 und 21,76 % S02FC1 bezogen auf die eingesetzte Eduktemenge isoliert werden.After carrying out the above-mentioned general test instructions, 16.40% S0 2 F 2 and 21.76% S0 2 FC1 could be isolated based on the amount of starting material used.
Beispiel 12: Herstellung von Monofluoromalonsäurediethyle- ster unter Extraktion mit Trifluoressigsäureethy- lesterExample 12: Preparation of diethyl monofluoromalonate by extraction with ethyl trifluoroacetate
(EtO)C(0)-CHCl-C(0) (OEt) • (EtO) C (O) CHF-C (O) (OEt)(EtO) C (0) -CHCl-C (0) (OEt) • (EtO) C (O) CHF-C (O) (OEt)
0,1 mol 2-Chlormalonsäurediethylester wurden mit 0,2 mol 1,5- Diazabicyclo[4.3.0]non-5-en- 1 , 4HF bei 80 °C über einen Zeitraum von 6 Stunden umgesetzt. Nach Abkühlen wurde dem Reaktionsgemisch Trifluoressigsäureethylester zugesetzt. Es bildeten sich zwei Phasen aus. Die Phase, die das Produkt und das Lösungsmittel enthält, wurde abgetrennt und der Trifluoressigsäureethylester zur Isolierung des Produktes abdestilliert. Im Bereich von 25 bis 70 mol-% beobachtete man die Phase trennung . Beispiel 13: Herstellung von Difluormalonsäurediethylester unter Extraktion mit Trifluoressigsäureethyle- ster0.1 mol of diethyl 2-chloromalonate was reacted with 0.2 mol of 1,5-diazabicyclo [4.3.0] non-5-en-1, 4HF at 80 ° C. over a period of 6 hours. After cooling, ethyl trifluoroacetate was added to the reaction mixture. Two phases developed. The phase containing the product and the solvent was separated off and the trifluoroacetic acid ethyl ester was distilled off to isolate the product. The phase separation was observed in the range from 25 to 70 mol%. Example 13: Preparation of difluoronic acid diethyl ester with extraction with trifluoroacetic acid ethyl ester
(EtO) C (0) -CC12-C (0) (OEt) • (EtO) C (0) CF2-C (0) (OEt)(EtO) C (0) -CC1 2 -C (0) (OEt) • (EtO) C (0) CF 2 -C (0) (OEt)
Wie in Beispiel 1 wurden 0,6 mol 1, 8-Diazabicyclo- [5.4.0] - undec-7-en- 1, 9 HF mit 0,15 mol des Dichlormalonesters umgesetzt. Nach Zugabe von Trifluoressigsäureethylester wurden die gebildeten Phasen getrennt und das Produkt isoliert.As in Example 1, 0.6 mol of 1,8-diazabicyclo- [5.4.0] - undec-7-ene-1 HF was reacted with 0.15 mol of the dichloromone ester. After adding trifluoroacetic acid ethyl ester, the phases formed were separated and the product isolated.
Test weiterer Extraktionsmittel:Test of other extractants:
Mit Trifluoressigsäureisopropylester, Trifluortrichlorethan, Hexan, und Cyclohexan konnte ebenfalls eine Phasentrennung erzielt werden.A phase separation could also be achieved with isopropyl trifluoroacetate, trifluorotrichloroethane, hexane and cyclohexane.
Das Extraktionsmittel konnte dann über eine Flashdestillation abgetrennt werden und das Produkt feindestilliert werden. The extractant could then be separated off by flash distillation and the product could be finely distilled.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von fluorhaltigen Verbindungen aus halogenhaltigen, vorzugsweise chlorhaltigen Verbindungen unter Halogen-Fluor-Austausch oder durch HF-Anlagerung an C-C-Mehrfachbindungen in Anwesenheit des HF-Addukts einer mono- oder bicyclischen Verbindung mit mindestens 2 Stickstoffatomen, wobei mindestens 1 Stickstoffatom in das Ringsystem eingebaut ist, als Katalysator oder Fluorierungs- mittel .1. A process for the preparation of fluorine-containing compounds from halogen-containing, preferably chlorine-containing compounds with halogen-fluorine exchange or by HF addition to CC multiple bonds in the presence of the HF adduct of a mono- or bicyclic compound having at least 2 nitrogen atoms, at least 1 nitrogen atom built into the ring system as a catalyst or fluorinating agent.
2. Verfahren nach Anspruch 1 , wobei man das HF-Addukt einer mono- oder bicyclischen Verbindung mit 2 Stickstoffatomen einsetzt, wobei ein oder beide Stickstoffatome in das Ringsystem eingebaut sind.2. The method according to claim 1, wherein the HF adduct of a mono- or bicyclic compound having 2 nitrogen atoms is used, one or both nitrogen atoms being incorporated in the ring system.
3. Verfahren nach Anspruch 1 oder 2 , dadurch gekennzeichnet, daß man als mono- oder bicyclische Verbindung eine Verbindung ausgewählt aus der Gruppe der aminosubstituierten Pyridine und bicyclischen Amidine einsetzt.3. The method according to claim 1 or 2, characterized in that a compound selected from the group of amino-substituted pyridines and bicyclic amidines is used as the mono- or bicyclic compound.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die mono- oder bicyclische Verbindung ausgewählt ist aus der Gruppe bestehend aus Diazabicyclononan, Diazabicylounde- can und Dialkylaminopyridin.4. The method according to claim 3, characterized in that the mono- or bicyclic compound is selected from the group consisting of diazabicyclononane, diazabicyloundecan and dialkylaminopyridine.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man anorganische oder organische Säurefluoride aus entsprechenden Säurechloriden herstellt .5. The method according to claim 1, characterized in that one produces inorganic or organic acid fluorides from corresponding acid chlorides.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß man Sulfurylchlorfluorid oder Sulfurylfluorid herstellt.6. The method according to claim 5, characterized in that one produces sulfuryl chlorofluoride or sulfuryl fluoride.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man fluorhaltige Verbindungen mit C-F-Bindung aus chlorhaltigen Verbindungen mit C-Cl-Bindung herstellt. 7. The method according to claim 1, characterized in that one produces fluorine-containing compounds with CF bond from chlorine-containing compounds with C-Cl bond.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß man Fluor enthaltende Kohlenstoff- oder KohlenwasserstoffVerbindungen herstellt.8. The method according to claim 7, characterized in that one produces fluorine-containing carbon or hydrocarbon compounds.
9. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß man Fluor enthaltende Carbonsäurederivate oder Carbonsaurefluoride herstellt.9. The method according to claim 7, characterized in that one produces fluorine-containing carboxylic acid derivatives or carboxylic acid fluorides.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man alkylenverbrückte Dicarbonsäurederivate herstellt, die in der Alkylenbrücke durch mindestens 1 Fluoratom substituiert sind.10. The method according to claim 9, characterized in that one produces alkylene-bridged dicarboxylic acid derivatives which are substituted in the alkylene bridge by at least 1 fluorine atom.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß man Mono- oder Difluormalonsaureester herstellt.11. The method according to claim 10, characterized in that one produces mono- or difluoronic acid esters.
12. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das HF-Addukt der mono- oder bicyclischen Verbindung als Katalysator einsetzt und Fluorwasserstoff als Fluorie- rungsmittel .12. The method according to claim 1, characterized in that the HF adduct of the mono- or bicyclic compound is used as a catalyst and hydrogen fluoride as a fluorinating agent.
13. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man verbrauchte HF-Addukte der mono- oder bicyclischen Verbindung unter Verwendung von Fluorwasserstoff wiederaufarbeitet.13. The method according to claim 1, characterized in that used HF adducts of the mono- or bicyclic compound are reprocessed using hydrogen fluoride.
14. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man durch mindestens 1 Fluoratom substituierte organische Verbindungen herstellt, wobei ein Gemisch von Amin-HF- Addukten und der oder den durch mindestens 1 Fluoratom substituierte Verbindungen resultiert, und man ein Lösungsmittel zugibt, welches die Bildung zweier flüssiger Phasen bewirkt, wobei die eine Phase das Lösungsmittel und die organische Verbindung (en) und die andere Phase das Amin-HF-Addukt enthält. 14. The method according to claim 1, characterized in that one produces organic compounds substituted by at least 1 fluorine atom, resulting in a mixture of amine HF adducts and the compound or compounds substituted by at least 1 fluorine atom, and adding a solvent which Formation of two liquid phases causes, one phase containing the solvent and the organic compound (s) and the other phase containing the amine-HF adduct.
15. HF-Addukte von 1, 5-Diazabicyclo [4.3.0]non-5-en und 1, 8-Diazabicyclo [5.4.0]undec-7-en.15. HF adducts of 1, 5-diazabicyclo [4.3.0] non-5-ene and 1, 8-diazabicyclo [5.4.0] undec-7-ene.
16. Addukte nach Anspruch 15, worin das Mol-Verhältnis von HF zum Amin gleich 1 oder größer als 1:1 ist.16. Adducts according to claim 15, wherein the molar ratio of HF to amine is 1 or greater than 1: 1.
17. HF-Addukte von N,N-Dialkylaminopyridin, wobei Alkyl C1-C4 bedeutet.17. HF adducts of N, N-dialkylaminopyridine, where alkyl is C1-C4.
18. Addukte nach Anspruch 17, worin das Mol-Verhältnis von HF zum Amin größer als 1:1 ist, vorzugsweise gleich oder kleiner 9 ist.18. Adducts according to claim 17, wherein the molar ratio of HF to amine is greater than 1: 1, preferably equal to or less than 9.
19. HF-Addukte, worin Alkyl für Methyl steht. 19. HF adducts, wherein alkyl is methyl.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10349971B2 (en) 2011-06-29 2019-07-16 CARDINAL HEALTH SWITZERLAND 515 GmbH System and method for dilating and adjusting flexibility in a guiding device

Families Citing this family (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10104663A1 (en) 2001-02-02 2002-08-08 Solvay Fluor & Derivate Production of fluorine compounds
DE10105592A1 (en) 2001-02-06 2002-08-08 Achim Goepferich Placeholder for drug release in the frontal sinus
DE10114565A1 (en) 2001-03-24 2002-09-26 Solvay Fluor & Derivate Improved ester production
DE10203044A1 (en) * 2002-01-26 2003-07-31 Solvay Fluor & Derivate extraction process
DE10261471A1 (en) 2002-02-08 2003-08-21 Solvay Fluor & Derivate Manufacture of alkenones
WO2003066558A2 (en) 2002-02-08 2003-08-14 Solvay Fluor Und Derivate Gmbh Production of alkenones
US8317816B2 (en) 2002-09-30 2012-11-27 Acclarent, Inc. Balloon catheters and methods for treating paranasal sinuses
WO2005007657A2 (en) * 2003-07-11 2005-01-27 Solvay Fluor Gmbh Use of dbn and dbu salts as ionic liquids
DE10337885A1 (en) * 2003-08-18 2005-03-24 Bayer Cropscience Ag Process for the preparation of α-fluoromalonic acid dialkyl esters
US7955738B2 (en) * 2004-03-05 2011-06-07 Honeywell International, Inc. Polymer ionic electrolytes
EP1720834A1 (en) 2004-03-05 2006-11-15 Honeywell International, Inc. Ionic liquids of heterocyclic amines
US8932276B1 (en) 2004-04-21 2015-01-13 Acclarent, Inc. Shapeable guide catheters and related methods
US7419497B2 (en) 2004-04-21 2008-09-02 Acclarent, Inc. Methods for treating ethmoid disease
US7803150B2 (en) 2004-04-21 2010-09-28 Acclarent, Inc. Devices, systems and methods useable for treating sinusitis
US20060063973A1 (en) 2004-04-21 2006-03-23 Acclarent, Inc. Methods and apparatus for treating disorders of the ear, nose and throat
US20190314620A1 (en) 2004-04-21 2019-10-17 Acclarent, Inc. Apparatus and methods for dilating and modifying ostia of paranasal sinuses and other intranasal or paranasal structures
US9089258B2 (en) 2004-04-21 2015-07-28 Acclarent, Inc. Endoscopic methods and devices for transnasal procedures
US9554691B2 (en) 2004-04-21 2017-01-31 Acclarent, Inc. Endoscopic methods and devices for transnasal procedures
US10188413B1 (en) 2004-04-21 2019-01-29 Acclarent, Inc. Deflectable guide catheters and related methods
US9399121B2 (en) 2004-04-21 2016-07-26 Acclarent, Inc. Systems and methods for transnasal dilation of passageways in the ear, nose or throat
US20070208252A1 (en) 2004-04-21 2007-09-06 Acclarent, Inc. Systems and methods for performing image guided procedures within the ear, nose, throat and paranasal sinuses
US7559925B2 (en) 2006-09-15 2009-07-14 Acclarent Inc. Methods and devices for facilitating visualization in a surgical environment
US20060004323A1 (en) 2004-04-21 2006-01-05 Exploramed Nc1, Inc. Apparatus and methods for dilating and modifying ostia of paranasal sinuses and other intranasal or paranasal structures
US8764729B2 (en) 2004-04-21 2014-07-01 Acclarent, Inc. Frontal sinus spacer
US9101384B2 (en) 2004-04-21 2015-08-11 Acclarent, Inc. Devices, systems and methods for diagnosing and treating sinusitis and other disorders of the ears, Nose and/or throat
US7654997B2 (en) 2004-04-21 2010-02-02 Acclarent, Inc. Devices, systems and methods for diagnosing and treating sinusitus and other disorders of the ears, nose and/or throat
US9351750B2 (en) 2004-04-21 2016-05-31 Acclarent, Inc. Devices and methods for treating maxillary sinus disease
US8747389B2 (en) 2004-04-21 2014-06-10 Acclarent, Inc. Systems for treating disorders of the ear, nose and throat
US8894614B2 (en) 2004-04-21 2014-11-25 Acclarent, Inc. Devices, systems and methods useable for treating frontal sinusitis
US8146400B2 (en) 2004-04-21 2012-04-03 Acclarent, Inc. Endoscopic methods and devices for transnasal procedures
US20070167682A1 (en) 2004-04-21 2007-07-19 Acclarent, Inc. Endoscopic methods and devices for transnasal procedures
US7410480B2 (en) 2004-04-21 2008-08-12 Acclarent, Inc. Devices and methods for delivering therapeutic substances for the treatment of sinusitis and other disorders
US8864787B2 (en) 2004-04-21 2014-10-21 Acclarent, Inc. Ethmoidotomy system and implantable spacer devices having therapeutic substance delivery capability for treatment of paranasal sinusitis
US7361168B2 (en) 2004-04-21 2008-04-22 Acclarent, Inc. Implantable device and methods for delivering drugs and other substances to treat sinusitis and other disorders
US8702626B1 (en) 2004-04-21 2014-04-22 Acclarent, Inc. Guidewires for performing image guided procedures
US7462175B2 (en) 2004-04-21 2008-12-09 Acclarent, Inc. Devices, systems and methods for treating disorders of the ear, nose and throat
US8951225B2 (en) 2005-06-10 2015-02-10 Acclarent, Inc. Catheters with non-removable guide members useable for treatment of sinusitis
US8114113B2 (en) 2005-09-23 2012-02-14 Acclarent, Inc. Multi-conduit balloon catheter
US8190389B2 (en) 2006-05-17 2012-05-29 Acclarent, Inc. Adapter for attaching electromagnetic image guidance components to a medical device
JP4940790B2 (en) * 2006-06-30 2012-05-30 セントラル硝子株式会社 Dehydroxy fluorinating agent
US9820688B2 (en) 2006-09-15 2017-11-21 Acclarent, Inc. Sinus illumination lightwire device
US8439687B1 (en) 2006-12-29 2013-05-14 Acclarent, Inc. Apparatus and method for simulated insertion and positioning of guidewares and other interventional devices
US8118757B2 (en) 2007-04-30 2012-02-21 Acclarent, Inc. Methods and devices for ostium measurement
US8485199B2 (en) 2007-05-08 2013-07-16 Acclarent, Inc. Methods and devices for protecting nasal turbinate during surgery
US10206821B2 (en) 2007-12-20 2019-02-19 Acclarent, Inc. Eustachian tube dilation balloon with ventilation path
US8182432B2 (en) 2008-03-10 2012-05-22 Acclarent, Inc. Corewire design and construction for medical devices
AU2009276553B2 (en) 2008-07-30 2015-02-05 Acclarent, Inc. Paranasal ostium finder devices and methods
BRPI0919195A2 (en) 2008-09-18 2019-09-24 Acclarent Inc Methods and Apparatus for the Treatment of Ear, Nose, and Throat Disorders
US20100241155A1 (en) 2009-03-20 2010-09-23 Acclarent, Inc. Guide system with suction
US7978742B1 (en) 2010-03-24 2011-07-12 Corning Incorporated Methods for operating diode lasers
US8435290B2 (en) 2009-03-31 2013-05-07 Acclarent, Inc. System and method for treatment of non-ventilating middle ear by providing a gas pathway through the nasopharynx
PL3214066T3 (en) * 2009-07-16 2024-07-01 Specialty Operations France Process for the preparation of fluoroalkyl fluoroformates
CA2769797A1 (en) 2009-08-10 2011-02-17 Solvay Fluor Gmbh Process for the manufacture of sevoflurane
US9155492B2 (en) 2010-09-24 2015-10-13 Acclarent, Inc. Sinus illumination lightwire device
CN104080780B (en) 2011-11-30 2018-04-13 索尔维公司 Derivative, its preparation method and its purposes as solvent additive of the meldrum's acid of fluorination
CN103159626B (en) * 2011-12-14 2015-09-30 中化蓝天集团有限公司 A kind of method preparing 3-fluorine propionic ester
JP5853772B2 (en) * 2012-03-01 2016-02-09 セントラル硝子株式会社 Method for producing α, α-difluoroaromatic compound
JP5853771B2 (en) * 2012-03-01 2016-02-09 セントラル硝子株式会社 Method for producing α, α-difluoroaromatic compound
JP2016508512A (en) * 2013-02-15 2016-03-22 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Process for producing bis-dihaloalkylpyrazole
US9433437B2 (en) 2013-03-15 2016-09-06 Acclarent, Inc. Apparatus and method for treatment of ethmoid sinusitis
US9629684B2 (en) 2013-03-15 2017-04-25 Acclarent, Inc. Apparatus and method for treatment of ethmoid sinusitis
CN108128758B (en) * 2017-12-20 2019-12-31 中国科学院上海有机化学研究所 SOF2And SOF4Gas preparation method and system
CN109824512B (en) * 2019-02-26 2021-06-08 国药集团化学试剂有限公司 Preparation method of 2-fluoro dimethyl malonate
WO2021149788A1 (en) * 2020-01-22 2021-07-29 関東電化工業株式会社 Method for purifying carboxylic acid fluoride
US20230322661A1 (en) * 2020-08-21 2023-10-12 Ses Holdings Pte. Ltd. Synthesis of N,N-Branched Sulfamoyl Fluoride Compounds Using Bismuth Trifluoride
CN114395767A (en) * 2022-01-29 2022-04-26 宁德时代新能源科技股份有限公司 Preparation method of sulfuryl fluoride by electrofluorination
EP4276062A4 (en) * 2022-01-29 2024-07-10 Contemporary Amperex Technology Co Ltd Method for preparing sulfuryl fluoride by using fluorination method for sulfuryl chloride

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2823969A1 (en) 1978-06-01 1979-12-13 Hoechst Ag PROCESS FOR PRODUCING ORGANIC FLUORINE COMPOUNDS
JPH075853B2 (en) * 1986-11-18 1995-01-25 三菱化学株式会社 Recording liquid
DE4237882A1 (en) * 1992-11-10 1994-05-11 Bayer Ag Process for the preparation of alpha-fluoro-beta-dicarbonyl compounds
WO1998043933A1 (en) 1997-03-31 1998-10-08 Nippon Zeon Co., Ltd. Process for producing aliphatic unsaturated fluorinated hydrocarbon compounds
DE19942374A1 (en) * 1998-11-30 2000-05-31 Solvay Fluor & Derivate Process for the preparation of acid fluorides from acid chlorides
JP3533134B2 (en) * 1999-02-15 2004-05-31 三井化学株式会社 Fluorinating agents and their production and use
AU7511300A (en) 1999-09-04 2001-04-10 Solvay Fluor Und Derivate Gmbh Regeneration of onium fluoride-hf adducts
DE10104663A1 (en) 2001-02-02 2002-08-08 Solvay Fluor & Derivate Production of fluorine compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02060838A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10349971B2 (en) 2011-06-29 2019-07-16 CARDINAL HEALTH SWITZERLAND 515 GmbH System and method for dilating and adjusting flexibility in a guiding device

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