CN110590847A - Process for preparing 2,2' - (1, 4-phenylene) bis (1-phenylphosphine isoindole-1-oxide) - Google Patents
Process for preparing 2,2' - (1, 4-phenylene) bis (1-phenylphosphine isoindole-1-oxide) Download PDFInfo
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- CN110590847A CN110590847A CN201910936618.1A CN201910936618A CN110590847A CN 110590847 A CN110590847 A CN 110590847A CN 201910936618 A CN201910936618 A CN 201910936618A CN 110590847 A CN110590847 A CN 110590847A
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- Prior art keywords
- reaction
- alkyne
- oxide
- phenyl
- bis
- Prior art date
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 11
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 alkyl alkyne Chemical class 0.000 claims abstract description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000004809 thin layer chromatography Methods 0.000 claims description 15
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 4
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical compound CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 claims description 4
- LMADLNJFWANXNP-UHFFFAOYSA-N C1=CC=C2NC(P(=O)=O)=CC2=C1 Chemical class C1=CC=C2NC(P(=O)=O)=CC2=C1 LMADLNJFWANXNP-UHFFFAOYSA-N 0.000 claims description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- QDEOKXOYHYUKMS-UHFFFAOYSA-N but-3-ynylbenzene Chemical compound C#CCCC1=CC=CC=C1 QDEOKXOYHYUKMS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- LTLVZQZDXQWLHU-UHFFFAOYSA-N 1-bromo-4-ethynylbenzene Chemical group BrC1=CC=C(C#C)C=C1 LTLVZQZDXQWLHU-UHFFFAOYSA-N 0.000 claims description 2
- DGLHLIWXYSGYBI-UHFFFAOYSA-N 1-chloro-2-ethynylbenzene Chemical group ClC1=CC=CC=C1C#C DGLHLIWXYSGYBI-UHFFFAOYSA-N 0.000 claims description 2
- GRBJPHPMYOUMJV-UHFFFAOYSA-N 1-chloro-3-ethynylbenzene Chemical group ClC1=CC=CC(C#C)=C1 GRBJPHPMYOUMJV-UHFFFAOYSA-N 0.000 claims description 2
- LFZJRTMTKGYJRS-UHFFFAOYSA-N 1-chloro-4-ethynylbenzene Chemical group ClC1=CC=C(C#C)C=C1 LFZJRTMTKGYJRS-UHFFFAOYSA-N 0.000 claims description 2
- OOZKONVIIMFOKW-UHFFFAOYSA-N 1-ethynyl-2-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C#C OOZKONVIIMFOKW-UHFFFAOYSA-N 0.000 claims description 2
- YFPQIXUNBPQKQR-UHFFFAOYSA-N 1-ethynyl-2-fluorobenzene Chemical group FC1=CC=CC=C1C#C YFPQIXUNBPQKQR-UHFFFAOYSA-N 0.000 claims description 2
- MYBSUWNEMXUTAX-UHFFFAOYSA-N 1-ethynyl-2-methylbenzene Chemical group CC1=CC=CC=C1C#C MYBSUWNEMXUTAX-UHFFFAOYSA-N 0.000 claims description 2
- ZASXCTCNZKFDTP-UHFFFAOYSA-N 1-ethynyl-3-methoxybenzene Chemical group COC1=CC=CC(C#C)=C1 ZASXCTCNZKFDTP-UHFFFAOYSA-N 0.000 claims description 2
- RENYIDZOAFFNHC-UHFFFAOYSA-N 1-ethynyl-3-methylbenzene Chemical group CC1=CC=CC(C#C)=C1 RENYIDZOAFFNHC-UHFFFAOYSA-N 0.000 claims description 2
- XTKBMZQCDBHHKY-UHFFFAOYSA-N 1-ethynyl-4-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=C(C#C)C=C1 XTKBMZQCDBHHKY-UHFFFAOYSA-N 0.000 claims description 2
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 claims description 2
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 claims description 2
- GAZZTEJDUGESGQ-UHFFFAOYSA-N 1-ethynyl-4-nitrobenzene Chemical group [O-][N+](=O)C1=CC=C(C#C)C=C1 GAZZTEJDUGESGQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- JPGRSTBIEYGVNO-UHFFFAOYSA-N methyl 4-ethynylbenzoate Chemical group COC(=O)C1=CC=C(C#C)C=C1 JPGRSTBIEYGVNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- OSSQSXOTMIGBCF-UHFFFAOYSA-N non-1-yne Chemical compound CCCCCCCC#C OSSQSXOTMIGBCF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical compound CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- LWISLHRIEATKTM-UHFFFAOYSA-N 2-Ethynylthiophene Chemical compound C#CC1=CC=CS1 LWISLHRIEATKTM-UHFFFAOYSA-N 0.000 claims 1
- NHUBNHMFXQNNMV-UHFFFAOYSA-N 2-ethynylpyridine Chemical compound C#CC1=CC=CC=N1 NHUBNHMFXQNNMV-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000012043 crude product Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 150000002475 indoles Chemical class 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- GFISDBXSWQMOND-UHFFFAOYSA-N 2,5-dimethoxyoxolane Chemical compound COC1CCC(OC)O1 GFISDBXSWQMOND-UHFFFAOYSA-N 0.000 description 7
- VNDYJBBGRKZCSX-UHFFFAOYSA-L Zinc bromide Inorganic materials Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 4
- MKHUUEKFSADWKL-UHFFFAOYSA-N COC1=CC=C(C=C1)O[P] Chemical compound COC1=CC=C(C=C1)O[P] MKHUUEKFSADWKL-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 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
- 125000005605 benzo group Chemical group 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- GJEKDPFHYOELGZ-UHFFFAOYSA-N 1-phenylphosphindole 1-oxide Chemical compound C1=CC2=CC=CC=C2P1(=O)C1=CC=CC=C1 GJEKDPFHYOELGZ-UHFFFAOYSA-N 0.000 description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000708 phosphoindolyl group Chemical class P(=O)(=O)C1=C(NC2=CC=CC=C12)* 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- YTVPZNFPDODQJL-UHFFFAOYSA-N 1-oxido-1-phenyl-1,2-benzazaphosphol-1-ium Chemical compound C1=CC=C(C=C1)[N+]2(C3=CC=CC=C3C=P2)[O-] YTVPZNFPDODQJL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HYPPXZBJBPSRLK-UHFFFAOYSA-N diphenoxylate Chemical compound C1CC(C(=O)OCC)(C=2C=CC=CC=2)CCN1CCC(C#N)(C=1C=CC=CC=1)C1=CC=CC=C1 HYPPXZBJBPSRLK-UHFFFAOYSA-N 0.000 description 2
- 229960004192 diphenoxylate Drugs 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000006677 Appel reaction Methods 0.000 description 1
- XLBGONCIWNKLSW-UHFFFAOYSA-N C1=CC=C(C=C1)[N+]2(C3=CC=CC=C3C=C2[P+](=O)[O-])[O-] Chemical class C1=CC=C(C=C1)[N+]2(C3=CC=CC=C3C=C2[P+](=O)[O-])[O-] XLBGONCIWNKLSW-UHFFFAOYSA-N 0.000 description 1
- MAGJRBBFUSELIB-UHFFFAOYSA-N CCC1=C([N+](C2=CC=CC=C21)(C3=CC=CC=C3)[O-])[P+](=O)[O-] Chemical compound CCC1=C([N+](C2=CC=CC=C21)(C3=CC=CC=C3)[O-])[P+](=O)[O-] MAGJRBBFUSELIB-UHFFFAOYSA-N 0.000 description 1
- SUPUWSLBZYVBMY-UHFFFAOYSA-N CCCCC1=C([N+](C2=CC=CC=C21)(C3=CC=CC=C3)[O-])[P+](=O)[O-] Chemical compound CCCCC1=C([N+](C2=CC=CC=C21)(C3=CC=CC=C3)[O-])[P+](=O)[O-] SUPUWSLBZYVBMY-UHFFFAOYSA-N 0.000 description 1
- XVEYUPAHAWBASN-UHFFFAOYSA-N COC1=CC=C(C=C1)[N+]2(C3=C(C=C(C=C3)OC)C=C2[P+](=O)[O-])[O-] Chemical compound COC1=CC=C(C=C1)[N+]2(C3=C(C=C(C=C3)OC)C=C2[P+](=O)[O-])[O-] XVEYUPAHAWBASN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 1
- RREGWFNURZJKNB-UHFFFAOYSA-N bis(4-methoxyphenyl)-oxophosphanium Chemical compound C1=CC(OC)=CC=C1[P+](=O)C1=CC=C(OC)C=C1 RREGWFNURZJKNB-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000004850 phospholanes Chemical class 0.000 description 1
- 150000004857 phospholes Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a preparation method of 2,2'- (1, 4-phenylene) bis (1-phenylphosphine heteroandole-1-oxide), which comprises the following steps of dissolving alkyne, phosphorus reagent, copper catalyst and organic peroxide in a solvent, reacting at 50 ~ 100 ℃ to obtain a phosphaindole derivative, heating and reacting a mixture of the phosphaindole derivative, acetonitrile, N-bromosuccinimide and tert-butyl peroxide, adding 1, 4-phenylboronic acid, palladium acetate, potassium carbonate, acetonitrile and water after the reaction is finished, and heating and reacting at 90 ℃ to obtain the 2,2' - (1, 4-phenylene) bis (1-phenylphosphine heteroandole-1-oxide), wherein the alkyne can be alkyl alkyne, aryl alkyne, pentavalent alkyne and hexatomic alkyne.
Description
The invention belongs to a phospha indole derivative, a benzo phospha indole derivative and a preparation method thereof, and divisional applications of invention application with application date of 2018, 10 and 8 and application number of 2018111699022, belonging to the parts of preparation methods of different products.
Technical Field
The invention belongs to the technical field of preparation of organic compounds, and particularly relates to a preparation method of 2,2' - (1, 4-phenylene) bis (1-phenylphosphine heteroandole-1-oxide).
Background
Phosphorus-containing heterocyclic compounds can be used for catalytic reactions, such as phospholanes, phospholes, benfozonandoles, etc., which can effectively catalyze organic reactions (references van Kalkeren, h. a., van Delft, f. l., rutjesf. p. j. t. ChemSusChem 2013, 6, 1615-. The catalytic action of these heterocyclic compounds results from the fact that the reduction rate in the reaction can be greatly increased (references van Kalkeren, h. a., Leenders, s.h.a. m., hommernom, r. a., Rutjes, f.p.j. t., van Delft, f.l. chem. -eur. j. 2011,17, 11290-. Current areas of development include catalytic Wittig and Appel reactions (references Denton, r. m., An, j., adeniiran, b., Blake, a. j., Lewis, w., Poulton, a. m.j. org. chem. 2011, 76, 6749-. For example, 5-phenylbenzo [ b ] phospha indole-5-oxide can be used as a catalyst for deoxidation condensation reaction, but in the disclosed synthetic route of 5-phenylbenzo [ b ] phospha indole-5-oxide, raw materials are difficult to obtain, reaction conditions are harsh, and the operation is complicated.
In addition, the conjugated system containing the phosphorindole structural unit can be applied to the synthesis of photoelectric materials, for example, 2'- (1, 4-phenylene) bis (1-phenylphosphindole-1-oxide) can absorb 387nm light and emit 431nm and 456nm light, and in the disclosed synthetic route of 2,2' - (1, 4-phenylene) bis (1-phenylphosphindole-1-oxide), raw materials are difficult to obtain, strong base is needed, and the yield is low. Therefore, it is very important to develop a synthesis method with mild reaction conditions, simple reaction steps and simple and easily available raw materials.
Disclosure of Invention
The invention aims to provide a phospha indole derivative, a benzo phospha indole derivative and a preparation method thereof, which have the advantages of simple raw material source, mild reaction condition, simple post-treatment, high yield and the like.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a process for preparing the phosphoindole derivative includes such steps as dissolving alkyne, phosphorus reagent, copper catalyst and organic peroxide in solvent, and reacting at 50 ~ 100 deg.C to obtain phosphoindole derivative;
the alkyne is shown as the following chemical structural general formula:
wherein R is selected from one of hydrogen, alkyl, aralkyl, aryl, heteroaralkyl and heteroaryl;
the phosphorus reagent is represented by the following structural general formula:
wherein Ar is selected from aryl.
A process for preparing benzophospha indole derivative includes such steps as dissolving alkyne, phosphorus reagent, copper catalyst and organic peroxide in solvent, reaction at 50 ~ 100 deg.C to obtain phospha indole derivative, reaction on 2, 5-dimethoxytetrahydrofuran to obtain benzophospha indole derivative;
the alkyne is shown as the following chemical structural general formula:
wherein R is selected from one of hydrogen, alkyl, aralkyl, aryl, heteroaralkyl and heteroaryl;
the phosphorus reagent is represented by the following structural general formula:
wherein Ar is selected from aryl.
Preferably, the benzo-phospha-indole derivative is prepared by using dichloromethane as solvent and ZnBr2Is a catalyst.
The invention also discloses the application of taking alkyne and phosphorus reagents as raw materials in preparing the phosphabendole derivative in the presence of a copper catalyst, organic peroxide and a solvent; the application of alkyne and phosphorus reagents as raw materials in the preparation of benzo-phospha-indole derivatives in the presence of a copper catalyst, organic peroxide, a solvent and 2, 5-dimethoxy tetrahydrofuran.
The invention also discloses a preparation method of the 2,2' - (1, 4-phenylene) bis (1-phenylphosphine heteroandole-1-oxide), which comprises the following steps:
(1) dissolving alkyne, phosphorus reagent, copper catalyst and organic peroxide in a solvent, and reacting at 50 ~ 100 ℃ to obtain a phosphabendole derivative;
(2) heating a mixture of the phosphoindole derivative, acetonitrile, N-bromosuccinimide and tert-butyl peroxide for reaction; after the reaction is finished, adding 1, 4-phenyl diboronic acid, palladium acetate, potassium carbonate, acetonitrile and water, and then heating to react at 90 ℃; to obtain 2,2' - (1, 4-phenylene) bis (1-phenylphosphine heteroindole-1-oxide) which can be used as an optoelectronic material. Preferably, the mol ratio of the phosphindole derivative, the N-bromosuccinimide, the tert-butyl peroxide, the 1, 4-phenyl diboronic acid, the palladium acetate and the potassium carbonate is 3: 6: 9: 4: 0.24: 10.
In the invention, the alkyne can be alkyl alkyne, aryl alkyne, five-membered heteroaryl alkyne and six-membered heteroaryl alkyne; the alkyl alkyne is represented by the following chemical structural general formula:
wherein R is5One selected from hydrogen, ethyl, butyl, heptyl, phenethyl or phenylbutyl;
the self-aryl alkyne is shown as the following chemical structural general formula:
wherein R is1Selected from: alkyl, alkoxy, halogen, nitro, trifluoromethyl and ester group.
The organic peroxide is shown as the following chemical structural general formula:
wherein R is2Selected from: one of methyl or phenyl; r3Selected from: one of hydrogen, tert-butyl or benzoyl;
the chemical formula of the copper catalyst is CuXn, wherein X is one of Cl, Br, I and SCN; n is 1 or 2.
The solvent is selected from: methanol, ethanol, acetonitrile, acetone, ethyl acetate, water, 1, 2-dichloroethane, toluene, N-dimethylformamide or N-methylpyrrolidone.
The phospha indole derivative is shown as the following chemical structural general formula:
the benzo phospha indole derivative is shown as the following chemical structural general formula:
preferably, the alkyne is selected from one of acetylene, butyne, hexyne, 4-phenyl-1-butyne, nonyne, phenylacetylene, 4-methylphenylacetylene, 4-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4- (trifluoromethyl) phenylacetylene, 4-nitrophenylacetylene, 4-methoxycarbonylphenylacetylene, 3-methylphenylacetylene, 3-chlorophenylacetylene, 3-methoxyphenylacetylene, 2-methylphenylacetylene, 2-fluorophenylacetylene, 2-chlorophenylacetylene, 2- (trifluoromethyl) phenylacetylene, 1-phenyl-1-propyne, 4-phenyl-1-butyne; the phosphorus reagent is selected from one of diphenyl phosphine oxide and bis (4-methoxyphenyl) phosphine oxide;
in the above technical scheme, the reaction is followed by Thin Layer Chromatography (TLC) until complete completion.
In the technical scheme, the molar ratio of alkyne, phosphorus reagent, copper catalyst and organic peroxide is 1: 2: 0.2: 2 (2 ~ 6), and the molar ratio of the phosphindole derivative to 2, 5-dimethoxytetrahydrofuran is 1: 2 (2 ~ 2.5.5).
In the technical scheme, after the reaction is finished, the product is subjected to column chromatography separation and purification treatment.
The reaction process of the above technical scheme can be represented as follows:
phosphoindoles
Benzophosphandoles
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention uses alkyne as the starting material, and the raw materials are easy to obtain and have various types.
2. The method disclosed by the invention has the advantages of mild reaction conditions, short reaction time, high yield of target products and simple reaction operation and post-treatment process.
Detailed Description
The invention is further described below with reference to the following examples:
the first embodiment is as follows: synthesis of 1-phenylphosphoindole-1-oxides
Acetylene and diphenyl phosphine oxide are used as raw materials, and the reaction steps are as follows:
(1) acetylene (0.026 g, 0.5 mmol), diphenylphosphine (0.202 g, 1 mmol) and CuCl were introduced into a reaction flask2(0.014g, 0.1 mmol), tert-butyl peroxybenzoate (0.15 g, 1.5 mmol) and methanol (2 mL), 50oC, reacting;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) the crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the objective product (yield 80%). Analytical data for the product are as follows:1H NMR (CDCl3, 500MHz): δ 7.73−7.69 (m, 2H, ArH), 7.62−7.59 (m, 1H, ArH), 7.34−7.53 (m, 6H, ArH; 1H, Ar−CH), 6.45 (dd, J = 25 Hz, 8 Hz,1H)。
example two: synthesis of 1-phenyl-3-ethylphosphoindole-1-oxide
Butyne and phosphorus diphenoxylate are taken as raw materials, and the reaction steps are as follows:
(1) butyne (0.027 g, 0.5 mmol), phosphorus diphenoxylate (0.202 g, 1 mmol), CuCl (0.01g, 0.1 mmol), di-tert-butyl peroxide (0.45 g, 3 mmol), and ethanol (2 mL), 60%oC, reacting;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) the crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the objective product (yield 82%). Analytical data for the product are as follows: 1H NMR (400 MHz, CDCl3): δ7.70−7.65 (m, 2H), 7.62−7.50 (m, 1H), 7.34−7.49 (m, 6H), 6.40 (m, 1H)。 2.05 (m, 2H), 1.08 (t, J= 7.6 Hz, 3H)。
example three: synthesis of 1-phenyl-3-butylphosphoindole-1-oxide
Hexyne and phosphorus diphenoxy are taken as raw materials, and the reaction steps are as follows:
(1) hexyne (0.041 g, 0.5 mmol), diphenylphosphine (0.202 g, 1 mmol) and CuBr were added to the reaction flask2 (0.022 g, 0.1 mmol), tert-butanol peroxide (0.15 mL, 1 mmol) and acetonitrile (2 mL), 60oC, reacting;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) the crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the objective product (yield 83%). Analytical data for the product are as follows:1H NMR (400 MHz, CDCl3): δ7.71−7.62 (m, 2H), 7.60−7.45 (m, 1H), 7.34−7.40 (m, 6H), 6.38 (m, 1H), 2.05 (m, 2H), 1.65−1.45 (m,4H), 1.08 (t, J = 7.6 Hz, 3H)。
example four: synthesis of 1- (4-methoxyphenyl) -5-methoxyphosphandole-1-oxide
Acetylene and di (4-methoxyphenyl) oxyphosphorus are taken as raw materials, and the reaction steps are as follows:
(1) acetylene (0.026 g, 0.5 mmol), bis (4-methoxyphenyl) oxyphosphorus (0.262 g, 1 mmol), CuBr (0.014g, 0.1 mmol), t-butyl peroxybenzoate (0.29 g, 3 mmol), and acetone (2 mL), 50oC, reacting;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) the crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the objective product (yield 84%). Analytical data for the product are as follows:1H NMR (400 MHz, CDCl3): δ7.80 (m, 1H), 7.75 (m, 2H), 7.68 (m, 1H), 7.50 (m, 2H), 7.46 (m, 1H), 7.30 (m, 1H), 6.55 (d, J = 7.6Hz, 1H), 3.88 (s, 3H), 3.86(s, 3H)。
example five: synthesis of 5-phenylbenzo [ b ] phosphinylindole-5-oxide
Acetylene and diphenyl phosphine oxide are used as raw materials, and the reaction steps are as follows:
(1) acetylene (0.026 g, 0.5 mmol), diphenylphosphine (0.202 g, 1 mmol) and CuCl were introduced into a reaction flask2(0.014g, 0.1 mmol)，Tert-butyl peroxybenzoate (0.15 g, 1.5 mmol) and methanol (2 mL), 50oC, reacting;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) separating the crude product obtained after the reaction by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain 1-phenylphosphidine-1-oxide;
1-phenylphosphaindole-1-oxide and 2, 5-dimethoxytetrahydrofuran are taken as raw materials, and the reaction steps are as follows:
(1) at 0 deg.C, 2.5mL of methylene chloride was added to the reaction flask, 1-phenylphosphidole-1-oxide (0.057 g, 0.25 mmol) and 2, 5-dimethoxytetrahydrofuran (0.073 mL, 0.55 mmol) were added, and ZnBr was added2(0.111 g, 0.5 mmol), the mixture was stirred for reaction;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) the crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1:10) to obtain the objective product (yield 81%) which was used as a catalyst. Analytical data for the product are as follows:1H NMR (300 MHz, CDCl3): δ7.85 – 7.80 (m, 2H), 7.75 – 7.55 (m, 6H), 7.52 – 7.45 (m, 1H), 7.43 – 7.34 (m, 4H)。
example six: synthesis of 2-methoxy-5- (4-methoxyphenyl) benzo [ b ] phosphinylindole-5-oxide
Acetylene and di (4-methoxyphenyl) oxyphosphorus are taken as raw materials, and the reaction steps are as follows:
(1) acetylene (0.026 g, 0.5 mmol), bis (4-methoxyphenyl) oxyphosphorus (0.262 g, 1 mmol), CuBr (0.014g, 0.1 mmol), t-butyl peroxybenzoate (0.29 g, 3 mmol), and acetone (2 mL), 50oC, reacting;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) separating the crude product obtained after the reaction by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain 1- (4-methoxyphenyl) -5-methoxyphosphoindole-1-oxide;
1- (4-methoxyphenyl) -5-methoxyphosphandole-1-oxide and 2, 5-dimethoxytetrahydrofuran are taken as raw materials, and the reaction steps are as follows:
(1) at 0 deg.C, 2.5mL of methylene chloride was added to the flask, followed by 1- (4-methoxyphenyl) -5-methoxyphosphandole-1-oxide (0.072 g, 0.25 mmol) and 2, 5-dimethoxytetrahydrofuran (0.073 mL, 0.55 mmol), and finally ZnBr2(0.111 g, 0.5 mmol), the mixture was stirred for reaction;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) the crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1:10) to obtain the objective product (yield 82%) which was used as a catalyst. Analytical data for the product are as follows:1H NMR (400 MHz, CDCl3): δ7.90– 7.82 (m, 2H), 7.76 – 7.58 (m, 6H), 7.51 – 7.42 (m, 1H), 7.40 – 7.32 (m, 4H),3.88 (s, 3H), 3.86 (s, 3H)。
example seven: synthesis of 2,2' - (1, 4-phenylene) bis (1-phenylphosphine isoindole-1-oxide)
Acetylene and diphenyl phosphine oxide are used as raw materials, and the reaction steps are as follows:
(1) acetylene (0.026 g, 0.5 mmol), diphenylphosphine (0.202 g, 1 mmol) and CuCl were introduced into a reaction flask2(0.014g, 0.1 mmol), tert-butyl peroxybenzoate (0.15 g, 1.5 mmol) and methanol (2 mL), 50oC, reacting;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) separating the crude product obtained after the reaction by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain 1-phenylphosphidine-1-oxide;
1-phenyl-phospha indole-1-oxide is taken as a raw material, and the reaction steps are as follows:
(1) 1-phenylphosphindole-1-oxide (0.678 g, 3 mmol), acetonitrile (26 mL), N-bromosuccinimide (1.056 g, 6 mmol) and tert-butyl peroxide (1.35 mL, 9 mmol) were added to a reaction flask, and the mixture was heated to react;
(2) TLC tracing the reaction until the reaction is completely finished;
(3) adding water (20 mL) into the reaction solution, extracting with ethyl acetate, washing the organic phase with a sodium sulfite solution and a saturated sodium chloride solution, drying, and concentrating under reduced pressure to dryness;
(4) to (3) was added 1, 4-benzenediboronic acid (0.657 g, 4.0 mmol), palladium acetate (0.054 g, 0.24 mmol), potassium carbonate (1.41 g, 10 mmol), acetonitrile (20 mL) and water (20 mL), and the mixture was heated at 90 ℃ for reaction;
(5) TLC tracing the reaction until the reaction is completely finished;
(6) water was added to the reaction solution, followed by extraction with ethyl acetate. The organic phase is washed by brine, dried and concentrated under reduced pressure to obtain a crude product, and then the crude product is separated and purified by column chromatography (n-hexane/diethyl ether (4: 1)) to obtain 2,2' - (1, 4-phenylene) bis (1-phenylphosphine heteroandole-1-oxide) (yield is 65%) which can be used as a photoelectric material. Analytical data for the product are as follows:1H NMR (300 MHz, CDCl3): δ7.25-7.71 (m, 24H)。
Claims (4)
1. a method for preparing 2,2' - (1, 4-phenylene) bis (1-phenylphosphine heteroindole-1-oxide), comprising the following steps:
(1) dissolving alkyne, phosphorus reagent, copper catalyst and organic peroxide in a solvent, and reacting at 50 ~ 100 ℃ to obtain a phosphabendole derivative;
the alkyne is shown as the following chemical structural general formula:
wherein R is selected from one of hydrogen, alkyl, aralkyl, aryl, heteroaralkyl and heteroaryl;
the phosphorus reagent is represented by the following structural general formula:
wherein Ar is selected from aryl;
(2) heating a mixture of the phosphoindole derivative, acetonitrile, N-bromosuccinimide and tert-butyl peroxide for reaction; after the reaction is finished, adding 1, 4-phenyl diboronic acid, palladium acetate, potassium carbonate, acetonitrile and water, and then heating to react at 90 ℃; to give 2,2' - (1, 4-phenylene) bis (1-phenylphosphine isoindole-1-oxide).
2. The method of claim 1, wherein the alkyl group is selected from the group consisting of ethyl, butyl, heptyl; the aralkyl is selected from one of phenethyl or phenylbutyl;
the aryl group is shown as the following chemical structural general formula:
wherein R is1Selected from: one of alkoxy, halogen, nitro, trifluoromethyl and ester group;
the organic peroxide is shown as the following chemical structural general formula:
wherein R is2Selected from: one of methyl or phenyl; r3Selected from: one of hydrogen, tert-butyl or benzoyl;
the chemical formula of the copper catalyst is CuXn, wherein X is one of Cl, Br, I and SCN; n is 1 or 2;
the solvent is selected from: methanol, ethanol, acetonitrile, acetone, ethyl acetate, water, 1, 2-dichloroethane, toluene, N-dimethylformamide or N-methylpyrrolidone.
3. The process according to claim 1, wherein the alkyne is selected from: acetylene, butyne, hexyne, 4-phenyl-1-butyne, nonyne, phenylacetylene, 4-methylphenylacetylene, 4-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4- (trifluoromethyl) phenylacetylene, 4-nitrophenylacetylene, 4-methoxycarbonylphenylacetylene, 3-methylphenylacetylene, 3-chlorophenylacetylene, 3-methoxyphenylacetylene, 2-methylphenylacetylene, 2-fluorophenylacetylene, 2-chlorophenylacetylene, 2- (trifluoromethyl) phenylacetylene, 1-phenyl-1-propyne, 4-phenyl-1-butyne, 2-ethynylthiophene or 2-ethynylpyridine.
4. The preparation method of claim 1, wherein the molar ratio of alkyne, phosphorus reagent, copper catalyst and organic peroxide is 1: 2: 0.2: 2 (2 ~ 6), the reaction is followed by Thin Layer Chromatography (TLC) until the reaction is completed, and the product is purified by column chromatography.
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