CN103703010B - 制备双(全氟烷基)次膦酸酐的方法 - Google Patents
制备双(全氟烷基)次膦酸酐的方法 Download PDFInfo
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- CN103703010B CN103703010B CN201280036598.9A CN201280036598A CN103703010B CN 103703010 B CN103703010 B CN 103703010B CN 201280036598 A CN201280036598 A CN 201280036598A CN 103703010 B CN103703010 B CN 103703010B
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- Prior art keywords
- acid
- perfluoroalkyl
- phospho acid
- pentafluoroethyl group
- phospho
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 phospho Chemical class 0.000 title claims abstract description 104
- 239000002253 acid Substances 0.000 title claims abstract description 77
- 150000008065 acid anhydrides Chemical class 0.000 title claims abstract description 53
- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 52
- 229910052731 fluorine Inorganic materials 0.000 description 29
- 239000002904 solvent Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000012925 reference material Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- DWPHWVJZBHLVPI-UHFFFAOYSA-N bromophosphonic acid Chemical group OP(O)(Br)=O DWPHWVJZBHLVPI-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 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 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000001457 metallic cations Chemical class 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001767 cationic compounds Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SZZRMCOLWUGEGL-UHFFFAOYSA-M N#C[O-].N#CO.N#CO.S.[K+] Chemical compound N#C[O-].N#CO.N#CO.S.[K+] SZZRMCOLWUGEGL-UHFFFAOYSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000000540 analysis of variance Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- WAZIDHPTVNFDQG-UHFFFAOYSA-N bis(1,1,2,2,3,3,4,4,4-nonafluorobutyl)phosphinic acid Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)P(=O)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WAZIDHPTVNFDQG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 125000005500 uronium group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/28—Selection of materials for use as drying agents
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/308—Pyrophosphinic acids; Phosphinic acid anhydrides
-
- 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)]
- C07F9/32—Esters thereof
-
- 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)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3294—Compounds containing the structure R2P(=X)-X-acyl, R2P(=X)-X-heteroatom, R2P(=X)-X-CN (X = O, S, 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/34—Halides thereof
-
- 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)]
- C07F9/44—Amides thereof
- C07F9/4461—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4484—Compounds containing the structure C-P(=X)(N-acyl)-X, C-P(=X)(N-heteroatom)-X or C-P(=X)(N-CN)-X (X = O, S, Se)
- C07F9/4492—Compounds containing the structure P(=X)(N-C(=X)-) (X = O, S, Se)
-
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Abstract
本发明涉及通过使双(全氟烷基)次膦酸与五氧化二磷反应而制备双(全氟烷基)次膦酸酐的方法,涉及新型双(全氟烷基)次膦酸酐,以及涉及双(全氟烷基)次膦酸酐的用途。(CxF2x+1)2P(O)OH?(II)。
Description
本发明涉及通过使双(全氟烷基)次膦酸与五氧化二磷反应制备双(全氟烷基)次膦酸酐的方法,新型双(全氟烷基)次膦酸酐和双(全氟烷基)次膦酸酐的用途。
R.C.Dobbie,J.Chem.Soc.(A),1971,2894-2897报道了通过在密封容器中在室温下使用4当量NO将P2(CF3)4(四-三氟甲基二膦)氧化而合成双(三氟甲基)次膦酸酐。
AntonB.Burg,InorganicChemistry,1978,17,2322-2324报道了通过双(三氟甲基)三价膦酸酐[(CF3)2POP(CF3)2]与双(三氟甲基)次膦酰氯反应而合成双(三氟甲基)次膦酸酐。
T.Mahmood和J.M.Shreeve,Inorg.Chem.1986,25,3128-3131报道了通过氯双(五氟乙基膦)[(C2F5)2PCl]与过量NO2在25℃下反应而合成双(五氟乙基)次膦酸酐,其作为反应期间的非挥发性产物保留在反应容器中。然而,所述参考文献中的NMR谱不符合双(五氟乙基)次膦酸酐的谱,所述双(五氟乙基)次膦酸酐为通过本发明方法得到的可蒸馏液体。T.Mahmood和J.M.Shreeve在Inorg.Chem.1986,25,3128-3131中描述的19F和31PNMR谱中的信号位置和它们的细结构更类似于双(五氟乙基)次膦酸的相应谱。双(五氟乙基)次膦酸的谱例如描述于实施例3中。双(五氟乙基)次膦酸[(C2F5)2P(O)OH]的CF2基团产生在-127.0ppm下的简单双峰,其中在氘化乙腈中的19FNMR谱中的耦合常数2JP,F=77Hz。该信号的位置非常类似于T.Mahmood和J.M.Shreeve描述的信号,即在氘化二甲亚砜中δCF2=-126.3和2JP,F=73Hz。如完全在实施例1中所示,双(五氟乙基)次膦酸酐的19FNMR谱完全不同。双(五氟乙基)次膦酸酐[(C2F5)2P(O)OP(O)(C2F5)2]中的CF2基团中的氟原子在光谱分析下是不同的,而是形成CFAFB体系,这产生在-122.0和-127.0ppm下的两个双双峰(所谓的ABX自旋体系),且耦合常数2JP,F(A)=90Hz且2JP,F(B)=107Hz。实施例1的双(五氟乙基)次膦酸酐的31PNMR谱与如T.Mahmood和J.M.Shreeve所述的酐相比也不同:实施例1描述了复杂的多重峰,而参考文献指出简单五重峰。因此不能由该参考文献的反应得到这一化合物,因此该化合物仍是新的。
Mahmood等人所报道的双(五氟乙基)次膦酸酐的谱:19F:-81.4s(CF3),-126.3d(JCF2-P)73.24Hz;31P:-0.3.五重峰。
RajendraP.Singh和J.M.Shreeve,Inorg.Chem.2000,39,1787-1789描述了式(RF)2P(O)OP(O)(RF)2的酐,其中RF=C6F13,C7F15且C8F17,其作为通过使用NO2将(RF)2PI氧化而制备相应双(全氟烷基)次膦酸中的中间体。然而,没有分离和分析作为中间体的酐,也没有给出使用物理化学方法的表征。因此,也不能由该参考文献的反应得到这些化合物,因此,这些化合物仍应被认为是新的。
羧酸和烷基磺酸的酐是用于有机合成的重要试剂。双(全氟烷基)次膦酸及其衍生物是质子传导膜的重要组分或者例如适用作有机化学中的催化剂。此外,它们适于合成含氟表面活性剂或进一步转化成相应的酰氯,所述酰氯又适于合成新型材料如离子液体。
至今公布的如上所述用于制备双(全氟烷基)次膦酸酐的方法都未得到所需产物或者不能在工业规模上使用。因此,理想的是可经济地且在工业规模上合成这些化合物,以致可研究这类重要的双(全氟烷基)次膦酸酐及其应用。
因此,本发明的目的是开发制备双(全氟烷基)次膦酸酐的改进方法,所述方法满足工业规模经济合成的要求。
令人惊讶的是,发现双(全氟烷基)次膦酸可与五氧化二磷反应并可将所需酐从其中分离。
K.Moedritzer,J.oftheAmericanChemicalSociety,1961,83,4381-4384描述了次膦酸酐不能通过将相应的次膦酸脱氢而制备。
G.M.Kosolapoff,R.M.Watson,J.oftheAmericanChemicalSociety,1951,73,5466-5467描述了基于二烷基次膦酰氯[(Alk)2P(O)Cl]与相应二烷基次膦酸或其酯[(Alk)2P(O)OH或(Alk)2P(O)OR]的反应而制备未氟化二烷基次膦酸酐的典型方法。
M.Fimke和H.-J.Kleiner,LiebigsAnn.Chem.,1974,741-750描述了用光气(COCl2)作为脱氢剂将未氟化二烷基次膦酸或其盐或酯脱氢以制备未氟化二烷基次膦酸酐。
因此,本发明涉及通过双(全氟烷基)次膦酸与五氧化二磷反应而制备双(全氟烷基)次膦酸酐的方法。
五氧化二磷意指化合物P2O5或同义地P4O10。
根据本发明得到的化合物是挥发性的且可与反应混合物分离并任选通过蒸馏提纯。
优选制备式I的双(全氟烷基)次膦酸酐:
(CxF2x+1)2(O)POP(O)(CxF2x+1)2I
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12。
这些为对称的酸酐。
起始化合物,即双(全氟烷基)次膦酸,特别是式II的双(全氟烷基)次膦酸为市售的或者可通过标准合成方法,例如通过已公开的说明书WO03/087110或WO2010/012359中所述的方法制备:
(CxF2x+1)2P(O)OHII
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12。
特别优选制备其中x代表2、3、4或5,非常特别优选x代表2或4的式I化合物。
如上所述方法在20-250℃的温度下,优选在60-210℃的温度下进行。此处应考虑相应双(全氟烷基)次膦酸的反应性。如实验部分中具体解释的,双(九氟丁基)次膦酸酐的制备在60℃下在惰性溶剂(1,1,1,3,3-五氟丁烷)中进行,而双(五氟乙基)次膦酸酐在210℃下制备而不使用溶剂。精确的反应温度由有机合成领域中的技术人员决定。
该方法可不使用溶剂或者在溶剂的存在下进行。合适的溶剂例如为氟代烷烃、氯代烷烃或氟氯烷烃,特别是1,1,1,3,3-五氟丁烷或1,1,2-三氯三氟乙烷。反应优选不用溶剂或者在溶剂1,1,1,3,3-五氟丁烷中进行。
双(全氟烷基)次膦酸与五氧化二磷的反应可不用保护气体气氛进行。然而,反应优选在干燥空气下或者在惰性气体气氛中进行。
此外,本发明涉及式I的双(全氟烷基)次膦酸酐:
(CxF2x+1)2(O)POP(O)(CxF2x+1)2I
其中:
x表示2、3、4、5、6、7、8、9、10、11或12。
x优选代表3、4、5、6、7、8、9、10、11或12,特别优选代表2、3、4、5、6、7或8,非常特别优选代表2、3、4或5或者非常特别优选代表3、4、6或12。特别是,x优选代表2和4,非常特别优选代表4。
通过或可通过本发明方法制备的双(全氟烷基次膦酸)酐,优选如上所述式I化合物特别优选作为脱水剂或干燥剂,其中x表示1、2、3、4、5、6、7、8、9、10、11或12。
此外,通过或可通过本发明方法制备的双(全氟烷基)次膦酸酐,优选如上所述式I化合物为用于制备母体双(全氟烷基)次膦酸的其它衍生物或具有相应双(全氟烷基)次膦酸根阴离子的盐的理想起始化合物,其中x表示1、2、3、4、5、6、7、8、9、10、11或12。
优选的双(全氟烷基)次膦酸衍生物例如为:
-双(全氟烷基)次膦酰氯,特别是式III的双(全氟烷基)次膦酰氯:
(CxF2x+1)2P(O)ClIII
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12,
-双(全氟烷基)次膦酰溴,特别是式IV的双(全氟烷基)次膦酰溴:
(CxF2x+1)2P(O)BrIV,
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12,
-双(全氟烷基)次膦酸三烷基甲硅烷基醚,特别是式V的双(全氟烷基)次膦酸三烷基甲硅烷基醚:
(CxF2x+1)2P(O)OSi(烷基)3V
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12,且
烷基表示具有1-4个C原子的直链或支化烷基,
-N,N-二烷基双(全氟烷基)次膦酰基胺或-酰胺,特别是式VI的那些:
(CxF2x+1)2P(O)N(R)2VI
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12,且
R每种情况下相互独立地表示H或具有1-12个C原子的直链或支化烷基,-双(全氟烷基)次膦酰基氰化物,特别是式VII的那些:
(CxF2x+1)2P(O)CNVII
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12,或者
-双(全氟烷基)次膦酰基异硫氰酸酯,特别是式VIII的那些:
(CxF2x+1)2P(O)NCSVIII
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12。
这些其它衍生过程的反应条件是本领域技术人员充分了解的。工作实施例描述于实施例中。
具有1-4个C原子的直链(或同义地,线性)或支化烷基为例如甲基、乙基、正丙基、异丙基、正丁基、仲丁基或叔丁基。具有1-12个C原子的线性或支化烷基包括具有1-4个C原子的线性或支化烷基的实施方案,以及例如正戊基、正己基、正庚基、正辛基、乙基己基、正壬基、正癸基、正十一烷基或正十二烷基。
作为除上述衍生物,特别是式III-VIII化合物外的其它产物,衍生化通常还得到相应的双(全氟烷基)次膦酸盐,其中此处的阳离子可以为无机或有机的。
特别地,衍生化得到式IX的化合物:
Kt[OP(O)(CxF2x+1)2]IX
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12,且
Kt为无机或有机阳离子。
Kt的有机阳离子例如选自铵阳离子、锍阳离子、鏻阳离子、脲鎓(uronium)阳离子、硫脲鎓(thiouronium)阳离子、胍鎓阳离子或杂环阳离子。
Kt的无机阳离子例如选自周期表1-12族的金属阳离子,选自碱金属阳离子、Ag+、Mg2+、Cu+、Cu2+、Zn2+、Ca2+、Y+3、Yb+3、La+3、Sc+3、Ce+3、Nd+3、Tb+3、Sm+3或配合物(含配体)金属阳离子,所述配合物(含配体)金属阳离子含有稀土金属、过渡金属或贵金属,例如铑、钌、铱、钯、铂、锇、钴、镍、铁、铬、钼、钨、钒、钛、锆、铪、钍、铀、金。
以下工作实施例意欲解释本发明而不限制本发明。本发明可在整个所述范围内相应地进行。起始于实施例,也可衍生出可能的变化方案。特别地,实施例中所述反应的特征和条件也可适于未详细描述,但属于权利要求书的保护范围内的其它反应。
实施例
所得物质通过拉曼光谱法、元素分析和NMR谱表征。NMR谱在具有氘锁的BrukerAvanceIII分光计上在氘化丙酮-D6溶液中测量。各个核的测量频率为:1H:400.17MHz,19F:376.54MHz,11B:128.39MHz,31P:161.99MHz且13C:100.61MHz。参比用外部参比进行:TMS用于1H和13C光谱;CCl3F–用于19F且BF3·Et2O–用于11B谱。
实施例1:双(五氟乙基)次膦酸酐
将8.8g(29.1毫摩尔)双(五氟乙基)次膦酸(C2F5)2P(O)OH加入16.8g(118毫摩尔)五氧化二磷P2O5中,并将混合物在回流下在210℃(油浴中的温度)下加热6小时。随后将透明无色液体在减压(P=100毫巴)中蒸馏。沸点:78℃(100毫巴)。双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2的收率基于所用双(五氟乙基)次膦酸为7.2g(84%)。
NMR数据:外锁:丙酮-D6;参比物质:1H和13C谱—TMS,19F谱—CCl3F,31P谱—在D2O中的85%H3PO4):
31PNMR谱,δ,ppm:3.2m。
19FNMR谱,δ,ppm:-83.2s(12F,4CF3);-122.0d,d(4FA,CF2),2JP,F(A)=90Hz,2JF(A),F(B)=340Hz;-127.0d,d(4FB,CF2),2JP,F(B)=107Hz,2JFA,FB=340Hz。
13CNMR谱,δ,ppm:111.3t,d,q(4C,4CF2),1JF,C=286Hz,1JP,C=150Hz,2JF,C=43Hz;117.9q,t,d(4C,4CF3),1JF,C=286Hz,2JF,C=30Hz,2JP,C=23Hz。
(C2F5)2P(O)OP(O)(C2F5)2的拉曼光谱,cm-1:1356s,1224m,1166m,759vs,700m,638s,597,541,370m,280s,260s,253s,151s。
(C2F5)2P(O)OP(O)(C2F5)2的IR(ATR),cm-1:1354w,1339w,1305s,1219vs,1148vs,1001s,932s,760m,753m,628m,598m,567m,507s,468w,415w。
实施例2:双(九氟丁基)次膦酸酐
将7.0g(14.0毫摩尔)双(全氟丁基)次膦酸(C4F9)2P(O)OH溶于25ml1,1,1,3,3-五氟丁烷中,加入7.9g(55.7毫摩尔)五氧化二磷P2O5,并将混合物在回流下在60℃下加热4天。在分馏以后,得到3.3g作为透明无色液体的双(全氟丁基)次膦酸酐。这相当于基于所用双(九氟丁基)次膦酸为48%的收率。
沸点:77℃(0.6毫巴)。
NMR数据:外锁:D2O;参比物质:1H和13C谱—TMS,19F谱—CCl3F,31P谱—在D2O中的85%H3PO4):
31PNMR谱,δ,ppm:2.4m。
19FNMR谱,δ,ppm:-83.3s(12F,4CF3);-115.8d,d(4FA,CF2)2JP,F(A)=88Hz,2JF(A),F(B)=337Hz;-119.7d,d(4FB,CF2),2JP,F(B)=107Hz;-120.6m(8F,4CF2);-127.6s(8F,4CF2)。
实施例3:双(五氟乙基)次膦酸酐的水解
(C2F5)2(O)POP(O)(C2F5)2+H2O2(C2F5)2P(O)OH
将0.19g(10.5毫摩尔)水在0℃下,在剧烈搅拌下,加入5.90g(10.0毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2中。得到6.09g透明无色液体。双(五氟乙基)次膦酸的收率是定量的。
NMR数据(溶剂/锁:CD3CN;参比物质:19FCCl3F,31P85%H3PO4):19FNMR谱,δ,ppm:-82.1s(6F,2CF3);-127.0d(4F,2CF2),2JP,F=77Hz。31PNMR谱,δ,ppm:-0.1quin,2JP,F=76Hz。
实施例4:双(五氟乙基)次膦酰氯的制备
A:
将6.1g(10.4毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2加入2.5g(12.3毫摩尔)1-丁基-3-甲基咪唑氯化物EMIMCl中,并将混合物在室温下搅拌15分钟。在随后的蒸馏(沸点:86℃)以后,得到2.9g双(五氟乙基)次膦酰氯(C2F5)2P(O)Cl,这相当于88%的收率。
双(五氟乙基)次膦酰氯:
31PNMR谱(溶剂:CD3CN;参比物质:85%H3PO4),δ,ppm:21.6t,t;2JP,F=95Hz,2JP,F=98Hz;
19FNMR谱(溶剂:CD3CN;参比物质:CCl3F),δ,ppm:-79.8s(6F,2CF3);-118.2d,d(2FA,CF2),2JP,F(A)=92Hz,2JF(A),F(B)=326Hz;-122.4d,d(2FB,CF2),2JP,F(B)=100Hz,2JF(A),F(B)=325Hz。
B:
[(CH3)4N]Cl+(C2F5)2(O)POP(O)(C2F5)2[(CH3)4)N][(C2F5)2P(O)O]+(C2F5)2P(O)Cl
将11.1g(18.9毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2加入1.98g(18.1毫摩尔)四甲基氯化铵中。将反应混合物在回流下在190℃(油浴中的温度)下搅拌2小时。然后将形成的5.73g双(五氟乙基)次膦酰氯(C2F5)2P(O)Cl冷凝出,这相当于99%的收率。
实施例5:双(五氟乙基)次膦酰溴的制备
将10.2g(17.4毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2加入3.2g(16.7毫摩尔)1-乙基-3-甲基咪唑溴化物中,并将混合物在室温下搅拌10分钟。随后将混合物在回流下加热5分钟以完成反应。在随后的蒸馏(沸点:97℃)以后,得到5.3g双(五氟乙基)次膦酰溴(C2F5)2P(O)Br,这相当于87%的收率。
双(五氟乙基)次膦酰溴的NMR数据(外锁:D2O;参比物质:19FNMR谱—CCl3F,31PNMR谱—85%H3PO4):
31PNMR谱,δ,ppm:15.2quin;2JP,F=94Hz。
19FNMR谱,δ,ppm:-80.6s(6F,2CF3);-117.4d,d(2F,CF2),2JP,F(A)=93Hz,2JF(A),F(B)=322Hz;-122.8d,d(2FB,CF2),2JP,F(B)=96Hz,2JF(A),F(B)=322Hz。
实施例6:双(五氟乙基)次膦酸三甲基甲硅烷基醚的制备
A:
(CH3)3SiCl+(C2F5)2(O)POP(O)(C2F5)2(C2F5)2P(O)OSi(CH3)3+(C2F5)2P(O)Cl
将4.91g(45毫摩尔)三甲基氯硅烷在室温下加入4.72g(8毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2中,将混合物搅拌10分钟,随后经受分馏。得到2.13g双(五氟乙基)次膦酰氯和2.81g双(五氟乙基)次膦酸三甲基甲硅烷基醚。这分别相当于83和93%的收率。
双(五氟乙基)次膦酸三甲基甲硅烷基醚:
31PNMR谱(溶剂:CD3CN;参比物质:85%H3PO4),δ,ppm:-2.7br.m;
19FNMR谱(溶剂:CD3CN;参比物质:CCl3F),δ,ppm:-81.1br.s(6F,2CF3);-125.4br.m(4F,2CF2)
1HNMR谱(溶剂:CD3CN;参比物质:TMS),δ,ppm:0.45br.s(9H,3CH3)。
B:
(CH3)3SiOSi(CH3)3+(C2F5)2(O)POP(O)(C2F5)22(C2F5)2P(O)OSi(CH3)3
将7.7g(47.4毫摩尔)六甲基二硅氧烷(CH3)3SiOSi(CH3)3加入14.4g(24.6毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2中,并将混合物在室温下搅拌20分钟。在真空(P=8毫巴)下分馏以后,得到15.0g双(五氟乙基)次膦酸三甲基甲硅烷基醚,这相当于81%的收率。沸点:58℃(8毫巴)。实施例7:N,N-二丁基双(五氟乙基)次膦酰基酰胺的制备
将0.58g(4.5毫摩尔)二丁胺(C4H9)2NH在0℃下缓慢地加入1.21g(2.1毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2中,并将混合物搅拌15分钟。在随后的真空蒸馏以后,得到0.65gN,N-二丁基双(五氟乙基)次膦酰基酰胺(C2F5)2P(O)N(C4H9)2,这相当于76%的收率。
31PNMR谱(溶剂:CD3CN;参比物质:85%H3PO4),δ,ppm:13.0quin,quin;2JP,F=76Hz,3JP,H=11Hz。
19FNMR谱(溶剂:CD3CN;参比物质:CCl3F),δ,ppm:-81.4s(6F,2CF3);-122.3d(4F,2CF2),2JP,F=75Hz。
1HNMR谱(溶剂:CD3CN;参比物质:TMS),δ,ppm:0.93t(6H,2CH3),3JH,H=7Hz;1.30d,q(4H,2CH2),3JH,H=7Hz;1.59m(4H,2CH2);3.21m(4H,2CH2)。
实施例8:双(五氟乙基)次膦酰基氰化物的制备
A:
(C2F5)2(O)POP(O)(C2F5)2+KCN(C2F5)2P(O)CN+(C2F5)2P(O)OK
首先将0.78g(12.0毫摩尔)细碎***引入24.4g环丁砜中并在真空下在90℃下搅拌1小时且除去挥发性组分。在将反应混合物冷却至40℃以后,加入6.68g(11.4毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2,将混合物加热至55℃,并搅拌另外3.5小时。随后冷凝出3.15g的由摩尔比为1:9的双(五氟乙基)次膦酸酐和双(五氟乙基)次膦酰基氰化物(C2F5)2P(O)CN组成的混合物。在该混合物的分馏以后,得到2.1g的沸点为72℃的双(五氟乙基)次膦酰基氰化物。这相当于59%的收率(基于酐)。
双(五氟乙基)次膦酰基氰化物的NMR数据(外锁:D2O;参比物质:19FNMR谱—CCl3F,31PNMR谱—85%H3PO4):
31PNMR谱,δ,ppm:-13.9t,t;2JP,F=90Hz,2JP,F=101Hz。
19FNMR谱,δ,ppm:-81.0s(6F,2CF3);-119.1d,d(2F,CF2),2JP,F(A)=90Hz,2JF(A),F(B)=333Hz;-125.6d,d(2FB,CF2),2JP,F(B)=101Hz,2JF(A),F(B)=333Hz。
(C2F5)2P(O)CN的拉曼光谱,cm-1:2204vs,1337s,1300s,1226m,1133m,995w,757vs,672w,634m,592w,542w,468w,369m,328m,281s,257s,198w,144s,109s。
(C2F5)2P(O)CN的IR(ATR),cm-1:2202s,1354w,1295vs,1218vs,1143vs,993s,758s,713m,674s,564s,506s,490s,423w。
B:
首先将0.97g(14.9毫摩尔)细碎***引入19.4g环丁砜中并在真空下在60℃下搅拌整夜并除去挥发性组分。在反应混合物冷却至30℃以后,加入12.43g(21.2毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2,并将混合物在该温度下搅拌24小时。随后将挥发性组分在真空下冷凝至冷却至-196℃的烧瓶中。将由摩尔比为2:3的双(五氟乙基)次膦酸酐和双(五氟乙基)次膦酰基氰化物的7.7g冷凝出的混合物温热至-40℃,并将3.4g双(五氟乙基)次膦酰基氰化物(C2F5)2P(O)CN在真空下冷凝至冷却至-196℃的接收器中。这相当于73%的收率(基于所用***)。
实施例9:双(五氟乙基)次膦酰基异硫氰酸酯
(C2F5)2(O)POP(O)(C2F5)2+KSCN(C2F5)2P(O)NCS+(C2F5)2P(O)OK
首先将1.02g(10.5毫摩尔)细碎硫氰酸钾KSCN引入19.6g环丁砜中并在真空下在40℃下搅拌整夜并除去挥发性组分。在将溶液冷却至40℃以后,加入6.38g(11.4毫摩尔)双(五氟乙基)次膦酸酐(C2F5)2(O)POP(O)(C2F5)2,并将混合物在70℃下搅拌1小时。在挥发性组分冷凝至冷却至-196℃的烧瓶中并随后分馏以后,得到3.39g的沸点为120℃的透明无色液体-双(五氟乙基)次膦酰基异硫氰酸酯。这相当于94%的收率(基于所用酐)。
双(五氟乙基)次膦酰基氰化物的NMR数据(外锁:D2O;参比物质:19FNMR谱—CCl3F,31PNMR谱—85%H3PO4):
31PNMR谱,δ,ppm:-12.2t,t;2JP,F=99Hz,2JP,F=84Hz,
19FNMR谱,δ,ppm:-81.7s(6F,2CF3);-122.1d,d(2F,CF2),2JP,FA=85Hz,2JFA,FB=334Hz;-126.0d,d(2FB,CF2),2JP,FB=100Hz,2JFA,FB=332Hz。
(C2F5)2P(O)NCS的拉曼光谱,cm-1:1971vw,1332s,1303s,1227m,1156m,1088m,983w,755vs,655w,634m,541w,442w,414s,366m,330m,265s,163m,144m。
(C2F5)2P(O)NCS的IR(ATR),cm-1:1946vs,1294s,1217vs,1148vs,995m,928m,758m,.622w,596w,562m,499s。
Claims (3)
1.通过使双(全氟烷基)次膦酸与五氧化二磷反应制备双(全氟烷基)次膦酸酐的方法。
2.根据权利要求1的方法,其特征在于所述双(全氟烷基)次膦酸符合式II:
(CxF2x+1)2P(O)OHII,
其中:
x表示1、2、3、4、5、6、7、8、9、10、11或12。
3.根据权利要求1或2的方法,其特征在于反应在20-250℃的温度下进行。
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Title |
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Bis( trifluoromethyl) phosphoryl-μ-oxo-bis( trifluoromethy1)-phosphine. The Mixed Anhydride of a Phosphinous and Phosphinic Acid;Anton B. Burg;《Inorganic Chemistry》;19780831;第17卷(第8期);第2322-2324页 * |
C6, C7, and C8 Perfluoroalkyl-Substituted Phosphinic Acids;Rajendra P. Singh et al;《Inorg. Chem.》;20000401;第39卷;第1787-1789页 * |
Commercial Synthesis of Monoalkyl Phosphates;David J. Tracya et al;《Journal of Surfactants and Detergents》;20021231;第5卷(第2期);第169-172页 * |
New Perfluoroalkylphosphonic and Bis( perfluoroalky1)phosphinic Acids and Their Precursors;Tariq Mahmood et al;《Inorg. Chem.》;19860831;第25卷;第3128-3131页 * |
The Reaction of Tridluoromethylphosphino-compounds with Nitric Oxide;R. C. Dobbie et al;《J. Chem. SOC. (A)》;19711231;第2894-2897页 * |
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