CN116396209A - 一种烷基全氟烷基酮类化合物及其制备方法 - Google Patents
一种烷基全氟烷基酮类化合物及其制备方法 Download PDFInfo
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- CN116396209A CN116396209A CN202310358452.6A CN202310358452A CN116396209A CN 116396209 A CN116396209 A CN 116396209A CN 202310358452 A CN202310358452 A CN 202310358452A CN 116396209 A CN116396209 A CN 116396209A
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- -1 Alkyl perfluoroalkyl ketone compound Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 176
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 61
- 229910000077 silane Inorganic materials 0.000 claims abstract description 31
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 81
- 125000000217 alkyl group Chemical group 0.000 claims description 66
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 54
- 229910052799 carbon Inorganic materials 0.000 claims description 50
- KCOAKHHWUNSENO-UHFFFAOYSA-N 2,6-dipropoxypyridine Chemical compound CCCOC1=CC=CC(OCCC)=N1 KCOAKHHWUNSENO-UHFFFAOYSA-N 0.000 claims description 40
- 229910052731 fluorine Inorganic materials 0.000 claims description 38
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 30
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims description 29
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003153 chemical reaction reagent Substances 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 150000001721 carbon Chemical group 0.000 claims description 21
- 125000005842 heteroatom Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 8
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- RBBLIBVGQHKKJV-UHFFFAOYSA-N 2,4,6-triethoxypyridine Chemical compound CCOC1=CC(OCC)=NC(OCC)=C1 RBBLIBVGQHKKJV-UHFFFAOYSA-N 0.000 claims description 6
- IBTGEEMBZJBBSH-UHFFFAOYSA-N 2,6-dimethoxypyridine Chemical compound COC1=CC=CC(OC)=N1 IBTGEEMBZJBBSH-UHFFFAOYSA-N 0.000 claims description 6
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- ISUYTITXRVKOQA-UHFFFAOYSA-N 2,4,6-trimethoxypyridine Chemical compound COC1=CC(OC)=NC(OC)=C1 ISUYTITXRVKOQA-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- FILKGCRCWDMBKA-UHFFFAOYSA-N 2,6-dichloropyridine Chemical compound ClC1=CC=CC(Cl)=N1 FILKGCRCWDMBKA-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052740 iodine Chemical group 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 2
- YFWBZTGWBHEIBA-UHFFFAOYSA-N 2,6-dicyclohexylpyridine Chemical compound C1(CCCCC1)C1=NC(=CC=C1)C1CCCCC1 YFWBZTGWBHEIBA-UHFFFAOYSA-N 0.000 claims description 2
- RLVWFCXXXDOSJO-UHFFFAOYSA-N 2,6-diethoxypyridine Chemical compound CCOC1=CC=CC(OCC)=N1 RLVWFCXXXDOSJO-UHFFFAOYSA-N 0.000 claims description 2
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 claims description 2
- QMXFUIUEGUOSEV-UHFFFAOYSA-N 3,4,5,6-tetra(carbazol-9-yl)benzene-1,2-dicarbonitrile Chemical compound N#Cc1c(C#N)c(c(c(c1-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12 QMXFUIUEGUOSEV-UHFFFAOYSA-N 0.000 claims description 2
- VPCXVCNTHAMRBT-UHFFFAOYSA-N 3,5-difluoro-2,4,6-tris(n-phenylanilino)benzonitrile Chemical compound FC1=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C(C#N)=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C(F)=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 VPCXVCNTHAMRBT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000002619 bicyclic group Chemical group 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
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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
- 125000006343 heptafluoro propyl group Chemical group 0.000 claims description 2
- 125000001041 indolyl group Chemical group 0.000 claims description 2
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 claims description 2
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 2
- SCHZCUMIENIQMY-UHFFFAOYSA-N tris(trimethylsilyl)silicon Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)[Si](C)(C)C SCHZCUMIENIQMY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 125000005843 halogen group Chemical group 0.000 claims 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 92
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 186
- 238000001228 spectrum Methods 0.000 description 89
- 238000005481 NMR spectroscopy Methods 0.000 description 78
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 77
- 239000000243 solution Substances 0.000 description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 62
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 62
- 239000001257 hydrogen Substances 0.000 description 62
- 229910052739 hydrogen Inorganic materials 0.000 description 62
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 61
- 229920006395 saturated elastomer Polymers 0.000 description 61
- 239000012074 organic phase Substances 0.000 description 55
- 238000000746 purification Methods 0.000 description 33
- 238000000926 separation method Methods 0.000 description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 31
- 238000004440 column chromatography Methods 0.000 description 31
- 239000011737 fluorine Substances 0.000 description 31
- 239000007788 liquid Substances 0.000 description 31
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 31
- 235000017557 sodium bicarbonate Nutrition 0.000 description 31
- KXFSUVJPEQYUGN-UHFFFAOYSA-N trimethyl(phenyl)silane Chemical compound C[Si](C)(C)C1=CC=CC=C1 KXFSUVJPEQYUGN-UHFFFAOYSA-N 0.000 description 31
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 30
- 239000008346 aqueous phase Substances 0.000 description 30
- 239000011780 sodium chloride Substances 0.000 description 30
- 239000012299 nitrogen atmosphere Substances 0.000 description 28
- 238000004611 spectroscopical analysis Methods 0.000 description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 230000009286 beneficial effect Effects 0.000 description 17
- 229940125904 compound 1 Drugs 0.000 description 16
- 238000012216 screening Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- YQOLEILXOBUDMU-KRWDZBQOSA-N (4R)-5-[(6-bromo-3-methyl-2-pyrrolidin-1-ylquinoline-4-carbonyl)amino]-4-(2-chlorophenyl)pentanoic acid Chemical compound CC1=C(C2=C(C=CC(=C2)Br)N=C1N3CCCC3)C(=O)NC[C@H](CCC(=O)O)C4=CC=CC=C4Cl YQOLEILXOBUDMU-KRWDZBQOSA-N 0.000 description 4
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 4
- RFOMGVDPYLWLOC-UHFFFAOYSA-N 2,6-dichloro-1-oxidopyridin-1-ium Chemical compound [O-][N+]1=C(Cl)C=CC=C1Cl RFOMGVDPYLWLOC-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229940125844 compound 46 Drugs 0.000 description 4
- 239000012973 diazabicyclooctane Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 3
- ABJSOROVZZKJGI-OCYUSGCXSA-N (1r,2r,4r)-2-(4-bromophenyl)-n-[(4-chlorophenyl)-(2-fluoropyridin-4-yl)methyl]-4-morpholin-4-ylcyclohexane-1-carboxamide Chemical compound C1=NC(F)=CC(C(NC(=O)[C@H]2[C@@H](C[C@@H](CC2)N2CCOCC2)C=2C=CC(Br)=CC=2)C=2C=CC(Cl)=CC=2)=C1 ABJSOROVZZKJGI-OCYUSGCXSA-N 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
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- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 description 1
- VNUPRKZUPUBXOD-UHFFFAOYSA-N 1,2-dimethoxyethane;1,4-dioxane Chemical compound COCCOC.C1COCCO1 VNUPRKZUPUBXOD-UHFFFAOYSA-N 0.000 description 1
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- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 1
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- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D211/30—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom
- C07D211/32—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
- C07C235/80—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms having carbon atoms of carboxamide groups and keto groups bound to the same carbon atom, e.g. acetoacetamides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
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Abstract
本发明提供烷基全氟烷基酮类化合物及其制备方法,属于化学合成技术领域。所述制备方法包括:化合物a和化合物b在光敏剂和硅烷存在并于惰性气体氛围条件下,在溶剂中,经光照照射发生反应,得到化合物c。所述制备方法具有绿色环保、产率高、反应条件温和、选择性高等优点。
Description
技术领域
本发明属于化学合成技术领域,具体涉及一种烷基全氟烷基三氟甲基酮类化合物及其制备方法。
背景技术
酮基是有机化学中最重要的官能团之一,如何直接高效、原子经济性和环境友好的构建酮类化合物尤为重要。在众多的酮类化合物中,烷基三氟甲基酮因为引入了氟原子,显著的提高了该类化合物的亲脂性和膜通透性,从而具有很高的生物活性。因此,烷基三氟甲基酮类化合物在生物医药和材料化学等领域有着非常广泛的应用(T.absoluta,A.Dominguez,M.Puigmart,M.P.Bosch,G.Rosell,R.Crehuet,A.Ortiz,C.Quero,A.Guerrero,J.Agric.Food Chem.,2016,64,3523-3532)。传统的三烷基氟甲基酮类化合物的构建主要依靠烷基三氟甲基醇类化合物的氧化(M.Mertens,P.Wessig,F.Meyer-Almes,Chem.Eur.J.,2017,23,3107-3116.),以及对酮类化合物的亲核取代等(C.B.Kelly,M.A.Mercadantea,N.E.Leadbeater,Chem.Commun.,2013,49,11133-11148.),严苛的反应条件和昂贵的三氟甲基化试剂极大地阻碍了该类化合物的构建。近年来通过自由基路径来高效构建烷基三氟甲基酮类化合物逐渐成为人们关注的热点,但是目前的研究还不够成熟,还需要进一步的完善和突破。
因此,亟待一种绿色环保、产率高的烷基全氟烷基酮类化合物的制备方法。
发明内容
为解决上述技术问题,本发明提供一种烷基全氟烷基酮类化合物及其制备方法。
一方面,本发明提供一种化合物c的制备方法,其包括:
化合物a和化合物b在光敏剂和硅烷存在并于惰性气体氛围条件下,在溶剂中,经光照照射发生反应,得到化合物c,
其中,
R选自取代或未取代的C1-C30烷基、取代或未取代的C1-C30杂烷基、取代或未取代的C1-C30环杂烷基;
Rf选自全氟取代的C1-C10烷基;
X选自氯原子、溴原子或碘原子,优选为溴原子。
在一些实施例中,所述烷基是包含正碳原子、仲碳原子、叔碳原子或环碳原子的烃。
在一些实施例中,所述C1-C30烷基为C1烷基、C2烷基、C3烷基、C4烷基、C5烷基、C6烷基、C7烷基、C8烷基、C9烷基、C10烷基、C11烷基、C12烷基、C13烷基、C14烷基、C15烷基、C16烷基、C17烷基、C18烷基、C19烷基、C20烷基、C21烷基、C22烷基、C23烷基、C24烷基、C25烷基、C26烷基、C27烷基、C28烷基、C29烷基或C30烷基。
在一些实施例中,所述C1-C10烷基为C1烷基、C2烷基、C3烷基、C4烷基、C5烷基、C6烷基、C7烷基、C8烷基、C9烷基或C10烷基。
在一些实施例中,所述C1-C10烷基为甲基(Me、-CH3)、乙基(Et、-CH2CH3)、1-丙基(i-Pr、i-丙基、-CH2CH2CH3)、2-丙基(i-Pr、i-丙基、-CH(CH3)2)、1-丁基(n-Bu、n-丁基、-CH2CH2CH2CH3)、2-甲基-1-丙基(i-Bu、i-丁基、-CH2CH(CH3)2)、2-丁基(s-Bu、s-丁基、-CH(CH3)CH2CH3)、2-甲基-2-丙基(t-Bu、t-丁基、-C(CH3)3)、1-戊基(n-戊基、-CH2CH2CH2CH2CH3)、2-戊基(-CH(CH3)CH2CH2CH3)、3-戊基(-CH(CH2CH3)2)、2-甲基-2-丁基(-C(CH3)2CH2CH3)、3-甲-2-丁基(-CH(CH3)CH(CH3)2)、3-甲基-1-丁基(-CH2CH2CH(CH3)2)、2-甲基-1-丁基(-CH2CH(CH3)CH2CH3)、1-己基(-CH2CH2CH2CH2CH2CH3)、2-己基(-CH(CH3)CH2CH2CH2CH3)、3-己基(-CH(CH2CH3)(CH2CH2CH3))、2-甲基-2-戊基(-C(CH3)2CH2CH2CH3)、3-甲基-2-戊基(-CH(CH3)CH(CH3)CH2CH3)、4-甲基-2-戊基(-CH(CH3)CH2CH(CH3)2)、3-甲基-3-戊基(-C(CH3)(CH2CH3)2)、2-甲基-3-戊基(-CH(CH2CH3)CH(CH3)2)、2,3-二甲基-2-丁基(-C(CH3)2CH(CH3)2)、3,3-二甲基-2-丁基(-CH(CH3)C(CH3)3和辛基(-(CH2)7CH3)。
在一些实施例中,所述取代或未取代的C1-C30杂烷基中的杂烷基表示直链或支化的饱和烃基中一个或多个碳原子独立地被一个或多个杂原子取代,所述一个或多个杂原子分别独立选自氮原子、氧原子、磷原子和硫原子。
在一些实施例中,所述取代或未取代的C1-C30环杂烷基中的环杂烷基表示饱和环烃基中一个或多个碳原子独立地被一个或多个杂原子取代,所述一个或多个杂原子分别独立选自氮原子、氧原子、磷原子和硫原子。
在一些实施例中,所述全氟取代的C1-C10烷基选自三氟甲基、五氟乙基、七氟丙基、九氟丁基、十一氟戊基、十三氟己基、十五氟庚基、十七氟辛基、十九氟壬基、二十一氟癸基。
在一些实施例中,所述取代或未取代的C1-C30烷基包括未取代直链C1-C30烷基、未取代环状C1-C30烷基、未取代支链C1-C30烷基、芳基取代直链C1-C30烷基、芳基取代支链C1-C30烷基、酯基取代直链C1-C30烷基、酯基取代支链C1-C30烷基、杂原子取代直链C1-C30烷基、杂原子取代支链C1-C30烷基、杂原子取代环状C1-C30烷基、卤素取代直链C1-C30烷基、卤素取代支链C1-C30烷基、卤素取代环状C1-C30烷基。
在一些实施例中,所述芳基可以具有6至20个碳原子(例如C6芳基、C7芳基、C8芳基、C9芳基、C10芳基、C11芳基、C12芳基、C13芳基、C14芳基、C15芳基、C16芳基、C17芳基、C18芳基、C19芳基或C20芳基)、6至14个碳原子或6至10个碳原子。在一些实施例中,所述芳基包括苯基、取代的苯基、萘基、蒽基、联苯基等衍生的基团或类似基团。
在一些实施例中,所述卤素选自氟原子、氯原子和溴原子。
在一些实施例中,所述“取代或未取代的”中的取代分別独立表示基团上的一个或多个氢被选自下组的取代基取代:酯基、苯甲酰基、叔丁氧羰基、=O、氟原子、氯原子、溴原子、氰基、C1~C10烷基、C3~C10环烷基、C1~C10杂烷基、C3~C10环杂烃基、C2~C6烯基、C2~C6炔基、C6~C10芳基或C6~C10杂芳基、
其中R1、R2、R3、R4分别独立选自氢原子、氟原子、氯原子、溴原子、氰基、甲基或乙基。
在一些实施例中,所述环烷基表示含有3-20个碳原子的,单价或多价的饱和单环,双环或三环体系。在一实施方案中,环烷基包含3-20个碳原子。在一实施方案中,环烷基包含3-12个碳原子。在另一实施方案中,环烷基包含3-8个碳原子;在又一实施方案中,环烷基包含3-6个碳原子。所述环烷基基团可以独立地未被取代或被一个或多个本发明所描述的取代基所取代。
在一些实施例中,所述烯基是包含具有至少一个不饱和部位,即碳-碳sp2双键的正碳原子、仲碳原子、叔碳原子或环碳原子的烃。在一些实施例中,所述烯基可以具有2至10个碳原子(C2-C10烯基)、2至12个碳原子(C2-C12烯基)或2至6个碳原子(C2-C6烯基)。在一些实施例中,所述烯基包括选自乙烯或乙烯基(-CH=CH2)、烯丙基(-CH2CH=CH2)、环戊烯基(-C5H7)或5-己烯基(-CH2CH2CH2CH2CH=CH2)。
在一些实施例中,所述炔基是包含具有至少一个不饱和部位,即碳-碳sp三键的正碳原子、仲碳原子、叔碳原子或环碳原子的烃。在一些实施例中,所述炔基可以具有2至10个碳原子(C2-C10炔基)、2至12个碳原子(C2-C12炔基)或2至6个碳原子(C2-C6炔基)。在一些实施例中,所述炔基包括选自乙炔基(-C=CH)、炔丙基(-CH2C=CH)或其类似物。
在一些实施例中,所述芳基为通过从母体芳环系统的单个碳原子除去一个氢原子衍生的芳族烃基。在一些实施例中,所述芳基可以具有6至20个碳原子、6至14个碳原子或6至10个碳原子。在一些实施例中,所述芳基包括苯基、萘、蒽、联苯、取代的苯或其衍生的基团或类似基团。
在一些实施例中,所述杂芳基是指在环中具有至少一个杂原子的芳族杂环基,即芳基中的至少一个环碳原子被至少一个杂原子所替代所得芳族杂环基。在一些实施例中,所述杂芳基中的杂原子可以为氧原子、硫原子或氮原子。在一些实施例中,所述杂芳基包括以下任一基团:吲哚基、异吲哚基、1,3-二氧代异吲哚基、嘌呤基、苯并呋喃基、苯并噻吩基、咔唑基、喹啉基、异喹啉基、哒嗪基或嘧啶基等。
在一些实施例中,所述化合物a选自以下化合物1-a至化合物47-a的结构:
在一些实施例中,所述化合物b选自以下化合物1-b、化合物2-b、化合物3-b的结构:
在一些实施例中,所述化合物c选自以下化合物1-化合物47的结构:
在一些实施例中,所述光敏剂选自铱类光敏剂、钌类光敏剂或有机光敏剂中的至少一种。
在一些实施例中,所述铱类光敏剂包括[Ir(dF(Me)ppy2)(dtbbpy)]PF、[Ir(dF(CF3)(ppy)2(dtbbpy)]PF6、[Ir(p-F(CF3)ppy)2(bpy)]PF6、[Ir(ppy)2(bpy)]PF6、[Ir(p-CF3-ppy)2(bpy)]PF6、[Ir(dtbppy)2(dtbbpy)]PF6、
[Ir(m-CF3(CF3)ppy)2bpy]PF6、[Ir(ppyCF3)2bpy]PF6、fac-Ir(ppy)3、[Ir(dmppy)2(dtbbpy)]PF6、
[Ir(ppy)2(dtbbpy)]PF6或[Ir(dF(CF3)ppy)2bpy]PF6、[Ir(dF(CF3)(ppy)2(5,5’-dCF3bpy)]PF6、
[Ir(dF(CF3)(ppy)2(4,4’-dCF3bpy)]PF6中的至少一种。
在一些优选的实施例中,所述铱类光敏剂包括[Ir(dF(Me)ppy2)(dtbbpy)]PF6,
在一些实施例中,所述钌类光敏剂包括[Ru(bpy)3](PF6)或[Ru(bpz)3](PF6)中的至少一种。
在一些优选的实施例中,所述钌类光敏剂包括Ru(bpy)3(PF6)2,
在一些实施例中,所述有机光敏剂包括EosinY、4-CzIPN、4CzPN、3DPA2FBN或3DPAIFPN中的至少一种。
在一些优选的实施例中,所述有机光敏剂包括3DPAIFPN,
在一些实施例中,所述硅烷包括三苯基硅烷(Ph3SiH)、三(三甲基硅基)硅烷((TMS)3SiH)、二苯基硅烷(Ph2SiH2)、苯基二甲基硅烷(PhMe2SiH)、三甲氧基硅烷((MeO)3SiH)、三乙氧基硅烷((EtO)3SiH)、二乙氧基甲基硅烷((MeO)2MeSiH)中的至少一种。在一些优选的实施例中,所述硅烷包括三苯基硅烷(Ph3SiH)。
在一些实施例中,所述惰性气体包括氮气、氦气、氖气、氩气中的至少一种。
在一些实施例中,所述溶剂包括甲基叔丁基醚(MTBE)、二甲基亚砜(DMSO)、乙腈(CH3CN)、四氢呋喃(THF)、2-甲基四氢呋喃(2-Me-THF)、乙二醇二甲醚(DME)、1,4-二氧六环(1,4-dioxane)、乙醚(Et2O)、二氯甲烷(DCM)、N,N-二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)、甲苯(Toluene)的至少一种。在一些优选的实施例中,所述溶剂为甲基叔丁基醚(MTBE)或1,4-二氧六环(1,4-dioxane)中的至少一种。在一些更优选的实施例中,所述溶剂为甲基叔丁基醚(MTBE)。
在一些实施例中,所述光照为蓝光。
在一些实施例中,所述蓝光的波长为400nm~480nm。在一些实施例中,所述蓝光的波长为440nm。
在一些实施例中,所述化合物b与化合物a的投料摩尔比为1.0:1.0-15.0:1.0。在一些实施例中,所述化合物b与化合物a的投料摩尔比为1.0:1.0-10.0:1.0。在一些实施例中,所述化合物b与化合物a的投料摩尔比为1.0:1.0-6.0:1.0。在一些实施例中,所述化合物b与化合物a的投料摩尔比为1.0:1.0-
5.0:1.0。在一些实施例中,所述化合物b与化合物a的投料摩尔比为1.0:1.0-4.0:1.0。
在一些实施例中,所述硅烷与化合物a的投料摩尔比为1.0:1.0-20.0:1.00。在一些优选的实施例中,所述硅烷与化合物a的投料摩尔比为2.0:1.0-10.0:1.0。在一些优选的实施例中,所述硅烷与化合物a的投料摩尔比为2.0:1.0-8.0:1.0。在一些更优选的实施例中,所述硅烷与化合物a的投料摩尔比为4.0:1.0。
在一些实施例中,所述光敏剂与化合物a的投料摩尔比为0.005:1.000-0.100:1.000。在一些优选的实施例中,所述光敏剂与化合物a的投料摩尔比为0.010:1.000-0.050:1.000。在一些更优选的实施例中,所述光敏剂与化合物a的投料摩尔比为0.020:1.000-0.040:1.000。
在一些实施例中,所述吡啶类试剂与化合物a的投料摩尔比为0.1:1.0-5.0:1.0。在一些优选的实施例中,所述吡啶类试剂与化合物a的投料摩尔比为0.5:1.0-3.0:1.0。在一些更优选的实施例中,所述吡啶类试剂与化合物a的投料摩尔比为1.0:1.0-2.0:1.0。
在一些实施例中,所述反应的反应温度为10℃-40℃。在一些实施例中,所述反应的反应温度为15℃-35℃。在一些实施例中,所述反应的反应温度为20℃-30℃。在一些实施例中,所述反应的反应温度为22℃-28℃。在一些实施例中,所述反应的反应温度为24℃-26℃。
在一些实施例中,所述制备方法进一步包括:化合物a和化合物b在光敏剂、硅烷、碱和吡啶类试剂存在并于惰性气体氛围条件下,在溶剂中,经光照照射发生反应,得到化合物c。
在一些实施例中,所述碱包括磷酸氢二钾(K2HPO4)、磷酸二氢钾(KH2PO4)、磷酸三钾
(K3PO4)、碳酸锂(Li2CO3)、碳酸铯(Cs2CO3)、碳酸钾(K2CO3)、醋酸钾(KOAc)、三乙烯二胺(DABCO)中的至少一种。在一些优选的实施例中,所述碱包括三乙烯二胺(DABCO)或磷酸氢二钾(K2HPO4)中的至少一种。在一些更优选的实施例中,所述碱为磷酸氢二钾(K2HPO4)。
在一些实施例中,所述吡啶类试剂包括吡啶、4-二甲氨基吡啶(DMAP)、2-甲基吡啶、2-溴吡啶、2,6-二甲氧基吡啶、2,6-二甲基吡啶、2,6-二氯吡啶、2,6-二乙氧基吡啶、2,6-二丙氧基吡啶、2,6-二环己基吡啶、2,4,6-三甲氧基吡啶、2,4,6-三乙氧基吡啶、2,6-二氯吡啶氮氧化物中的至少一种。在一些优选的实施例中,所述吡啶类试剂为2,6-二正丙氧基吡啶或2,4,6-三乙氧基吡啶中的至少一种。在一些优选的实施例中,所述吡啶类试剂为2,6-二正丙氧基吡啶。
在一些实施例中,所述碱与化合物a的投料摩尔比为0.1:1.0-5.0:1.0,优选为0.2:1.0-1.5:1.0,更优选为0.3:1.0-1.0:1.0。
在一些实施例中,所述化合物c为化合物1~化合物44和化合物47中的任一项,所述化合物a分别对应为化合物1-a~化合物44-a和化合物47-a,所述化合物b为化合物1-b。
在一些实施例中,所述化合物c为化合物45,所述化合物a为化合物45-a,所述化合物b为化合物2-b。
在一些实施例中,所述化合物c为化合物46,所述化合物a为化合物46-a,所述化合物b为化合物3-b。
另一方面,本发明提供一种化合物,所述化合物选自以下化合物1-化合物47的结构:
有益效果
相比现有技术,本发明的某一个实施例至少包括以下一种有益效果:
(1)采用本发明所提供的光敏剂、硅烷,尤其是采用本发明优选的光敏剂和硅烷,有利于将一级、二级、三级烷基溴顺利的在温和的条件下转化为烷基三氟甲基酮类化合物,同时克服了现有技术反应条件苛刻、选择性差,原料来源受限等缺点。
(2)采用本发明所提供的光敏剂和硅烷,尤其是采用本发明优选的光敏剂和硅烷,有利于大大促进和加速反应的发生并提高产物的收率。
(3)本发明所提供的反应中,光敏剂可以为铱类光敏剂、钌类光敏剂或有机光敏剂;其中铱类光敏剂优选为[Ir(dF(Me)ppy2)(dtbbpy)]PF6;钌类光敏剂优选为Ru(bpy)3(PF6)2;有机光敏剂优选为3DPAIFPN;在所有光敏剂中,最优选为[Ir(dF(Me)ppy2)(dtbbpy)]PF6,有利于提高产物产率。
(4)本发明所提供的反应中,硅烷优选为三苯基硅烷、二苯基硅烷,更优选为三苯基硅烷,有利于提高产物产率。
(5)本发明所提供的反应中,所述硅烷与化合物a的投料摩尔比优选为.0:1.0-20.0:1.00,有利于提高产物的收率。所述硅烷与化合物a的投料摩尔比更优选为4.0:1,更有利于提高产物的收率。
(6)采用本发明所提供的碱,有利于提高产物的收率,其中所述碱优选为磷酸氢二钾或三乙烯二胺中的至少一种;更优选为磷酸氢二钾。
(7)本发明所述碱与化合物a的投料摩尔比优选为0.1:1.0-5.0:1.0,有利于提高产物的收率。所述碱与化合物a的投料摩尔比更优选为0.3:1,更有利于提高产物的收率。
(8)采用本发明所提供的吡啶类试剂,所述吡啶类试剂优选为2,6-二正丙氧基吡啶、2,4,6-三乙氧基吡啶、2,6-二氯吡啶-1-氧化物、2,6-二甲氧基吡啶、2,4,6-三甲氧基吡啶、2,6-二异丙氧基吡啶、2,4,6-三甲基吡啶中的至少一种,更优选为2,6-二正丙氧基吡啶、2,6-二氯吡啶-1-氧化物、2,6-二甲氧基吡啶中的至少一种,最优选为2,6-二正丙氧基吡啶,有利于提高产物产率。。
(9)本发明所提供的反应中,所述吡啶与化合物a的投料摩尔比优选为0.1:1.0-5.0:1.0,有利于提高产物的收率。所述碱与化合物a的投料摩尔比更优选为1.0:1,更有利于提高产物的收率。
(10)本发明所提供的反应中,所述溶剂优选为MTBE、THF或1,4-dioxane,更优选为MTBE,有利于提高产物产率。
(11)采用本发明所提供的光敏剂、硅烷和光照为反应的必要条件,缺失任何一个条件,反应均无法进行;另外,除光敏剂、硅烷和光照外,加入吡啶和碱进行反应,更有利于提高产物产率;光敏剂、硅烷、吡啶、碱和光照彼此相互协同,共同促进产物产率的提高。
术语说明
除非另外说明,否则如本文使用的以下术语和短语意图具有以下含义:
术语“多个”表示2个或2个以上,例如2个、3个、4个或5个。
本发明中,如“化合物a”、“式a化合物”和“式a所示化合物”的表述,表示的是同一含义,其他化合物以此类推。
本发明中“室温”指的是环境温度,温度由大约10℃到大约40℃。在一些实施例中,“室温”指的是温度由大约15℃到大约35℃;在一些实施例中,“室温”指的是温度由大约20℃到大约30℃;在一些实施例中,“室温”指的是温度由大约20℃到大约35℃;在另一些实施例中,“室温”指的是温度由大约25℃到大约30℃;在另一些实施例中,“室温”指的是温度由大约22℃到大约28℃;在另一些实施例中,“室温”指的是温度由大约24℃到大约26℃;在又一些实施例中,“室温”指的是10℃、15℃、20℃、25℃、30℃、35℃、40℃等。
术语“和/或”应理解为意指可选项中的任一项或可选项中的任意两项或多项的组合。
术语“任选的”或“任选地”是指随后描述的事件或情形可以但不一定出现,并且该描述包括其中所述事件或情形出现的情况以及其中它不出现的情况。例如,“任选地缩合剂”表示缩合剂可以存在或可以不存在。
术语“杂原子”表示氧原子、氮原子或硫原子。
术语“卤素”表示氟原子、氯原子、溴原子或碘原子。
在本发明的上文中,无论是否使用“大约”或“约”等字眼,所有在此公开了的数字均为近似值。基于公开的数字,每一个数字的数值有可能会出现±10%以下的差异或者本领域人员认为的合理的差异,如±1%、±2%、±3%、±4%或±5%的差异。
基团“Ph”表示苯基。
基团“Boc”表示叔丁氧羰基。
基团“Bz”表示苯甲酰基。
基团“Me”表示甲基。
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外,在不相互矛盾的情况下,本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
术语“芳基”意指通过从母体芳环系统的单个碳原子除去一个氢原子衍生的芳族烃基。
术语“全氟取代”表示所述基团中与碳原子链接的氢原子全部被氟原子所取代。
本发明中,“mmol”表示毫摩尔;“mol”表示摩尔;“Kg”表示千克;“g”表示克;“mg”表示毫克;“eq”或“equiv”表示当量;“L”表示升;“mL”表示毫升;“μl”表示微升;“℃”表示摄氏度;“h”表示小时。
具体实施方式
为了使本领域的技术人员更好地理解本发明的技术方案,下面进一步披露一些非限制实施例以对本发明作进一步的详细说明。
本发明所使用的试剂均可以从市场上购得或者可以通过本发明所描述的方法制备而得。
本发明所用试剂的简称或化学式所对应的中文含义:
简称或化学式 | 中文含义 |
TFAA | 三氟乙酸酐 |
DMSO | 二甲亚砜 |
CH3CN | 乙腈 |
THF | 四氢呋喃 |
2-Me-THF | 2-甲基四氢呋喃 |
DME | 乙二醇二甲醚 |
1,4-dioxane | 1,4-二氧六环 |
Et2O | 乙醚 |
DCM | 二氯甲烷 |
DMF | N,N-二甲基甲酰胺 |
NMP | N甲基吡咯烷酮 |
Toluene | 甲苯 |
DABCO | N,N-二甲基乙醇胺 |
MTBE | 甲基叔丁基醚 |
本发明所用试剂的简称或化学式所对应的结构或CAS号:
实施例1:光敏剂的筛选
分别将如表1所述光敏剂(0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物1-a(26.4mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率,结果见表1。柱层析分离纯化,得到化合物1(无色油状液体),化合物1-a的转化率和分离纯化后产物的产率结果见表1。取适量所得化合物1进行氢谱和氟谱检测,结果如下:
1H NMR(400MHz,Chloroform-d)δ4.16–4.11(m,2H),2.95(tt,J=11.2,3.7Hz,1H),2.84(t,J=12.9Hz,2H),1.92–1.87(m,2H),1.67–1.57(m,2H),1.46(s,9H).
19F NMR(376MHz,Chloroform-d)δ–77.30。
表1:光敏剂的筛选
结论:
(1)在碱、吡啶类试剂和硅烷存在并于惰性气体氛围条件下,相比不加入光敏剂,加入适合的光敏剂能促使化合物1-a和化合物1-b在光照条件下反应得到化合物1;
(2)本发明可采用的光敏剂可以为铱类光敏剂、钌类光敏剂或有机光敏剂;其中铱类光敏剂优选为Ir[dF(Me)ppy]2(dtbbpy)PF6、Ir[dF(CF3)ppy]2(5,5’-dCF3bpy)PF6或Ir[dF(CF3)ppy]2(4,4’-dCF3bpy)PF6;钌类光敏剂优选为Ru(bpy)3(PF6)2;有机光敏剂优选为3DPAIFPN;在所有光敏剂中,最优选为Ir[dF(Me)ppy]2(dtbbpy)PF6,最有利于提高产物产率。
实施例2:硅烷的筛选
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物1-a(26.4mg,0.1mmol,1.0equiv.)和如表2中所示的硅烷(0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率,结果见表2。柱层析分离纯化,得到化合物1(无色油状液体),化合物1-a的转化率和分离纯化后产物的产率结果见表2。取适量所得化合物1进行氢谱和氟谱检测,结果同实施例1。
表2:硅烷的筛选
结论:
(1)在光敏剂、碱和吡啶类试剂存在并于惰性气体氛围条件下,相比不加入硅烷化合物,加入适合的硅烷化合物能促使化合物1-a和化合物1-b在光照条件下反应得到化合物1;
(2)本发明所述硅烷复合物优选为Ph3SiH、Ph2SiH2、PhMe2SiH,更优选为Ph3SiH,有利于提高产物产率。
实施例3:碱的筛选
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),如表3中所示的碱(0.03mmol,0.3equiv.),化合物1-a(26.4mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率,结果见表3。柱层析分离纯化,得到化合物1(无色油状液体),化合物1-a的转化率和分离纯化后产物的产率结果见表3。取适量所得化合物1进行氢谱和氟谱检测,结果同实施例1。
表3:碱的筛选
结论:在化合物1的制备方法中,相比不加入碱,加入适合的碱有利于提高产物产率,所述碱优选为K2HPO4、KOAc或DABCO,更优选为K2HPO4。
实施例4:溶剂的筛选
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物1-a(26.4mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL如表4中所示的溶剂,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率,结果见表4。柱层析分离纯化,得到化合物1(无色油状液体),化合物1-a的转化率和分离纯化后产物的产率结果见表4。取适量所得化合物1进行氢谱和氟谱检测,结果同实施例1。
表4:溶剂的筛选
结论:所述溶剂优选为MTBE、THF或1,4-dioxane,更优选为MTBE,有利于提高产物产率。
实施例5:吡啶类试剂的筛选
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物1-a(26.4mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,如表5中所示的吡啶类试剂(0.1mmol,1equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率,产率结果(即表5中yield)见表5。柱层析分离纯化,得到化合物1(无色油状液体),化合物1-a的转化率(即表5中conv.of 1-a)结果见表5。取适量所得化合物1进行氢谱和氟谱检测,结果同实施例1。
表5:吡啶类试剂的筛选
结论:在化合物1的制备过程中,所述吡啶类试剂优选为2,6-二正丙氧基吡啶、2,4,6-三乙氧基吡啶、2,6-二氯吡啶-1-氧化物、2,6-二甲氧基吡啶、2,4,6-三甲氧基吡啶、2,6-二异丙氧基吡啶、2,4,6-三甲基吡啶等中的至少一种,更优选为2,6-二正丙氧基吡啶、2,6-二氯吡啶-1-氧化物、2,6-二甲氧基吡啶等中的至少一种,最优选为2,6-二正丙氧基吡啶,有利于提高产物产率。
实施例6:控制实验
将如表6所示的光敏剂(0.002mmol,0.02equiv.),如表6所示的硅烷(0.4mmol,4.0equiv),如表6所示的碱(0.03mmol,0.3equiv),如表6所示的吡啶类试剂(0.1mmol,1.0equiv)混和,于氮气氛围条件下分别加入0.3mL甲基叔丁基醚,化合物1-a(26.4mg,0.1mmol,1.0equiv)和化合物1-b(84.0mg,0.40mmol,4.0equiv),在室温条件下,表6中实验1~4和6于30W蓝光灯照射12小时,表6中实验5在暗处放置12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率,产率结果见表6。柱层析分离纯化,得到化合物1(无色油状液体)。取适量所得化合物1进行氢谱和氟谱检测,结果同实施例1。
表6:控制实验各试剂
结论:光敏剂、硅烷和光照为反应的必要条件,缺失任何一个条件,反应均无法进行;另外,若要获得高产率的产物,除光敏剂、硅烷和光照外,加入吡啶和碱进行反应,更有利于提高产物产率;光敏剂、硅烷、吡啶、碱和光照彼此相互协同,共同促进产物产率的提高。
实施例7:化合物2的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物2-a(26.7mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为63%。柱层析分离纯化,得到化合物2(无色油状液体),产率为57%。取适量所得化合物2进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(400MHz,Chloroform-d)δ7.45–7.36(m,5H),4.68(brs,1H),3.86(brs,1H),3.15–2.99(m,3H),1.74(brs,2H).
13C NMR(101MHz,Chloroform-d)δ192.7(q,J=34.0Hz),170.7,135.7,130.1,128.8,127.0,115.8(q,J=291.1Hz),43.2,29.9,27.1.
19F NMR(376MHz,Chloroform-d)δ–77.26。
实施例8:化合物4的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物4-a(24.6mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为70%。柱层析分离纯化,得到化合物4(无色油状液体),产率为61%。取适量所得化合物4进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(400MHz,Chloroform-d)δ3.06(p,J=6.1Hz,1H),1.76–1.56(m,4H),1.44–1.29(m,18H).13C NMR(101MHz,Chloroform-d)δ195.4(q,J=33.0Hz),116.0(q,J=291.6Hz),42.4,25.8,23.7,25.6,23.5,23.4,22.4
19F NMR(376MHz,Chloroform-d)δ-77.98。
实施例9:化合物6的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物6-a(19.8mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为81%。柱层析分离纯化,得到化合物6(无色油状液体),产率为76%。取适量所得化合物6进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(400MHz,Chloroform-d)δ7.43–7.31(m,4H),7.27–7.23(m,1H),3.37(h,J=7.5Hz,1H),3.21(dd,J=13.7,6.4Hz,1H),2.75(dd,J=13.7,7.9Hz,1H),1.30(d,J=6.9Hz,3H).
13C NMR(151MHz,Chloroform-d)δ194.9(q,J=34.0Hz),138.1,129.2,128.8,127.0,115.8(q,J=293.2Hz),43.0,38.3,16.0.
19F NMR(376MHz,Chloroform-d)δ-77.98.
实施例10:化合物7的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物7-a(26.9mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为45%。柱层析分离纯化,得到化合物7(无色油状液体),产率为37%。取适量所得化合物7进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(400MHz,Chloroform-d)δ7.50(d,J=8.0Hz,2H),7.35–7.29(m,2H),7.1893–7.0539(m,2H),3.02(h,J=6.7Hz,1H),2.44–2.30(m,2H),1.90–1.74(m,2H),1.70–1.60(m,2H),1.24(d,J=7.0Hz,3H)。
13C NMR(101MHz,Chloroform-d)δ195.3(q,J=33.5Hz),170.3,137.8,129.2,124.5,119.9,116.0(q,J=293.2Hz),40.9,37.3,31.8,22.8,16.3。
19F NMR(376MHz,Chloroform-d)δ-77.85。
实施例11:化合物8的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物8-a(29.5mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为85%。柱层析分离纯化,得到化合物8(无色油状液体),产率为77%。取适量所得化合物8进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(400MHz,Chloroform-d)δ7.85(dd,J=5.4,3.1Hz,2H),7.72(dd,J=5.5,3.1Hz,2H),3.69(t,J=7.0Hz,2H),3.03(h,J=6.9Hz,1H),1.89–1.77(m,1H),1.73–1.64(m,2H),1.55–1.44(m,1H),1.21(d,J=6.9Hz,3H).。
13C NMR(101MHz,Chloroform-d)δ195.0(q,J=33.5Hz),168.5,134.2,132.2,123.4,115.8(q,J=291.3Hz),40.5,37.5,29.4,26.1,16.3.。
19F NMR(376MHz,Chloroform-d)δ-78.00。
实施例12:化合物9的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物9-a(32.0mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为88%。柱层析分离纯化,得到化合物9(无色油状液体),产率为78%。取适量所得化合物9进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(400MHz,Chloroform-d)δ7.93–7.88(m,2H),7.69–7.63(m,1H),7.59–7.53(m,2H),4.04(t,J=6.3Hz,2H),2.91(h,J=6.8Hz,1H),1.75–1.62(m,3H),1.44–1.24(m,3H),1.17(d,J=6.9Hz,3H)。
13C NMR(101MHz,Chloroform-d)δ195.1(q,J=33.3Hz),136.2,133.9,129.4,128.0,115.8(q,J=291.3Hz),70.3,40.8,31.6,28.8,23.0,16.2。
19F NMR(376MHz,Chloroform-d)δ-77.99。
实施例13:化合物10的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物10-a(33.8mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为75%。柱层析分离纯化,得到化合物10(无色油状液体),产率为63%。取适量所得化合物10进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(400MHz,Chloroform-d)δ7.96–7.89(m,2H),7.28–7.21(m,3H),4.04(t,J=6.2Hz,2H),2.93(h,J=6.9Hz,1H),1.79–1.62(m,3H),1.47–1.24(m,3H),1.19(d,J=6.9Hz,3H)。
13C NMR(101MHz,Chloroform-d)δ195.1(q,J=33.4Hz),165.9(d,J=255.2Hz),132.3(d,J=33.8Hz),130.8(d,J=94.4Hz),116.8(d,J=22.5Hz),115.8(q,J=291.3Hz),70.4,40.8,31.7,28.8,23.0,16.2。
19F NMR(376MHz,Chloroform-d)δ-78.02,-103.07。
实施例14:化合物12的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物12-a(28.4mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为58%。柱层析分离纯化,得到化合物12(无色油状液体),产率为50%。取适量所得化合物12进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(600MHz,Chloroform-d)δ8.05–8.01(m,2H),7.58–7.54(m,1H),7.47–7.42(m,2H),4.32(t,J=6.6Hz,2H),3.01(h,J=6.9Hz,1H),1.90–1.82(m,1H),1.82–1.75(m,2H),1.57–1.40(m,3H),1.23(d,J=6.9Hz,3H)。
13C NMR(151MHz,Chloroform-d)δ195.3(q,J=33.3Hz),166.8,133.1,130.4,129.7,128.5,115.7(q,J=291.3Hz),64.6,40.9,32.0,28.7,23.6,16.2。
19F NMR(565MHz,Chloroform-d)δ-77.98。
实施例15:化合物15的制备
将Ir[dF(Me)ppy]2(dtbbpy)PF6(2.0mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物15-a(29.8mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为60%。柱层析分离纯化,得到化合物15(无色油状液体),产率为57%。取适量所得化合物15进行氢谱、碳谱和氟谱检测,结果如下:1H NMR(600MHz,Chloroform-d)δ4.07(t,J=6.5Hz,2H),3.55(t,J=6.1Hz,2H),2.98(h,J=6.9Hz,1H),2.34(t,J=6.9Hz,2H),1.86–1.75(m,5H),1.67–1.60(m,2H),1.51–1.43(m,1H),1.40–1.31(m,2H),1.22(d,J=6.9Hz,3H)。
13C NMR(151MHz,Chloroform-d)δ195.3(q,J=33.7Hz),173.3,115.9(q,J=293.4Hz),64.1,44.6,40.9,33.5,32.0,28.6,23.5,22.4,16.2。
19F NMR(565MHz,Chloroform-d)δ-78.01。
实施例16:化合物17的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物17-a(25.0mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为60%。柱层析分离纯化,得到化合物17(无色油状液体),产率为49%。取适量所得化合物17进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(400MHz,Chloroform-d)δ4.07(t,J=6.7Hz,2H),2.99(h,J=6.8Hz,1H),2.31(td,J=7.2,2.0Hz,2H),1.85–1.75(m,1H),1.72–1.58(m,4H),1.53–1.43(m,1H),1.43–1.32(m,2H),1.22(d,J=6.9Hz,3H),0.93(t,J=7.4Hz,3H)。
13C NMR(101MHz,Chloroform-d)δ195.1(q,J=33.4Hz),173.2,115.8(q,J=291.3Hz),64.5,40.8,34.0,31.7,30.8,22.4,19.3,16.1,13.8。
19F NMR(376MHz,Chloroform-d)δ-77.94。
实施例17:化合物18的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物18-a(27.6mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为51%。柱层析分离纯化,得到化合物18(无色油状液体),产率为39%。取适量所得化合物18进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(400MHz,Chloroform-d)δ4.79–4.71(m,1H),2.98(h,J=6.8Hz,1H),2.29(td,J=7.2,1.4Hz,2H),1.87–1.77(m,3H),1.77–1.59(m,4H),1.59–1.30(m,7H),1.22(d,J=7.0Hz,3H)。
13C NMR(101MHz,Chloroform-d)δ195.1(q,J=33.4Hz),172.6,115.9(q,J=291.4Hz),72.9,40.8,34.4,31.8,31.7,25.5,23.9,22.5,16.1。
19F NMR(376MHz,Chloroform-d)δ-77.93。
实施例18:化合物21的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物21-a(35.2mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为68%。柱层析分离纯化,得到化合物21(无色油状液体),产率为55%。取适量所得化合物21进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(400MHz,Chloroform-d)δ2.86(tt,J=12.4,3.5Hz,1H),2.43(dd,J=19.2,8.7Hz,1H),2.08(dt,J=18.8,8.9Hz,1H),1.96–1.89(m,3H),1.84–1.77(m,1H),1.67–1.24(m,14H),1.23–1.14(m,1H),1.14–1.01(m,1H),0.99(s,3H),0.85(s,3H)。
13C NMR(101MHz,Chloroform-d)δ221.3,194.7(q,J=33.3Hz),116.0(q,J=293.5Hz),51.4,47.9,46.0,42.8,40.8,36.2,36.1,35.5,35.1,31.7,28.3,26.9,25.3,23.8,22.8,21.9,20.3,13.9。
19F NMR(376MHz,Chloroform-d)δ-77.60。
实施例19:化合物22的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(5.3mg,0.03mmol,0.3equiv.),化合物22-a(34.8mg,0.1mmol,1.0equiv.)和三苯基硅烷(104.2mg,0.4mmol,4.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(84.0mg,0.4mmol,4.0equiv.),在室温条件下于30W蓝光灯照射12小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为59%。柱层析分离纯化,得到化合物22(无色油状液体),产率为55%。取适量所得化合物22进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(400MHz,Chloroform-d)δ7.93–7.88(m,2H),7.70–7.63(m,1H),7.60–7.53(m,2H),4.03(td,J=6.4,2.1Hz,2H),2.88(p,J=6.8Hz,1H),1.72–1.60(m,4H),1.51–1.38(m,2H),1.31–1.21(m,4H),0.90(t,J=7.3Hz,3H)。
13C NMR(101MHz,Chloroform-d)δ195.2(q,J=33.7Hz),136.2,133.9,129.4,128.0,115.7(q,J=291.2Hz),70.3,46.2,33.4,30.5,28.9,23.2,20.3,14.0。
19F NMR(376MHz,Chloroform-d)δ-78.76。
实施例20:化合物24的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物24-a(21.2mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为82%。柱层析分离纯化,得到化合物24(无色油状液体),产率为82%。取适量所得化合物24进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(400MHz,Chloroform-d)δ7.32–7.26(m,2H),7.23–7.15(m,3H),2.73(t,J=6.7Hz,2H),2.65(t,J=7.1Hz,2H),1.78–1.63(m,4H)。
13C NMR(101MHz,Chloroform-d)δ190.5(q,J=34.7Hz),141.8,128.6,128.5,126.1,115.7(q,J=290.4Hz),36.3,35.6,30.6,22.1。
19F NMR(376MHz,Chloroform-d)δ-79.34。
实施例21:化合物26的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物26-a(26.7mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为70%。柱层析分离纯化,得到化合物26(无色油状液体),产率为69%。取适量所得化合物26进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(400MHz,Chloroform-d)δ7.60–7.55(m,2H),6.95–6.89(m,2H),4.01(t,J=6.3Hz,2H),2.76(t,J=7.1Hz,2H),1.88–1.81(m,2H),1.80–1.73(m,2H),1.56–1.50(m,2H)。
13C NMR(101MHz,Chloroform-d)δ190.9(q,J=34.8Hz),162.4,134.1,119.4,116.0(q,J=290.2Hz),104.1,68.0,36.3,28.8,25.4,22.2。
19F NMR(565MHz,Chloroform-d)δ-79.33。
实施例22:化合物27的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物27-a(30.9mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为73%。柱层析分离纯化,得到化合物27(无色油状液体),产率为66%。取适量所得化合物27进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(400MHz,Chloroform-d)δ7.86–7.81(m,2H),7.73–7.68(m,2H),3.68(t,J=7.2Hz,2H),2.70(t,J=7.2Hz,2H),1.72–1.64(m,4H),1.41–1.34(m,4H)。
13C NMR(101MHz,Chloroform-d)δ190.6(q,J=35.0Hz),168.6,134.1,132.3,123.4,115.8(q,J=292.3Hz),37.9,36.4,28.5,28.4,26.5,22.3。
19F NMR(565MHz,Chloroform-d)δ-79.32。
实施例23:化合物30的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物30-a(29.2mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为80%。柱层析分离纯化,得到化合物30(无色油状液体),产率为71%。取适量所得化合物30进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(600MHz,Chloroform-d)δ4.08(t,J=6.6Hz,2H),3.96(dt,J=11.6,3.6Hz,2H),3.43(td,J=11.3,3.0Hz,2H),2.72(t,J=7.1Hz,2H),2.58–2.48(m,1H),1.88–1.74(m,4H),1.74–1.60(m,4H),1.43–1.34(m,4H)。
13C NMR(151MHz,Chloroform-d)δ191.6(q,J=34.9Hz),174.7,115.7(q,J=290.3Hz),67.3,64.5,40.3,36.3,28.8,28.5,28.5,25.7,22.4。
19F NMR(376MHz,Chloroform-d)δ-79.34。
实施例24:化合物32的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物32-a(28.4mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为75%。柱层析分离纯化,得到化合物32(无色油状液体),产率为68%。取适量所得化合物32进行氢谱、碳谱和氟谱检测,结果如下:1HNMR(600MHz,Chloroform-d)δ8.05–8.01(m,2H),7.58–7.53(m,1H),7.46–7.42(t,J=7.8Hz,2H),4.32(t,J=6.8Hz,2H),2.72(t,J=7.2Hz,2H),1.78(p,J=6.8Hz,2H),1.71(p,J=7.2Hz,2H),1.52–1.38(m,4H)。
13C NMR(151MHz,Chloroform-d)δ191.6(q,J=34.6Hz),166.8,133.0,130.5,129.7,128.5,115.7(q,J=290.3Hz),64.9,36.4,28.6,28.5,25.9,22.4。
19F NMR(565MHz,Chloroform-d)δ-79.34。
实施例25:化合物35的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物35-a(30.9mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为71%。柱层析分离纯化,得到化合物35(无色油状液体),产率为66%。取适量所得化合物35进行氢谱、碳谱和氟谱检测,结果如下:
1H NMR(600MHz,Chloroform-d)δ8.15–8.11(m,2H),7.77–7.73(m,2H),4.35(t,J=6.6Hz,2H),2.73(t,J=7.1Hz,2H),1.80(p,J=6.6Hz,2H),1.72(p,J=7.1Hz,2H),1.51–1.38(m,4H)。
13C NMR(151MHz,Chloroform-d)δ191.6(q,J=35.0Hz),165.1,134.3,132.4,130.2,118.1,116.5,115.7(q,J=290.4Hz),65.7,36.3,28.51,28.50,25.8,22.4。
19F NMR(565MHz,Chloroform-d)δ-79.34。
实施例26:化合物36的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物36-a(27.4mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为66%。柱层析分离纯化,得到化合物36(无色油状液体),产率为62%。取适量所得化合物36进行氢谱、碳谱和氟谱检测,结果如下:
1H NMR(600MHz,Chloroform-d)δ7.58(dd,J=1.8,0.9Hz,1H),7.17(dd,J=3.5,0.9Hz,1H),6.51(dd,J=3.5,1.7Hz,1H),4.30(t,J=6.6Hz,2H),2.72(t,J=7.2Hz,2H),1.80–1.67(m,4H),1.48–1.38(m,4H)。
13C NMR(151MHz,Chloroform-d)δ191.6(q,J=34.7Hz),159.0,146.4,144.9,118.0,115.7(q,J=290.3Hz),112.0,64.9,36.4,28.6,28.5,25.7,22.4。
19F NMR(565MHz,Chloroform-d)δ-79.34。
实施例27:化合物37的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物37-a(32.0mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为65%。柱层析分离纯化,得到化合物37(无色油状液体),产率为57%。取适量所得化合物37进行氢谱、碳谱和氟谱检测,结果如下:
1H NMR(600MHz,Chloroform-d)δ7.94–7.89(m,2H),7.69–7.63(m,1H),7.60–7.53(m,2H),4.05(t,J=6.3Hz,2H),2.68(t,J=7.2Hz,2H),1.71–1.60(m,4H),1.40–1.27(m,4H)。
13C NMR(151MHz,Chloroform-d)δ191.5(q,J=34.7Hz),136.3,133.9,129.4,128.0,115.7(q,J=290.3Hz),70.6,36.3,28.7,28.2,25.2,22.2。
19F NMR(376MHz,Chloroform-d)δ-79.34。
实施例28:化合物38的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物24-a(35.4mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为63%。柱层析分离纯化,得到化合物38(无色油状液体),产率为59%。取适量所得化合物38进行氢谱、碳谱和氟谱检测,结果如下:
1H NMR(600MHz,Chloroform-d)δ7.94–7.89(m,2H),7.69–7.64(m,1H),7.59–7.53(m,2H),4.05(t,J=6.3Hz,2H),2.68(t,J=7.2Hz,2H),1.70–1.60(m,4H),1.40–1.27(m,4H)。
13C NMR(151MHz,Chloroform-d)δ191.5(q,J=34.6Hz),136.3,133.9,129.4,128.0,115.7(q,J=290.3Hz),70.6,36.3,28.7,28.2,25.2,22.2。
19F NMR(376MHz,Chloroform-d)δ-79.34。
实施例29:化合物41的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物41-a(26.0mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为62%。柱层析分离纯化,得到化合物41(无色油状液体),产率为55%。取适量所得化合物41进行氢谱、碳谱和氟谱检测,结果如下:
1H NMR(600MHz,Chloroform-d)δ4.12–4.08(m,2H),2.72(t,J=7.2Hz,2H),2.57–2.47(m,4H),1.98(s,1H),1.73–1.60(m,4H),1.41–1.35(m,4H)。
13C NMR(151MHz,Chloroform-d)δ191.6(q,J=34.6Hz),172.0,115.7(q,J=290.4Hz),82.6,69.1,64.7,36.3,33.5,28.4,25.7,22.3,14.5。
19F NMR(376MHz,Chloroform-d)δ-79.32。
实施例30:化合物44的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物44-a(24.2mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物1-b(126.0mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为64%。柱层析分离纯化,得到化合物44(无色油状液体),产率为60%。取适量所得化合物44进行氢谱、碳谱和氟谱检测,结果如下:
1H NMR(600MHz,Chloroform-d)δ2.18(hept,J=3.0Hz,1H),1.79(d,J=2.3Hz,2H),1.57(q,J=12.6Hz,4H),1.44–1.34(m,4H),1.26–1.14(m,2H),0.88(s,6H)。
13C NMR(151MHz,Chloroform-d)δ195.1(q,J=31.3Hz),116.5(q,J=293.2Hz),50.5,47.1,43.3,42.6,36.0,30.9,30.5,28.9。
19F NMR(376MHz,Chloroform-d)δ-72.14。
实施例31:化合物46的制备
将Ir[dF(CF3)ppy]2(5,5’-dCF3bbpy)PF6(2.3mg,0.002mmol,0.02equiv.),K2HPO4(17.4mg,0.1mmol,1.0equiv.),化合物24-a(21.2mg,0.1mmol,1.0equiv.)和三苯基硅烷(208.4mg,0.8mmol,8.0equiv.)混和,在氮气氛围的条件下加入0.3mL甲基叔丁基醚,2,6-二正丙氧基吡啶(19.5mg,0.1mmol,1.0equiv.)和化合物3-b(246mg,0.6mmol,6.0equiv.),在室温条件下于30W蓝光灯照射20小时,然后加入5mL饱和碳酸氢钠水溶液和5mL乙酸乙酯稀释。待反应液分层后,水相用乙酸乙酯萃取两次(5mL×2)。然后合并有机相并用饱和氯化钠水溶液清洗,再用无水硫酸镁干燥,然后将有机相浓缩,加入苯基三甲基硅烷作为核磁内标,经核磁氢谱确定反应产率为46%。柱层析分离纯化,得到化合物46(无色油状液体),产率为40%。取适量所得化合物46进行氢谱、碳谱和氟谱检测,结果如下:
1H NMR(600MHz,Chloroform-d)δ7.26–7.32(m,2H),7.23–7.14(m,3H),2.76(t,J=6.7Hz,2H),2.65(t,J=7.2Hz,2H),1.77–7.62(m,4H)。
13C NMR(151MHz,Chloroform-d)δ194.13(t,J=26.0Hz),141.8,128.6,128.5,126.1,117.5(qt,J=287.9,33.5Hz),108.8(tt,J=267.8,32.1Hz),117.5(qt,J=266.3,33.4Hz),37.9,35.7,30.5,22.1。
19F NMR(377MHz,Chloroform-d)δ-80.60(t,J=8.8Hz),-121.17(q,J=9.0Hz),-126.64。
本发明的方法已经通过较佳实施例进行了描述,相关人员明显能在本发明内容、精神和范围内对本文所述的方法和应用进行改动或适当变更与组合,来实现和应用本发明技术。本领域技术人员可以借鉴本文内容,适当改进工艺参数实现。特别需要指出的是,所有类似的替换和改动对本领域技术人员来说是显而易见的,它们都被视为包括在本发明内。
Claims (12)
2.根据权利要求1所述的制备方法,所述取代或未取代的C1-C30烷基中的烷基为包含正碳原子、仲碳原子、叔碳原子或环碳原子的烃;和/或
所述取代或未取代的C1-C30杂烷基中的杂烷基表示直链或支化的饱和烃基中一个或多个碳原子独立地被一个或多个杂原子取代,所述一个或多个杂原子分别独立选自氮原子、氧原子、磷原子和硫原子;和/或
所述取代或未取代的C1-C30环杂烷基中的环杂烷基表示饱和环烃基中一个或多个碳原子独立地被一个或多个杂原子取代,所述一个或多个杂原子分别独立选自氮原子、氧原子、磷原子和硫原子;和/或
所述全氟取代的C1-C10烷基选自三氟甲基、五氟乙基、七氟丙基、九氟丁基、十一氟戊基、十三氟己基、十五氟庚基、十七氟辛基、十九氟壬基、二十一氟癸基。
3.根据权利要求1所述的制备方法,所述取代或未取代的C1-C30烷基包括未取代直链C1-C30烷基、未取代环状C1-C30烷基、未取代支链C1-C30烷基、芳基取代直链C1-C30烷基、芳基取代支链C1-C30烷基、酯基取代直链C1-C30烷基、酯基取代支链C1-C30烷基、杂原子取代直链C1-C30烷基、杂原子取代支链C1-C30烷基、杂原子取代环状C1-C30烷基、卤素取代直链C1-C30烷基、卤素取代支链C1-C30烷基、卤素取代环状C1-C30烷基;和/或
所述卤素选自氟原子、氯原子和溴原子。
4.根据权利要求1所述的制备方法,所述“取代或未取代的”中的取代分別独立表示基团上的一个或多个氢被选自下组的取代基取代:酯基、苯甲酰基、叔丁氧羰基、=O、氟原子、氯原子、溴原子、氰基、C1~C10烷基、C3~C10环烷基、C1~C10杂烷基、C3~C10环杂烃基、C2~C6烯基、C2~C6炔基、C6~C10芳基或C6~C10杂芳基、
其中R1、R2、R3、R4、R5分别独立选自氢原子、氟原子、氯原子、溴原子、氰基、甲基或乙基;和/或
所述环烷基表示含有3-20个碳原子的,单价或多价的饱和单环,双环或三环体系;和/或
所述烯基是包含具有至少一个不饱和部位,即碳-碳sp2双键的正碳原子、仲碳原子、叔碳原子或环碳原子的烃;和/或
所述炔基是包含具有至少一个不饱和部位,即碳-碳sp三键的正碳原子、仲碳原子、叔碳原子或环碳原子的烃;和/或
所述芳基为通过从母体芳环系统的单个碳原子除去一个氢原子衍生的芳族烃基;和/或
所述杂芳基是指在环中具有至少一个杂原子的芳族杂环基;和/或
所述杂芳基包括以下任一基团:吲哚基、异吲哚基、1,3-二氧代异吲哚基、嘌呤基、苯并呋喃基、苯并噻吩基、咔唑基、喹啉基、异喹啉基、哒嗪基或嘧啶基。
6.根据权利要求1所述的制备方法,所述光敏剂选自铱类光敏剂、钌类光敏剂或有机光敏剂中的至少一种。
7.根据权利要求6所述的制备方法,所述铱类光敏剂包括[Ir(dF(Me)ppy2)(dtbbpy)]PF、[Ir(dF(CF3)(ppy)2(dtbbpy)]PF6、[Ir(p-F(CF3)ppy)2(bpy)]PF6、[Ir(ppy)2(bpy)]PF6、[Ir(p-CF3-ppy)2(bpy)]PF6、[Ir(dtbppy)2(dtbbpy)]PF6、[Ir(m-CF3(CF3)ppy)2bpy]PF6、[Ir(ppyCF3)2bpy]PF6、fac-Ir(ppy)3、[Ir(dmppy)2(dtbbpy)]PF6、[Ir(ppy)2(dtbbpy)]PF6或[Ir(dF(CF3)ppy)2bpy]PF6、[Ir(dF(CF3)(ppy)2(5,5’-dCF3bpy)]PF6、[Ir(dF(CF3)(ppy)2(4,4’-dCF3bpy)]PF6中的至少一种;
优选地,所述铱类光敏剂包括[Ir(dF(Me)ppy2)(dtbbpy)]PF6,
所述钌类光敏剂包括[Ru(bpy)3](PF6)或[Ru(bpz)3](PF6)中的至少一种;
优选地,所述钌类光敏剂包括[Ru(bpy)3](PF6),
所述有机光敏剂包括EosinY、4-CzIPN、4CzPN、3DPA2FBN或3DPAIFPN中的至少一种;
优选地,所述有机光敏剂包括3DPAIFPN,
8.根据权利要求1-7任一项所述的制备方法,所述硅烷包括三苯基硅烷、三(三甲基硅基)硅烷、二苯基硅烷、苯基二甲基硅烷、三甲氧基硅烷、三乙氧基硅烷、二乙氧基甲基硅烷中的至少一种,优选为三苯基硅烷;和/或
所述惰性气体包括氮气、氦气、氖气、氩气中的至少一种;和/或
所述溶剂包括甲基叔丁基醚、二甲基亚砜、乙腈、四氢呋喃、2-甲基四氢呋喃、乙二醇二甲醚、1,4-二氧六环、乙醚、二氯甲烷、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲苯的至少一种,优选为甲基叔丁基醚或1,4-二氧六环中的至少一种,更优选为甲基叔丁基醚;和/或
所述光照为蓝光;和/或
所述蓝光的波长为400nm~480nm;和/或
所述化合物b与化合物a的投料摩尔比为1.0:1.0-15.0:1.0、1.0:1.0-10.0:1.0、1.0:1.0-6.0:1.0、1.0:1.0-5.0:1.0或1.0:1.0-4.0:1.0;和/或
所述硅烷与化合物a的投料摩尔比为1.0:1.0-20.0:1.00,优选为2.0:1.0-10.0:1.0或2.0:1.0-8.0:1.0,更优选为4.0:1.0;和/或
所述光敏剂与化合物a的投料摩尔比为0.005:1.000-0.100:1.000,优选为0.010:1.000-0.050:1.000,更优选为0.020:1.000-0.040:1.000。
9.根据权利要求1-8任一项所述的制备方法,所述制备方法进一步包括:化合物a和化合物b在光敏剂、硅烷、碱和吡啶类试剂存在并于惰性气体氛围条件下,在溶剂中,经光照照射发生反应,得到化合物c。
10.根据权利要求9所述的制备方法,所述碱包括磷酸氢二钾、磷酸二氢钾、磷酸三钾、碳酸锂、碳酸铯、碳酸钾、醋酸钾、三乙烯二胺中的至少一种,优选为三乙烯二胺或磷酸氢二钾中的至少一种,更优选为磷酸氢二钾;和/或
所述吡啶类试剂包括吡啶、4-二甲氨基吡啶、2-甲基吡啶、2-溴吡啶、2,6-二甲氧基吡啶、2,6-二甲基吡啶、2,6-二氯吡啶、2,6-二乙氧基吡啶、2,6-二丙氧基吡啶、2,6-二环己基吡啶、2,4,6-三甲氧基吡啶、2,4,6-三乙氧基吡啶、2,6-二氯吡啶氮氧化物中的至少一种;优选地,所述吡啶类试剂为2,6-二正丙氧基吡啶或2,4,6-三乙氧基吡啶中的至少一种;更优选地,所述吡啶类试剂为2,6-二正丙氧基吡啶。
11.根据权利要求9所述的制备方法,所述碱与化合物a的投料摩尔比为0.1:1.0-5.0:1.0,优选为0.2:1.0-1.5:1.0,更优选为0.3:1.0-1.0:1.0;和/或
所述吡啶类试剂与化合物a的投料摩尔比为0.1:1.0-5.0:1.0,优选为0.5:1.0-3.0:1.0,更优选为1.0:1.0-2.0:1.0。
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