CN110903316B - 一种膦酸酯类化合物及其制备方法与应用 - Google Patents
一种膦酸酯类化合物及其制备方法与应用 Download PDFInfo
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- CN110903316B CN110903316B CN201911231702.XA CN201911231702A CN110903316B CN 110903316 B CN110903316 B CN 110903316B CN 201911231702 A CN201911231702 A CN 201911231702A CN 110903316 B CN110903316 B CN 110903316B
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- trifluoromethanesulfonate
- compound
- reaction
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- aryl
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- -1 Phosphonate compound Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000012074 organic phase Substances 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 20
- 235000011009 potassium phosphates Nutrition 0.000 claims description 20
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- GRJHONXDTNBDTC-UHFFFAOYSA-N phenyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CC=C1 GRJHONXDTNBDTC-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- OAMXTIOQCFCLRR-UHFFFAOYSA-N (3-methoxyphenyl) trifluoromethanesulfonate Chemical compound COC1=CC=CC(OS(=O)(=O)C(F)(F)F)=C1 OAMXTIOQCFCLRR-UHFFFAOYSA-N 0.000 claims description 3
- UNYUEWLAYXLXHK-UHFFFAOYSA-N (4-bromophenyl) trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=C(Br)C=C1 UNYUEWLAYXLXHK-UHFFFAOYSA-N 0.000 claims description 3
- KKETVWGQXANCHL-UHFFFAOYSA-N (4-cyanophenyl) trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=C(C#N)C=C1 KKETVWGQXANCHL-UHFFFAOYSA-N 0.000 claims description 3
- XSTNIRWDULKNJE-UHFFFAOYSA-N (4-methoxyphenyl) trifluoromethanesulfonate Chemical compound COC1=CC=C(OS(=O)(=O)C(F)(F)F)C=C1 XSTNIRWDULKNJE-UHFFFAOYSA-N 0.000 claims description 3
- DJHQEXVEXPOXGG-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl] trifluoromethanesulfonate Chemical compound FC(F)(F)C1=CC=C(OS(=O)(=O)C(F)(F)F)C=C1 DJHQEXVEXPOXGG-UHFFFAOYSA-N 0.000 claims description 3
- JMCNGFNJWDJIIV-UHFFFAOYSA-N dibutyl(oxo)phosphanium Chemical compound CCCC[P+](=O)CCCC JMCNGFNJWDJIIV-UHFFFAOYSA-N 0.000 claims description 3
- RBOGJRXPKONDGC-UHFFFAOYSA-N (2-methylphenyl) trifluoromethanesulfonate Chemical compound CC1=CC=CC=C1OS(=O)(=O)C(F)(F)F RBOGJRXPKONDGC-UHFFFAOYSA-N 0.000 claims description 2
- JKQWRNLLUVAYLV-UHFFFAOYSA-N (3-methylphenyl) trifluoromethanesulfonate Chemical compound CC1=CC=CC(OS(=O)(=O)C(F)(F)F)=C1 JKQWRNLLUVAYLV-UHFFFAOYSA-N 0.000 claims description 2
- VLTNGOOPPMFDHK-UHFFFAOYSA-N (4-butylphenyl) trifluoromethanesulfonate Chemical compound CCCCC1=CC=C(OS(=O)(=O)C(F)(F)F)C=C1 VLTNGOOPPMFDHK-UHFFFAOYSA-N 0.000 claims description 2
- NIIJLHLBNABUFL-UHFFFAOYSA-N (4-chlorophenyl) trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=C(Cl)C=C1 NIIJLHLBNABUFL-UHFFFAOYSA-N 0.000 claims description 2
- FEHSEZUGDOTYAE-UHFFFAOYSA-N (4-fluorophenyl) trifluoromethanesulfonate Chemical compound FC1=CC=C(OS(=O)(=O)C(F)(F)F)C=C1 FEHSEZUGDOTYAE-UHFFFAOYSA-N 0.000 claims description 2
- LNLGXWZOBTUQSC-UHFFFAOYSA-N (4-tert-butylphenyl) trifluoromethanesulfonate Chemical compound CC(C)(C)C1=CC=C(OS(=O)(=O)C(F)(F)F)C=C1 LNLGXWZOBTUQSC-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- MDWRQYBWVTXIIJ-UHFFFAOYSA-N naphthalen-2-yl trifluoromethanesulfonate Chemical compound C1=CC=CC2=CC(OS(=O)(=O)C(F)(F)F)=CC=C21 MDWRQYBWVTXIIJ-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- MWYXORYWUKRJEX-UHFFFAOYSA-N bis(2-methoxyphenyl)-oxophosphanium Chemical compound COC1=CC=CC=C1[P+](=O)C1=CC=CC=C1OC MWYXORYWUKRJEX-UHFFFAOYSA-N 0.000 claims 1
- ZHIPXAFNKGZMSC-UHFFFAOYSA-N bis(4-methylphenyl)-oxophosphanium Chemical compound C1=CC(C)=CC=C1[P+](=O)C1=CC=C(C)C=C1 ZHIPXAFNKGZMSC-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- 239000008346 aqueous phase Substances 0.000 description 19
- 239000012043 crude product Substances 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 18
- 238000000926 separation method Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000004821 distillation Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- XAFMVNOFAMDPMI-UHFFFAOYSA-N CCCCC1=CC=C(C=C1)C2=CC=CC=C2P(=O)(C3=CC=CC=C3)O Chemical compound CCCCC1=CC=C(C=C1)C2=CC=CC=C2P(=O)(C3=CC=CC=C3)O XAFMVNOFAMDPMI-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KKENJBBLHSMHHZ-UHFFFAOYSA-N Cc1ccc(O[PH2]=O)cc1 Chemical compound Cc1ccc(O[PH2]=O)cc1 KKENJBBLHSMHHZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 231100000086 high toxicity Toxicity 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- CRWZFIKUPVUVFU-UHFFFAOYSA-N 1-diphenylphosphoryloxy-3-methylbenzene Chemical compound CC1=CC=CC(OP(=O)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 CRWZFIKUPVUVFU-UHFFFAOYSA-N 0.000 description 2
- MXUTXGVBQWSBJT-UHFFFAOYSA-N 1-diphenylphosphoryloxy-4-methylbenzene Chemical compound C1=CC(C)=CC=C1OP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MXUTXGVBQWSBJT-UHFFFAOYSA-N 0.000 description 2
- YAVDSKOLCPTYDQ-UHFFFAOYSA-N 2-diphenylphosphoryloxynaphthalene Chemical compound O=P(Oc1ccc2ccccc2c1)(c1ccccc1)c1ccccc1 YAVDSKOLCPTYDQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RZDGARCZXPYMPG-UHFFFAOYSA-N C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)Br)O Chemical compound C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)Br)O RZDGARCZXPYMPG-UHFFFAOYSA-N 0.000 description 2
- KQCYGWWELRQKEB-UHFFFAOYSA-N C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)C#N)O Chemical compound C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)C#N)O KQCYGWWELRQKEB-UHFFFAOYSA-N 0.000 description 2
- GEOKTZIEKQYHHL-UHFFFAOYSA-N C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)C(F)(F)F)O Chemical compound C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)C(F)(F)F)O GEOKTZIEKQYHHL-UHFFFAOYSA-N 0.000 description 2
- PYOQEKYWIYVTCN-UHFFFAOYSA-N CC(C)(C)C(C=C1)=CC=C1C(C=CC=C1)=C1P(C1=CC=CC=C1)(O)=O Chemical compound CC(C)(C)C(C=C1)=CC=C1C(C=CC=C1)=C1P(C1=CC=CC=C1)(O)=O PYOQEKYWIYVTCN-UHFFFAOYSA-N 0.000 description 2
- YGGWXWXBKAKKFV-UHFFFAOYSA-N COC1=CC=C(C=C1)C2=CC=CC=C2P(=O)(C3=CC=CC=C3)O Chemical compound COC1=CC=C(C=C1)C2=CC=CC=C2P(=O)(C3=CC=CC=C3)O YGGWXWXBKAKKFV-UHFFFAOYSA-N 0.000 description 2
- RIWSSEIAZYDHIC-UHFFFAOYSA-N COC1=CC=CC(=C1)C2=CC=CC=C2P(=O)(C3=CC=CC=C3)O Chemical compound COC1=CC=CC(=C1)C2=CC=CC=C2P(=O)(C3=CC=CC=C3)O RIWSSEIAZYDHIC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- IDLYBOQBLMESMY-UHFFFAOYSA-N [PH2](OC1=C(C=CC=C1)OC)=O Chemical compound [PH2](OC1=C(C=CC=C1)OC)=O IDLYBOQBLMESMY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- RLUVFZVHGFGPBK-UHFFFAOYSA-N dibutylphosphoryloxybenzene Chemical compound CCCCP(=O)(CCCC)OC1=CC=CC=C1 RLUVFZVHGFGPBK-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XXSBXVHIYGQWDV-UHFFFAOYSA-N (4-methylphenyl) trifluoromethanesulfonate Chemical compound CC1=CC=C(OS(=O)(=O)C(F)(F)F)C=C1 XXSBXVHIYGQWDV-UHFFFAOYSA-N 0.000 description 1
- AMKDSUBPBQOGAN-UHFFFAOYSA-N 1-diphenylphosphoryloxy-2-methylbenzene Chemical compound CC1=CC=CC=C1OP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 AMKDSUBPBQOGAN-UHFFFAOYSA-N 0.000 description 1
- QSROKLAAJQVMQY-UHFFFAOYSA-N 1-diphenylphosphoryloxy-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1OP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 QSROKLAAJQVMQY-UHFFFAOYSA-N 0.000 description 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000003383 Atherton-Todd reaction Methods 0.000 description 1
- GPNOKZLGWRNBDJ-UHFFFAOYSA-N C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)Cl)O Chemical compound C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)Cl)O GPNOKZLGWRNBDJ-UHFFFAOYSA-N 0.000 description 1
- DWEPWEXXVQCKIA-UHFFFAOYSA-N C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)F)O Chemical compound C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2C3=CC=C(C=C3)F)O DWEPWEXXVQCKIA-UHFFFAOYSA-N 0.000 description 1
- YISLGXWOMJKMAQ-UHFFFAOYSA-N CC(C=CC=C1)=C1C(C=CC=C1)=C1P(C1=CC=CC=C1)(O)=O Chemical compound CC(C=CC=C1)=C1C(C=CC=C1)=C1P(C1=CC=CC=C1)(O)=O YISLGXWOMJKMAQ-UHFFFAOYSA-N 0.000 description 1
- PHGRKTBHLLCFND-UHFFFAOYSA-N CC1=CC=C(C=C1)[PH2]=O Chemical compound CC1=CC=C(C=C1)[PH2]=O PHGRKTBHLLCFND-UHFFFAOYSA-N 0.000 description 1
- UVKFLQUHNOHBJU-UHFFFAOYSA-N COC1=C(C=CC=C1)[PH2]=O Chemical compound COC1=C(C=CC=C1)[PH2]=O UVKFLQUHNOHBJU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000005819 Potassium phosphonate Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- CIJWIJSYZZLMGD-UHFFFAOYSA-N diphenylphosphoryloxybenzene Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)OC1=CC=CC=C1 CIJWIJSYZZLMGD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 244000053095 fungal pathogen Species 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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Abstract
本发明提供了一种膦酸酯类化合物及其制备方法与应用,所述方法包括如下步骤:在氮气氛围下,将P(O)‑H化合物、芳基三氟甲烷磺酸酯类化合物、碱试剂与有机溶剂混合,在80~130℃下搅拌反应15~24h,反应结束后经冷却、洗涤和萃取,得到有机相;对所得有机相进行干燥和蒸馏,得到膦酸酯类化合物;其中,P(O)‑H化合物、芳基三氟甲烷磺酸酯类化合物与碱试剂的摩尔比为1~3:1:2~3。该方法具有原料简单易得、反应条件简单、官能团兼容性广、产率高、适用性广的优点,所得膦酸酯类化合物的结构式如式(Ⅰ)所示,将其应用在锂离子萃取领域的萃取率在53%以上。
Description
技术领域
本发明涉及有机合成领域,特别涉及一种膦酸酯类化合物及其制备方法与应用。
背景技术
膦酸酯类化合物是一种重要的有机合成原料和中间体,广泛应用于工业材料的生产、有机磷配体的合成、医药化学等领域,并且具有广泛的生物学特性。如中国专利CN1974612公开了将磷酸酯类化合物作为给电子体用于制备聚丙烯催化剂;中国专利CN106967120A公开了含生物碱的磷酸酯类化合物对致病病原真菌和病毒具有良好的抑制作用,为新农药的研发和创制提供重要的科学基础;中国专利CN108218937A公开了核苷氨基磷酸酯类化合物作为治疗病毒感染性疾病治疗药物的用途。近年来,磷酸酯类化合物在溶剂萃取分离、矿物浮选领域也有重要应用。中国专利CN105149107A公开了磷酸酯类化合物在含钙矿物浮选中的应用;中国专利CN107955036A公开了磷酸酯类离子液体作为锂萃取剂的应用。
目前,已有大量的文献报道了膦酸酯类化合物的合成方法。传统的方法通常使用卤化磷与酚类物质进行亲核取代反应制取(Fukuto T R,Metcalf R L.Journal of theAmerican Chemical Society,1959,81(2):372-377),这些卤化磷试剂具有毒性大、活性高,对水氧敏感的特点,不易于保存和操作。磷卤化合物作为反应中间体的Atherton-Todd反应(P(O)-H化合物与醇或酚在四氯化碳和碱的作用下反应)也广泛用于合成此类物质(Atherton F R,Openshaw H T,Todd A R.Journal of the Chemical Society,1945(SEP):660-663;Li S,Chen T,Saga Y,et al.RSC Advances,2015,5(88):71544-71546.)。与磷卤试剂相比,P(O)-H化合物简单易得,绿色稳定,是合成有机磷化合物的重要原料。近年来,通过过渡金属催化P(O)-H化合物与亲核试剂直接脱氢偶联反应制备有机磷化合物受到广泛关注,采用铁催化可实现P(O)-H化合物与醇类化合物交叉脱氢偶联合成重要的膦酸酯类化合物(Li C,Chen T,Han L B.Dalton Transactions,2016,45(38):14893-14897)。中国专利CN107522741A公开了一种以廉价易得的醇和H-亚磷酸酯类化合物作为反应的起始原料,二价钴盐和N-羟基邻苯二甲酰亚胺为共催化剂,氧气为氧化剂,通过需氧氧化偶联来高效合成磷酸酯类目标化合物的新方法。中国专利CN106749396A公开了一种高效、高选择性合成含不同取代官能团的有机膦酸酯类衍生物的方法,其采用多肽催化剂作为缩合试剂,以含P(O)-OH类化合物与醇作为反应底物,通过催化剂、氧化剂、碱和活化剂以及有机溶剂的综合选择与协同,从而可以高产率得到二苯基膦酸酯化合物的方法。三氟甲烷磺酸酯类化合物及其衍生物是合成芳基膦酸酯类化合物的重要原料。以二烷基膦酸酯和二芳基碘三氟甲磺酸盐为原料,铜催化O-芳基化反应可用于制备混合芳基膦酸盐(M,Feringa B L.Journal of the American Chemical Society,2014,136(28):9894-9897)。在铜盐和CCl4作用下,二芳基碘三氟甲磺酸盐可与P(O)-OH化合物交叉偶联合成膦酸酯类化合物,(Xiong B,Feng X,Zhu L,et al.ACS Catalysis,2014,5(2):537-543)。此外,在零下33℃下,将简单易得的芳基三氟甲烷磺酸酯滴加至二乙基亚磷酸钾的液氨溶液(金属钾与亚磷酸二乙酯在液氨中制得)中可直接得到芳基磷酸酯类化合物,(Creary X,Benage B,Hilton K.The Journal of Organic Chemistry,1983,48(17):2887-2891)。
上述反应存在以下不足:①磷卤试剂毒性大,对水氧敏感,反应条件苛刻;②需添加过渡金属催化剂及配体,成本相对较高,且不够绿色环保;③部分反应需使用金属钾,反应安全性差。
针对上述研究方法的不足,有必要提供一种简单高效,无需过渡金属催化剂及配体参与的合成膦酸酯类化合物的新途径,提高安全性和应用价值。
发明内容
本发明提供了一种膦酸酯类化合物及其制备方法与应用,其目的是为了提供一种简单、高效、安全,且无需过渡金属催化剂及配体参与的合成膦酸酯类化合物的方法,并将其应用于锂离子的萃取。
为了达到上述目的,本发明提供如下技术方案:
一种膦酸酯类化合物及其制备方法,所述制备方法包括如下步骤:
在氮气氛围下,将P(O)-H化合物、芳基三氟甲烷磺酸酯类化合物、碱试剂与有机溶剂混合,在80~130℃下搅拌反应15~24h,反应结束后经冷却、洗涤和萃取,得到有机相;对所得有机相进行干燥和蒸馏,得到膦酸酯类化合物;
其中,P(O)-H化合物、芳基三氟甲烷磺酸酯类化合物与碱试剂的摩尔比为1~3:1:2~3。
优选地,所述P(O)-H化合物为二苯基膦氧、二正丁基膦氧、双4-甲基苯基氧化膦或双2-甲氧基苯基氧化膦。
优选地,所述的芳基三氟甲烷磺酸酯类化合物为苯酚三氟甲烷磺酸酯、2-甲基苯酚三氟甲烷磺酸酯、3-甲基苯酚三氟甲烷磺酸酯、对甲基苯酚三氟甲烷磺酸酯、对甲氧基苯酚三氟甲烷磺酸酯、3-甲氧基苯酚三氟甲烷磺酸酯、4-正丁基苯酚三氟甲烷磺酸酯、4-叔丁基苯酚三氟甲烷磺酸酯、4-三氟甲基苯酚三氟甲烷磺酸酯、4-氰基苯酚三氟甲烷磺酸酯、4-氟苯酚三氟甲烷磺酸酯、4-氯苯酚三氟甲烷磺酸酯、4-溴苯酚三氟甲烷磺酸酯或2-萘基三氟甲烷磺酸酯。
优选地,所述碱试剂为磷酸钾、碳酸铯、碳酸钠、叔丁醇钠和叔丁醇钾中的一种或多种。
优选地,所述有机溶剂为甲苯、N,N-二甲基甲酰胺、1,4-二氧六环和正己烷或二氯甲烷中的一种或多种。
优选地,所述萃取具体为用萃取剂萃取,所述萃取剂为二氯甲烷、乙酸乙酯和三氯甲烷中的一种或多种。
本发明还提供一种上述方法制备而成的膦酸酯类化合物,所述膦酸酯类化合物的结构式如式(Ⅰ)所示:
其中,R1是芳基或脂肪基;R2是芳基或脂肪基,R3是芳基或脂肪基。
本发明还提供一种上述膦酸酯类化合物在锂离子萃取中的应用。
优选地,所述应用具体步骤为:
(1)首先取膦酸酯类化合物和煤油混合作为有机相;其中,膦酸酯类化合物的质量分数为5%~15%;
(2)然后按照铁与锂的摩尔比为1~2的比例配置水相;
(3)最后将有机相与水相按照体积比为0.5~2的比例进行萃取。
优选地,所述萃取温度为20~25℃。
本发明的上述方案有如下的有益效果:
本发明所提供了一种直接以P(O)-H化合物与芳基三氟甲烷磺酸酯类化合物一步制备膦酸酯类化合物的方法。与磷卤试剂相比,使用P(O)-H化合物简单易得、更为绿色稳定,原子经济性更高。并且该反应条件简单,只需加入一定量的磷酸钾即可使反应高效进行,反应产率为56~94%。同时该反应也具有官能团兼容性广、多种底物均可高效反应的优点。该方法避免了其他合成方法中所存在的原料毒性大、反应条件较为苛刻、底物适用性较窄的问题。另外,该方法也避免了过渡金属的使用,解决了过渡金属成本较高以及部分过渡金属在空气下较为敏感使得操作复杂等问题。
相比于传统的使用醇、酮类萃取体系,有机磷类萃取体系和胺盐、偶氮类离子螯合一缔合萃取体系,本发明提供的膦酸酯类化合物作为萃取剂的合成方法简单,且膦酸酯类化合物在水中溶解度非常小,使其基本不在有机相中损失。另外,该萃取体系所使用FeCl3作为协萃剂,成本较低,能够在酸性条件下将锂离子的萃取率达到53%以上。
附图说明
图1为合成有机磷酸酯类化合物的反应式
图2为实施例1所得苯基-二苯基次膦酸酯的核磁氢谱图;
图3为实施例2所得2-甲基苯基-二苯基次膦酸酯的核磁氢谱图;
图4为实施例3所得3-甲基苯基-二苯基次膦酸酯的核磁氢谱图;
图5为实施例4所得4-甲基苯基-二苯基次膦酸酯的核磁氢谱图;
图6为实施例5所得4-甲氧基苯基-二苯基次膦酸酯的核磁氢谱图;
图7为实施例6所得3-甲氧基苯基-二苯基次膦酸酯的核磁氢谱图;
图8为实施例7所得4-正丁基苯基-二苯基次膦酸酯的核磁氢谱图;
图9为为实施例8所得4-叔丁基苯基-二苯基次膦酸酯的核磁氢谱图;
图10为为实施例9所得4-三氟甲基苯基-二苯基次膦酸酯的核磁氢谱图;
图11为实施例10所得4-氰基苯基-二苯基次膦酸酯的核磁氢谱图;
图12为实施例11所得4-氟苯基-二苯基次膦酸酯的核磁氢谱图;
图13为实施例12所得4-氯苯基-二苯基次膦酸酯的核磁氢谱图;
图14为实施例13所得4-溴苯基-二苯基次膦酸酯的核磁氢谱图;
图15为实施例14所得2-萘基-二苯基次膦酸酯的核磁氢谱图;
图16为实施例15所得苯基-二正丁基次膦酸酯的核磁氢谱图;
图17为实施例16所得苯基-双(4-甲基苯基)次膦酸酯的核磁氢谱图;
图18为实施例17所得苯基-双(2-甲氧基苯基)次膦酸酯的核磁氢谱图。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚,下面将结合具体实施例进行详细描述。
本发明提供的由P(O)-H化合物与芳基三氟甲烷磺酸酯类化合物合成膦酸酯类化合物的合成步骤为:
(1)在氮气氛围下,取芳基三氟甲烷磺酸酯类化合物、碱试剂、P(O)-H化合物及有机溶剂置于反应容器中,混合;
(2)在氮气氛围下,于反应温度为80~130℃下,持续搅拌反应15~24h,反应结束后冷却至室温;
(3)水洗,除去反应中过量的碱和生成的盐;
(4)用萃取剂萃取水相得到含粗产品的有机相,采用干燥剂对有机相进行干燥后减压蒸馏除去溶剂得到膦酸酯类化合物。
(5)粗产品经柱色谱分离,即得目标产物。合成步骤如图1所示:
实施例1
本实施例提供一种苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率94%。1H NMR(400MHz,CDCl3)δ7.82(dd,J=11.8,7.7Hz,4H),7.48–7.39(m,6H),7.219–7.11(m,4H),7.00(t,J=6.9Hz,1H)。
实施例2
本实施例提供一种2-甲基苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol2-甲基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率73%。1H NMR(400MHz,CDCl3)δ7.84–7.78(m,4H),7.48–7.36(m,6H),7.17(d,J=8.1Hz,1H),7.06(d,J=7.1Hz,1H),6.96–6.87(m,2H),2.23(s,3H)。
实施例3
本实施例提供一种3-甲基苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol3-甲基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率83%。1H NMR(400MHz,CDCl3)δ7.94–7.89(dm,4H),7.57–7.45(m,6H),7.14–7.08(m,2H),7.00(d,J=8.1Hz,1H),6.90(d,J=7.5Hz,1H),2.29(s,3H)。
实施例4
本实施例提供一种4-甲基苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol 4-甲基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率73%。1H NMR(400MHz,CDCl3)δ7.81(dd,J=12.5,7.2Hz,4H),7.46–7.35(m,6H),6.97(dd,J=24.5,8.4Hz,4H),2.16(s,3H)。
实施例5
本实施例提供一种4-甲氧基苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol 4-甲氧基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率75%。1H NMR(400MHz,CDCl3)δ7.92–7.87(m,4H),7.54–7.43(m,6H),7.13–7.11(m,2H),6.76–6.74(m,2H),3.70(s,3H)。
实施例6
本实施例提供一种3-甲氧基苯基-二苯基次膦酸酯的制备方法,具体如下:
在反应器中加入0.30mmol二苯基氧化膦,0.20mmol3-甲氧基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率87%。1H NMR(400MHz,CDCl3)δ7.81(dd,J=12.5,7.0Hz,4H),7.48–7.30(m,6H),7.03(t,J=8.1Hz,1H),6.70(d,J=8.1Hz,2H),6.54(d,J=9.2Hz,1H),3.62(s,3H)。
实施例7
本实施例提供一种4-正丁基苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol4-正丁基基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率90%。1H NMR(400MHz,CDCl3)δ7.83–7.78(m,4H),7.46–7.35(m,6H),7.02–6.93(m,4H),2.42(t,J=8.0Hz,2H),1.47–1.40(m,2H),1.26–1.17(m,2H),0.81(t,J=7.3Hz,3H)。IR:3447.57,2923.68,1507.86,1444.21,1223.18,1212.66,921.50,728.78cm-1。
实施例8
本实施例提供一种4-叔丁基苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol 4-叔丁基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率68%。1H NMR(400MHz,CDCl3)δ7.84–7.79(m,4H),7.47–7.35(m,6H),7.18–7.15(m,2H),7.03–7.00(m,2H),1.16(s,9H)。
实施例9
本实施例提供一种4-三氟甲基苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol 4-三氟甲基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率89%。1H NMR(400MHz,CDCl3)δ7.82(dd,J=12.1,7.8Hz,4H),7.49–7.41(m,8H),7.25(d,J=8.2Hz,2H).
实施例10
本实施例提供一种4-氰基苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol 4-氰基苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率78%。1H NMR(400MHz,CDCl3)δ7.80(dd,J=12.7,7.7Hz,4H),7.52–7.39(m,8H),7.26(d,J=8.6Hz,2H)。
实施例11
本实施例提供一种4-氟苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol 4-氟苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率79%。1H NMR(400MHz,CDCl3)δ7.83–7.78(m,4H),7.49–7.37(m,6H),7.09–7.06(m,2H),6.86–6.82(m,2H)。
实施例12
本实施例提供一种4-氯苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol 4-氯苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率58%。1H NMR(400MHz,CDCl3)δ7.81–7.76(m,4H),7.47–7.35(m,6H),7.11–7.04(m,4H)。
实施例13
本实施例提供一种4-溴苯基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol 4-溴苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到110℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率83%。1H NMR(400MHz,CDCl3)δ7.79(dd,J=12.4,7.6Hz,4H),7.48–7.38(m,6H),7.26(d,J=8.6Hz,2H),7.02(d,J=8.6Hz,2H)。
实施例14
本实施例提供一种2-萘基-二苯基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二苯基氧化膦,0.20mmol2-萘基三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到110℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率61%。1HNMR(400MHz,CDCl3)δ8.20(d,J=13.9Hz,1H),7.82–7.77(m,3H),7.65–7.38(m,13H)。
实施例15
本实施例提供一种苯基-二正丁基次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol二正丁基氧化膦,0.20mmol苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到100℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率56%。1HNMR(400MHz,CDCl3)δ7.26–7.20(m,2H),7.15–7.05(m,3H),1.86–1.70(m,4H),1.61–1.50(m,4H),1.39–1.30(m,4H),0.84(t,J=7.3Hz,6H)。
实施例16
本实施例提供一种苯基-双(4-甲基苯基)次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol双4-甲基苯氧化膦,0.20mmol苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到110℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率71%。1H NMR(400MHz,CDCl3)δ7.68(dd,J=12.3,8.0Hz,4H),7.19–7.10(m,8H),6.98(t,J=6.7Hz,1H),2.30(s,6H)。
实施例17
本实施例提供一种苯基-双(2-甲氧基-苯基)次膦酸酯的制备方法,具体如下:
在氮气氛围下,在反应器中加入0.30mmol双2-甲基-邻-苯基氧化膦,0.20mmol苯酚三氟甲烷磺酸酯,0.50mmol磷酸钾,1.5mL甲苯溶剂,封管后加热到110℃,持续搅拌20h,停止反应,冷却至室温,水洗除去反应中过量的碱和生成的盐,用二氯甲烷萃取水相得到有机相,无水硫酸钠干燥,减压蒸馏除去溶剂,粗产品经柱色谱分离即得目标产物,分离收率75%。1H NMR(400MHz,CDCl3)δ7.95–7.89(m,2H),7.38(t,J=7.5Hz,2H),7.14–7.09(m,4H),6.98–6.94(m,3H),6.77–6.73(m,2H),3.54(s,6H).IR:3431.41,2926.33,1484.49,1592.14,1198.69,921.29,770.55,584.58,499.63cm-1。
实施例18
4-正丁基苯基-二苯基次膦酸酯对金属离子萃取性能的测试:
实验采用合成例7中的4-正丁基苯基-二苯基次膦酸酯对金属离子锂离子进行萃取实验。萃取的基本流程为:
(1)称取0.32g 4-正丁基苯基-二苯基次膦酸酯溶于4ml煤油中配制成质量分数为10%的有机相,
(2)称取1.22g LiCl于100ml容量瓶中,加入蒸馏水定容,配制为溶度为2g/L的锂离子标准液。
(3)按照铁与锂的摩尔比为1.5配置水相,需要配制标准铁离子溶液,称取11.4g六水合三氯化铁溶于100ml容量瓶中,加蒸馏水定容至刻度线。
(4)在(2)的锂离子标准液中添加上述(3)标准铁离子溶液,使水相中铁锂比为1.5(上述FeCl3为萃取体系的添加剂,与次膦酸酯形成螯合作用,增加锂离子的萃取效果)。
(5)将上述水相和有机相以1:1的体积比混合,在20~25℃下,在锥形瓶中用手用力震荡30分钟静置待液体分层后,取下层水相,稀释100倍后,用原子吸光光度计检测萃取前后锂离子的浓度。
(6)经过原子吸光光度计检测,萃取前锂离子的浓度为18.95mg/L,萃取后锂离子的浓度为8.74mg/L,4-正丁基苯基-二苯基次膦酸酯对锂离子的萃取率达到了53.4%。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明所述原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (3)
1.一种次膦酸酯化合物的制备方法,其特征在于,所述制备方法包括如下步骤:
在氮气氛围下,将P(O)-H化合物、芳基三氟甲烷磺酸酯类化合物、碱试剂与有机溶剂混合,在80~130℃下搅拌反应15~24h,反应结束后经冷却、洗涤和萃取,得到有机相;对所得有机相进行干燥和蒸馏,得到次膦酸酯化合物;
其中,P(O)-H化合物、芳基三氟甲烷磺酸酯类化合物与碱试剂的摩尔比为1~3:1:2~3;
其中,所述P(O)-H化合物为二苯基膦氧、二正丁基膦氧、双(4-甲基苯基)氧化膦或双(2-甲氧基苯基)氧化膦;
其中,所述碱试剂为磷酸钾、碳酸铯、叔丁醇钠和叔丁醇钾中的一种或多种;
其中,所述的芳基三氟甲烷磺酸酯类化合物为苯酚三氟甲烷磺酸酯、2-甲基苯酚三氟甲烷磺酸酯、3-甲基苯酚三氟甲烷磺酸酯、对甲基苯酚三氟甲烷磺酸酯、对甲氧基苯酚三氟甲烷磺酸酯、3-甲氧基苯酚三氟甲烷磺酸酯、4-正丁基苯酚三氟甲烷磺酸酯、4-叔丁基苯酚三氟甲烷磺酸酯、4-三氟甲基苯酚三氟甲烷磺酸酯、4-氰基苯酚三氟甲烷磺酸酯、4-氟苯酚三氟甲烷磺酸酯、4-氯苯酚三氟甲烷磺酸酯、4-溴苯酚三氟甲烷磺酸酯或2-萘基三氟甲烷磺酸酯。
2.根据权利要求1所述制备方法,其特征在于,所述有机溶剂为甲苯、N,N-二甲基甲酰胺、1,4-二氧六环和正己烷或二氯甲烷中的一种或多种。
3.根据权利要求1所述制备方法,其特征在于,所述萃取用萃取剂进行萃取,所述萃取剂为二氯甲烷、乙酸乙酯和三氯甲烷中的一种或多种。
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CN107619934A (zh) * | 2016-07-15 | 2018-01-23 | 中国科学院上海有机化学研究所 | 一种萃取组合物、萃取体系及其应用 |
-
2019
- 2019-12-05 CN CN201911231702.XA patent/CN110903316B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107619934A (zh) * | 2016-07-15 | 2018-01-23 | 中国科学院上海有机化学研究所 | 一种萃取组合物、萃取体系及其应用 |
CN107082789A (zh) * | 2017-03-06 | 2017-08-22 | 湖南理工学院 | 一种以含p(o)‑oh类化合物与酚高效酯化制备有机磷酸酯类化合物的方法 |
Non-Patent Citations (3)
Title |
---|
"Base-promoted selective O-phosphorylation of aryl triflates with P(O)-H compounds";Mingyue Wang等;《Tetrahedron Letters》;20200426;第61卷;第2页表1 * |
"Metal-free electrophilic phosphination of electron-rich arenes, arenols and aromatic thiols with diarylphosphine oxides";Tao Yuan等;《Org. Biomol. Chem.》;20171127;第16卷;第32页方案4 * |
Reaction of Triflates with Potassium Diethyl Phosphite.Formation of Phosphate Esters;Xavier Creary等;《J. Org. Chem.》;19830801;第48卷;第2887-2891页 * |
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