JP5926797B2 - ビス(パーフルオロアルキル)ホスフィン酸無水物の調製方法 - Google Patents
ビス(パーフルオロアルキル)ホスフィン酸無水物の調製方法 Download PDFInfo
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- JP5926797B2 JP5926797B2 JP2014521971A JP2014521971A JP5926797B2 JP 5926797 B2 JP5926797 B2 JP 5926797B2 JP 2014521971 A JP2014521971 A JP 2014521971A JP 2014521971 A JP2014521971 A JP 2014521971A JP 5926797 B2 JP5926797 B2 JP 5926797B2
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- JP
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- Prior art keywords
- bis
- pentafluoroethyl
- phosphinic
- perfluoroalkyl
- anhydride
- 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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- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims description 35
- 150000008064 anhydrides Chemical class 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 20
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 17
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 15
- LLNFBSOQTBOBDN-UHFFFAOYSA-N 1-[bis(1,1,2,2,2-pentafluoroethyl)phosphoryloxy-(1,1,2,2,2-pentafluoroethyl)phosphoryl]-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)P(=O)(C(F)(F)C(F)(F)F)OP(=O)(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F LLNFBSOQTBOBDN-UHFFFAOYSA-N 0.000 description 21
- -1 alkyl sulfonic acid Chemical compound 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 12
- 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 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- XIRIIYFSKJWHLQ-UHFFFAOYSA-N bis(1,1,2,2,2-pentafluoroethyl)phosphorylformonitrile Chemical compound FC(F)(F)C(F)(F)P(=O)(C#N)C(F)(F)C(F)(F)F XIRIIYFSKJWHLQ-UHFFFAOYSA-N 0.000 description 6
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012925 reference material Substances 0.000 description 6
- ICIJWVXTJKISHG-UHFFFAOYSA-N 1-[chloro(1,1,2,2,2-pentafluoroethyl)phosphoryl]-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)P(Cl)(=O)C(F)(F)C(F)(F)F ICIJWVXTJKISHG-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000004508 fractional distillation Methods 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
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 3
- COYSOSDFPWYDRA-UHFFFAOYSA-N 1-[bis(1,1,2,2,3,3,4,4,4-nonafluorobutyl)phosphoryloxy-(1,1,2,2,3,3,4,4,4-nonafluorobutyl)phosphoryl]-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)P(=O)(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)OP(=O)(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F COYSOSDFPWYDRA-UHFFFAOYSA-N 0.000 description 3
- GASNOVZTZYLIPC-UHFFFAOYSA-N 1-[bromo(1,1,2,2,2-pentafluoroethyl)phosphoryl]-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)P(Br)(=O)C(F)(F)C(F)(F)F GASNOVZTZYLIPC-UHFFFAOYSA-N 0.000 description 3
- PMMRSBZIFCBVAW-UHFFFAOYSA-N [bis(trifluoromethyl)phosphoryloxy-(trifluoromethyl)phosphoryl]-trifluoromethane Chemical compound FC(F)(F)P(=O)(C(F)(F)F)OP(=O)(C(F)(F)F)C(F)(F)F PMMRSBZIFCBVAW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000001212 derivatisation Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- PLLIPWAOHKYEMU-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-2-[isothiocyanato(1,1,2,2,2-pentafluoroethyl)phosphoryl]ethane Chemical compound FC(F)(F)C(F)(F)P(=O)(N=C=S)C(F)(F)C(F)(F)F PLLIPWAOHKYEMU-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
- KHKIYNGGDSKWLC-UHFFFAOYSA-N O=[PH2]NC(C(F)(F)F)(F)F Chemical compound O=[PH2]NC(C(F)(F)F)(F)F KHKIYNGGDSKWLC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001767 cationic compounds Chemical group 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 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
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 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
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- GTBKKOXCGAYKAP-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethylphosphane Chemical compound FC(F)(F)C(F)(F)P GTBKKOXCGAYKAP-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- 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
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 1
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000191368 Chlorobi Species 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- YJLQNZCCABDCEW-UHFFFAOYSA-N O=P(C(C(F)(F)F)(F)F)N=C=S Chemical compound O=P(C(C(F)(F)F)(F)F)N=C=S YJLQNZCCABDCEW-UHFFFAOYSA-N 0.000 description 1
- CDTCXUBQFUTFFA-UHFFFAOYSA-N O=P(C(C(F)(F)F)(F)F)OP(C(C(F)(F)F)(F)F)=O Chemical compound O=P(C(C(F)(F)F)(F)F)OP(C(C(F)(F)F)(F)F)=O CDTCXUBQFUTFFA-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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- STSSBAPKNFQORT-UHFFFAOYSA-N [PH2](OC(C(F)(F)F)(F)F)=O Chemical compound [PH2](OC(C(F)(F)F)(F)F)=O STSSBAPKNFQORT-UHFFFAOYSA-N 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 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
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 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
- 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 229910000510 noble metal Inorganic materials 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
- 230000000737 periodic effect Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000001681 protective effect 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
- 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 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
- 238000005292 vacuum distillation Methods 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
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- 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)
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- C07F9/34—Halides thereof
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- 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)
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Description
Anton B. Burg, Inorganic Chemistry, 1978, 17, 2322-2324には、ビス(トリフルオロメチル)亜ホスフィン酸無水物[(CF3)2POP(CF3)2]とビス(トリフルオロメチル)ホスフィニルクロリドとの反応による、ビス(トリフルオロメチル)ホスフィン酸無水物の合成が報告されている。
T. Mahmood and J.M. Shreeve, Inorg. Chem. 1986, 25, 3128-3131に記載されている、19Fおよび31P NMRスペクトルにおけるシグナルの位置およびそれらの詳細構造は、ビス(ペンタフルオロエチル)ホスフィン酸に対応するスペクトルと、より類似している。ビス(ペンタフルオロエチル)ホスフィン酸のスペクトルは、例えば、例3に記載されている。ビス(ペンタフルオロエチル)ホスフィン酸[(C2F5)2P(O)OH]2のCF2基は、重水素化アセトニトリル中、19F NMRスペクトルにおいて、−127.0ppmに、2JP,F=77Hzの結合定数で、単純な二重線を生成する。このシグナルの位置は、T. MahmoodおよびJ.M. Shreeveによって記載されたシグナルと極めて類似しており、すなわち重水素化ジメチルスルホキシド中、δCF2=126.3および2JP,F=73Hzである。
19F:−81.4s(CF3),−126.3d(JCF2−P)73.24Hz
31P:−0.3.五重線
G.M. Kosolapoff, R.M. Watson, J. of the American Chemical Society, 1951, 73, 5466-5467には、ジアルキルホスフィニルクロリド[(Alk)2P(O)Cl]と、対応するジアルキルホスフィン酸またはそれらのエステル[(Alk)2P(O)OHまたは(Alk)2P(O)OR]との反応に基づいた、非フッ素化ジアルキルホスフィン酸無水物の典型的な調製方法が記載されている。
五酸化リンは、化学化合物P2O5または同義にP4O10を意味するものと解釈される。
本発明によって得られる化合物は揮発性であり、反応混合物から分離し、任意に、蒸留によって精製することができる。
xは、1、2、3、4、5、6、7、8、9、10、11または12を示す、
で表されるビス(パーフルオロアルキル)ホスフィン酸無水物が調製される。
これらは、対称酸無水物である。
xは、1、2、3、4、5、6、7、8、9、10、11または12を示す、
で表されるビス(パーフルオロアルキル)ホスフィン酸(単数/複数)は、市販されているか、または、例えば公開されている明細書WO 03/087110またはWO 2010/012359に記載されたような方法によって、標準的な合成方法により調製することができる。
xは、2、3、4、5、6、7、8、9、10、11または12を示す、
で表されるビス(パーフルオロアルキル)ホスフィン酸無水物に関する。
xは、好ましくは3、4、5、6、7、8、9、10、11または12、特に好ましくは2、3、4、5、6、7または8、極めて特に好ましくは2、3、4または5あるいは極めて特に好ましくは3、4、6または12を表す。特に、xは好ましくは2および4、極めて特に好ましくは4を表す。
− ビス(パーフルオロアルキル)ホスフィニルクロリド、特に式III
− ビス(パーフルオロアルキル)ホスフィニルブロミド、特に式IV
アルキルは1〜4個のC原子を有する直鎖または分枝アルキル基を示す、で表されるもの、
− N,N−ジアルキルビス(パーフルオロアルキル)ホスフィニルアミンまたは−アミド、特に式VI
Rは、各場合において、互いに独立して、Hあるいは1〜12個のC原子を有する直鎖または分枝アルキル基を示す、で表されるもの、
− ビス(パーフルオロアルキル)ホスフィニルイソチオシアナート、特に式VIII
1〜4個のC原子を有する直鎖(もしくは同義的に直線状)または分枝アルキル基は、例えば、メチル、エチル、n−プロピル、イソプロピル基、n−ブチル、sec−ブチルまたはtert−ブチルである。1〜12個のC原子を有する直線状または分枝アルキル基としては、1〜4個のC原子を有する直線状または分枝アルキル基の態様、例えばn−ペンチル、n−ヘキシル、n−ヘプチル、n−オクチル、エチルヘキシル、n−ノニル基、n−デシル、n−ウンデシルまたはn−ドデシルが挙げられる。
Ktは無機または有機カチオンである、で表される化合物が得られる。
Ktである有機カチオンは、例えば、アンモニウムカチオン、スルホニウムカチオン、ホスホニウムカチオン、ウロニウムカチオン、チオウロニウムカチオン、グアニジニウムカチオンまたは複素環カチオンから選択される。
得られた物質は、ラマン分光法、元素分析およびNMR分光法により特徴付けられる。NMRスペクトルは、重水素ロック付きBrukaer Avance III分光計で、重水素化アセトン−D6中の溶液を測定する。種々の核の測定周波数は、以下のとおりである:1H:400.17MHz、19F:376.54MHz、11B:128.39MHz、31P:161.99MHzおよび13C:100.61MHz。参照は、以下の外部参照で行う:1Hおよび13CスペクトルではTMS;19FではCCl3F、ならびに1BスペクトルではBF3・Et2Oである。
8.8g(29.1mmol)のビス(ペンタフルオロエチル)ホスフィン酸、(C2F5)2P(O)OHを、16.8g(118mmol)の五酸化リン、P2O5に添加し、該混合物を還流下、210℃(油浴温度)で6時間加熱する。続いて、無色透明の液体を減圧真空(P=100mbar)で留去する。沸点:78℃(100mbar)。ビス(ペンタフルオロエチル)ホスフィン酸無水物、(C2F5)2(O)POP(O)(C2F5)2の収率は、用いたビス(ペンタフルオロエチル)ホスフィン酸に基づいて、7.2g(84%)である。
7.0g(14.0mmol)のビス(パーフルオロブチル)ホスフィン酸(C4F9)2P(O)OHを、25mlの1,1,1,3,3−ペンタフルオロブタンに溶解し、7.9g(55.7mmol)の五酸化リンP2O5、を添加し、該混合物を還流下、60℃で4日間加熱する。分別蒸留後、3.3gのビス(パーフルオロブチル)ホスフィン酸無水物が透明な無色の液体として得られる。これは、用いたビス(ノナフルオロブチル)ホスフィン酸に基づいて、48%の収率に相当する。
沸点:77℃(0.6mbar)。
A:
ビス(ペンタフルオロエチル)ホスフィニルクロリド:
A:
ビス(ペンタフルオロエチル)ホスフィン酸トリメチルシリルエーテル:
0.58g(4.5mmol)のジブチルアミン(C4H9)2NHを、1.21g(2.1mmol)のビス(ペンタフルオロエチル)ホスフィン酸無水物(C2F5)2(O)POP(O)(C2F5)2に0℃でゆっくり添加し、混合物を15分間攪拌する。続く真空蒸留後、0.65gのN、N−ジブチルビス(ペンタフルオロエチル)ホスフィニルアミド(C2F5)2P(O)N(C4H9)2が得られ、これは76%の収率に相当する。
A:
0.97g(14.9mmol)の細かく粉砕したシアン化カリウムは、最初に19.4gのスルホランに導入し、60℃で、終夜、真空中で攪拌し、揮発性成分を取り除く。反応混合物を30℃に冷却後、12.43g(21.2mmol)のビス(ペンタフルオロエチル)ホスフィン酸無水物(C2F5)2(O)POP(O)(C2F5)2を添加し、混合物をこの温度で24時間撹拌する。続いて、揮発性成分を、−196℃に冷却したフラスコに、真空中で凝縮する。ビス(ペンタフルオロエチル)ホスフィン酸無水物とビス(ペンタフルオロエチル)ホスフィニルシアニドとのモル比2:3からなる7.7gの凝縮された混合物を−40℃まで加温し、3.4gのビス(ペンタフルオロエチル)ホスフィニルシアニド(C2F5)2P(O)CNを、真空中、−196℃まで冷却した受容器で凝縮する。これは、73%の収率(用いたシアン化カリウムに基づいて)に相当する。
Claims (4)
- ビス(パーフルオロアルキル)ホスフィン酸と五酸化リンとの反応による、ビス(パーフルオロアルキル)ホスフィン酸無水物の調製方法。
- ビス(パーフルオロアルキル)ホスフィン酸が、
式II
に従うことを特徴とする、請求項1に記載の方法。 - 式I
で表されるビス(パーフルオロアルキル)ホスフィン酸無水物が調製されることを特徴とする、請求項1または2に記載の方法。 - 反応が、20℃〜250℃の温度で行われることを特徴とする、請求項1〜3のいずれか一項に記載の方法。
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