ZA200409161B - Method for the production of monohydro-perflouroalkanes, bis(perflouroalkyl)phosphinates, and perfluoroalkylphosphonates. - Google Patents
Method for the production of monohydro-perflouroalkanes, bis(perflouroalkyl)phosphinates, and perfluoroalkylphosphonates. Download PDFInfo
- Publication number
- ZA200409161B ZA200409161B ZA200409161A ZA200409161A ZA200409161B ZA 200409161 B ZA200409161 B ZA 200409161B ZA 200409161 A ZA200409161 A ZA 200409161A ZA 200409161 A ZA200409161 A ZA 200409161A ZA 200409161 B ZA200409161 B ZA 200409161B
- Authority
- ZA
- South Africa
- Prior art keywords
- process according
- bis
- group
- perfluoroalkylphosphonates
- phosphorane
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title description 4
- 230000008569 process Effects 0.000 claims abstract description 55
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000012429 reaction media Substances 0.000 claims abstract description 9
- 239000002585 base Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- -1 alkylammonium hydrox- ides Chemical class 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- HEJQMLUVXZXFRS-UHFFFAOYSA-N difluoro-tris(1,1,2,2,2-pentafluoroethyl)-$l^{5}-phosphane Chemical compound FC(F)(F)C(F)(F)P(F)(F)(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F HEJQMLUVXZXFRS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000004679 hydroxides Chemical class 0.000 claims description 7
- 150000007529 inorganic bases Chemical class 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000004795 grignard reagents Chemical class 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical compound C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 4
- 210000001217 buttock Anatomy 0.000 claims 2
- 239000004094 surface-active agent Substances 0.000 claims 1
- 230000000875 corresponding effect Effects 0.000 description 13
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- YIHKYBZZZHSBHP-UHFFFAOYSA-M lithium;bis(1,1,2,2,2-pentafluoroethyl)phosphinate Chemical compound [Li+].FC(F)(F)C(F)(F)P(=O)([O-])C(F)(F)C(F)(F)F YIHKYBZZZHSBHP-UHFFFAOYSA-M 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229960003975 potassium Drugs 0.000 description 5
- 235000007686 potassium Nutrition 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MZADBHZWIYQXNJ-UHFFFAOYSA-M potassium;bis(1,1,2,2,2-pentafluoroethyl)phosphinate Chemical compound [K+].FC(F)(F)C(F)(F)P(=O)([O-])C(F)(F)C(F)(F)F MZADBHZWIYQXNJ-UHFFFAOYSA-M 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013519 translation Methods 0.000 description 2
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 description 1
- ZQTIKDIHRRLSRV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluorobutane Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)F ZQTIKDIHRRLSRV-UHFFFAOYSA-N 0.000 description 1
- 241001535291 Analges Species 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940124326 anaesthetic agent Drugs 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- YSRVDLQDMZJEDO-UHFFFAOYSA-N bis(1,1,2,2,2-pentafluoroethyl)phosphinic acid Chemical compound FC(F)(F)C(F)(F)P(=O)(O)C(F)(F)C(F)(F)F YSRVDLQDMZJEDO-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 101150061397 cnfn gene Proteins 0.000 description 1
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0291—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
- B01J31/0232—Halogen-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0228
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0289—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
- B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a process for the preparation of mono-hydroperfluoroalkanes, bis(perfluoroalkyl)phosphinates and perfluoroalkyl-phosphonates which comprises at least the treatment of at least one perfluoroalkylphosphorane with at least one base in a suitable reaction medium.
Description
) ® WO 03/087111 PCT/EP03/02744 e
Process for the preparation of monohydroperfluoroalkanes, bis(perfluoroalkyl)phosphinates and perfluoroalkylphosphonates
The present invention relates to a process for the preparation of mono- hydroperfluoroalkanes, bis(perfluoroalkyl)phosphinates and perfluoroalkyl- phosphonates which comprises at least the treatment of at least one per- fluoroalkylphosphorane with at least one base in a suitable reaction medium.
Monohydroperfluoroalkanes have been known for some time and have found broad application in various areas, inter alia as ozone-friendly refrig- erants (WO 01/40400, WO 01/23494, W001/23491, WO99/36485,
WQ98/08913), as cleaning agents (WO 01/32323), as a constituent of etchants for the microelectronics area (US 2001/0005637, US 6228775) in fire extinguishers (W0O010/5468, Combust. Flame, 121, No. 3 (2000) pages 471-487, CN 1218702), as blowing agents in foams (US 6225365,
WO 01/18098) and for the preparation of polymeric materials and potential anaesthetics (Anesth. Analg (N.Y.), 79, No. 2 (1994), pages 245-251,
T. Hudlicky et al., J. of Fluorine Chem., 59, No. 1 (1992), pages 9-14).
Some of these monohydroperfluoroalkanes, such as, for example, penta- fluoroethane, are already produced industrially on a tonne scale, the pro- duction usually being carried out by catalytic hydrofluorination of chlorina- ted hydrocarbons (WO01/77048, EP 1052235).
Disadvantageous in teses processes is firstly the risk associated with the use of hydrogen fluoride at relatively high temperatures. Furthermore, the processes require particular catalysts, which have to be prepared in advance by comparatively complex processes. A further disadvantage of these processes is that the preparation of the chlorinated hydrocarbons using chlorine is ecologically dubious, and the production costs further increased. Finally, the known processes for the preparation of pentafluoro- \
’ ® WO 03/087111 PCT/EP03/02744 ethane are not readily suitable for the preparation of longer-chain mono- hydroperfluoroalkanes, such as, for example, 1-hydrononafluorobutanes.
Furthermore, some further processes are known in which pentafluoro- ethane is prepared using special fluorinating agents, such as, for example,
BrF; (R. A. Devis, J. Org. Chem. 32 (1967), page 3478), XeF. (JP2000/ 119201), SF, (G. Siegemund, Liebigs Ann. Chem., 1979, page 1280,
E.R. Bissell, J. of Organic Chem., 29, (1964), page 1591), SbFs (G.G.
Belenkii et al., Izv. Akad. Nauk SSSR, Ser. Khim., 1972, pages 983, Chem.
Abstr. 77 (1972) 75296, A.F.Ermolov et al., Zh. Org. Khim., 17 (1981), page 2239, J. Org. Chem. USSR (Engl. Translation), 17 (1981), page 1999, US 2426172), MoF¢ (L.D. Shustov et al., Zh. Obshch. Khim., 53 (1983), page 103, J. Gen. Chem. USSR (Engl. translation), 53 (1983), page 85) and CoF3; (US6162955).
However, the above-mentioned processes have not achieved industrial significance since both the respective starting compounds and the fluori- nating agents themselves are very expensive.
By contrast, only few processes are known for the preparation of long- chain monohydroperfluoroalkanes.
According to a first process, monohydroperfluoroalkanes are prepared by decarboxylation of salts of perfluorinated carboxylic acids (J.D. LaZerte et al., J. Am. Chem. Soc., 75 (1953), page 4525; R.N. Haszeldine, J. Chem.
Soc. 1953, page 1548) or corresponding esters (E. Bergman, J. Org.
Chem., 23, (1958) page 476) by treatment with strong bases, such as, for example, sodium ethoxide.
According to another process, monohydroperfluoroalkanes are prepared by treatment of perfluorinated ketones having a trifluoromethyl group on the carbonyl carbon atom with aqueous alkali (L.V. Saloutina et al, 1zv. Akad.
’ ® WO 03/087111 PCT/EP03/02744 ® -3-
Nauk SSSR, Ser. Khim., 1984, No. 5, pages 1114-1116, Chem. Abstr. 101 (1984) 210504x). These processes also have the disadvantage of the use of expensive starting materials and the high temperatures necessary.
S 1-Hydro-n-nonafluorobutane is furthermore prepared by reduction of per- fluorobuty! iodide using various reducing agents, such as, for example, zinc dust in methanol (T. Hudlicky et al., J. of Fluorine Chem., 59, No. 1 (1992), pages 9-14), sodium methoxide (J.L. Howell et al., J. of Fluorine Chem, 72, No. 1 (1995), pages 61-68), by hydrogen in the gas phase at high tem- peratures (EP 6 32 001), and with the aid of the thallium complex [TaCp2(C,H.4)H] (P.H. Russel et al., Polyhedron 17, No. 7 (1998), pages 1037-1043).
However, these processes likewise have the disadvantage that they start from the starting compound perfluorobutyl iodide, which can only be pre- pared by comparatively expensive production processes.
The object of the present invention was therefore to provide a process which enables the simple and inexpensive preparation of monohydroper- fluoroalkanes in good yields. The monohydroperfluoroalkanes should pref- erably be obtained in high purity. A further object was to prepare bis(per- fluoroalkyl)phosphinates and perfluoroalkylphosphonates.
This object has been achieved by the process according to the invention for the preparation of monohydroperfluoroalkanes of the general formula
CHF 2h, in which 1 <n < 8, preferably 1 <n < 4, bis(perfluoroalkyl)phos- phinates and perfluoroalkylphosphonates which comprises at least the treatment of at least one perfluoroalkylphosphorane with at least one base in a suitable reaction medium.
’ ® WO 03/087111 PCT/EP03/02744
In accordance with the invention, the preparation of monohydroperfluoro- alkanes by the process according to the invention can in each case be car- ried out using a perfiuoroalkylphosphorane or mixtures of two or more per- fluoroalkylphosphoranes. Preferably, only one perfluoroalkylphosphorane is in each case reacted by the process according to the invention.
The perfluoroalkylphosphoranes used in the process according to the invention can be prepared by conventional methods known to the person skilled in the art.
The perfluoroalkylphosphoranes are preferably prepared by electrochemi- cal fluorination of suitable starting compounds, as described in V. Ya.
Semenii et al., Zh. Obshch.Khim., 55, No. 12 (1985), pages 2716-2720; N.
Ignatiev, J. of Fluorine Chem., 103 (2000), pages 57-61 and WO 00/21969.
The corresponding descriptions are incorporated herein by way of refer- ence and are regarded as part of the disclosure.
In a preferred embodiment of the process according to the invention, use is made of at least one perfluoroalkylphosphorane of the general formula (CaF 2ne1)mPFsm
I in which 1 <n <8, preferably 1 <n <4, and m in each case denotes 1, 2 or 3
Particularly preferred perfluoroalkylphosphorane compounds are selected from the group consisting of difluorotris(pentafluoroethyl)phosphorane, di- fluorotris(n-nonafluorobutyl)phosphorane, difluorotris(n-heptafluoropropyl)- phosphorane and trifluorobis(n-nonafluorobutyl)phosphorane.
® WO 03/087111 PCT/EP03/02744 ® 5
The treatment of the perfluoroalkylphosphorane compound(s) by the proc- ess according to the invention is preferably in each case carried out using only one base. It is of course however also possible to use mixtures of two or more bases in the process according to the invention. The respective
S bases can also be used in the form of corresponding solvates, preferably in the form of corresponding hydrates, or in the form of conventional adducts known to the person skilled in the art.
In a further preferred embodiment of the process according to the invention for the preparation of monohydroperfluoroalkanes, use is made of a base generally (a), preferably an inorganic base (b) or organic base (c). The inorganic base (b) is preferably selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
If an alkali metal hydroxide is used as base (b) in the process according to the invention, this can preferably be selected from the group consisting of lithium hydroxide, lithium hydroxide monohydrate, sodium hydroxide and potassium hydroxide.
If an alkaline earth metal hydroxide is used as base (b) in the process according to the invention, this can preferably be selected from the group consisting of barium hydroxide, barium hydroxide octahydrate and calcium hydroxide.
The process according to the invention for the preparation of monohydro- perfluoroalkanes can likewise preferably be carried out using an organic base (c) or organometallic compounds. The base (c) can preferably be selected from the group consisting of alkylammonium hydroxides, aryl- ammonium hydroxides, alkylarylammonium hydroxides, alkylphosphonium hydroxides, arylphosphonium hydroxides, alkylarylphosphonium hydrox- ides, alkylamines, arylamines, alkylarylamines, alkylphosphines, arylphos- phines and alkylarylphosphines.
) ® WO 03/087111 PCT/EP03/02744 ® 6
Preferred organometallic compounds can be selected from the group con- sisting of metal alkoxides, preferably alkali metal alkoxides, metal aryl- oxides, metal alkylthiooxides, metal arylthiooxides, alkylmetal compounds, arylmetal compounds and Grignard reagents.
If one of the above-mentioned classes of bases contains an alkyl radical, this can preferably contain from 1 to 4 carbon atoms. If the corresponding base contains two or more alkyl radicals, these may in each case be iden- tical or different, identical alkyl radicals being preferred.
If one of the above-mentioned classes of bases contains an aryl radical, this can preferably be an unsubstituted or at least monosubstituted phenyl radical.
If an alkali metal alkoxide is used as base in the process according to the invention, this can preferably be derived from sodium and can preferably have from 1 to 3 carbon atoms.
Suitable reaction media for use in the process according to the invention are conventional reaction media which are known to the person skilled in the art so long as these do not undergo an irreversible chemical reaction with the respective base or the respective monohydroperfluoroalkane obtained.
In a further preferred embodiment of the process according to the inven- tion, the reaction medium is water, if desired mixed with one or more organic solvents, where two-phase systems, such as, for example, mixtures of water and hydrocarbon, are also included in accordance with the inven- tion.
) ® WO 03/087111 PCT/EP03/02744 ® -7-
The process according to the invention for the preparation of monohydro- perfluoroalkanes can likewise preferably be carried out using one or more organic solvents, where, in the case where at least two solvents are used, these can, if desired, be in the form of a two-phase system.
Suitable organic solvents which are used in the process according to the invention, in each case alone or in any desired combination with one another, if desired also mixed with water, can preferably be selected from the group consisting of alcohols, ethers, acylamides, sulfoxides, sulfones, nitriles and hydrocarbons.
Preferred alcohols are those having from 1 to 4 carbons in the alkyl moiety.
Corresponding alcohols can preferably be selected from the group con- sisting of methanol, ethano!, isopropanol and mixtures of at least two of these above-mentioned alcohols.
The amount of the monohydroperfluoroalkane formed from the respective perfluoroalkylphosphorane(s) employed and the type of the further reaction products can be controlled in a targeted manner in accordance with the process according to the invention, for example via the temperature and/or pressure during the reaction or via the molar ratio of perfluoroalkylphos- phorane to base.
Through the choice of parameters, it is possible, for example, for one, two or three perfluoroalky! groups to be cleaved off specifically from the respective difluorotrisperfluoroalkylphosphorane employed.
On removal of one perfluoroalky! group from the respective difluorotrisper- fluoroalkylphosphorane, the corresponding bis(perfluoroalkyl)phosphinate, inter alia, is also formed in addition to the desired monohydroperfluoro- alkane.
: ® WO 03/087111 PCT/EP03/02744 ® _8-
On removal of two perfluoroalky! groups from the respective difluorotris- perfluoroalkylphosphorane, the corresponding perfluoroalkylphosphonate, inter alia, is also formed in addition to the desired monohydroperfluoro- alkane.
If all three perfluoroalky! groups are removed from the respective difluoro- trisperfluoroalkylphosphorane, the corresponding phosphate, inter alia, is also obtained in addition to the desired monohydroperfluoroalkane.
The respective choice of optimum parameters for the desired combination of the corresponding monohydroperfluoroalkane, the amount thereof and the respective further reaction products can be determined by the person skilled in the art by means of simple preliminary experiments.
If, for example, it is intended to remove one perfiuoroalkyl group from the respective difluorotrisperfluoroalkylphosphorane employed, the process according to the invention can preferably be carried out at a temperature of from -10°C to 100°C and a mole-equivalent ratio of difluorotrisperfluoro- alkylphosphorane to base of 1:3.
If, for example, it is intended to remove two perfluoroalkyl groups from the respective difluorotrisperfluoroalkylphosphorane employed, the process according to the invention can preferably be carried out at a temperature of from 50°C to 150°C and a mole-equivalent ratio of difluorotrisperfluoro- alkylphosphorane to base of 1.4.
If, for example, it is intended to remove the three perfluoroalkyl groups from . the respective difluorotrisperfluoroaikylphosphorane employed, the proc- ess according to the invention can preferably be carried out at a tempera-
ture of from 100°C to 250°C and a mole-equivalent ratio of difluorotrisper- fluoroalkylphosphorane to base of 1:5.
The monohydroperfluoroalkanes prepared by the process according to the invention can, if necessary, be isolated and, if necessary, purified by con- ventional methods known to the person skilled in the art.
If they are readily volatile compounds, they can be isolated from the reac- tion mixture by, for example, condensation in one or more cold traps, which are preferably cooled with liquid nitrogen or dry ice.
Any isolation and purification of further reaction products is likewise carried out by conventional methods known to the person skilled in the art, such as, for example, by fractional crystallisation or extraction with suitable sol- vents.
If the perflucroalkylphosphorane is reacted with an inorganic base (b), the bis(perfluoroalkyl)phosphinates and perfluoroalkylphosphonates thus formed can be converted directly or after isolation using an acid, preferably using sulfuric acid, into the corresponding bis(perfluoroalkyl)phosphinic acids and perfluoroalkyiphosphonic acids.
The bis(perfluoroalky!)phosphinic acids and perfluoroalkylphosphonic acids obtained in this way can be converted into the salts by neutralisation, preferably using organic bases (c).
Through selection of suitable bases, the partially alkylated and peralkyl- ated ammonium, phosphonium, sulfonium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium and triazolium salts salts are preferably prepared.
Particular preference is given to the preparation of salts having a cation selected from the group consisting of
R1 RA
R6 x R2 RG LR? + | +
RS” “NT TR3 RS nN
R4 R4
R1
BO: Bod
R5 Pe R5 nN R3
R4 R4
R5 R1 RS R1 5! PE
NUNS ’
R4 R2 R4 ss” R2 he
RS _R1 R1
I A
R4 SN Ra” NTR
R3 where R' to R® are identical or different, are optionally bonded directly to one another via a single or double bond and are each, individually or together, defined as follows: - H, - halogen, where the halogens are not bonded directly to N, 05 - an alkyl radical (C, to Cs), which may be partially or completely substi- tuted by further groups, preferably F, Cl, N(CnFn+1-9Hx)2, O(CrF 2ne19Hx),
SO2(ChF 2n+159Hx), CrF 2n1-9Hx where 1 <n<6and 0 <x <2n+1.
These salts can also be obtained if the salt formed after the reaction of the perfluoroalkylphosphorane with an inorganic base (b) is subjected to salt interchange, directly or after isolation.
® WO 03/087111 PCT/EP03/02744
C “11 -
The salt interchanges can be carried out with aryl-, alkyl- or alkylaryl- ammonium or -phosphonium salts. Preference is given to the use of hexafluorophosphates, tetrafluoroborates, hexafluoroarsenates, sulfates, fluorides, chlorides or bromides.
The salts obtained in this way can be worked up in a conventional manner known to the person skilled in the art.
The process according to the invention for the preparation of monohydro- perfluoroalkanes enables the simple, inexpensive and reliable preparation of these compounds in very good yields. In particular, the perfluoroalkyl- phosphoranes used as starting compounds can be prepared inexpensively in large quantities.
It is furthermore advantageous that the by-products obtained in the process according to the invention, such as, for example, the bis(perfluoroalkyl)- phosphinates and perfluoroalkylphosphonates, are themselves valuable raw materials which are suitable, inter alia, for the preparation of the corre- sponding bis(perfluoroalkyl)phosphinic acids and perfluoroalkylphosphonic acids and thus can be utilised economically. Neutralisation using suitable bases enables preparation from them of, for example, bis(perfluoroalkytl)- phosphinates and perfluoroalkylphosphonates, which are suitable for use as ionic liquids, surfactants or phase-transfer catalysts.
This furthermore has the advantage that the environmental impact in the reaction by the process according to the invention is kept small, which fur- thermore has a positive effect on the production costs of the monohydro- perfluoroalkanes prepared by the process according to the invention.
® -12-
The respective monohydroperfluoroalkanes are furthermore obtained in high purity immediately after their preparation, i.e. without complex purifi- cation steps.
S The invention is explained below with reference to examples. These exam- ples serve merely to explain the invention and do not restrict the general inventive idea.
® WO 03/087111 PCT/EP03/02744 ® -13-
Example 1 10.40 g (185.4 mmol) of potassium hydroxide are dissolved in 330 cm” of water in a flask, and the resultant solution is cooled at a bath temperature of -5°C. 25.53 g (59.9 mmol) of difluorotris(pentafiuoroethyl)phosphorane are subsequently added via a dropping funnel over the course of 15 min- utes with stirring. The reaction mixture is subsequently brought to room temperature. The gaseous pentafluoroethane formed by alkaline hydrolysis of the difluorotris(pentafiuoroethyl)phosphorane is collected in two subse- quent traps, each of which is cooled with liquid nitrogen. 6.67 g of solid pentafluoroethane having a boiling point of -48°C are obtained in the cooled traps. This value corresponds to that indicated in the literature by L. Conte et al. in J. Fluor. Chem., 38, (1988), pages 319- 326.
The yield of pentafluoroethane is 92.8%, based on a pentafluoroethyl group removed from the difluorotris(pentafluoroethyl)phosphorane under these conditions.
The reaction mixture in the flask furthermore contains a solution of potas- sium bis(pentafluoroethyl)phosphinate ((C2Fs).P(O)OK) and potassium fluoride. In order to isolate the potassium bis(pentafluoroethyi)phosphinate, firstly the excess potassium hydroxide is neutralised using a few drops of an aqueous hydrogen fluoride solution, and the water is removed under reduced pressure. The resultant solid residue is dried under reduced pres- sure at 120 Pa and a bath temperature of 100°C for two hours.
® WO 03/087111 PCT/EP03/02744
Potassium bis(pentafluoroethyl)phosphinate is extracted from the dried residue using 150 cm® of methanol. The methanol is subsequently distilled off under reduced pressure at 120 Pa, and the solid residue of potassium bis(pentafluoroethyl)phosphinate is dried. The yield is 19.0 g, correspond-
S ing to 93.2%, based on the difluorotris(pentafluoroethyl)phosphorane employed.
The pentafluoroethane is characterised by means of 'H- and '*F-NMR spectroscopy and the potassium bis(pentafluoroethyl)phosphinate by means of '°F- and *'P-NMR spectroscopy.
Pentafluoroethane
The 'H- and "°F-NMR spectra are recorded on a Bruker WP 80 SY spec- trometer at a frequency of 80.1 MHz for 'H and 75.4 MHz for °F and a temperature of -70°C. To this end, use is made of an FEP (fluoroethylene polymer) tube inside a thin-walied 5 mm NMR tube with an acetone-Dg film as external lock and TMS or CCIsF, dissolved in the acetone-Ds film, as external reference. "H-NMR spectrum: (acetone-Ds film, reference TMS in the film, 8, ppm) 5.80 tq; nr = 52.3 Hz; *Jur = 2.1 Hz
F-NMR spectrum: (acetone-Ds film, reference CCI5F in the film, 5, ppm) -86.54 s (CFs); -138.55 d (CHF>); 2Jyf = 52.5 Hz
The data obtained correspond to the values disclosed in the literature by
M.D. Bartberger et al. in Tetrahedron, 53, No. 29 (1997), pages 9857-9880
® WO 03/087111 PCT/EP03/02744 ® -15- and N. Ignatiev et al. in Acta Chem. Scand. 53, No. 12 (1999), pages 1110- 1116.
Potassium bis(pentafluoroethyl)phosphinate ((C2Fs),P(O)OK)
The "°F- and *'P-NMR spectra are recorded on a Bruker Avance 300 spec- trometer at a frequency of 282.4 MHz for "°F and 121.5 MHz for >'P. 'F-NMR spectrum: (solvent acetone-Dg, internal reference CCIsF, 8, ppm) -80.38 m (CF3); -125.12 dm (CF); 2Jps = 67.3 Hz *'P-NMR spectrum: (solvent acetone-Dg, reference 85% by weight HsPO4 in DO, 8, ppm) 0.72 quin; 2Jer = 67.2 Hz
Example 2: 5.99 g (142.8 mmol) of lithium hydroxide monohydrate are dissolved in 150 cm’ of water in a flask, and the resultant solution is cooled at a bath temperature of -10°C. 19.30 g (45.3 mmol) of difluorotris(pentafluoroethyl)- phosphorane are subsequently added via a dropping funnel over the course of 15 minutes with stirring. The reaction mixture is subsequently brought to room temperature. The gaseous pentafluoroethane formed by hydrolysis of the difluorotris(pentafluoroethyl)phosphorane is collected in two subsequent traps, each of which is cooled with liquid nitrogen. 4.95 g of pentafluoroethane as a solid are obtained in the cooled traps.
The yield of pentafluoroethane is 91.2%, based on the a pentafluoroethyl group removed from the difluorotris(pentafluoroethyl)phosphorane under these conditions.
® WO 03/087111 PCT/EP03/02744 ® -16 -
The reaction mixture in the flask furthermore contains a solution of lithium bis(pentafluoroethyl)phosphinate ((C.Fs).P(O)OLi) and lithium fluoride. In order to isolate the lithium bis(pentafluoroethyl)phosphinate, firstly the
S excess lithium hydroxide is neutralised using a few drops of an aqueous hydrogen fluoride solution, the precipitate of lithium fluoride is filtered off, and the water is removed under reduced pressure. The resultant white solid of lithium bis(pentafluoroethyl)phosphinate is dried under reduced pressure at 120 Pa and a bath temperature of 100°C for two hours. 13.1 g of lithium bis(pentafluoroethyl)phosphinate containing about 2% by weight of lithium fluoride are obtained, corresponding to a yield of 93.7%, based on the difluorotris(pentafluoroethyl)phosphorane employed.
The pentafluoroethane is characterised by means of 'H- and '*F-NMR spectroscopy and the lithium bis(pentafluoroethyl)phosphinate by means of *F- and >'P-NMR spectroscopy.
The chemical shifts determined for pentafluoroethane correspond to the values indicated in Example 1.
Lithium bis(pentafluoroethyl)phosphinate
The "°F- and *'P-NMR spectra are recorded on a Bruker Avance 300 spec- trometer at a frequency of 282.4 MHz for °F and 121.5 MHz for *'P. '*F-NMR spectrum: (solvent acetone-Ds, internal reference CClsF, 6, ppm) -80.32 m (CFs); -125.08 dm (CF); *Jpr = 72.6 Hz
® WO 03/087111 PCT/EP03/02744 ® 17 - *'P-NMR spectrum: (solvent acetone-De, reference 85% by weight HsPO4 15% by weight D20 in acetone-De, 8, ppm) 0.27 quin; 2p = 72.7 Hz
Example 3: 4.1 g (73.1 mmol) of potassium hydroxide are dissolved in 150 cm?’ of water in a flask, and the resultant solution is cooled at a bath temperature of 0°C. 16.87 g (23.2 mmol) of difluorotris(n-nonafluorobutyl)phosphorane are subsequently added via a dropping funnel over the course of 3 minutes with stirring. The reaction mixture is subsequently brought to room tem- perature, stirred at this temperature for eight hours and subsequently refluxed for a further eight hours. The gaseous 1H-nonafluoro-n-butane formed by hydrolysis of the difluorotris(n-nonafluorobutyl)phosphorane is collected in a subsequent trap cooled with dry ice. 3.63 g of liquid 1H-nonafluoro-n-butane having a boiling point of 14°C are obtained in the cooled trap.
The yield of 1H-n-nonafluorobutane is 71.2%, based on an n-nonafiuoro- butyl group removed from the difluorotris(n-nonafiuorobuty!)phosphorane under these conditions.
The solution remaining in the flask is separated from the viscous residue likewise remaining in the flask and neutralised using hydrochloric acid.
In order to isolate the potassium bis(n-nonafluorobutyl)phosphinate, the water is removed under reduced pressure. The resultant solid residue is dried under reduced pressure at 120 Pa and a bath temperature of 100°C for two hours. The dried residue is subsequently extracted with three por- tions of 50 cm’ of methanol each, the fractions are combined, the is subse- quently distilled off under reduced pressure at 125 Pa, and the solid resi- due is dried. The yield of potassium bis(n-nonafluorobutyl)phosphinate is
® -18- 7.88 g, corresponding to 62.9%, based on the difluorotris(n-nonafluoro- butyl)phosphorane employed.
The 1H-n-nonafluorobutane is characterised by means of 'H- and *F-NMR
S spectroscopy and the potassium bis(n-nonafluorobutyl)phosphinate by means of *F- and *'P-NMR spectroscopy. 1H-Nonafluorobutane
The "H- and "*F-NMR spectra are recorded on a Bruker WP 80 SY spec- trometer at a frequency of 80.1 MHz for 'H and 75.4 MHz for "°F and a temperature of -60°C. To this end, use is made of an FEP (fluoroethylene polymer) tube inside a thin-walled 5 mm NMR tube with an acetone-Dg film as external lock and TMS or CCIsF, dissolved in the acetone-De film, as external reference. "H-NMR spectrum: (acetone-Ds film, reference TMS in the film, §, ppm) 6.14 tt; Zur = 52.0 Hz; 3Jur = 5.0 Hz
F-NMR spectrum: (acetone-Dg film, CCIsF in the film, §, ppm) -81.31 t (CF3); -127.93 m (CF,); -131.06 m (CF); -137.92 dm (CF>);
Jur =52.0 Hz
The data obtained correspond to the values disclosed in the literature pub- lication by T. Hudlicky et al. in J. of Fluorine Chem., 59, No. 1 (1992), pages 9-14.
Claims (20)
1. Process for the preparation of monohydroperfluoroalkanes, bis(per- fluoroalkyl)phosphinates and perfluoroalkylphosphonates, comprising S at least the treatment of at least one perfluoroalkylphosphorane with at least one base and, if desired, an acid in a suitable reaction medium.
2. Process for the preparation of monohydroperfluoroalkanes according to Claim 1, characterised in that at least one perfluoroalkylphosphorane is reacted with at least one base (a) or an organometallic compound in a suitable solvent.
3. Process for the preparation of bis(perfluoroalkyl)phosphinates and per- fluoroalkylphosphonates according to Claim 1, characterised in that at least one perfluoroalkylphosphorane is reacted with at least one inor- ganic base (b) in a suitable solvent, the bis(perfluoroalkyl)phosphinates and perfluoroalkylphosphonates formed in addition to the monohydro- perfluoroalkanes are converted into the corresponding bis(perfluoro- alkyl)phosphinic acids and perfluoroalkylphosphonic acids directly or after isolation by salt interchange or subsequent treatment with an acid, preferably sulfuric acid, and the salts are obtained by subsequent neu- tralisation, preferably using organic bases (c).
4. Process according to Claim 1, characterised in that the perfluoroalkyi- phosphorane employed is a compound of the general formula (CaF 2n+1)mPFsm I
C -39- in which 1 <n < 8, preferably 1 <n <4, and m in each case denotes 1, 2o0r3.
5. Process according to Claim 1, characterised in that the perfluoroalkyl- S phosphorane is selected from the group consisting of difluorotris(penta- fluoroethyl)phosphorane, difluorotris(n-nonafluorobutyl)phosphorane, difluorotris(n-heptafluoropropyl)phosphorane and trifiuorobis(n-nona- fluorobutyi)phosphorane.
6. Process according to Claim 2 or 3, characterised in that the base (a) or (c) employed is at least one organic base.
7. Process according to Ciaim 6, characterised in that the organic base(s) is (are) selected from the group consisting of alkylammonium hydrox- ides, arylammonium hydroxides, alkylarylammonium hydroxides, alkyl- phosphonium hydroxides, arylphosphonium hydroxides, alkylarylphos- phonium hydroxides alkylamines, arylamines, alkylarylamines, alkyl- phosphines, arylphosphines and alkylarylphosphines.
8. Process according to Claim 2 or 3, characterised in that at least one inorganic base (a) or (b) is employed.
9. Process according to Claim 8, characterised in that the inorganic base(s) is (are) selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
10. Process according to Claim 9, characterised in that the alkali metal hydroxide is selected from the group consisting of lithium hydroxide, lithium hydroxide monohydrate, sodium hydroxide and potassium hydroxide.
® WO 03/087111 PCT/EP03/02744 @® - 40 -
11. Process according to Claim 9, characterised in that the alkaline earth metal hydroxide is selected from the group consisting of barium hydroxide, barium hydroxide octahydrate and calcium hydroxide.
12. Process according to Claim 2, characterised in that the organometallic compounds are selected from the group consisting of metal alkoxides, preferably alkali metal alkoxides, metal aryloxides, metal alkylthio- oxides, metal arylthiooxides, alkylmetal compounds, arylmetal com- pounds and Grignard reagents.
13. Process according to Claim 1, characterised in that the reaction medium is water, if desired mixed with one or more organic solvents.
14. Process according to Claim 1, characterised in that the reaction medium employed is one or more organic solvents.
15. Process according to Claim 13 or 14, characterised in that the organic solvent is selected from the group consisting of alcohols, ethers, acyl- amides, sulfoxides, sulfones, nitriles and hydrocarbons.
16. Process according to Claim 15, characterised in that the alcohol has from one to four carbon atoms in the alkyl moiety and is preferably selected from the group consisting of methanol, ethanol, isopropanol and mixtures of at least two of these alcohols.
17. Perfluoroalkylphosphonates and bis(perfluoroal)kylphosphinates selected from the group consisting of partially alkylated and peralkyi- ated ammonium, phosphonium, sulfonium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxa- zolium and triazolium salts salts.
Co WO 03/087111 PCT/EP03/02744 @® -41 -
18. Perfluoroalkylphosphonates and bis(perfluoroalkyl)phosphinates according to Claim 16, having a cation selected from the group con- sisting of 5) R1 RA R6 RZ RG (UR? , | t | + N RS” "NT “Rs RS N? R4 ha R1 Bo R6 Na R2 § TX R5 Peo R5 N R3 R4 R4 RS R1 RS _R1 TA NS NS ’ R4 R2 R4™ Sg” TR2 pe RS R1 JR1 I} 3 R4 SN. re R3 where R' to R® are identical or different, are optionally bonded directly to one another via a single or double bond and are each, individually or together, defined as follows: -H, - halogen, where the halogens are not bonded directly to N, - an alkyl radical (C, to Cg), which may be partially or completely substi- tuted by further groups, preferably F, Cl, N(CoF 2ne1-9Hx)2, O(CrF ans 19H), SO2(CoF 2ns1-9Hx), CF 2n+19Hx, where1<n<6and0<x<2n+1.
19. Use of the perfluoroalkylphosphonates and bis(perfluoroalky!)phosphi- nates according to Claim 17 or 18 as ionic liquids.
Co WO 03/087111 PCT/EP03/02744 ® az
20. Use of the perfluoroalkylphosphonates and bis(perfiuoroalkyl)phosphi- nates according to Claim 17 or 18 as phase-transfer catalyst or surfac- tants.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10216995 | 2002-04-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
ZA200409161B true ZA200409161B (en) | 2005-05-31 |
Family
ID=28798484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200409161A ZA200409161B (en) | 2002-04-16 | 2004-11-11 | Method for the production of monohydro-perflouroalkanes, bis(perflouroalkyl)phosphinates, and perfluoroalkylphosphonates. |
Country Status (7)
Country | Link |
---|---|
JP (1) | JP4739678B2 (en) |
KR (1) | KR100937128B1 (en) |
AT (1) | ATE440102T1 (en) |
DE (2) | DE10220547A1 (en) |
ES (1) | ES2330427T3 (en) |
TW (1) | TWI328010B (en) |
ZA (1) | ZA200409161B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10216997A1 (en) * | 2002-04-16 | 2003-10-30 | Merck Patent Gmbh | Process for the preparation of bis (perfluoroalkyl) phosphinic acids and their salts |
DE10353759A1 (en) * | 2003-11-17 | 2005-06-16 | Merck Patent Gmbh | Process for the preparation of mono- and bis / perfluoroalkyl) phosphoranes and corresponding phosphates |
DE102006005579A1 (en) * | 2006-02-06 | 2007-08-09 | Cognis Ip Management Gmbh | Process for the preparation of organic substances |
FR2912748B1 (en) * | 2007-02-16 | 2009-11-13 | Centre Nat Rech Scient | ALKYL H-PHOSPHONATES OF N, N'-DIALKYLIMIDAZOULIUMS, QUATERNARY AMMONIUMS AND USES THEREOF |
DE102008035174A1 (en) * | 2008-07-28 | 2010-02-11 | Merck Patent Gmbh | Process for the preparation of bis (fluoroalkyl) phosphinic acid or fluoroalkylphosphonic acid |
DE102009058969A1 (en) * | 2009-12-18 | 2011-06-22 | Merck Patent GmbH, 64293 | Compound with (perfluoroalkyl) fluorohydrogenphosphate anions |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2233941C3 (en) * | 1972-07-11 | 1978-03-02 | Cassella Farbwerke Mainkur Ag, 6000 Frankfurt | Use of perfluoroalkylphosphorus compounds as foam suppressants |
-
2002
- 2002-05-08 DE DE10220547A patent/DE10220547A1/en not_active Withdrawn
-
2003
- 2003-03-17 ES ES03718689T patent/ES2330427T3/en not_active Expired - Lifetime
- 2003-03-17 JP JP2003584067A patent/JP4739678B2/en not_active Expired - Fee Related
- 2003-03-17 DE DE50311833T patent/DE50311833D1/en not_active Expired - Lifetime
- 2003-03-17 AT AT03718689T patent/ATE440102T1/en not_active IP Right Cessation
- 2003-03-17 KR KR1020047016667A patent/KR100937128B1/en not_active IP Right Cessation
- 2003-04-14 TW TW092108540A patent/TWI328010B/en not_active IP Right Cessation
-
2004
- 2004-11-11 ZA ZA200409161A patent/ZA200409161B/en unknown
Also Published As
Publication number | Publication date |
---|---|
TW200306980A (en) | 2003-12-01 |
JP4739678B2 (en) | 2011-08-03 |
ATE440102T1 (en) | 2009-09-15 |
DE50311833D1 (en) | 2009-10-01 |
KR100937128B1 (en) | 2010-01-18 |
DE10220547A1 (en) | 2003-11-06 |
KR20040103965A (en) | 2004-12-09 |
ES2330427T3 (en) | 2009-12-10 |
TWI328010B (en) | 2010-08-01 |
JP2005522511A (en) | 2005-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5307747B2 (en) | Bis (perfluoroalkyl) phosphinic acid and process for producing the salt | |
US6774240B2 (en) | Process for preparing ambient temperature ionic liquids | |
US7247733B2 (en) | Process for preparing nuclear-fluorinated aromatics | |
JP4946864B2 (en) | Method for producing disulfonyl fluoride compound | |
ZA200409161B (en) | Method for the production of monohydro-perflouroalkanes, bis(perflouroalkyl)phosphinates, and perfluoroalkylphosphonates. | |
CA2482657C (en) | Process for the preparation of monohydroperfluoroalkanes, bis(perfluoroalkyl)phosphinates and perfluoroalkylphosphonates | |
US7692048B2 (en) | Method for producing fluorine-containing halide | |
KR20120046783A (en) | Method for producing perfluorosulfonic acid having ether structure and derivative thereof, and surfactant containing fluorine-containing ether sulfonic acid compound and derivative thereof | |
US6645904B2 (en) | Aminophosphonium compounds | |
US20140339096A1 (en) | Method for producing perfluorosulfonic acid having ether structure and derivative thereof, and surfactant containing fluorine-containing ether sulfonic acid compound and derivative thereof | |
US20060167235A1 (en) | Process for the preparation of ayl diazonium salts and reaction with nucleophiles | |
JP4531561B2 (en) | Method for synthesizing derivatives containing hydrofluoromethylenesulfonyl group | |
IE904242A1 (en) | Process for the preparation of a perfluoroalkylbromide | |
JP3443644B2 (en) | Method for producing esters and amides | |
JP2012214401A (en) | Method for manufacturing alkanoyl diaryl sulfide | |
JP3799580B2 (en) | Process for producing N-substituted-N-sulfonylamides | |
JP3625028B2 (en) | Method for producing fluoroacetone | |
GB2033362A (en) | Inert organic solvent dispersion of alkaline hydroxide andreaction using the same | |
JP2000053650A (en) | Production of fluorinating agent |