EP1370506A1 - Preparation de composes de fluor - Google Patents

Preparation de composes de fluor

Info

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
Authority
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.)
Withdrawn
Application number
EP02708176A
Other languages
German (de)
English (en)
Inventor
Max Braun
Carsten Brosch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Fluor GmbH
Original Assignee
Solvay Fluor und Derivate GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Solvay Fluor und Derivate GmbH filed Critical Solvay Fluor und Derivate GmbH
Publication of EP1370506A1 publication Critical patent/EP1370506A1/fr
Withdrawn legal-status Critical Current

Links

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

Selon l'invention, des composés minéraux et organiques contenant du fluor peuvent être préparés par exemple à partir de composés correspondants contenant du chlore, grâce à un échange chlore-fluor au moyen d'agents de fluoration. Il a été démontré que des composés monocycliques ou bicycliques comprenant au moins 2 atomes d'azote dont au moins l'un est intégré à la partie cyclique, peuvent être utilisés comme catalyseurs ou agents de fluoration pour des réactions d'échange chlore-fluor. Ceci permet la préparation de chlorofluorure de sulfuryle, de fluorure de sulfuryle ou de fluorures d'acide carboxylique. L'addition HF au niveau de liaisons C-C multiples et l'échange chlore-fluor au niveau d'atomes de carbone sont tous deux possibles. Par exemple, un ester d'acide mono- ou dichloromalonique peut être converti en ester d'acide mono- ou difluoromalonique. L'utilisation de solvant appropriés permet de faire passer le mélange réactionnel dans une zone à deux phases et simplifie ainsi le processus de préparation. DRAWING: 0 YES 1 NO 0 NOTHING TO TRANSLATE
EP02708176A 2001-02-02 2002-01-26 Preparation de composes de fluor Withdrawn EP1370506A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10104663A DE10104663A1 (de) 2001-02-02 2001-02-02 Herstellung von Fluorverbindungen
DE10104663 2001-02-02
PCT/DE2002/000276 WO2002060838A1 (fr) 2001-02-02 2002-01-26 Preparation de composes de fluor

Publications (1)

Publication Number Publication Date
EP1370506A1 true EP1370506A1 (fr) 2003-12-17

Family

ID=7672591

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02708176A Withdrawn EP1370506A1 (fr) 2001-02-02 2002-01-26 Preparation de composes de fluor

Country Status (8)

Country Link
US (1) US7145046B2 (fr)
EP (1) EP1370506A1 (fr)
JP (1) JP2004537502A (fr)
CN (1) CN1230403C (fr)
DE (1) DE10104663A1 (fr)
HK (1) HK1063179A1 (fr)
RU (1) RU2285686C2 (fr)
WO (1) WO2002060838A1 (fr)

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US7145046B2 (en) 2006-12-05
CN1230403C (zh) 2005-12-07
WO2002060838A1 (fr) 2002-08-08
RU2003125646A (ru) 2005-03-20
JP2004537502A (ja) 2004-12-16
HK1063179A1 (en) 2004-12-17
RU2285686C2 (ru) 2006-10-20
CN1489560A (zh) 2004-04-14

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