CN106543224A - A kind of synthetic method of carbonate-modified floride-free organophosphorus ligand - Google Patents
A kind of synthetic method of carbonate-modified floride-free organophosphorus ligand Download PDFInfo
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- CN106543224A CN106543224A CN201610960272.5A CN201610960272A CN106543224A CN 106543224 A CN106543224 A CN 106543224A CN 201610960272 A CN201610960272 A CN 201610960272A CN 106543224 A CN106543224 A CN 106543224A
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- floride
- carbonate
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- 239000003446 ligand Substances 0.000 title claims abstract description 36
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- -1 organic carbonate ester compounds Chemical class 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 14
- 238000004440 column chromatography Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000006837 decompression Effects 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- 229940125898 compound 5 Drugs 0.000 claims description 9
- 239000012044 organic layer Substances 0.000 claims description 9
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000007836 KH2PO4 Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 6
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005052 trichlorosilane Substances 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 3
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 2
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims 3
- 230000020477 pH reduction Effects 0.000 claims 2
- 238000005292 vacuum distillation Methods 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 29
- 238000003786 synthesis reaction Methods 0.000 abstract description 25
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 15
- 238000006073 displacement reaction Methods 0.000 abstract description 5
- 239000003863 metallic catalyst Substances 0.000 abstract description 5
- 125000002524 organometallic group Chemical group 0.000 abstract description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 5
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003495 polar organic solvent Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000017858 demethylation Effects 0.000 abstract 1
- 238000010520 demethylation reaction Methods 0.000 abstract 1
- 238000009432 framing Methods 0.000 abstract 1
- 230000000269 nucleophilic effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000012805 post-processing Methods 0.000 description 10
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 4
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000011260 aqueous acid Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 2
- SHAHPWSYJFYMRX-GDLCADMTSA-N (2S)-2-(4-{[(1R,2S)-2-hydroxycyclopentyl]methyl}phenyl)propanoic acid Chemical compound C1=CC([C@@H](C(O)=O)C)=CC=C1C[C@@H]1[C@@H](O)CCC1 SHAHPWSYJFYMRX-GDLCADMTSA-N 0.000 description 2
- KAFZOLYKKCWUBI-HPMAGDRPSA-N (2s)-2-[[(2s)-2-[[(2s)-1-[(2s)-3-amino-2-[[(2s)-2-[[(2s)-2-(3-cyclohexylpropanoylamino)-4-methylpentanoyl]amino]-5-methylhexanoyl]amino]propanoyl]pyrrolidine-2-carbonyl]amino]-5-(diaminomethylideneamino)pentanoyl]amino]butanediamide Chemical compound N([C@@H](CC(C)C)C(=O)N[C@@H](CCC(C)C)C(=O)N[C@@H](CN)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CC(N)=O)C(N)=O)C(=O)CCC1CCCCC1 KAFZOLYKKCWUBI-HPMAGDRPSA-N 0.000 description 2
- VIMMECPCYZXUCI-MIMFYIINSA-N (4s,6r)-6-[(1e)-4,4-bis(4-fluorophenyl)-3-(1-methyltetrazol-5-yl)buta-1,3-dienyl]-4-hydroxyoxan-2-one Chemical compound CN1N=NN=C1C(\C=C\[C@@H]1OC(=O)C[C@@H](O)C1)=C(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VIMMECPCYZXUCI-MIMFYIINSA-N 0.000 description 2
- IGVKWAAPMVVTFX-BUHFOSPRSA-N (e)-octadec-5-en-7,9-diynoic acid Chemical compound CCCCCCCCC#CC#C\C=C\CCCC(O)=O IGVKWAAPMVVTFX-BUHFOSPRSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TZYWCYJVHRLUCT-VABKMULXSA-N N-benzyloxycarbonyl-L-leucyl-L-leucyl-L-leucinal Chemical compound CC(C)C[C@@H](C=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)C)NC(=O)OCC1=CC=CC=C1 TZYWCYJVHRLUCT-VABKMULXSA-N 0.000 description 2
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
- RWWYLEGWBNMMLJ-YSOARWBDSA-N remdesivir Chemical compound NC1=NC=NN2C1=CC=C2[C@]1([C@@H]([C@@H]([C@H](O1)CO[P@](=O)(OC1=CC=CC=C1)N[C@H](C(=O)OCC(CC)CC)C)O)O)C#N RWWYLEGWBNMMLJ-YSOARWBDSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VUDZSIYXZUYWSC-DBRKOABJSA-N (4r)-1-[(2r,4r,5r)-3,3-difluoro-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-4-hydroxy-1,3-diazinan-2-one Chemical compound FC1(F)[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)N[C@H](O)CC1 VUDZSIYXZUYWSC-DBRKOABJSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- LDIOUQIXNSSOGU-UHFFFAOYSA-N 8-(3-pentylamino)-2-methyl-3-(2-chloro-4-methoxyphenyl)-6,7-dihydro-5h-cyclopenta[d]pyrazolo[1,5-a]pyrimidine Chemical compound CC1=NN2C(NC(CC)CC)=C3CCCC3=NC2=C1C1=CC=C(OC)C=C1Cl LDIOUQIXNSSOGU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101001031591 Mus musculus Heart- and neural crest derivatives-expressed protein 2 Proteins 0.000 description 1
- AZJRCAJRCOVDIE-UHFFFAOYSA-N P.[F] Chemical compound P.[F] AZJRCAJRCOVDIE-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000001335 demethylating effect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The present invention relates to organic synthesis field, a kind of synthetic method of carbonate-modified floride-free organophosphorus ligand is provided, the synthetic method is prepared into Grignard reagent as raw material with para-bromoanisole or derivatives thereof and reacts framing structure molecule of the generation with triphenylphosphine with phosphorus source, through oxidation, demethylation, nucleophilic displacement of fluorine, reduction, obtains target molecular structure.The invention has the advantages that the organophosphorus ligand of synthesizing new parent's carbon dioxide, improves Phosphine ligands in supercritical CO2In dissolubility, to realize floride-free Phosphine ligands organo-metallic catalyst in supercritical CO2In application.And organic carbonate ester compounds in weak (non-) polar organic solvent (such as, alkane derivative) in it is insoluble, this property can make carbonate-modified floride-free Phosphine ligands have split-phase function in reaction system, realize the recycling and reuse of catalyst.
Description
Technical field
The present invention relates to chemical organic synthesis field, there is provided a kind of synthesis side of carbonate-modified floride-free organophosphorus ligand
Method.
Background technology
Phosphine ligands are in supercritical CO2Middle dissolubility is very poor, limits its correspondence organo-metallic catalyst in supercritical CO2In
Catalytic applications, then we which is modified.Most successful at present is to introduce fluoro-containing group.But, changed with fluoro-alkyl
Property the critical defect of Phosphine ligands be that fluorohydrocarbon and corresponding fluorine-containing part price are sufficiently expensive, and fluorochemical is a large amount of
Using serious environmental problem can be caused.So, design, synthesizing new parent CO2Phosphine ligands become supercritical CO2Transition in medium
One of research emphasis of metal-complexing catalytic reaction.
In close CO2The modified aspect of floride-free Phosphine ligands, professor Jessop of Canadian Queen ' s universities find：By readily soluble
In supercritical CO2And the full acetylated sugar with ad hoc structure is modified to triphenylphosphine or introduces on its aromatic ring
Lewis alkalescence hetero atoms, can improve the complex catalyst of corresponding Phosphine ligands in supercritical CO2In solubility property.This is which
The close CO of its type2The design of floride-free Phosphine ligands, synthesis provide new approaches.
Many organic carbonate ester compounds (e.g., Allyl carbonate etc.) are with supercritical CO2In it is readily soluble the characteristics of.It is based on
This, we are according to MOLECULE DESIGN and cut out viewpoint and in organic synthesiss and the Research foundation of catalytic field, propose design synthesis
The new carbonate-modified floride-free function Phosphine ligands of one class, to realize floride-free Phosphine ligands organo-metallic catalyst in supercritical CO2In
Application.Organic carbonate ester compounds are insoluble in weak (non-) polar organic solvent (e.g., alkane derivative), and this property can
Make carbonate-modified floride-free Phosphine ligands that there is in reaction system split-phase function, realize the recycling and reuse of catalyst.
The content of the invention
The present invention provides a kind of synthetic method of carbonate-modified floride-free organophosphorus ligand, and what is prepared is carbonate-modified
Floride-free organophosphorus ligand can realize floride-free Phosphine ligands organo-metallic catalyst in supercritical CO2In application.
In order to achieve the above object, the technical scheme is that：
A kind of synthetic method of carbonate-modified floride-free organophosphorus ligand, comprises the following steps：
The first step, synthesis compound 2 (to methoxyl group triphenyl phosphine compound)
Brand-new Mg powder is added in there-necked flask, N2Displacement 3 times, sequentially adds a little I2Grain and 20～100mlTHF.To change
Compound 1 (para-bromoanisole class compound) is slowly dropped in there-necked flask, and room temperature reaction 1h is prepared into Grignard reagent.40
Phosphorus source is added in Grignard reagent under the conditions of～80 DEG C, after reacting 1～4 hour, compound is obtained to reaction mixture post processing
2.Described compound 1 is (3-n) with the mol ratio of phosphorus source：1, wherein n=0,1,2；Described phosphorus source is Phosphorous chloride., hexichol
Base phosphorus chloride, phenyl dichloro phosphorus.Described post processing is slowly added in 10% cryosel aqueous acid, successively for reaction mixture
Carry out extractant extraction, decompression steam solvent, recrystallization after, obtain solid compounds 2.Described extractant is ether, dichloro
Methane.
Second step, synthesis compound 3 (to methoxyl group triphenylphosphine oxide class compound)
Under room temperature condition, after compound 2 is dissolved in dichloromethane or acetone solvent, 30% H is added2O2To chemical combination
Thing 2 carries out oxidation processes, obtains compound 3.Described compound 2 and H2O2Mol ratio be 1：1.5～5.0.
3rd step, synthesis compound 4 (to hydroxyl triphenylphosphine oxide class compound)
Under the conditions of 60～140 DEG C, the compound 3 that second step is obtained 48% hydrobromic acid HBr aqueous solutions effect
Under carry out demethylating reaction, be cooled to room temperature after 2～5h of reaction, reaction mixture post processing obtains compound 4.Described chemical combination
Thing 3 is 1 with the mol ratio of HBr:5* (3-n), wherein n=0,1,2.Described post processing is：It is slowly added in reaction mixture
NaOH solution, after filtering insoluble matter, adds KH2PO4 solution, is slowly acidified to pH=7, filter, deionization in reaction mixture
Solid compounds 4 are obtained after water washing.
4th step, synthesis compound 5 (to glycidyl ether triphenylphosphine oxide class compound)
Compound 4 and epoxychloropropane are added in reaction vessel, 50～120 DEG C are heated with stirring to, 2～5h is reacted, is obtained
To viscous solution.Again viscous solution is cooled to after 30～50 DEG C, speed is slowly added dropwise 30%NaOH aqueous solutions, 2h completion of dropping,
Viscous mixture is obtained after continuing water bath with thermostatic control reaction 2h；Viscous mixture post processing obtains compound 5.Described compound 4 with
The mol ratio of epoxychloropropane is 1：5* (3-n), wherein n=0,1,2；Described compound 4 is 1 with the mol ratio of NaOH：
1.2* (3-n), wherein n=0,1,2.Described post processing is viscous mixture KH2PO4Wash into saturation NaCl solution
After property, recovered under reduced pressure epoxychloropropane at 100 DEG C, column chromatography obtain compound 5.
5th step, synthesis compound 6 (to (+)-2,3-Epoxy-1-propanol ester group triphenylphosphine oxide class compound)
Under the conditions of 60～120 DEG C, the compound 5 that the 4th step is obtained is positioned over full of CO2Autoclave in, compound
5 and CO2Reaction 8h, after decompression, reactant mixture carries out post processing and obtains compound 6.Described carbon dioxide initial pressure is 1
～4MPa.Described post processing is dissolved in ethyl acetate for reactant mixture, carry out successively deionized water wash, point liquid, drying,
Filter, remove ethyl acetate, column chromatography under reduced pressure after, obtain compound 6.
6th step, synthesis compound 7 (to (+)-2,3-Epoxy-1-propanol ester group triphenylphosphine class compound)
Compound 6 is added in reaction vessel, the toluene of 50～150ml degassing eliminating waters is added.By reaction substrate frozen water
Bath cooling, adds mol ratio to be 1:1 trichlorosilane and triethylamine；1～5h is stirred under the conditions of 60～120 DEG C, reaction is completed
Afterwards, 30% NaOH aqueous solutions are added, is stirred under the conditions of ice-water bath to white precipitate and is disappeared；Reactant mixture post processing
Compound 7.Described compound 6 is 1 with the mol ratio of trichlorosilane:2～15.Described post processing is to shift reactant mixture
To separatory funnel point liquid, lower aqueous layer is extracted with degassed dichloromethane, after merging organic layer, is dried successively, is filtered, cold-trap
Decompression steams organic layer, column chromatography, obtains solid product for compound 7.
Compound 1,2,3,4,5,6,7 described in above-mentioned synthesis step and described carbonate-modified floride-free organophosphite ligand
Compound 1,2,3,4,5,6,7 in the synthetic route chart of body is corresponded.
The synthetic route chart of described carbonate-modified floride-free organophosphorus ligand is as follows：
Wherein, R1,R2,R3,R4=H, (CH2)mCH3Or NO2；M=0,1,2,3,4；N=0,1,2.
The invention has the advantages that the organophosphorus ligand of synthesizing new parent's carbon dioxide, improves Phosphine ligands and faces super
Boundary CO2In dissolubility, to realize floride-free Phosphine ligands organo-metallic catalyst in supercritical CO2In application.And organic carbonate
Ester compounds are insoluble in weak (non-) polar organic solvent (e.g., alkane derivative), and this property can make carbonate-modified nothing
Fluorine Phosphine ligands have split-phase function in reaction system, realize the recycling and reuse of catalyst.
Specific embodiment
Embodiment 1
The first step, the synthesis of compound 2a (two (4- methoxyphenyls) Phenylphosphine)
Magnesium powder hydrochloric acid and acetone are washed respectively, is drained.THF metal Na are back to benzophenone and become darkviolet.
Brand-new Mg powder is added into reaction unit, N2Displacement 3 times, sequentially adds I2Grain and refined THF.N2Under protection, by dried change
Compound 1a (4- bromoanisoles) is transferred in Dropping funnel.Heating initiation reaction, is slowly added dropwise the THF solution of 4- bromoanisoles.
1h is stirred under completion of dropping, room temperature, atrouss mixture is obtained.Phenyl dichloro phosphorus is slowly dropped in Grignard reagent, is dripped
Add complete, stirring 2h.Reactant mixture is slowly added to into 10% cryosel aqueous acid, ether extraction, decompression steam solvent, obtain slightly
Product yellow solid.By crude product ethyl alcohol recrystallization, white solid is obtained.Yield：78%.
Second step, the synthesis of compound 3a (two (4- methoxyphenyls) phenyl phosphine oxide)
5g compound 2a are transferred in round-bottomed flask, 50ml acetone are added, is slowly added dropwise H2O2(1.1eq).Stir under room temperature
1h is mixed, acetone is removed under reduced pressure.Crude product is dissolved in dichloromethane, and saturated common salt water washing is to the constant indigo plant of KI reagent paper.Dichloromethane is evaporated off
Alkane, obtains oil product.Stand overnight, oily mater crystallization, is that solvent recrystallization obtains white solid with hexamethylene, and yield is
96%.
3rd step, the synthesis of compound 4a (two (4- hydroxy phenyls) phenyl phosphine oxide)
Reaction unit N2Displacement three times, adds 48% hydrobromic acid and KI (3eq) solid of compound 3a and excess, HBr
Input amount be 40eq, 120 DEG C reaction 4h.Reaction is cooled to room temperature after terminating, and is slowly added to 30%NaOH solution, filters insoluble
Thing.With the KH of 1mol/L2PO4Solution is slowly acidified to pH=7, filters, and deionized water wash obtains needle-like solid.Column chromatography obtains nothing
Color needle-like solid, yield are 90%.
4th step, the synthesis of compound 5a (two (4- glycidyl ether phenyl) phenyl phosphine oxide)
In 100ml there-necked flasks, add compound 4a, refined epoxychloropropane (10eq) to be heated with stirring to 85 DEG C,
Reaction 2h, obtains viscous solution.The solution is cooled to into 30 DEG C, 30%NaOH solution is taken, uniform speed slow Deca, 2h are dripped
Finish.Continue water bath with thermostatic control reaction 2h, obtain viscous mixture.Reactant mixture is transferred to into separatory funnel, warm water is washed 2 times, quiet
Put layering.Then 1mol/L KH are used respectively2PO4Wash with saturation NaCl solution, until neutral.Water mutually uses CH2Cl2Solution back extraction
Take, merge organic layer, decompression steams CH2Cl2.Surplus solution is transferred in round-bottomed flask, 100 DEG C of recovered under reduced pressure epoxychloropropane,
Obtain yellow viscous liquid.Column chromatography obtains colorless viscous transparency liquid, and yield is 78%.
5th step, the synthesis of compound 6a (two (4- (+)-2,3-Epoxy-1-propanol ester group phenyl) phenyl phosphine oxide)
After autoclave is hunted leak, compound 5a and tetrabutyl ammonium bromide are transferred in autoclave.CO2Put
After changing 3 times, the CO of 3MPa is filled with2Gas, 120 DEG C of stirring reactions 8h.Deflate and reduce pressure, reactant mixture is dissolved in ethyl acetate.With
Deionized water wash, point liquid are dried, after filtration, remove ethyl acetate under reduced pressure, obtain crude yellow oil.Crude product column chromatography
White foam solid is obtained, yield is 96%.
6th step, the synthesis of compound 7a (two (4- (+)-2,3-Epoxy-1-propanol ester group phenyl) Phenylphosphine)
Compound 6a is transferred in 100ml there-necked flask bottles, the toluene of degassing eliminating water is added.By reaction substrate frozen water
Bath cooling, adds trichlorosilane (10eq) and triethylamine (10eq), 80 DEG C of stirring 2h.After the completion of reaction, 30% is added
NaOH solution, low temperature 15min to white precipitate disappear.Reactant mixture is transferred to into separatory funnel point liquid, lower floor's water
Layer is extracted with degassed dichloromethane.Merge organic layer, be dried, filter, organic layer is steamed with cold-trap decompression.Column chromatography obtains solid
Product, yield are 91%.1H NMR (500MHz, Chloroform-d) δ 7.28-7.11 (m, 9H), 6.80 (d, J=8.1Hz,
4H), 4.97-4.90 (m, 2H), 4.51 (t, J=8.4Hz, 2H), 4.42 (dd, J=10.0,4.1Hz, 2H), 4.15 (dd, J=
10.6,3.6Hz, 2H), 4.04 (dd, J=8.9,5.1Hz, 2H) .31P NMR (202MHz, Chloroform-d) δ -8.55.
The concrete synthetic route of embodiment 1 is：
Embodiment 2
The first step, the synthesis of compound 2b ((4- methoxyphenyls) diphenylphosphine)
Magnesium powder hydrochloric acid and acetone are washed respectively, is drained.THF metal Na are back to benzophenone and become darkviolet.
Brand-new Mg powder is added into Deca back flow reaction device, N is then used2Displacement 3 times, sequentially adds I2Grain and refined THF, in N2Protect
Under shield, dried compound 1a (4- bromoanisoles) is transferred in Dropping funnel.Heating initiation reaction, is slowly added dropwise 4- bromines
The THF solution of methyl phenyl ethers anisole.1h is stirred under completion of dropping, room temperature, atrouss mixture is obtained.Diphenyl phosphorus chloride is slowly added dropwise
To in Grignard reagent, completion of dropping stirs 2h.Reactant mixture is slowly added in 10% cryosel aqueous acid, dichloro is used
Methane is extracted, and decompression steams solvent, obtains crude product yellow solid.Recrystallization, obtains white solid.Yield：95%.
Second step, the synthesis of compound 3b ((4- methoxyphenyls) diphenyl phosphine oxide)
5g compound 2b are transferred in round-bottomed flask, 50ml dichloromethane are added, is slowly added dropwise H2O2(1.1eq).Deca
Finish, under room temperature, stir 1h, with saturated common salt water washing to the constant indigo plant of KI reagent paper.Dichloromethane is steamed, oil product is obtained, is tied again
Brilliant to obtain white solid, yield is 98%.
3rd step, the synthesis of compound 4b ((4- hydroxy phenyls) diphenyl phosphine oxide)
Compound 3b is added into reaction bulb and excessive 48% hydrobromic acid and KI (1eq) solid is added, the input amount of HBr
For 20eq, 95 DEG C of reaction 3h, reaction are cooled to room temperature after terminating.30%NaOH solution is slowly added to, insoluble matter is filtered, is used
The KH of 1mol/L2PO4Solution is slowly acidified to pH=7, filters, is washed with deionized and obtains solid, and yield is 90%.
4th step, the synthesis of compound 5b ((4- glycidyl ether phenyl) diphenyl phosphine oxide)
Compound 4b is added in 100ml there-necked flasks, epoxychloropropane (5eq), agitating heating are warming up to 80 DEG C.Reaction
2h, obtains clarification viscous solution.The solution is cooled to into 30 DEG C, 30%NaOH solution, uniform speed slow Deca, 2h completion of dropping is taken.
2h is reacted in continuation in water bath with thermostatic control, obtains viscous mixture.Reactant mixture is transferred to into separatory funnel, is washed with warm water 2 times,
Stratification.Use 1mol/L KH2PO4Wash to neutrality with saturation NaCl solution.100 DEG C of recovered under reduced pressure epoxychloropropane.Until
There is no longer fraction to steam, obtain yellow viscous liquid.Colorless viscous transparency liquid is obtained after column chromatography, yield is 78%.
5th step, the synthesis of compound 6b ((4- (+)-2,3-Epoxy-1-propanol ester group phenyl) diphenyl phosphine oxide)
Compound 5b and a small amount of tetrabutyl ammonium bromide (TBAB) are transferred in autoclave, CO is used2Replace 3 times repeatedly,
It is filled with 3MPa CO2Gas, 120 DEG C of stirring reactions 8h.Reaction terminates, decompression of deflating, and reactant mixture is dissolved in ethyl acetate,
Wash with water, point liquid is dried, and filters, and decompression steams ethyl acetate, obtains crude yellow oil column chromatography, obtains white foam
Solid.Yield 96%.
6th step, the synthesis of compound 7b ((4- (+)-2,3-Epoxy-1-propanol ester group phenyl) diphenylphosphine)
Compound 6b is transferred in 100ml there-necked flask bottles, the toluene of degassing eliminating water is added.By reaction substrate frozen water
Bath cooling, adds trichlorosilane (6eq) and triethylamine (6eq), 80 DEG C of stirring 2h.After the completion of reaction, 30% NaOH is added
Solution, low temperature 15min to white precipitate disappear.Reactant mixture is transferred to into separatory funnel point liquid, lower aqueous layer is used
Degassed dichloromethane is extracted, and merges organic layer, is dried, and is filtered, and steams organic layer with cold-trap decompression.Column chromatography obtains solid product
Thing, yield are 94%.1H NMR (400MHz, Chloroform-d) δ 7.32-7.27 (m, 12H), 6.89 (d, J=8.4Hz,
2H), 4.98 (dq, J=8.8,3.7Hz, 1H), 4.55 (t, J=8.5Hz, 1H), 4.47 (dd, J=8.4,6.0Hz, 1H),
4.21 (dd, J=10.7,3.7Hz, 1H), 4.09 (dd, J=10.7,3.6Hz, 1H) .31P NMR (162MHz,
Chloroform-d)δ-7.02。
The synthetic route of embodiment 2 is：
Claims (8)
1. a kind of synthetic method of carbonate-modified floride-free organophosphorus ligand, it is characterised in that following steps：
The first step, synthesizes compound 2
Under room temperature, compound 1 is prepared into into Grignard reagent, under the conditions of 40～80 DEG C, phosphorus source is added in Grignard reagent, reaction
1～4 hour, reaction mixture is carried out extracting, vacuum distillation, compound 2 is obtained after recrystallization process；Described compound 1
Mol ratio with phosphorus source is (3-n)：1, n=0,1,2；
Second step, synthesizes compound 3
Under room temperature, after compound 2 is dissolved in a solvent, 30%H is added2O2Oxidation processes are carried out to compound 2, chemical combination is obtained
Thing 3；Described compound 2 and H2O2Mol ratio be 1：1.5～5.0；
3rd step, synthesizes compound 4
Under the conditions of 60～140 DEG C, the compound 3 that second step is obtained is taken off in the presence of 48% hydrobromic acid aqueous solution
Methyl reacts, and is cooled to room temperature, NaOH solution is added in reaction mixture, filter after removing insoluble matter, to anti-after 2～5h of reaction
Answer mixed liquor to carry out acidification, after filtration washing, obtain solid compounds 4；Described compound 3 is 1 with the mol ratio of HBr:5*
(3-n), n=0,1,2；
4th step, synthesizes compound 5
During compound 4 and epoxychloropropane add reaction vessel, 50～120 DEG C are heated to, 2～5h of stirring reaction obtains sticky
Solution；Viscous solution is cooled to after 30～50 DEG C, uniform speed slow Deca 30%NaOH aqueous solution, 2h completion of dropping, continues anti-
Viscous mixture is obtained after answering 2h；Viscous mixture detergent is washed to neutrality, and after vacuum distillation, column chromatography obtains compound 5；
Described compound 4 is 1 with the mol ratio of epoxychloropropane：5* (3-n), described compound 4 and the mol ratio of NaOH are 1：
1.2* (3-n), n=0,1,2；
5th step, synthesizes compound 6
Under the conditions of 60～120 DEG C, compound 5 is positioned over full of CO2Autoclave in, compound 5 and CO2Reaction 8h；Subtract
Pressure, reactant mixture is dissolved in solvent, carry out successively deionized water wash, point liquid, drying, filter, remove under reduced pressure ethyl acetate,
Compound 6 is obtained after column chromatography；Described carbon dioxide initial pressure is 1～4MPa；
6th step, synthesizes compound 7
Compound 6 is added in toluene solution, after the cooling of reaction substrate ice-water bath, adds mol ratio to be 1:1 trichlorosilane and
Triethylamine；1～5h of stirring reaction under the conditions of 60～120 DEG C；After reaction terminates, NaOH aqueous solutions are added, under the conditions of ice-water bath
Stir to white precipitate and disappear；Reactant mixture point liquid, merges organic layer after lower aqueous layer extraction, be dried successively, filter,
Cold-trap decompression obtains solid compounds 7 after steaming organic layer, column chromatography；Described compound 6 with the mol ratio of trichlorosilane is
1:2～15；
The synthetic route chart of described carbonate-modified floride-free organophosphorus ligand is as follows：
Wherein, R1,R2,R3,R4=H, (CH2)mCH3Or NO2；M=0,1,2,3,4；N=0,1,2.
2. the synthetic method of a kind of carbonate-modified floride-free organophosphorus ligand according to claim 1, it is characterised in that
Phosphorus source described in one step is Phosphorous chloride., diphenyl phosphorus chloride, phenyl dichloro phosphorus.
3. the synthetic method of a kind of carbonate-modified floride-free organophosphorus ligand according to claim 1 and 2, its feature exist
In the acidification in the 3rd described step is the addition KH2PO4 solution in reaction mixture, is acidified to pH=7.
4. the synthetic method of a kind of carbonate-modified floride-free organophosphorus ligand according to claim 1 and 2, its feature exist
In the detergent of the 4th described step is KH2PO4With saturation NaCl solution.
5. a kind of synthetic method of carbonate-modified floride-free organophosphorus ligand according to claim 3, it is characterised in that institute
The detergent of the 4th step stated is KH2PO4With saturation NaCl solution.
6. the synthetic method of a kind of carbonate-modified floride-free organophosphorus ligand according to claim 1 or 2 or 5, its feature
It is that solvent is dichloromethane or acetone in described second step；The solvent of the 5th described step is ethyl acetate；Described
The extractant of six steps is dichloromethane.
7. a kind of synthetic method of carbonate-modified floride-free organophosphorus ligand according to claim 3, it is characterised in that institute
In the second step stated, solvent is dichloromethane or acetone；The solvent of the 5th described step is ethyl acetate；The 6th described step
Extractant is dichloromethane.
8. a kind of synthetic method of carbonate-modified floride-free organophosphorus ligand according to claim 4, it is characterised in that institute
In the second step stated, solvent is dichloromethane or acetone；The solvent of the 5th described step is ethyl acetate；The 6th described step
Extractant is dichloromethane.
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| CN107573379A (en) * | 2017-07-17 | 2018-01-12 | 大连理工大学 | A kind of synthetic method of new carbonate-modified floride-free organophosphorus ligand |
| CN109438511A (en) * | 2018-12-11 | 2019-03-08 | 河南省科学院化学研究所有限公司 | A method of synthesis tetrafluoro boric acid di-tert-butyl-phenyl phosphonium salt |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573379A (en) * | 2017-07-17 | 2018-01-12 | 大连理工大学 | A kind of synthetic method of new carbonate-modified floride-free organophosphorus ligand |
| CN109438511A (en) * | 2018-12-11 | 2019-03-08 | 河南省科学院化学研究所有限公司 | A method of synthesis tetrafluoro boric acid di-tert-butyl-phenyl phosphonium salt |
| CN109438511B (en) * | 2018-12-11 | 2020-11-06 | 河南省科学院化学研究所有限公司 | Method for synthesizing di-tert-butyl phenyl phosphonium tetrafluoroborate |
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