CN1646546A - 二(全氟烷基)次膦酸及其盐的制备方法 - Google Patents
二(全氟烷基)次膦酸及其盐的制备方法 Download PDFInfo
- Publication number
- CN1646546A CN1646546A CNA038084910A CN03808491A CN1646546A CN 1646546 A CN1646546 A CN 1646546A CN A038084910 A CNA038084910 A CN A038084910A CN 03808491 A CN03808491 A CN 03808491A CN 1646546 A CN1646546 A CN 1646546A
- Authority
- CN
- China
- Prior art keywords
- perfluoroalkyl
- salt
- phosphorane
- phospho acid
- difluoro
- 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.)
- Pending
Links
- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims abstract description 57
- 150000003839 salts Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 50
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 19
- 239000011541 reaction mixture Substances 0.000 claims abstract description 19
- 239000012429 reaction media Substances 0.000 claims abstract description 6
- -1 phospho Chemical class 0.000 claims description 81
- 239000002253 acid Substances 0.000 claims description 73
- 229910052731 fluorine Inorganic materials 0.000 claims description 62
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 37
- 239000011737 fluorine Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000002916 oxazoles Chemical class 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 150000003216 pyrazines Chemical class 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 150000004892 pyridazines Chemical class 0.000 claims description 2
- 150000003230 pyrimidines Chemical class 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 29
- 238000005481 NMR spectroscopy Methods 0.000 description 26
- 238000001228 spectrum Methods 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical class [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010025 steaming Methods 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
- B01J31/0231—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
- B01J31/0277—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
-
- 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
-
- 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
- C07F9/54—Quaternary phosphonium compounds
-
- 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
- C07F9/5456—Arylalkanephosphonium 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fireproofing Substances (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Saccharide Compounds (AREA)
Abstract
本发明涉及一种制备二(全氟烷基)次膦酸的方法,该方法至少包括在合适的反应介质中将至少一种二氟三(全氟烷基)正膦或至少一种三氟二(全氟烷基)正膦与氟化氢反应,和加热所得的反应混合物。本发明还涉及二(全氟烷基)次膦酸盐及其用途。
Description
本发明涉及一种制备二(全氟烷基)次膦酸的方法,其至少包括在合适的反应介质中将至少一种二氟三(全氟烷基)正膦或至少一种三氟二(全氟烷基)正膦与氟化氢反应和加热所得的反应混合物。本发明还涉及二(全氟烷基)次膦酸盐及其用途。
二(全氟烷基)次膦酸已经为人所知一段时间了,并适于制备多种化学品例如相应的甲酯,这类甲酯是强甲基化试剂(N.V.Pavlenko等,Zh.Obshch.Khim.,59,No.3(1989),第534-537页)。此外,二(全氟烷基)次膦酸及其相应盐的使用可基于其表面活性作用(DE-A 22 33 941;N.N.Kalibabchuk等,Teor.Eksp.Khim.,11,No.6(1975),第838-841页;N.N.Kalibabchuk等,Ukr.Khim.Zh.,44,No.1(1978),第67-70页)并可用于燃料电池中(T.Mahmood,Inorganic Chemistry,25(1986),第3128-3131页)。
二(五氟乙基)次膦酸的锂盐在锂电池中用作导电盐具有很好的前景(F.Kita等,Proc.Electrochem.Soc.,99-25,(2000),第480-484页;F.Kita等,J.Power Sources,90,No.1(2000),第27-32页)。
二(三氟甲基)次膦酸是通过使二(三氟甲基)三氯化磷水解而制备的,但是二(三氟甲基)三氯化磷的获得存在困难(H.J.Emeleus等,J.Chem.Soc.(1955),第563-574页)。已经由相应的二氟三(全氟烷基)正膦得到了二(全氟甲基)次膦酸的高级同系物(V.Ya.Semenii等,苏联专利U.S.S.R498,311)。
这些文献实质上公开了两种不同的制备二(全氟烷基)次膦酸的方法。
在第一种方法中,第一步是将二氟三(全氟烷基)正膦与六甲基二硅氧烷反应得到相应的氧化膦。然后在第二步中将其水解成为相应的二(全氟烷基)次膦酸。该方法的缺点在于必须非常精确地控制和调节水解期间的温度,并且通常仅获得极少量的所需的二(全氟烷基)次膦酸(T.Mahmood,Inorganic Chemistry,25(1986),第3128-3131页;苏联专利U.S.S.R.498,311,第57-61页;T.Mahmood等,Inorganic Chemistry,27(1988),第2913-2916页)。
另一已知的方法是将二氟三(全氟烷基)正膦直接水解成二(全氟烷基)次膦酸(T.Mahmood等,Inorganic Chemistry,27(1988),第2913-2916页)。该方法的缺点在于由于正膦特别是具有长链烷基的正膦与水的混溶性很差,因而水解只能非常缓慢地进行并且通常得到非常复杂的产物混合物。
因此,本发明的目的在于提供一种能够简单而经济地以优良的产率制备二(全氟烷基)次膦酸的方法。应当优选获得高纯度的二(全氟烷基)次膦酸。本发明的另一目的是提供二(全氟烷基)次膦酸盐。
可以通过本发明的制备二(全氟烷基)次膦酸的方法实现该目的,该方法包括至少如下工艺步骤:
a)在合适的反应介质中将至少一种二氟三(全氟烷基)正膦或至少一种三氟二(全氟烷基)正膦与氟化氢反应,和
b)加热步骤a)中所得的反应混合物。
可以通过本领域技术人员已知的常规方法制备二氟三(全氟烷基)正膦和三氟二(全氟烷基)正膦。
优选通过对适当的起始化合物进行电化学氟化而制备这些化合物,如V.Ya.Semenii等,Zh.Obshch.Khim.,55,No.12(1985),第2716-2720页;N.Ignatiev,J.of Fluorine Chem.,103(2000),第57-61页和WO 00/21969中所述。将这些相应的说明通过引用并入本文,并视为本公开的一部分。
还可以在本发明的方法中使用两种或多种二氟三(全氟烷基)正膦和/或两种或多种三氟二(全氟烷基)正膦的混合物。优选在本发明方法的各种情况中仅使用一种二氟三(全氟烷基)正膦或三氟二(全氟烷基)正膦。
在本发明方法的优选实施方案中,使用的是至少一种具有通式I的二氟三(全氟烷基)正膦或至少一种三氟二(全氟烷基)正膦
(CnF2n+1)mPF5-m
I
其中1≤n≤8,优选1≤n≤4,和在各种情况中m=2或3。
特别优选的二氟三(全氟烷基)正膦化合物可选自二氟三(五氟乙基)正膦、二氟三(正九氟丁基)正膦和二氟三(正七氟丙基)正膦。
可用于本发明方法的特别优选的三氟二(全氟烷基)正膦化合物是三氟二(正九氟丁基)正膦。
在合适的反应介质中至少一种二氟三(全氟烷基)正膦或至少一种三氟二(全氟烷基)正膦与氟化氢的反应优选按照DE 101 30 940.6所述的方法进行。将相应的说明通过引用并入本文,并视为本公开的一部分。
在工艺步骤b)中加热工艺步骤a)中所得的反应混合物的温度优选为室温至150℃,特别优选100~145℃,非常特别优选135~140℃。
在工艺步骤b)中优选加热工艺步骤a)中所得的反应混合物1~150小时,特别优选10~25小时,非常特别优选18~22小时。
如果需要,可以有利地在工艺步骤b)中的加热期间向所述反应混合物再次添加一些相同的或不同的反应介质。
为了加速水解,还可以优选在封闭的受压不漏气的设备(如高压釜)中于升高的温度(优选140~200℃)下加热工艺步骤a)中所得的反应混合物。
除了所需的二(全氟烷基)次膦酸,根据本发明方法的反应还得到氟化氢和分别作为另外反应产物的相应一氢全氟烷烃。
可以通过本领域技术人员熟悉的常规方法(例如通过在合适的冷阱中通过冷凝)根据需要分离这些反应产物、根据需要收集这些反应产物和根据需要析出这些反应产物。
氟化氢和一氢全氟烷烃本身是重要而有用的化学原料。因此,还可以收集和循环氟化氢以用于工艺步骤a)的反应中。
如有必要,可以在通过本发明的方法制备二(全氟烷基)次膦酸后进行纯化,和如果需要的话使用本领域技术人员熟悉的常规方法分离这些化合物。
优选通过蒸馏进行纯化,优选在降低的压力下于升高的温度进行纯化。
可优选通过中和二(全氟烷基)次膦酸的方式分离二(全氟烷基)次膦酸各自的盐。
所述的盐可由各二(全氟烷基)次膦酸通过与至少一种本领域的技术人员公知的常规碱反应而制备,优选在溶液中实现这种制备方式。
为了制备所述的盐,使用碱中和二(全氟烷基)次膦酸,该碱优选选自氢氧化物、氧化物、氢化物、酰胺类、碳酸盐、膦类和胺类。
中和后,用本领域技术人员公知的方法处理所得的盐。可以洗涤和随后干燥该盐。
本申请还涉及二(全氟烷基)次膦酸盐,其选自部分烷基化和全部烷基化的铵盐、鏻盐、锍盐、吡啶盐、哒嗪盐、嘧啶盐、吡嗪盐、咪唑盐、吡唑盐、噻唑盐、噁唑盐和三唑盐。优选制备具有选自如下阳离子的二(全氟烷基)次膦酸盐:
其中R1至R5相同或不同,可选择地彼此通过单键或双键直接结合,各自独立地或者一起定义如下:
-H,
-卤素,其中卤素不直接连接到N上,
-烷基(C1-C8),其可被其它基团部分或完全取代,优选被以下基团取代:F、Cl、N(CnF(2n+1-x)Hx)2、O(CnF(2n+1-x)Hx)、SO2(CnF(2n+1-x)Hx)、CnF(2n+1-x)Hx,其中1<n<6和0<x≤2n+1。
令人惊讶的是已经发现这些盐可用作离子液体、相转移催化剂或表面活性剂。
本发明的制备二(全氟烷基)次膦酸的方法使得能够简单、经济而可靠地以很高的产率制备这些化合物。所得的二(全氟烷基)次膦酸通常具有高纯度而不必进一步进行复杂的纯化步骤。通过与碱反应可以得到迄今为止未曾获得的盐。
此外有利的是本发明方法所得的副产物即氟化氢和一氢全氟烷烃本身就是重要的有用原料。这使得根据本发明方法的反应对环境的影响低并使得本发明方法的成本降低。
下面参照实施例说明本发明。这些实施例仅用于说明本发明而不是对总的发明思想的限制。
实施例
使用Bruker Avance 300 NMR波谱仪在以下频率下记录NMR谱图:
对于1H 300.1MHz
对于19F 282.4MHz和
对于31P 121.5MHz
实施例1:
二(五氟乙基)次膦酸(C2F5)2P(O)OH的合成
a)
在FEP(氟乙烯聚合物)烧瓶中将3.53g水(相当于混合物中总水量为294mmol)加入2.93g 40重量%氢氟酸(相当于58.6mmol HF)中。然后用冰浴冷却所得的混合物。随后在使用磁力搅拌器进行搅拌的情况下于3分钟内添加25.03g(58.7mmol)二氟三(五氟乙基)正膦(C2F5)3PF2。二氟三(五氟乙基)正膦在另外3分钟内完全溶解,得到无色澄清的H+[(C2F5)3PF3]-水溶液。
在室温下再搅拌所得的溶液15分钟,随后在油浴温度135~140℃下回流14小时。随后向该溶液再加入4.83g水,和在相同温度下再回流该混合物6小时。冷却至室温后,得到24.81g澄清溶液。
在用干冰冷却的中间阱中收集得到3.95g两相液体。该液体包含2.11gC2F5H、1.5g HF和0.34g起始化合物二氟三(五氟乙基)正膦。
为了分离二(五氟乙基)次膦酸,将氟化氢水溶液从反应混合物中馏出,得到15.13g实际上纯净的二(五氟乙基)次膦酸。以所用的二氟三(五氟乙基)正膦计,产率为86.5%。
为了进一步纯化,在降低的压力125Pa下蒸馏所述二(五氟乙基)次膦酸。沸点为63-64℃。
通过19F-、31P-和1H-NMR波谱仪及元素分析表征所得的二(五氟乙基)次膦酸:
19F-NMR谱图;δ,ppm:
(溶剂:丙酮-D6,参比:CCl3F)
-80.55s(CF3);-125.37d(CF2);J2 P,F=78.2Hz
1H-NMR谱图;δ,ppm:
(溶剂:丙酮-D6,参比:TMS)
12.71br.s(OH)
31P-NMR谱图;δ,ppm:
(溶剂:丙酮-D6,参比:85重量%的H3PO4)
-0.03quin;J2 P,F=78.3Hz
所得的化学位移值与出版物T.Mahmood的Inorganic Chemistry,25(1986),第3128-3131页所公开的值一致。
元素分析:
实验值:C 15.76%;H 0.40%
((C2F5)2P(O)OH)的计算值:C 15.91%;H 0.33%
b)
在FEP烧瓶中将2.50g水(相当于混合物中总水量为166.5mmol)加入0.834g 40重量%含水氢氟酸(相当于16.7mmol的HF)中。然后用冰浴冷却所得的混合物。最后在使用磁力搅拌器进行搅拌的情况下于3分钟内添加7.11g(16.7mmol)的二氟三(五氟乙基)正膦(C2F5)3PF2。二氟三(五氟乙基)正膦在另外3分钟内完全溶解,得到无色澄清的H+[(C2F5)3PF3]-水溶液。在油浴温度115~120℃下回流该反应混合物108小时。为了分离二(五氟乙基)次膦酸,将水/HF溶液从该反应混合物中馏出,得到3.97g实际上纯净的二(五氟乙基)次膦酸(C2F5)2P(O)OH。以所用的二氟三(五氟乙基)正膦计,产率为78.8%。通过19F-NMR波谱仪表征所得产物。相应的标记与实施例1a中所述的标记一致。
c)
在FEP容器中用冰浴冷却2.59g(56.2mmol)乙醇。首先在用磁力搅拌器进行搅拌的情况下向该乙醇中缓慢添加0.49g(24.5mmol)的氟化氢(HF),和在另外3分钟内向该反应混合物中加入9.59g(22.5mmol)二氟三(五氟乙基)正膦(C2F5)3PF2。当所述正膦溶解后,向该溶液中添加2.21g(122.6mmol)水,在油浴温度120℃下回流该反应混合物144小时(在44小时后向该反应混合物中加入2.1g水和在94小时后另外加入2.0g水)。
为了分离二(五氟乙基)次膦酸,将乙醇/水/HF溶液从所述反应混合物中馏出,得到5.21g实际上纯净的二(五氟乙基)次膦酸(C2F5)2P(O)OH。以所用的二氟三(五氟乙基)正膦计,产率为76.6%。通过19F-NMR波谱仪表征所得产物。相应的标记与实施例1a中所述的标记一致。
实施例2
二(正九氟丁基)次膦酸(n-C4F9)2P(O)OH的合成
a)
在FEP(氟乙烯聚合物)烧瓶中将4.25g水(相当于混合物中总水量为371mmol)加入4.07g 40重量%的氢氟酸(相当于81.4mmol的HF)中。然后用冰浴冷却所得的混合物。随后在用磁力搅拌器进行搅拌的情况下于10分钟内加入51.42g(70.8mmol)的二氟三(正九氟丁基)正膦n-(C4F9)3PF2。
在室温下再搅拌所得的溶液20分钟,随后将其在油浴温度135~140℃下回流11.5小时。随后向该溶液中再加入5.00g水,于相同温度下再回流该混合物8.5小时。冷却至室温后,得到46.47g澄清溶液。
在用干冰冷却的中间阱中收集得到15.03g两相液体。该液体包含13.06g n-C4F9H和1.97g HF(上层相)。
为了分离二(正九氟丁基)次膦酸,在油浴温度145℃下将氟化氢水溶液从所述反应混合物中馏出,得到34.62g实际上纯净的固体形式的二(正九氟丁基)次膦酸。以所用的二氟三(正九氟丁基)正膦计,产率为97.4%。
为了进行进一步纯化,在降低的压力下于125Pa蒸馏该二(正九氟丁基)次膦酸。沸点为124℃。冷却期间,所得的二(正九氟丁基)次膦酸凝固得到熔点为103-104℃的固体。
在文献出版物T.Mahmood的Inorganic Chemistry,25(1986),第3128-3131页中,二(正九氟丁基)次膦酸被描述为非挥发性液体,其可能是该化合物的水合物形式。
通过19F-、31P-和1H-NMR波谱仪及元素分析表征所得的二(正九氟丁基)次膦酸:
19F-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:CCl3F)
-80.90t(CF3);-120.50br.s(CF2);-121.38d(CF2);-125.58m(CF2);
J2 P,F=79.5Hz;J4 F,F=9.9Hz
1H-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:TMS)
9.25br.s(OH)
31P-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:85重量%H3PO4)
1.74quin;J2 P,F=79.0Hz
所得的化学位移值与出版物T.Mahmood的Inorganic Chemistry,25(1986),第3128-3131页公开的值一致。
元素分析:
实验值:C 19.05%;H 0.20%
((n-C4F9)2P(O)OH)的计算值:C 19.14%;H 0.20%
b)
在FEP烧瓶中将1.45g水(相当于混合物中总水量为116.1mmol)加入1.08g 40重量%含水氢氟酸(相当于21.6mmol的HF)中。然后用冰浴冷却所得的混合物。最后在用磁力搅拌器进行搅拌的情况下于10分钟内加入7.98g(15.2mmol)的三氟二(正九氟丁基)正膦(C4F9)2PF3。在室温下搅拌该反应混合物15小时,随后在油浴温度110℃下回流该混合物35小时(在17小时后向该反应混合物中加入0.6g水和在25小时后再加入1.2g水)。为了分离二(正九氟丁基)次膦酸,将水/HF溶液从该反应混合物中馏出,得到6.34g实际上纯净的二(正九氟丁基)次膦酸。以所用的三氟二(正九氟丁基)正膦计,产率为83.2%。通过19F-NMR波谱仪表征所得产物。相应的标记与实施例2a中所述的标记一致。
实施例3
在50cm3水中用7.48g 20重量%的四乙基氢氧化铵水溶液中和按照实施例1制备的3.07g二(五氟乙基)次膦酸。随后蒸除水,在降低的压力120Pa和温度70℃(浴温)下干燥所得的残留物。
得到4.38g熔点为100~102℃的二(五氟乙基)次膦酸四乙基铵的白色固体。以所用的二(五氟乙基)次膦酸计,其产率实际上是定量的。
通过19F-、31P-和1H-NMR波谱仪及元素分析表征二(五氟乙基)次膦酸四乙基铵:
19F-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:CCl3F)
-80.23s(CF3);-124.90d(CF2);J2 P,F=64.8Hz;
1H-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:TMS)
1.36tm(CH3);3.48q(CH2);J3 H,H=7.3Hz;
31P-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:85重量%的H3PO4)
0.28quin;J2 P,F=64.5Hz
元素分析:
实验值:C 33.36%;H 4.60%;N 3.22%
(C2F5)2P(O)ON(C2H5)4的计算值:C 33.42%;H 4.67%;N 3.25%
实施例4
在20cm3水中用0.577g碳酸钾中和按照实施例1制备的2.52g二(五氟乙基)次膦酸。随后蒸除水,在降低的压力120Pa和浴温100℃下干燥所得的残留物。得到2.83g二(五氟乙基)次膦酸钾的白色固体。以所用的二(五氟乙基)次膦酸计,其产率实际上是定量的。该盐在203~205℃下分解。
通过19F-和31P-NMR波谱仪和元素分析表征所得的二(五氟乙基)次膦酸钾:
19F-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:CCl3F)
-80.40m(CF3);-125.11d(CF2);J2 P,F=67.4Hz;
31P-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:85重量%的H3PO4)
0.73quin;J2 P,F=67.2Hz
元素分析:
实验值:C 14.6%;
(C2F5)2P(O)OK的计算值:C 14.13%;
实施例5
在50cm3水中用5.86g 20重量%的四乙基氢氧化铵水溶液中和按照实施例2制备的4.00g二(正九氟丁基)次膦酸。在该过程中,形成白色沉淀物,将其过滤出来并在降低的压力120Pa和浴温70℃下干燥。得到4.93g熔点为99-100℃的二(正九氟丁基)次膦酸四乙基铵的白色固体。以所用的二(正九氟丁基)次膦酸计,其产率为98%。
通过19F-、31P-和1H-NMR波谱仪及元素分析表征所得的二(正九氟丁基)次膦酸四乙基铵。
19F-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:CCl3F)
-80.75tt(CF3);-120.35m(CF2);-121.17dm(CF2);-125.30m(CF2);J2 P,F=65.0Hz;J4 F,F=9.9Hz;JF,F=3.1Hz;
1H-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:TMS)
1.37tm(CH3);3.48q(CH2);J3 H,H=7.3Hz;
31P-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:85重量%的H3PO4)
1.70quin;J2 P,F=64.9Hz
元素分析:
实验值:C 30.32%;H 3.05%;N 2.10%
(n-C4F9)2P(O)ON(C2H5)4的计算值:C 30.44%;H 3.19%;N 2.22%
实施例6
在50cm3水中用0.371g(3.19mmol)1,6-二氨基己烷在15cm3水中的溶液中和按照实施例1制备的1.93g(6.39mmol)二(五氟乙基)次膦酸。将水蒸除,在降低的压力120Pa和浴温100℃下干燥所得残留物。得到2.21g熔点为208~210℃的二(五氟乙基)次膦酸亚己基-1,6-二铵盐的白色固体。以所用的二(五氟乙基)次膦酸计,其产率为96.1%。
通过19F-、31P-和1H-NMR波谱仪及元素分析表征所得的二(五氟乙基)膦酸亚己基-1,6-二铵盐:
19F-NMR波谱;δ,ppm
(溶剂:DMSO-D6,参比:CCl3F)
-79.59m(CF3);-124.66ppm d(CF2);J2 P,F=65.6Hz
1H-NMR波谱;δ,ppm
(溶剂:DMSO-D6,参比:TMS)
1.30m(2CH2);1.51m(2CH2);2.76m(2CH2);7.53br.s(2NH3 +)
31P-NMR波谱;δ,ppm
(溶剂:DMSO-D6,参比物质:85重量%的H3PO4)
-2.15quin;J2 P,F=65.5Hz
元素分析:
实验值:C 23.61%;H 2.49%;N 4.07%
[(n-C2F5)2P(O)]2 2-[H3N(CH2)6NH3]2+的计算值:C 23.35%;H 2.52%;N3.89%
实施例7
在50cm3水中用0.324g(2.79mmol)1,6-二氨基己烷在15cm3水中的溶液中和按照实施例2制备的2.80g(5.58mmol)二(正九氟丁基)次膦酸。在该过程中,形成白色沉淀物,将其过滤出来,在降低的压力120Pa和浴温100℃下干燥。得到2.87g熔点>250℃的二(正九氟丁基)次膦酸亚己基-1,6-二铵盐的白色固体。以所用的二(正九氟丁基)次膦酸计,其产率为92%。
通过19F-、31P-和1H-NMR波谱仪及元素分析表征所述的二(正九氟丁基)次膦酸亚己基-1,6-二铵盐:
19F-NMR波谱;δ,ppm
(溶剂:DMSO-D6,参比:CCl3F)
-80.03t(CF3);-120.46m(CF2);-121.28dm(CF2);-125.11m(CF2);J2 P,F=65.6Hz;J4 F,F=9.5Hz;
1H-NMR波谱;δ,ppm
(溶剂:DMSO-D6,参比:TMS)
1.29m(2CH2);1.51m(2CH2);2.76m(2CH2);7.61br.s(2NH3 +)
31P-NMR波谱;δ,ppm
(溶剂:DMSO-D6,参比:85重量%的H3PO4)
-0.76quin;J2 P,F=65.5Hz
元素分析:
实验值:C 23.76%;H 1.58%;N 2.48%
[(C4F9)2P(O)O]2 2-[H3N(CH2)6NH3]2+的计算值:C 25.59%;H 1.62%;N2.50%
实施例8
在50cm3水中用1.20g(4.45mmol)三正己基胺在20cm3 1∶1(体积/体积)的水/乙醇混合物中的溶液中和按照实施例2制备的2.23g(4.44mmol)二(正九氟丁基)次膦酸。随后加入15cm3乙醇,回流该混合物5分钟。
冷却至室温后,形成白色沉淀物,将其过滤出来,在降低的压力120Pa和浴温60℃下干燥。得到3.22g熔点为74~75℃的二(正九氟丁基)次膦酸三正己基铵盐的白色固体。以所用的二(正九氟丁基)次膦酸计,其产率为93.9%。
通过19F-、31P-和1H-NMR波谱仪及元素分析表征所述的二(正九氟丁基)次膦酸三正己基铵盐:
19F-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:CCl3F)
-80.82tt(CF3);-120.36m(CF2);-121.32dm(CF2);-125.53m(CF2);J2 P,F=70.1Hz;J4 F,F=9.9Hz;JF,F=3.0Hz;
1H-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:TMS)
0.89m(3CH2);1.35m(9CH2);1.82m(3CH2);3.21m(2CH2);9.62br.s(NH+)
31P-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:85重量%的H3PO4)
1.76quin;J2 P,F=70.1Hz
元素分析:
实验值:C 40.51%;H 5.20%;N 1.80%
(C4F9)2P(O)O-+HN(C6H13)3的计算值:C 40.45%;H 5.22%;N 1.82%
实施例9
将按照实施例2制备的1.55g(3.09mmol)二(正九氟丁基)次膦酸的15cm3水溶液与1.20g(3.09mmol)三苯基苄基氯化鏻的30cm3水溶液混合,在室温下搅拌该混合物5分钟。在该过程中,形成白色沉淀物,将其过滤出来,在降低的压力120Pa和浴温60℃下干燥。得到2.50g熔点为138-139℃的二(正九氟丁基)次膦酸三苯基苄基鏻的白色固体。以所用的二(正九氟丁基)次膦酸计,其产率为95.1%。
通过19F-、31P-和1H-NMR波谱仪及元素分析表征二(正九氟丁基)次膦酸三苯基苄基鏻:
19F-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比CCl3F)
-80.76t(CF3);-120.36m(CF2);-121.21dm(CF2);-125.38m(CF2);J2 P.F=65.9Hz;J4 F,F=9.9Hz;
1H-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:TMS)
5.22d(CH2,PhCH2);7.11-7.17m(2H,PhCH2);7.19-7.27m(2H,PhCH2);
7.30-7.37m(iH,PhCH2);7.72-7.87m(12H,3Ph);7.91-7.99(3H,3Ph);J2 P,H=15.1Hz
31P-NMR波谱;δ,ppm
(溶剂:丙酮-D6,参比:85重量%的H3PO4)
1.78quin;25.68br.s;J2 P,F=65.8Hz
元素分析:
实验值:C 46.10%;H 2.48%
[(C4F9)2P(O)O]-[(C6H5)3C6H5CH2P]+的计算值:C 46.39%;H 2.60%
实施例10
在持续搅拌的条件下于室温将2.08g(11.9mmol)的1-丁基-3-甲基氯化咪唑鎓的3cm3水溶液加入按照实施例4制备的4.05g(11.9mmol)二(五氟乙基)次膦酸钾的15cm3水溶液中。在该过程中,形成油状沉淀物。在降低的压力下蒸除水分,在降低的压力120Pa和浴温60℃下干燥所得残留物1小时。随后向残留物中加入10cm3异丙醇,过滤出白色沉淀物并用5cm3异丙醇冲洗两次。在降低的压力下将异丙醇蒸出,在降低的压力120Pa和浴温80℃下干燥所得残留物2小时。
得到4.99g二(五氟乙基)次膦酸1-丁基-3-甲基氯化咪唑鎓的油状液体。以所用的二(五氟乙基)次膦酸钾计,其产率为95.4%。
通过19F-、31P-和1H-NMR波谱仪表征二(五氟乙基)次膦酸1-丁基-3-甲基咪唑鎓:
19F-NMR波谱,ppm
(溶剂:乙腈-D3;参比:CCl3F)
-80.19m(CF3);-124.93d(CF2);J2 P,F=66.9Hz
1H-NMR波谱,ppm
(溶剂:乙腈-D3;参比:TMS)
0.93t(3H,CH3);1.33tq(2H,CH2);1.83tt(2H,CH2);3.87s(3H,CH3);4.17t(2H,CH2);7.48dd(1H);7.54dd(1H);8.99s(1H);J3 H,H=1.6Hz;J3 H, H=7.3Hz;J3 H,H=7.6Hz
31P-NMR波谱,ppm
(溶剂:乙腈-D3;参比:85重量%的H3PO4)
-1.86quin;J2 P,F=66.8Hz
Claims (13)
1.制备二(全氟烷基)次膦酸或其盐的方法,其至少包括如下步骤:
a)在合适的反应介质中将至少一种二氟三(全氟烷基)正膦或至少一种三氟二(全氟烷基)正膦与氟化氢反应,和
b)加热步骤a)中所得的反应混合物。
2.根据权利要求1所述的制备二(全氟烷基)次膦酸或其盐的方法,其特征在于通过后续的中和作用制备所述的盐。
3.根据权利要求1所述的方法,其特征在于所用的二氟三(全氟烷基)正膦或三氟二(全氟烷基)正膦是具有通式I的化合物
(CnF2n+1)mPF5-m
I
其中1≤n≤8,优选1≤n≤4,和在各种情况下m=2或3。
4.根据权利要求1所述的方法,其特征在于所用的二氟三(全氟烷基)正膦是选自二氟三(五氟乙基)正膦、二氟三(正九氟丁基)正膦和二氟三(正七氟丙基)正膦的化合物。
5.根据权利要求1所述的方法,其特征在于所用的三氟二(全氟烷基)正膦化合物是三氟二(正九氟丁基)正膦。
6.根据权利要求1所述的方法,其特征在于步骤b)的加热期间的温度为室温至150℃,优选100~145℃,特别优选135~140℃。
7.根据权利要求1所述的方法,其特征在于步骤b)中加热的持续时间为1~150小时,优选10~25小时,特别优选18~22小时。
8.根据权利要求1所述的方法,其特征在于所述反应介质为水或基于水的混合物。
9.根据权利要求2所述的方法,其特征在于使用碱,优选氢氧化物、氧化物、氢化物、酰胺类、碳酸盐、膦类或胺类来制备所述的盐。
10.二(全氟烷基)次膦酸盐,其选自部分烷基化和全部烷基化的铵盐、鏻盐、锍盐、吡啶盐、哒嗪盐、嘧啶盐、吡嗪盐、咪唑盐、吡唑盐、噻唑盐、噁唑盐和三唑盐。
12.根据权利要求10或11的二(全氟烷基)次膦酸盐用作离子液体的用途。
13.根据权利要求10或11的二(全氟烷基)次膦酸盐用作相转移催化剂或表面活性剂的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10216997.7 | 2002-04-16 | ||
DE10216997A DE10216997A1 (de) | 2002-04-16 | 2002-04-16 | Verfahren zur Herstellung von Bis(perfluoralkyl)phosphinsäuren und deren Salze |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1646546A true CN1646546A (zh) | 2005-07-27 |
Family
ID=28685133
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA038084910A Pending CN1646546A (zh) | 2002-04-16 | 2003-03-17 | 二(全氟烷基)次膦酸及其盐的制备方法 |
Country Status (14)
Country | Link |
---|---|
US (1) | US7202379B2 (zh) |
EP (1) | EP1495035B1 (zh) |
JP (2) | JP4550429B2 (zh) |
KR (1) | KR100937125B1 (zh) |
CN (1) | CN1646546A (zh) |
AT (1) | ATE472368T1 (zh) |
AU (1) | AU2003218774A1 (zh) |
BR (1) | BR0309222A (zh) |
CA (1) | CA2482656A1 (zh) |
DE (2) | DE10216997A1 (zh) |
RU (1) | RU2004133373A (zh) |
TW (1) | TWI325427B (zh) |
WO (1) | WO2003087110A1 (zh) |
ZA (1) | ZA200409160B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101092412B (zh) * | 2007-07-24 | 2012-12-12 | 中国科学院长春应用化学研究所 | 四氢噻吩鎓类离子液体、制备方法及用途 |
CN101883814B (zh) * | 2007-12-04 | 2013-06-05 | 默克专利有限公司 | 次膦酸和/或膦酸在聚合方法中的用途 |
CN115286587A (zh) * | 2022-07-06 | 2022-11-04 | 珠海中科先进技术研究院有限公司 | 一种高离域的碱金属化合物及其制备方法和应用 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040052843A1 (en) * | 2001-12-24 | 2004-03-18 | Lerner E. Itzhak | Controlled release dosage forms |
EP1465606A4 (en) * | 2001-12-24 | 2009-04-22 | Teva Pharma | DOSAGE FORM WITH PASTILLE CORE ACTIVE PRINCIPLE COATED IN COMPRESSED ANNULAR BODY OF POWDER OR GRANULAR SUBSTANCE, AND METHOD AND TOOLS FOR PRODUCTION OF SAID DOSAGE FORM |
CA2527785A1 (en) | 2003-06-02 | 2004-12-09 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Ionic liquid comprising uronium cations or thiouronium cations |
DE10353758A1 (de) * | 2003-11-17 | 2005-06-23 | Merck Patent Gmbh | Verfahren zur Herstellung von organischen Salzen mit Bis(perfluoralkyl)phosphinat-Anionen |
DE10353759A1 (de) * | 2003-11-17 | 2005-06-16 | Merck Patent Gmbh | Verfahren zur Herstellung von Mono- und Bis/perfluoralkyl)phosphoranen und korrespondierenden Phosphaten |
DE102004060075A1 (de) * | 2004-12-14 | 2006-07-06 | Merck Patent Gmbh | Verfahren zur Herstellung von Onium-Salzen mit Dialkylphosphat-, Dialkylphosphinat oder (O-Alkyl)-alkyl- oder Alkyl-phosphonat-Anionen mit geringem Halogenid-Gehalt |
DE102005025315A1 (de) * | 2005-06-02 | 2006-12-14 | Merck Patent Gmbh | Ionische Flüssigkeiten mit niedriger Viskosität |
KR100750158B1 (ko) | 2006-01-20 | 2007-08-17 | 삼성전자주식회사 | Ap에서의 ra, rs 메시지 전송 방법 및 장치 |
DE102006005579A1 (de) * | 2006-02-06 | 2007-08-09 | Cognis Ip Management Gmbh | Verfahren zur Herstellung organischer Substanzen |
DE102006023649A1 (de) | 2006-05-17 | 2008-01-03 | Philipps-Universität Marburg | Hydrophobe ionische Flüssigkeiten |
DE102007004698A1 (de) * | 2007-01-31 | 2008-08-07 | Merck Patent Gmbh | Verbindungen enthaltend Organofluorochlorophosphatanionen |
US8378157B2 (en) | 2008-07-25 | 2013-02-19 | MERCK Patent Gesellschaft mit beschränkter Haftung | Method for producing bis(fluoralkyl)phosphinic acid chlorides or fluoralkylphosphonic acid chlorides |
DE102008035174A1 (de) * | 2008-07-28 | 2010-02-11 | Merck Patent Gmbh | Verfahren zur Herstellung von Bis(fluoralkyl)-phosphinsäure oder Fluoralkylphosphonsäure |
DE102009058969A1 (de) * | 2009-12-18 | 2011-06-22 | Merck Patent GmbH, 64293 | Verbindung mit (Perfluoralkyl)fluorohydrogenphosphat - Anionen |
DE102011108324A1 (de) | 2011-07-25 | 2013-01-31 | Merck Patent Gmbh | Verfahren zur Herstellung von Bis(perfluoralkyl)phosphinsäureanhydriden |
DE102012013071A1 (de) * | 2012-07-02 | 2014-01-02 | Merck Patent Gmbh | Verfahren zur Herstellung von Tris(perfluoralkyl)phosphinoxiden und Bis(perfluoralkyl)phosphinsäuren |
WO2016074757A1 (de) | 2014-11-11 | 2016-05-19 | Merck Patent Gmbh | Verfahren zur herstellung von mono- und bis(perfluoralkyl)fluorophosphatsalzen und deren säuren |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU498311A1 (ru) | 1973-02-16 | 1976-01-05 | Институт Органической Химии Ан Усср | Способ получени бис-(перфторалкил)фосфиновых кислот |
DE3804499A1 (de) | 1988-02-13 | 1989-08-24 | Delbrouck Franz Gmbh | Verfahren zum sortieren von kaesten fuer getraenkeflaschen sowie kasten zur verwendung bei diesem verfahren und vorrichtung zur durchfuehrung des verfahrens |
DE4416671A1 (de) | 1994-05-11 | 1995-12-07 | Steinle Karin | Verfahren und Vorrichtung zum Auspacken von Kunststoffflaschen aus Flaschenkästen |
DE19500290C2 (de) | 1994-09-09 | 1997-07-24 | Baumueller Anlagen Systemtech | Verfahren zum Aufeinanderstapeln von mit einer Greifeinrichtung erfaßbaren, nach oben offenen Behältern sowie Greifeinrichtung zum Auf- und Abstapeln von nach oben offenen Behältern |
DE10130940A1 (de) * | 2001-06-27 | 2003-01-16 | Merck Patent Gmbh | Supersäuren, Herstellverfahren und Verwendungen |
DE10220547A1 (de) * | 2002-04-16 | 2003-11-06 | Merck Patent Gmbh | Verfahren zur Herstellung von Monohydro-Pefluoralkanen, Perfluoralkylphosphinaten und Perfluoralkylphosphonaten |
-
2002
- 2002-04-16 DE DE10216997A patent/DE10216997A1/de not_active Withdrawn
-
2003
- 2003-03-17 US US10/511,157 patent/US7202379B2/en not_active Expired - Fee Related
- 2003-03-17 DE DE50312844T patent/DE50312844D1/de not_active Expired - Lifetime
- 2003-03-17 AT AT03712030T patent/ATE472368T1/de active
- 2003-03-17 KR KR1020047016411A patent/KR100937125B1/ko not_active IP Right Cessation
- 2003-03-17 RU RU2004133373/04A patent/RU2004133373A/ru not_active Application Discontinuation
- 2003-03-17 WO PCT/EP2003/002740 patent/WO2003087110A1/de active Application Filing
- 2003-03-17 EP EP03712030A patent/EP1495035B1/de not_active Expired - Lifetime
- 2003-03-17 AU AU2003218774A patent/AU2003218774A1/en not_active Abandoned
- 2003-03-17 JP JP2003584066A patent/JP4550429B2/ja not_active Expired - Fee Related
- 2003-03-17 CN CNA038084910A patent/CN1646546A/zh active Pending
- 2003-03-17 BR BR0309222-4A patent/BR0309222A/pt not_active Application Discontinuation
- 2003-03-17 CA CA002482656A patent/CA2482656A1/en not_active Abandoned
- 2003-04-14 TW TW092108542A patent/TWI325427B/zh not_active IP Right Cessation
-
2004
- 2004-11-11 ZA ZA200409160A patent/ZA200409160B/en unknown
-
2010
- 2010-02-22 JP JP2010036014A patent/JP5307747B2/ja not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101092412B (zh) * | 2007-07-24 | 2012-12-12 | 中国科学院长春应用化学研究所 | 四氢噻吩鎓类离子液体、制备方法及用途 |
CN101883814B (zh) * | 2007-12-04 | 2013-06-05 | 默克专利有限公司 | 次膦酸和/或膦酸在聚合方法中的用途 |
CN115286587A (zh) * | 2022-07-06 | 2022-11-04 | 珠海中科先进技术研究院有限公司 | 一种高离域的碱金属化合物及其制备方法和应用 |
CN115286587B (zh) * | 2022-07-06 | 2024-02-23 | 珠海中科先进技术研究院有限公司 | 一种高离域的碱金属化合物及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
TWI325427B (en) | 2010-06-01 |
TW200306981A (en) | 2003-12-01 |
JP2010180211A (ja) | 2010-08-19 |
DE10216997A1 (de) | 2003-10-30 |
AU2003218774A1 (en) | 2003-10-27 |
DE50312844D1 (de) | 2010-08-12 |
US20050256334A1 (en) | 2005-11-17 |
EP1495035B1 (de) | 2010-06-30 |
ZA200409160B (en) | 2005-05-31 |
CA2482656A1 (en) | 2003-10-23 |
US7202379B2 (en) | 2007-04-10 |
WO2003087110A1 (de) | 2003-10-23 |
JP2005522510A (ja) | 2005-07-28 |
JP4550429B2 (ja) | 2010-09-22 |
JP5307747B2 (ja) | 2013-10-02 |
KR20050000505A (ko) | 2005-01-05 |
EP1495035A1 (de) | 2005-01-12 |
KR100937125B1 (ko) | 2010-01-18 |
BR0309222A (pt) | 2005-02-09 |
RU2004133373A (ru) | 2005-06-10 |
ATE472368T1 (de) | 2010-07-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1646546A (zh) | 二(全氟烷基)次膦酸及其盐的制备方法 | |
CN1798741A (zh) | 改进的罗苏伐他汀钙盐的制备方法 | |
CN1308326C (zh) | 吲哚满酮衍生物的制备方法 | |
CN1301977C (zh) | 氨基嘧啶化合物的制备方法 | |
CN1639175A (zh) | 新型膦酰胺化合物、其制造方法及用途 | |
CN1237890C (zh) | 分级大豆蛋白及其生产方法 | |
CN1070907A (zh) | 制备4-取代-1,4-二氢吡啶的新方法 | |
CN1286818C (zh) | 制备三唑啉硫酮衍生物的方法 | |
CN1974547A (zh) | 烷基胍盐离子液体及其制备方法 | |
CN1072661C (zh) | 新的取代[2-(1-哌嗪基)乙氧基]甲基化合物 | |
CN1628087A (zh) | 链烯酮的制备方法 | |
CN1014975B (zh) | 含聚合氧化物夹层的层状氧化物的制备方法 | |
CN1874844A (zh) | 镍(0)-磷配体配合物的制备方法 | |
CN1898255A (zh) | 制备吡啶衍生物的方法 | |
CN1076429A (zh) | 新型聚氯硫酸铝及其制备和应用 | |
CN1297560C (zh) | 次膦酸鏻化合物及其制备 | |
CN87108378A (zh) | 液晶材料 | |
CN1008522B (zh) | 草甘膦及草甘膦衍生物的制备方法 | |
CN1217722A (zh) | 制备嘧啶衍生物的方法 | |
CN1034362A (zh) | 芳香羟基羧酸的制备方法 | |
CN1164577C (zh) | 2-氨基-4-(4-氟苯基)-6-烷基嘧啶-5-羧酸酯的制备方法 | |
CN1237160A (zh) | 取代的吡啶的制备方法 | |
CN1232511C (zh) | 噁唑基乙酸酯衍生物及其盐的制备方法 | |
CN100340563C (zh) | 尤其用作合成中间体的卤化单有机氧基硅烷的制备方法 | |
CN1714044A (zh) | 在氟离子不存在下合成itq-17 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |