CN108558932B - 二(2-吡啶基)甲基取代氨基酚氧基镁络合物及其制备方法和应用 - Google Patents
二(2-吡啶基)甲基取代氨基酚氧基镁络合物及其制备方法和应用 Download PDFInfo
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- CN108558932B CN108558932B CN201810469175.5A CN201810469175A CN108558932B CN 108558932 B CN108558932 B CN 108558932B CN 201810469175 A CN201810469175 A CN 201810469175A CN 108558932 B CN108558932 B CN 108558932B
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- pyridyl
- methyl
- bis
- substituted
- lactide
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- -1 Bis (2-pyridyl) methyl-substituted aminophenoxy magnesium Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000010668 complexation reaction Methods 0.000 title description 2
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003446 ligand Substances 0.000 claims abstract description 39
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000002596 lactones Chemical class 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 186
- 238000006243 chemical reaction Methods 0.000 claims description 105
- 239000011777 magnesium Substances 0.000 claims description 87
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 66
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 43
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 229910052749 magnesium Inorganic materials 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 11
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 150000003938 benzyl alcohols Chemical class 0.000 claims description 4
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- QPOWUYJWCJRLEE-UHFFFAOYSA-N dipyridin-2-ylmethanone Chemical class C=1C=CC=NC=1C(=O)C1=CC=CC=N1 QPOWUYJWCJRLEE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- WYPTZCBYSQFOQS-UHFFFAOYSA-N magnesium;bis(trimethylsilyl)azanide Chemical compound [Mg+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C WYPTZCBYSQFOQS-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 20
- 238000003786 synthesis reaction Methods 0.000 abstract description 20
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000004626 polylactic acid Substances 0.000 abstract description 9
- FCGLICWCDOOFJH-UHFFFAOYSA-M N[Mg]OC1=CC=CC=C1 Chemical class N[Mg]OC1=CC=CC=C1 FCGLICWCDOOFJH-UHFFFAOYSA-M 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 67
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 66
- 238000005481 NMR spectroscopy Methods 0.000 description 34
- 229910052786 argon Inorganic materials 0.000 description 33
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 31
- 238000009826 distribution Methods 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 28
- 239000007787 solid Substances 0.000 description 17
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 16
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 238000004809 thin layer chromatography Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 8
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DHVHFHPLOHDSTL-UHFFFAOYSA-N 2-(bromomethyl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(CBr)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 DHVHFHPLOHDSTL-UHFFFAOYSA-N 0.000 description 4
- BPXSTKLPJOGEDW-UHFFFAOYSA-N 2-(bromomethyl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(CBr)=C(O)C(C(C)(C)C)=C1 BPXSTKLPJOGEDW-UHFFFAOYSA-N 0.000 description 4
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002680 magnesium Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- FZJCXIDLUFPGPP-UHFFFAOYSA-N propan-2-ol;toluene Chemical compound CC(C)O.CC1=CC=CC=C1 FZJCXIDLUFPGPP-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- WIMDKCGAUGHBFY-UHFFFAOYSA-N 2-(bromomethyl)-4-methyl-6-tritylphenol Chemical compound CC1=CC(CBr)=C(O)C(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 WIMDKCGAUGHBFY-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000012694 Lactone Polymerization Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 2
- 229920006237 degradable polymer Polymers 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XMBWFLKSDZBLJB-UHFFFAOYSA-N 1h-pyrazol-5-ylboron Chemical compound [B]C1=CC=NN1 XMBWFLKSDZBLJB-UHFFFAOYSA-N 0.000 description 1
- OZZQHCBFUVFZGT-UHFFFAOYSA-N 2-(2-hydroxypropanoyloxy)propanoic acid Chemical compound CC(O)C(=O)OC(C)C(O)=O OZZQHCBFUVFZGT-UHFFFAOYSA-N 0.000 description 1
- GNIHGYYYCAZOCF-UHFFFAOYSA-N 2-(bromomethyl)-4,6-dichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1CBr GNIHGYYYCAZOCF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WSJYLXHEBYSASF-UHFFFAOYSA-N C[Si](C)(C)N([Mg])[Si](C)(C)C Chemical compound C[Si](C)(C)N([Mg])[Si](C)(C)C WSJYLXHEBYSASF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PPTOKWQPWFOWSR-UHFFFAOYSA-N N1N=C(C=C1)[Mg]N Chemical compound N1N=C(C=C1)[Mg]N PPTOKWQPWFOWSR-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- 229940066769 systemic antihistamines substituted alkylamines Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
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Abstract
本发明公开了一类二(2‑吡啶基)甲基取代氨基酚氧基镁络合物及其制备方法和在高活性、较高选择性催化内酯开环聚合中的应用。本发明的二(2‑吡啶基)甲基取代氨基酚氧基镁络合物可通过中性配体直接与镁金属原料化合物在有机介质中反应得到,是一种高效的内酯开环聚合催化剂,可用于催化丙交酯等内酯的聚合反应;特别对于外消旋丙交酯聚合可得到较高等规度的聚乳酸。本发明的二(2‑吡啶基)甲基取代氨基酚氧基镁络合物优点十分明显:原料易得,合成路线简单,产物收率高,具有很高的催化活性和较高立体选择性,能获得较高规整度、高分子量聚酯材料,能够满足工业部门的需要。其结构式如下所示:
Description
技术领域
本发明涉及一类二(2-吡啶基)甲基取代的氨基酚氧基镁络合物,以及这类络合物在内酯聚合中的应用。
背景技术
聚烯烃材料具有质轻、耐用以及价格低廉等优点,业已成为人们不可或缺的生产生活用品。聚烯烃材料的广泛使用也带来严重的能源与环境问题,危害动植物生长,威胁人类生存与健康,因此寻找可再生、可降解的新型聚合物材料代替聚烯烃材料已刻不容缓。在众多可降解聚合物中,被称为“绿色塑料”的聚乳酸因其具有良好的生物相容性、可降解性和优异的加工性能而被广泛研究。聚乳酸(PLA)目前在医用领域有着广泛的应用,如被用作药物释缓材料、体内植入材料、手术缝合线、骨折固定材料、组织工程材料等,在包装行业、纺织行业、电子行业、汽车行业的应用也取得一定进展。聚乳酸的原料为乳酸,可由可再生的植物资源经加工得到,其原料来源广泛,且废弃物在自然界的微生物等介质作用下完全分解,最终产物CO2和H2O对人体无害,对环境无污染。这些良好的特性和广泛的应用前景吸引着各国科学家对聚乳酸的合成及相关催化剂的设计展开研究。
高分子量聚乳酸通常通过乳酸的二聚体丙交酯在催化剂催化下开环聚合得到。丙交酯存在三种异构体:L-丙交酯、D-丙交酯、内消旋丙交酯(meso-LA);等当量的L-丙交酯和D-丙交酯混合物称为外消旋丙交酯(rac-LA)。外消旋丙交酯因其廉价易得而被广泛应用于开环聚合研究,采用不同选择性的催化剂催化外消旋丙交酯开环聚合可以得到无规、杂规、等规、等规立体嵌段等不同微观立体结构的聚乳酸。等规立体嵌段PLA可形成立体复合物,具有机械加工性能良好、熔点高等优良特性,因此设计合成具有高活性、高等规选择性催化剂催化外消旋丙交酯聚合成为该领域的研究热点。镁元素在地壳中含量丰富,具有无色无毒以及生物相容性等特点,其金属络合物作为催化剂使用时,即使在聚合物中有少量金属离子残余,也对人体无害,符合聚乳酸在食品包装及医药领域的要求,因此开发对丙交酯聚合具有高催化活性、高可控性的镁络合物已成为该领域的研究热点。
1999年,Coates小组报道了首例以β-二亚氨基为配体的双核镁络合物用于催化rac-LA开环聚合,具有很高的催化剂活性,但未表现出立体选择性(J.Am.Chem.Soc.1999,121,11583–11584)。2000年,Chisholm等人合成了[NNN]-三齿吡唑硼类配体的镁络合物,其中含有手性薄荷基并吡唑基团的镁络合物对rac-L和meso-LA的配位插入表现出非对映立体选择性,等量混合两种单体,只选择性聚合meso-LA,得到偏间规聚合物(J.Am.Chem.Soc.2000,122,11845–11854)。2007年,Carpentier小组合成了吡唑基氨基镁络合物并用来催化外消旋丙交酯开环聚合,表现出较好的催化活性,但仅得到无规聚丙交酯(Polyhedron 2007,26,3817)。2009年,Lin等人合成了一系列席夫碱镁络合物,这些络合物能够有效地催化L-丙交酯开环聚合,并且表现出可控活性聚合的特征,得到了分子量分布较窄的聚丙交酯(Inorg.Chem.2009,48,728–734)。2010年,本组报道了一类爪型氨基酚类配体的镁络合物,对rac-LA的聚合表现出超高的催化活性,在异丙醇存在下,催化5000当量rac-LA聚合,仅2min即可达到高转化率(90.5%)(Macromolecules 2010,43,6535–6537)。2012年,本组报道了一系列类salan配体的镁络合物,对rac-LA聚合具有很高的催化活性,室温、THF中,催化200当量rac-LA单体聚合仅需1min就可达到高转化率(DaltonTrans.2012,42,14200–14211)。2013年,本组报道了具有联苯骨架的亚氨酚氧基镁络合物,室温条件下、在四氢呋喃中,聚合200当量rac-LA,仅1.5min单体转化率可达94%,得到杂规度为Pr=0.72的聚丙交酯;降低温度至-38℃下Pr提高至0.81(Inorg.Chem.2013,52:11821–11835)。2014年,本组报道了一系列具有悬垂四氢吡咯的手性氨基酚氧基镁络合物,催化rac-LA聚合通过链端控制机理得到较高杂规度(Pr=0.81)的聚合物(Macromolecules2014,47,7750–7764)。2014年,Cui小组报道了非对称β-单膦亚氨镁络合物,所有络合物在四氢呋喃中对外消旋丙交酯开环聚合均表现出较高的催化活性,并且在0℃时表现出Pr=0.98的杂规选择性,是目前镁络合物中杂规选择性最高的(Organometallics 2014,33,722–730)。2014年,Redshaw小组报道了含杯芳烃配体的镁烷基络合物,在甲苯中得到偏等规聚合物(Pm=0.65),在四氢呋喃中获得杂规聚合物(Pr=0.85)(ChemCatChem 2014,6:1892–1898.)。
科学家们通过设计合成具有不同配体结构的镁络合物催化外消旋丙交酯开环聚合,期望得到具有高活性、高等规选择性的镁络合物催化剂。但到目前为止,镁络合物催化外消旋丙交酯开环聚合除具有高活性外,仅得到高杂规或偏等规倾向的聚丙交酯。所以设计合成集高活性、高等规选择性为一体的高效镁络合物催化剂的研究工作有待于进一步开展。
发明内容
本发明目的之一在于公开一类二(2-吡啶基)甲基取代的氨基酚氧基镁络合物。
本发明目的之二在于公开二(2-吡啶基)甲基取代的氨基酚氧基镁络合物的制备方法。
本发明目的之三在于公开二(2-吡啶基)甲基取代的氨基酚氧基镁络合物作为催化剂在内酯聚合中的应用。
本发明的技术构思:
从文献报道可知,多齿配体的镁络合物能高效催化外消旋丙交酯聚合,但仅个别表现出高杂规或等规倾向选择性,尚未有集高催化活性、高等规立体选择性于一体的高效镁络合物催化剂。本发明在氨基酚类配体的结构中引入二(2-吡啶基)甲基,形成NNNO四齿配体结构,配体中的所有杂原子能有效地与金属中心配位,形成五配位的镁络合物。通过改变配体骨架上各取代基,可以起到调整金属中心的空间位阻以及手性环境的作用,从而期望能筛选出集高催化活性、高等规立体选择性于一体的高效镁络合物催化剂。
本发明提供的二(2-吡啶基)甲基取代氨基酚类配体(I)及其金属镁络合物(II),具有以下通式:
式(I)、(II)中:
R1~R2分别代表氢,C1~C20直链、支链或环状结构的烷基,C7~C30单或多芳基取代的烷基,C6~C18的芳基,卤素;
R3代表C1~C20直链、支链或环状结构的烷基,C7~C30单或多芳基取代的烷基,C6~C18的芳基;
R4代表氨基NR5R6,其中R5~R6分别为C1~C6直链、支链或环状结构的烷基,三甲基硅基,三乙基硅基,二甲基氢硅基,R5和R6可以相同或不同;
M代表镁。
式(I)、(II)中,R1~R2优选为C1~C8直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基,C6~C12的芳基,卤素;
R3优选为C1~C8直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基,C6~C12的芳基;
R4优选为二(三甲基硅)氨基,二(三乙基硅)氨基,二(二甲基氢硅)氨基。
式(I)、(II)中,更为特征的是,R1~R2优选为甲基、异丙基、叔丁基、枯基、三苯甲基、苯基、氯;R3优选为甲基、乙基、异丙基、正丁基、叔丁基、金刚基、环戊基、环己基、正己基、正辛基、苯基、苄基、苯乙基;R4优选为二(三甲基硅)氨基。
优选的含二(2-吡啶基)甲基取代氨基酚类配体,其结构式如下:
优选的二(2-吡啶基)甲基取代四齿氨基酚氧基镁络合物结构为:
本发明的含二(2-吡啶基)甲基取代氨基酚类配体(I)及其金属镁络合物(II)制备方法如下步骤:
二(2-吡啶基)甲酮和伯胺R3NH2缩合生成相应亚胺(III),亚胺(III)经硼氢化钠还原生成仲胺(IV);仲胺(IV)和2-溴甲基取代酚(V)发生反应,反应温度为25~150℃,反应时间为2~72小时,然后从反应产物中收集目标二(2-吡啶基)甲基取代氨基酚类配体(I);
任选的,将式(I)所示的二(2-吡啶基)甲基取代氨基酚类配体和镁金属原料化合物在有机介质中反应,反应温度为0~100℃,反应时间为2~96小时,然后从反应产物中收集目标二(2-吡啶基)甲基取代氨基酚氧基镁络合物(II);
反应式中取代基R1~R4与权利要求1~3任一项所述的二(2-吡啶基)甲基取代氨基酚类配体(I)及其金属镁络合物(II)的各相应基团的要求一致;
镁金属原料络合物优选二{二(三甲基硅)氨基}镁;
二(2-吡啶基)甲基取代氨基酚类配体(I)与镁金属原料化合物的摩尔比为1:0.5~1.5;
所述的有机介质选自四氢呋喃、乙醚、甲苯、苯、石油醚和正己烷中的一种或两种。
本发明的二(2-吡啶基)甲基取代氨基酚氧基镁络合物是一种高效的内酯聚合催化剂,可用于L-丙交酯,D-丙交酯,rac-丙交酯,meso-丙交酯,己内酯,β-丁内酯的聚合反应,聚合方式为溶液聚合和熔融聚合。
以本发明二(2-吡啶基)甲基取代氨基酚氧基镁络合物为催化剂,使丙交酯在-40~130℃下聚合,聚合时催化剂与单体的摩尔比为1:1~10000。
以本发明二(2-吡啶基)甲基取代氨基酚氧基镁络合物为催化剂,在醇存在的条件下,使丙交酯在-40~130℃下聚合,聚合时催化剂与醇以及单体摩尔比为1:1~50:1~10000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,苄醇。
以本发明二(2-吡啶基)甲基取代氨基酚氧基镁络合物为催化剂,在醇存在下或不加醇,使ε-己内酯或β-丁内酯在-40~50℃下共聚合;所述的醇为C1~C10直链、支链或环状结构的烷基醇,苄醇。
本发明提供的催化剂其配体原料易得,催化剂制备方便、性质稳定,同时具有高的催化活性及较高立体选择性,易获得较高立体规整度和高分子量的聚内酯。能够满足工业部门的要求,有着广泛的应用前景。下面通过实施例进一步说明本发明,但本发明不限于此。
具体实施方式
原料的合成
将2-二吡啶基甲酮(2.00g,10.86mmol)、20mL无水甲醇、适量无水硫酸钠和过量的伯胺(108.6mmol)加入100mL的单口烧瓶。充分搅匀后,滴入10滴冰乙酸,在90℃的油浴中回流反应24小时,冷却至室温,用100mL无水乙醇将反应物涮洗至250mL单口烧瓶中。充分搅拌后,冰浴下分批次加入硼氢化钠(108.6mmol)。冰浴下反应1小时,室温搅拌过夜。向瓶内加入50mL的NaOH溶液(1mol/L),搅拌0.5小时后,用NaOH溶液(1mol/L)200mL洗涤,用100mL×2二氯甲烷萃取,再用饱和食盐水洗,合并有机相。用无水硫酸钠干燥,减压旋除溶剂及剩余的伯胺,得到红色油状物质N-[二(2-吡啶基)甲基)]取代烷基胺,经1H NMR分析产率约67.4%-80%,直接用于下一步反应。
实施例1
配体L1的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]丁胺(1.30g,约3.9mmol),2-溴甲基-4,6-二氯苯酚(1.48g,5.78mmol),K2CO3(0.88g,6.38mmol)和20mL N,N-二甲基甲酰胺,反应过夜。反应液经水洗、乙酸乙酯萃取后,用无水硫酸镁干燥,过滤,减压旋除溶剂,剩余黄色油状物经薄层层析(乙酸乙酯:三乙胺=100:1)分离提纯得到橙黄色油状物(1.04g,63.4%)。
1H NMR(CDCl3,400MHz,298K):δ12.51(br s,1H,OH),8.64(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.64(td,2H,3J=7.8Hz,4J=1.8Hz,PyH),7.33(d,2H,3J=7.8Hz,PyH),7.24–7.19(m,3H,2H of PyH and 1H of ArH),6.79(d,1H,4J=2.5Hz,ArH),5.30(s,1H,PyCHPy),3.68(s,2H,ArCH2),2.48(t,2H,3J=7.5Hz,NCH2CH2CH2CH3),1.50–1.41(m,2H,NCH2CH2CH2CH3),1.14–1.04(m,2H,NCH2CH2CH2CH3),0.71(t,3H,3J=7.4Hz,NCH2CH2CH2CH3).13C NMR(CDCl3,100MHz,298K):δ158.9,152.9,149.1,136.9,128.6,128.1,126.3,124.3,122.8,122.6,121.7(all Ar-C),71.5(PyCHPy),53.8(ArCH2),49.5(NCH2),26.8(NCH2CH2CH2CH3),20.2(NCH2CH2CH2CH3),13.8(NCH2CH2CH2CH3).HRMS(ESI)calcd.forC22H24Cl2N3O(M+H):416.1295;Found:416.1296.
实施例2
配体L2的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]丁胺(1.30g,约3.9mmol)和2-溴甲基-4,6-二叔丁基苯酚(1.61g,5.38mmol),K2CO3(0.82g,5.93mmol)和20mL N,N-二甲基甲酰胺,反应过夜。反应液经水洗、乙酸乙酯萃取后,用无水硫酸镁干燥,过滤。减压旋除溶剂,剩下的淡黄色油状物经薄层层析(石油醚:乙酸乙酯=5:1)分离提纯得到白色固体(1.61g,89.0%)。
1H NMR(CDCl3,400MHz,298K):δ10.88(br s,1H,OH),8.58(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,NCH of PyH),7.61(td,2H,3J=7.8Hz,4J=1.8Hz,PyH),7.48(d,2H,3J=7.8Hz,PyH),7.17–7.12(m,3H,2H of PyH and 1H of ArH),6.71(d,1H,4J=2.3Hz,ArH),5.22(s,1H,PyCHPy),3.77(s,2H,ArCH2),2.60(t,2H,3J=7.8Hz,NCH2CH2CH2CH3),1.52–1.40(m,2H,NCH2CH2CH2CH3),1.46(s,9H,C(CH3)3),1.24(s,9H,C(CH3)3),1.13–1.03(m,2H,NCH2CH2CH2CH3),0.71(t,3H,3J=7.6Hz,NCH2CH2CH2CH3).13C NMR(CDCl3,100MHz,298K):δ159.6,154.4,149.3,140.1,136.5,135.3,124.2,122.7,122.5,122.1(all Ar-C),73.2(PyCHPy),55.6(ArCH2),50.3(NCH2),35.0(C(CH3)3),34.2(C(CH3)3),31.8(C(CH3)3),29.7(C(CH3)3),27.1(NCH2CH2CH2CH3),20.4(NCH2CH2CH2CH3),14.0(NCH2CH2CH2CH3).HRMS(EI)calcd.for C30H41N3O:459.3250;Found:459.3249.
实施例3
配体L3的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]正丁胺(2.0g,约8.2mmol)和25mL N,N-二甲基甲酰胺,充分搅拌均匀后,再加入2-溴甲基-4,6-二枯基苯酚(5.21g,12.30mmol)和K2CO3(1.70g,12.30mmol),反应搅拌过夜。反应液经水洗、乙酸乙酯萃取、饱和食盐水洗涤后,有机相用无水硫酸镁干燥,过滤。减压旋除溶剂,剩余棕红色油状物经薄层层析(乙酸乙酯:石油醚=8:1)分离提纯得到淡黄色固体(3.80g,79.4%)。
1H NMR(CDCl3,400MHz,298K):δ10.46(br s,1H,OH),8.47(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.51(td,2H,3J=7.6Hz,4J=1.8Hz,PyH),7.29–7.20(m,7H,4HofPyH and 3H of ArH),7.19–7.03(m,8H,ArH),6.57(d,1H,4J=2.3Hz,ArH),5.04(s,1H,PyCHPy),3.62(s,2H,ArCH2),2.54–2.42(m,2H,NCH2CH2CH2CH3),1.71(s,6H,C(CH3)2Ph),1.64(s,6H,C(CH3)2Ph),1.38–1.27(m,2H,NCH2CH2CH2CH3),1.07–0.94(m,2H,NCH2CH2CH2CH3),0.73–0.65(t,3H,3J=7.6Hz,NCH2CH2CH2CH3).13C NMR(CDCl3,100MHz,298K):δ159.2,154.0,151.7,151.6,149.1,139.6,136.4,135.0,127.9,127.5,126.9,126.7,125.9,125.4,124.7,124.6,124.1,122.6,122.3(all Ar-C),72.2(PyCHPy),55.3(Ar CH2),50.6(NCH2),42.5((CH3)2CPh),42.3((CH3)2CPh),31.2((CH3)2CPh),29.6((CH3)2CPh),28.1(NCH2CH2),20.4(NCH2CH2CH2CH3),13.9(NCH2CH2CH2CH3).HRMS(ESI)calcd.forC40H46N3O(M+H):584.3641;Found:584.3640.
实施例4
配体L4的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]丁胺(2.00g,约6.1mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(3.16g,8.28mmol),K2CO3(1.26g,9.12mmol)和N,N-二甲基甲酰胺20mL,反应过夜。反应液经水洗、乙酸乙酯萃取后,用无水硫酸钠干燥,过滤。溶剂经减压旋除,得到的橙黄色油状物,经薄层层析(石油醚:乙酸乙酯=1:1)分离提纯得到白色固体(2.24g,61.0%)。
1H NMR(CDCl3,400MHz,298K):δ10.64(br s,1H,OH),8.42(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.50(td,2H,3J=7.6Hz,4J=1.8Hz,PyH),7.24(d,6H,3J=7.0Hz,ArH),7.18(t,6H,3J=7.0Hz,ArH),7.13–7.07(m,7H,4H of PyH and 3H of ArH),6.84(d,1H,4J=1.6Hz,ArH),6.58(d,1H,4J=1.6Hz,ArH),5.10(s,1H,PyCHPy),3.68(s,2H,ArCH2),2.46(m,2H,NCH2CH2CH2CH3),2.10(s,3H,ArCH3),1.41–1.33(m,2H,NCH2CH2CH2CH3),1.08–0.99(m,2H,NCH2CH2CH2CH3),0.74(t,3H,3J=7.2Hz,NCH2CH2CH2CH3).13C NMR(CDCl3,100MHz,298K):δ159.2,154.3,149.0,146.4,136.4,133.7,131.4,130.5,129.0,126.9,126.2,125.3,124.0,123.2,122.3(all Ar-C),71.9(PyCHPy),63.5(CPh3),55.0(ArCH2),50.8(NCH2),27.8(NCH2CH2CH2CH3),21.0(NCH2CH2CH2CH3),20.6(ArCH3),14.0(NCH2CH2CH2CH2).HRMS(EI)calcd.for C42H41N3O:603.3250;Found:603.3252.
实施例5
配体L5的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]正己胺(2.34g,约5.8mmol)和2-溴甲基-4,6-二叔丁基苯酚(2.86g,9.54mmol),无水K2CO3(1.32g,9.55mmol)和20mLN,N-二甲基甲酰胺,反应过夜。反应液经水洗、乙酸乙酯萃取后,用无水硫酸镁干燥,过滤。减压旋除溶剂,得到橙色油状物。最后经薄层层析(石油醚:乙酸乙酯=5:1)分离提纯得到无色粘稠物(1.78g,62.5%)。
1H NMR(CDCl3,400MHz,298K):δ10.87(br s,1H,OH),8.59(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.61(td,2H,3J=7.8Hz,4J=1.8Hz,PyH),7.49(d,2H,3J=8.0Hz,PyH),7.17-7.12(m,3H,2H of PyH and 1H of ArH),6.71(d,1H,4J=2.3Hz,ArH),5.21(s,1H,PyCHPy),3.77(s,2H,ArCH2),2.65–2.55(m,2H,NCH2(CH2)4CH3),1.53–1.42(m,2H,CH2ofhexyl),1.45(s,9H,C(CH3)3),1.24(s,9H,C(CH3)3),1.19–1.11(m,2H,CH2ofhexyl),1.07–1.03(m,4H,CH2of hexyl),0.78(t,3H,3J=7.2Hz,CH3of hexyl).13C NMR(CDCl3,100MHz,298K):δ159.6,154.5,149.3,140.1,136.5,135.3,124.2,124.1,122.7,122.5,122.1(all Ar-C),73.3(PyCHPy),55.6(ArCH2),50.7(NCH2),35.0(C(CH3)3),34.2(C(CH3)3),31.8(C(CH3)3),31.5(C(CH3)3),29.7(CH2),26.9(CH2of hexyl),24.8(CH2ofhexyl),22.5(CH2of hexyl),14.1(CH3ofhexyl).HRMS(EI)calcd.for C32H45N3O:487.3563;Found:487.3562.
实施例6
配体L6的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]正己胺(2.92g,约7.3mmol)和25mL N,N-二甲基甲酰胺,充分搅拌均匀后,再加入2-溴甲基-4,6-二枯基苯酚(5.05g,11.92mmol)和K2CO3(1.65g,11.93mmol),搅拌反应过夜。反应液经水洗、乙酸乙酯萃取、饱和食盐水洗涤后,有机相用无水硫酸镁干燥,过滤。减压旋除溶剂,剩余棕红色油状物经薄层层析(乙酸乙酯:石油醚=8:1)分离提纯得到黄色油状物(2.46g,55.0%)。
1H NMR(CDCl3,400MHz,298K):δ10.44(br s,1H,OH),8.46(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.50(td,2H,3J=7.6Hz,4J=1.8Hz,PyH),7.30–7.19(m,7H,4HofPyH and 3H of ArH),7.19–7.12(m,5H,ArH),7.12–7.03(m,3H,ArH),6.56(d,1H,4J=2.3HzArH),5.05(s,1H,PyCHPy),3.63(s,2H,ArCH2),2.52–2.42(m,2H,NCH2(CH2)4CH3),1.70(s,6H,C(CH3)2Ph),1.64(s,6H,C(CH3)2Ph),1.39–1.22(m,2H,CH2of hexyl),1.20–1.11(m,2H,CH2of hexyl),1.10–0.92(m,4H,CH2of hexyl),0.80(t,3H,3J=7.2Hz,CH3of hexyl).13C NMR(CDCl3,100MHz,298K):δ159.2,154.0,151.7,151.6,149.1,139.6,136.4,135.0,127.9,127.5,126.8,126.5,125.9,125.4,124.7,124.6,124.1,122.5,122.3(all Ar-C),72.3(PyCHPy),55.3(ArCH2),50.9(NCH2),42.5((CH3)2CPh),42.3((CH3)2CPh),31.5(CH2ofhexyl),31.2((CH3)2CPh),29.6((CH3)2CPh),26.9(CH2of hexyl),25.7(CH2of hexyl),22.6(CH2of hexyl),14.1(CH3of hexyl).HRMS(ESI)calcd.for C42H50N3O(M+H):612.3954;Found:612.3953.
实施例7
配体L7的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]环戊胺(2.75g,约7.3mmol)和2-溴甲基-4,6-二叔丁基苯酚(2.75g,11.93mmol),K2CO3(2.75g,11.94mmol)和N,N-二甲基甲酰胺25mL,反应过夜。反应液经水洗、乙酸乙酯萃取后,用无水硫酸镁干燥,过滤。减压旋除溶剂,剩余淡黄色油状物经薄层层析(石油醚:乙酸乙酯=3:1)分离提纯得到白色固体(1.16g,33.7%)。
1H NMR(CDCl3,400MHz,298K):δ11.31(s,1H,OH),8.52(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.51(td,2H,3J=7.6Hz,4J=1.8Hz,PyH),7.43(d,2H,3J=8.0Hz,PyH),7.09–7.04(m,2H,PyH),7.03(d,1H,4J=2.3Hz,ArH),6.52(d,1H,4J=2.3Hz,ArH),5.25(s,1H,PyCHPy),3.95(s,2H,ArCH2),3.66–3.54(m,1H,CH of cyclopentyl),1.71–1.61(m,4H,CH2ofcyclopentyl),1.59–1.50(m,2H,CH2of cyclopentyl),1.45–1.33(m,2H,CH2of cyclopentyl),1.38(s,9H,C(CH3)3),1.20(s,9H,C(CH3)3).13C NMR(CDCl3,100MHz,298K):δ159.7,154.6,149.2,140.0,136.2,135.3,123.9,123.1,122.5,122.4,122.2(allAr-C),77.4(PyCHPy),61.7(ArCH2),51.5(NCH),34.9(C(CH3)3),34.1(C(CH3)3),31.8(C(CH3)3),29.6(C(CH3)3),27.0(CH2of cyclopentyl),24.5(CH2of cyclopentyl).HRMS(EI)calcd.for C31H41N3O:471.3250;Found:471.3253.
实施例8
配体L8的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]环戊胺(2.75g,约7.3mmol)和30mL N,N-二甲基甲酰胺,充分搅拌均匀后,再加入2-溴甲基-4,6-二枯基苯酚(5.06g,11.95mmol)和K2CO3(1.65g,11.93mmol),搅拌反应过夜。反应液经水洗、乙酸乙酯萃取,饱和食盐水洗涤后,有机相用无水硫酸镁干燥,过滤。减压旋除溶剂,剩余棕红色油状物经薄层层析(乙酸乙酯:石油醚=8:1)分离提纯得到淡黄色泡状固体(1.92g,44.0%)。
1H NMR(CDCl3,400MHz,298K):δ10.72(s,1H,OH),8.44(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.43(td,2H,3J=7.6Hz,4J=1.8Hz,PyH),7.32–7.22(m,4H,PyH),7.22–7.14(m,3H,ArH),7.14–6.97(m,8H,ArH),6.44(d,1H,4J=2.3Hz,ArH),5.11(s,1H,PyCHPy),3.80(s,2H,ArCH2),3.52–3.40(m,1H,CH of cyclopentyl),1.64(s,6H,C(CH3)2Ph),1.62(s,6H,C(CH3)2Ph),1.48–1.32(m,6H,CH2of cyclopentyl),1.28–1.21(m,2H,CH2ofcyclopentyl).13C NMR(CDCl3,100MHz,298K):δ159.4,154.2,151.5,151.4,149.1,139.7,136.2,135.1,127.9,127.3,126.9,125.9,125.4,124.7,124.1,123.8,122.7,122.2(all Ar-C),72.4(PyCHPy),61.5(ArCH2),50.8(NCH),42.5((CH3)2CPh),42.1((CH3)2CPh),31.1((CH3)2CPh),29.5((CH3)2CPh),27.4(CH2of cyclopentyl),24.4(CH2ofcyclopentyl).HRMS(ESI)calcd.forC41H46N3O(M+H):596.3641;Found:596.3642.
实施例9
配体L9的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]环己胺(3.19g,约8.0mmol)和2-溴甲基-4,6-二叔丁基苯酚(3.57g,11.92mmol),K2CO3(1.65g,11.94mmol)和20mL N,N-二甲基甲酰胺,反应过夜。反应液经水洗、乙酸乙酯萃取后,用无水硫酸镁干燥,过滤。减压旋除易挥发性溶剂,剩余淡黄色油状物经薄层层析(石油醚:乙酸乙酯=5:1)分离提纯得到白色泡状固体(2.56g,65.5%)。
1H NMR(CDCl3,400MHz,298K):δ11.26(br s,1H,OH),8.51(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.48(t,2H,3J=7.6Hz,PyH),7.42(d,2H,3J=7.8Hz,PyH),7.09–7.03(m,2H,PyH),7.01(d,1H,4J=2.3Hz,ArH),6.47(d,1H,4J=2.3Hz,ArH),5.35(s,1H,PyCHPy),3.93(s,2H,ArCH2),2.60(tt,1H,3J=12.0Hz,3J=2.8Hz,CH of cyclohexyl),1.86–1.78(m,2H,CH2of cyclohexyl),1.74–1.65(m,2H,CH2of cyclohexyl),1.56–1.47(m,1H,CH2of cyclohexyl),1.44–1.34(m,1H,CH2of cyclohexyl),1.39(s,9H,C(CH3)3),1.20(s,9H,C(CH3)3),1.11–0.94(m,4H,CH2of cyclohexyl).13C NMR(CDCl3,100MHz,298K):δ160.0,154.4,149.1,139.7,136.1,135.0,123.8,123.1,122.8,122.3,122.0(all Ar-C),72.7(PyCHPy),59.6(ArCH2),51.7(NCH),34.8(C(CH3)3),34.0(C(CH3)3),31.6(C(CH3)3),29.5(C(CH3)3),28.9(CH2of cyclohexyl),26.2(CH2of cyclohexyl),26.1(CH2ofcyclohexyl).HRMS(ESI)calcd.forC32H44N3O(M+H);486.3484;Found:486.3485.
实施例10
配体L10的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]环己胺(2.90g,约7.3mmol)和20mL N,N-二甲基甲酰胺,充分搅拌均匀后,再加入2-溴甲基-4,6-二枯基苯酚(5.05g,11.92mmol)和K2CO3(1.65g,11.93mmol),搅拌反应过夜。反应液经水洗、乙酸乙酯萃取、饱和食盐水洗涤后,有机相用无水硫酸镁干燥,过滤。减压旋除溶剂,剩余棕红色油状物经薄层层析(乙酸乙酯:石油醚=3:1)分离提纯得到淡白色固体(2.76g,61.9%)。
1H NMR(CDCl3,400MHz,298K):δ10.76(s,1H,OH),8.43(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.44(td,2H,3J=7.8Hz,4J=1.8Hz,PyH),7.31–7.19(m,10H,4H ofPyHand 6H of ArH),7.09–7.01(m,5H,ArH),6.40(d,1H,4J=2.3Hz,ArH),5.22(s,1H,PyCHPy),3.78(s,2H,ArCH2),2.71–2.60(m,1H,CH of cyclohexyl),1.66(s,6H,C(CH3)2Ph),1.61(s,6H,C(CH3)2Ph),1.52–1.41(m,1H,CH2of cyclohexyl),1.24–1.12(m,2H,CH2ofcyclohexyl),1.05–0.83(m,3H,CH2of cyclohexyl).13C NMR(CDCl3,100MHz,298K):δ160.1,154.1,151.6,151.5,149.1,139.4,136.3,134.9,127.9,127.3,126.9,126.0,125.7,125.4,124.7,124.1,123.8,123.3,122.3(all Ar-C),71.9(PyCHPy),59.5(ArCH2),51.2(NCH),42.5((CH3)2CPh),42.1((CH3)2CPh),31.2((CH3)2CPh),29.5((CH3)2CPh),29.2(CH2of cyclohexyl),26.3(CH2ofcyclohexyl),26.2(CH2of cyclohexyl).HRMS(ESI)calcd.for C42H48N3O(M+H):610.3797;Found:610.3798
实施例11
配体L11的合成
于100mL单口烧瓶中分别加入N-[二(2-吡啶基)甲基)]环己胺(2.90g,约7.3mmol)和20mL N,N-二甲基甲酰胺,充分搅拌均匀后,再加入2-溴甲基-4-甲基-6-三苯甲基苯酚(4.81g,10.85mmol),和K2CO3(1.65g,11.93mmol),搅拌反应过夜。反应液经水洗、乙酸乙酯萃取,饱和食盐水洗涤后,有机相用无水硫酸镁干燥,过滤。滤液减压旋除,剩余棕红色油状物经薄层层析(乙酸乙酯:石油醚=3:1)分离提纯得到淡白色固体(2.10g,45.6%)。
1H NMR(CDCl3,400MHz,298K):δ10.92(s,1H,OH),8.40(ddd,2H,3J=4.8Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.40(td,2H,3J=7.6Hz,4J=1.8Hz,PyH),7.24(d,6H,3J=7.8Hz,ArH),7.18(t,6H,3J=7.8Hz,ArH),7.13–7.07(m,3H,ArH),7.07–7.02(m,2H,PyH),6.93(d,2H,3J=7.6Hz,PyH),6.35(d,1H,4J=1.6Hz,ArH),6.70(d,1H,4J=1.6Hz,ArH),5.28(s,1H,PyCHPy),3.83(s,2H,ArCH2),2.62(m,1H,CH of cyclohexyl),2.04(s,3H,ArCH3),1.76–1.56(m,6H,CH2of cyclohexyl),1.24–1.12(m,1H,CH2of cyclohexyl),1.06–0.90(m,3H,CH2of cyclohexyl).13CNMR(CDCl3,100MHz,298K):δ160.2,154.3,148.9,146.3,136.3,133.3,131.4,130.0,128.0,126.9,126.0,125.2,124.0,123.7,122.1(all Ar-C),71.8(PyCHPy),63.4(CPh3),59.7(ArCH2),50.9(NCH),29.0(CH2of cyclohexyl),26.3(CH2ofcyclohexyl),26.2(CH2of cyclohexyl),20.9(ArCH3).HRMS(ESI)calcd.for C44H43N3O(M+H):630.3484;Found:630.3486.
实施例12
镁络合物Mg1的合成
氩气保护下,于50mL的Schlenk管中加入{Mg[N(SiMe3)2]2}2(346mg,0.500mmol)和15mL甲苯,将L2H(460mg,1.00mmol)的10mL甲苯溶液滴加到前述溶液中,反应搅拌过夜。过滤除去少量杂质,溶液经浓缩抽干得到深红色的泡状固体,用四氢呋喃和正己烷的混合溶剂重结晶,得到浅红色晶状固体,经少量正己烷洗涤后,抽干得目标络合物(231mg,35.8%)。
1H NMR(C6D6,400MHz,298K):δ 9.39(ddd,1H,3J=5.2Hz,4J=1.8Hz,5J=0.8Hz,PyH),8.72(ddd,1H,3J=5.2Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.62(d,1H,4J=2.8Hz,ArH),6.91(d,1H,4J=2.8Hz,ArH),6.72(td,1H,3J=7.8Hz,4J=1.8Hz,PyH),6.68(td,1H,3J=7.8Hz,4J=1.8Hz,PyH),6.50–6.44(m,2H,PyH),6.37(d,1H,3J=7.6Hz,PyH),6.25(ddd,1H,3J=5.2Hz,3J=7.8Hz,4J=1.0Hz,PyH),4.25(s,1H,PyCHPy),3.45(d,1H,2J=12.0Hz,ArCH2),3.16-3.05(m,1H,NCH2),3.00(d,1H,2J=12.0Hz,ArCH2),2.17–2.07(m,1H,NCH2),2.02(s,9H,C(CH3)3),1.65–1.56(m,1H,NCH2CH2CH2CH3),1.47(s,9H,C(CH3)3),1.24(m,8H×0.1,n-hexane),1.14–1.02(m,1H,NCH2CH2CH2CH3),0.93–0.81(m,2.6H,2H ofNCH2CH2CH2CH3and 6H×0.1of n-hexane),0.72(t,3H,3J=7.2Hz,NCH2CH2CH2CH3),0.54(s,18H,N(Si(CH3)3)2).13C NMR(C6D6,100MHz,298K):δ165.5,157.8,156.1,152.4,150.5,139.1,138.9,138.0,132.9,124.4,124.0,123.9,123.7,123.6,121.5,121.3(All Ar-C),69.8(PyCHPy),55.5(ArCH2),47.4(NCH2),36.0(C(CH3)3),34.1(C(CH3)3),32.5(C(CH2)3),32.0(n-hexane),31.3(C(CH3)3),23.0(n-hexane),21.6(NCH2CH2CH2CH3),20.5(NCH2CH2CH2CH3),14.3(n-hexane),14.1(NCH2CH2CH2CH3),6.8(N(Si(CH3)3)2).Anal.Calcd.for C36H58MgN4OSi2·0.1C6H14:C,67.43;H,9.18;N,8.59.Found:C,66.93;H,9.02;N,8.44%.
实施例13
镁络合物Mg2的合成
氩气保护下,于50mL的Schlenk管中加入{Mg[N(SiMe3)2]2}2(346mg,0.500mmol)和10mL甲苯,将配体L3H(488mg,1.00mmol)的5mL甲苯溶液滴加至前述溶液中,搅拌反应过夜。过滤除去少量杂质,溶液经浓缩抽干得到深红色泡状固体,用甲苯和正己烷的混合溶剂重结晶,析出橙红色晶状固体,抽干得到目标络合物(275mg,40.9%)。
1H NMR(C6D6,400MHz,298K):δ 9.40(ddd,1H,3J=5.2Hz,4J=1.8Hz,5J=0.8Hz,PyH),8.71(ddd,1H,3J=5.2Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.62(d,1H,4J=2.5Hz,ArH),6.93(d,1H,4J=2.5Hz,ArH),6.76(td,1H,3J=7.8Hz,4J=1.8Hz,PyH),6.73(td,1H,3J=7.8Hz,4J=1.8Hz,PyH),6.55–6.46(m,2H,PyH),6.42(d,1H,3J=7.6Hz,PyH),6.26(ddd,1H,3J=5.2Hz,3J=7.8Hz,4J=1.0Hz,PyH),4.30(s,1H,PyCHPy),3.46(d,1H,2J=12.0Hz,ArCH2),3.17–3.07(m,1H,NCH2),3.03(d,1H,2J=12.0Hz,ArCH2),2.22–2.11(m,1H,NCH2),2.02(s,9H,C(CH3)3),1.79–1.62(m,1H,NCH2CH2),1.59–1.40(m,1H,CH2of hexyl),1.48(s,9H,C(CH3)3),1.21–1.08(m,6H,CH2of hexyl),0.83(t,3H,3J=7.2Hz,CH3of hexyl),0.54(s,18H,N(Si(CH3)3)2).13C NMR(C6D6,100MHz,298K):δ165.5,157.7,156.1,152.4,150.4,139.3,139.0,138.0,132.9,124.4,124.0,123.9,123.8,123.7,121.6,121.4(All Ar-C),69.8(PyCHPy),55.6(ArCH2),47.7(NCH2),36.0(C(CH3)3),34.1(C(CH3)3),32.5(C(CH3)3),32.0(CH2of hexyl),31.3(C(CH3)3),26.9(CH2of hexyl),22.8(CH2of hexyl),19.5(CH2ofhexyl),14.1(CH3of hexyl),6.8(N(Si(CH3)3)2).Anal.Calcd.for C38H62MgN4OSi2:C,67.98;H,9.31;N,8.34.Found:C,67.69;H,9.23;N,7.89%.
实施例14
镁络合物Mg3的合成
氩气保护下,往50mL的Schlenk管中加入{Mg[N(SiMe3)2]2}2(346mg,0.500mmol)和8mL甲苯,将配体L5H(486mg,1.00mmol)分批次加入,然后反应搅拌过夜。过滤除去少量杂质,溶液经浓缩抽干得到深红色泡状固体,在四氢呋喃和正己烷溶液中重结晶,得到无色透明晶状固体,固体经少量四氢呋喃润洗后,抽干得到目标络合物(213mg,31.8%)。
1H NMR(C6D6,400MHz,298K):δ 9.40(br s,1H,PyH),8.65(br s,1H,PyH),7.50(d,1H,4J=2.5Hz,ArH),6.77(d,1H,4J=2.5Hz,ArH),6.76–6.61(m,2H,PyH),6.48(br s,1H,ArH),6.37(br d,1H,3J=7.2Hz,PyH),6.20(br s,1H,ArH),4.37(s,1H,PyCHPy),3.42(d,1H,2J=12.0Hz,ArCH2),3.35(d,1H,2J=12.0Hz,ArCH2),2.47–2.37(m,1H,CH ofcyclohexyl),2.16–2.04(m,1H,CH of cyclohexyl),2.00(s,9H,C(CH3)3),1.88–1.76(m,1H,CH2of cyclohexyl),1.54–1.44(m,3H,CH2of cyclohexyl),1.48(s,9H,C(CH3)3),1.33–1.21(m,2H,CH2of cyclohexyl),1.14–0.99(m,1H,CH2of cyclohexyl),0.90–0.74(m,2H,CH2of cyclohexyl),0.59(s,18H,N(Si(CH3)3)2).13C NMR(C6D6,100MHz,298K):δ165.07,157.8,157.4,152.1,150.1,139.1,137.9,132.9,124.1,123.8,123.6,123.5,122.9,121.8(All Ar-C),70.7(PyCHPy),61.2(NCH),55.4(ArCH2),36.0(C(CH3)3),34.1(C(CH2)3),32.6(C(CH2)3),31.2(C(CH3)3),27.0(CH2ofcyclohexyl),26.6(CH2of cyclohexyl),26.4(CH2ofcyclohexyl),26.0(CH2of cyclohexyl),7.1(N(Si(CH3)3)2).Anal.Calcd.forC38H60MgN4OSi2:C,68.18;H,9.03;N,8.37.Found:C,68.02;H,8.95;N,8.29%.
实施例15
镁络合物Mg4的合成
氩气保护下,往50mL的Schlenk管中加入{Mg[N(SiMe3)2]2}2(346mg,0.500mmol)和12mL甲苯,将配体L6H(584mg,1.00mmol)分批次加入,然后反应搅拌过夜。过滤除去少量杂质,溶液经抽干得到深红色泡状固体,在甲苯和正己烷溶液中重结晶,得到红色晶状固体,固体经少量甲苯洗涤后,抽干得到目标络合物(248mg,32.3%)。
1H NMR(C6D6,400MHz,298K):δ 9.34(ddd,1H,3J=5.2Hz,4J=1.8Hz,5J=0.8Hz,PyH),8.48(ddd,1H,3J=5.2Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.73–7.66(m,2H,ArH),7.42–7.36(m,3H,ArH),7.26(t,2H,3J=7.8Hz,ArH),7.20–7.09(m,3H,ArH),7.08–6.99(m,1H,ArH),6.71(td,1H,3J=7.6Hz,4J=1.8Hz,PyH),6.62(td,1H,3J=7.6Hz,4J=1.8Hz,PyH),6.58(d,1H,4J=2.8Hz,ArH),6.46(ddd,1H,3J=7.8Hz,3J=5.2Hz,4J=1.0Hz,ArH),6.35(d,1H,3J=7.8Hz,PyH),6.32(d,1H,3J=7.8Hz,PyH),6.20(ddd,1H,3J=7.8Hz,3J=5.2Hz,4J=1.0Hz,ArH),4.10(s,1H,PyCHPy),3.18(d,1H,2J=12.0Hz,ArCH2),3.05–2.94(m,1H,NCH2),2.71(d,1H,2J=12.0Hz,ArCH2),2.56(s,3H,C(CH3)2Ph),2.10–2.02(m,1H,NCH2),1.71(s,6H,C(CH3)2Ph),1.40–1.28(m,1H,NCH2CH2CH2CH3),1.24(m,8H×0.45,n-hexane),0.95–0.84(m,1H,NCH2CH2CH2CH3),0.84–0.72(m,2H,N CH2CH2CH2CH3),0.89(t,6H×0.45,n-hexane),0.66(t,3H,3J=7.2Hz,N(CH2)3CH3),0.50(s,18H,N(Si(CH3)3)2).13C NMR(C6D6,100MHz,298K):δ165.3,157.4,156.0,153.6,153.4,152.4,150.4,139.0,138.9,137.3,132.2,127.6,127.5,127.4,127.0,125.2,124.5,123.8,123.7,123.4,121.9,121.4(AllAr-C),69.6(PyCHPy),55.0(ArCH2),47.5(NCH2),43.9(C(CH3)2Ph),42.5(C(CH3)2Ph),32.5(C(CH3)2Ph),31.9(n-hexane),31.8(C(CH3)2Ph),31.4(C(CH3)2Ph),29.1(C(CH3)2Ph),23.0(n-hexane),21.6(NCH2CH2CH2CH3),20.5(NCH2CH2CH2CH3),14.3(n-hexane),14.1(N(CH2)3CH3),6.8(N(Si(CH3)3)2).Anal.Calcd.for C46H62MgN4OSi2·0.45C6H14:C,72.55;H,8.54;N,6.95.Found:C,72.44;H,8.25;N,6.99%.
实施例17
镁络合物Mg5的合成
氩气保护下,于50mL的Schlenk管中加入{Mg[N(SiMe3)2]2}2(346mg,0.500mmol)和10mL甲苯,将配体L7H(612mg,1.00mmol)的10mL甲苯溶液滴加至前述溶液中,然后反应搅拌过夜。过滤除去少量杂质,溶液经抽干得到深红色泡状固体,在甲苯和正己烷的混合溶液中重结晶,析出大量黄色片状固体,固体经少量甲苯洗涤后,抽干得到目标络合物(376mg,47.3%)。
1H NMR(C6D6,400MHz,298K):δ 9.36(ddd,1H,3J=5.2Hz,4J=1.8Hz,5J=0.8Hz,PyH),8.49(d,1H,3J=5.2Hz,4J=1.8Hz,5J=0.8Hz,PyH),7.72–7.67(m,2H,ArH),7.42–7.36(m,3H,ArH),7.29–7.23(m,2H,ArH),7.20–7.09(m,3H,ArH),7.05(t,1H,3J=7.8Hz,ArH),6.73(td,1H,3J=7.8Hz,4J=1.8Hz,PyH),6.62(td,1H,3J=7.8Hz,4J=1.8Hz,PyH),6.60(d,1H,4J=2.8Hz,ArH),6.47(ddd,1H,3J=7.8Hz,3J=5.2Hz,4J=1.0Hz,PyH),6.37(d,1H,3J=7.8Hz,PyH),6.35(d,1H,3J=7.8Hz,PyH),6.22(ddd,1H,3J=7.8Hz,3J=5.2Hz,4J=1.0Hz,PyH),4.13(s,1H,PyCHPy),3.20(d,1H,2J=12.0Hz,ArCH2),3.10–2.97(m,1H,NCH2),2.74(d,1H,2J=12.0Hz,ArCH2),2.56(s,3H,C(CH3)2Ph),2.17(s,3H,C(CH3)2Ph),2.15–2.05(m,1H,NCH2),1.71(s,3H,C(CH3)2Ph),1.69(s,3H,C(CH3)2Ph),1.46–1.37(m,1H,CH2of hexyl),1.21–1.03(m,4H,CH2of hexyl),1.00–0.90(m,1H,CH2of hexyl),0.90–0.74(m,5H,CH3andCH2of hexyl),0.52(s,18H,N(Si(CH3)3)2).13C NMR(C6D6,100MHz,298K):δ165.4,157.4,156.1,153.6,153.4,150.4,139.0,138.9,137.8(toluene),137.4,132.1,129.3(toluene),128.6(toluene),127.4,127.1,125.7(toluene),125.2,124.5,123.8,123.7,123.4,121.9,121.4(All Ar-C),69.6(PyCHPy),55.1(ArCH2),47.8(NCH2),43.9(C(CH3)2Ph),42.5(C(CH3)2Ph),32.5(C(CH3)2Ph),31.9(CH2of hexyl),31.7(C(CH3)2Ph),31.4(C(CH3)2Ph),29.1(C(CH3)2Ph),27.0(CH2of hexyl),22.9(CH2of hexyl),19.5(CH2ofhexyl),14.2(CH3of hexyl),6.8(N(Si(CH3)3)2).Anal.Calcd.for C48H66MgN4OSi2:C,72.47;H,8.36;N,7.04.Found:C,72.22;H,8.12;N,6.69%.
实施例18
镁络合物Mg6的合成
氩气保护下,于50mL的Schlenk管中加入{Mg[N(SiMe3)2]2}2(346mg,0.500mmol)和8mL甲苯,将配体(L9H)(610mg,1.00mmol)分批次加入上述溶液中,然后搅拌反应过夜。过滤除去少量不溶物,溶液经抽干得到深红色泡状固体,在甲苯和正己烷溶液重结晶,得到红棕色晶状固体,固体经少量甲苯洗涤后,抽干得到目标络合物(312mg,39.3%)。
1H NMR(C6D6,400MHz,298K):δ9.29(br s,1H,PyH),8.38(br s,1H,PyH),7.65(d,2H,3J=8.0Hz,ArH),7.39(d,2H,3J=8.0Hz,ArH),7.34(br s,1H,ArH),7.25(br t,2H,3J=7.8Hz,ArH),7.20–7.09(m,4H,ArH),7.13(m,2H×0.5H,toluene),7.02(m,3H×0.5H,toluene),6.75–6.66(m,1H,PyH),6.66–6.56(m,1H,PyH),6.52(br s,1H,ArH),6.48–6.41(m,1H,PyH),6.35-6.25(m,2H,PyH),6.25-6.18(m,1H,PyH),4.21(s,1H,PyCHPy),3.16(d,1H,2J=12.8Hz,ArCH2),2.99(d,1H,2J=12.8Hz,ArCH2),2.49(s,3H,C(CH3)2Ph),2.44(t,1H,2J=11.2Hz,CHof cyclohexyl),2.17(s,3H,C(CH3)2Ph),2.11(s,3H×0.5H,toluene),2.02–1.90(m,1H,CH2ofcyclohexyl),1.72(s,6H,C(CH3)2Ph),1.60–1.40(m,3H,CH2ofcyclohexyl),1.38–1.23(m,2H,CH2of cyclohexyl),0.84–0.62(m,4H,CH2of cyclohexyl),0.53(s,18H,N(Si(CH3)3)2).13C NMR(C6D6,100MHz,298K):δ165.1,157.5,157.3,153.7,153.6,151.9,150.5,138.9,138.9,137.8(toluene),137.1,132.1,129.3(toluene),128.6(toluene),125.7(toluene),127.6,127.5,127.4,125.9,125.2,124.4,123.6,123.2,121.7(All Ar-C),70.3(PyCHPy),61.0(NCH),55.0(ArCH2),43.8(C(CH3)2Ph),42.5(C(CH3)2Ph),32.2(C(CH3)2Ph),31.8(C(CH3)2Ph),31.6(C(CH3)2Ph),31.0(CH2of cyclohexyl),29.3(C(CH3)2Ph),27.3(CH2of cyclohexyl),26.9(CH2of cyclohexyl),26.7(CH2ofcyclohexyl),26.3(CH2of cyclohexyl),21.1(toluene),7.0(N(Si(CH3)3)2).Anal.Calcd.forC48H64MgN4OSi2·0.5C7H8:C,73.67;H,8.16;N,6.67.Found:C,73.16;H,8.06;N,6.55%.
实施例19
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL甲苯。量取催化剂Mg1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[rac-LA]0=1:500。控制反应温度25℃,反应5分钟,加入含水石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。将所得聚合物在60℃真空干燥8h。转化率:92%,Mn=26.6×104g/mol,分子量分布PDI=1.48,等规度Pm=0.70。
实施例20
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的甲苯溶液。量取催化剂Mg1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:500。控制反应温度25℃,反应3分钟。其余操作同实施例19。转化率:91%,Mn=7.50×104g/mol,分子量分布PDI=1.66,等规度Pm=0.68。
实施例21
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL四氢呋喃。量取催化剂Mg1的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应2分钟。其余操作同实施例19。转化率:91%,Mn=5.15×104g/mol,分子量分布PDI=1.47,等规度Pm=0.61。
实施例22
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的四氢呋喃溶液。量取催化剂Mg1的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应1分钟。其余操作同实施例19。转化率:96%,Mn=2.91×104g/mol,分子量分布PDI=1.38,等规度Pm=0.61。
实施例23
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL甲苯。量取催化剂Mg2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[rac-LA]0=1:500。控制反应温度25℃,反应7分钟。其余操作同实施例19。转化率:91%,Mn=20.3×104g/mol,分子量分布PDI=1.60,等规度Pm=0.65。
实施例24
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的甲苯溶液溶解。量取催化剂Mg2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:500。控制反应温度25℃,反应4分钟。其余操作同实施例19。转化率:91%,Mn=7.27×104g/mol,分子量分布PDI=1.46,等规度Pm=0.65。
实施例25
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL四氢呋喃。量取催化剂Mg2的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应2分钟。其余操作同实施例19。转化率:96%,Mn=4.51×104g/mol,分子量分布PDI=1.69,等规度Pm=0.61。
实施例26
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的四氢呋喃溶液。量取催化剂Mg2的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应0.7分钟。其余操作同实施例19。转化率:97%,Mn=2.11×104g/mol,分子量分布PDI=1.35,等规度Pm=0.58。
实施例27
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL甲苯。量取催化剂Mg3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[rac-LA]0=1:500。控制反应温度25℃,反应5分钟。其余操作同实施例19。转化率:95%,Mn=21.5×104g/mol,分子量分布PDI=1.56,等规度Pm=0.73。
实施例28
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的甲苯溶液。量取催化剂Mg3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:500。控制反应温度25℃,反应2分钟。其余操作同实施例19。转化率:93%,Mn=8.38×104g/mol,分子量分布PDI=1.67,等规度Pm=0.71。
实施例29
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL甲苯。量取催化剂Mg3甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应2分钟。其余操作同实施例19。转化率:93%,Mn=3.74×104g/mol,分子量分布PDI=1.48,等规度Pm=0.75。
实施例30
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的甲苯溶液。量取催化剂Mg3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应1分钟。其余操作同实施例19。转化率:93%,Mn=3.72×104g/mol,分子量分布PDI=1.45,等规度Pm=0.70。
实施例31
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL四氢呋喃。量取催化剂Mg3的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应2分钟。其余操作同实施例19。转化率:90%,Mn=8.20×104g/mol,分子量分布PDI=1.57,等规度Pm=0.70。
实施例32
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的四氢呋喃溶液。量取催化剂Mg3的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应1分钟。其余操作同实施例19。转化率:95%,Mn=3.95×104g/mol,分子量分布PDI=1.48,等规度Pm=0.69。
实施例33
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL甲苯。量取催化剂Mg4的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[rac-LA]0=1:500。控制反应温度25℃,反应10分钟。其余操作同实施例19。转化率:97%,Mn=21.2×104g/mol,分子量分布PDI=1.44,等规度Pm=0.60。
实施例34
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的甲苯溶液。量取催化剂Mg4的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:500。控制反应温度25℃,反应4分钟。其余操作同实施例19。转化率:98%,Mn=6.00×104g/mol,分子量分布PDI=1.47,等规度Pm=0.60。
实施例35
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL四氢呋喃。量取催化剂Mg4的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应3分钟。其余操作同实施例19。转化率:92%,Mn=4.20×104g/mol,分子量分布PDI=1.56,等规度Pm=0.57。
实施例36
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的四氢呋喃溶液。量取催化剂Mg4的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应2分钟。其余操作同实施例19。转化率:96%,Mn=2.20×104g/mol,分子量分布PDI=1.37,等规度Pm=0.57。
实施例37
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL甲苯。量取催化剂Mg5的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[rac-LA]0=1:500。控制反应温度25℃,反应8分钟。其余操作同实施例19。转化率:96%,Mn=27.8×104g/mol,分子量分布PDI=1.43,等规度Pm=0.60。
实施例38
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的甲苯溶液。量取催化剂Mg5的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:500。控制反应温度25℃,反应4分钟。其余操作同实施例19。转化率:95%,Mn=6.02×104g/mol,分子量分布PDI=1.39,等规度Pm=0.62。
实施例39
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL四氢呋喃。量取催化剂Mg5的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应2分钟。其余操作同实施例19。转化率:91%,Mn=4.61×104g/mol,分子量分布PDI=1.52,等规度Pm=0.48。
实施例40
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的四氢呋喃溶液。量取催化剂Mg5的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应1分钟。其余操作同实施例19。转化率:92%,Mn=2.02×104g/mol,分子量分布PDI=1.20,等规度Pm=0.46。
实施例41
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL甲苯溶解。量取催化剂Mg6的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[rac-LA]0=1:500。控制反应温度25℃,反应8分钟。其余操作同实施例19。转化率:98%,Mn=23.8×104g/mol,分子量分布PDI=1.45,等规度Pm=0.68。
实施例42
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的甲苯溶液。量取催化剂Mg6的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.002M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:500。控制反应温度25℃,反应4分钟。其余操作同实施例19。转化率:88%,Mn=4.32×104g/mol,分子量分布PDI=1.40,等规度Pm=0.68。
实施例43
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL四氢呋喃。量取催化剂Mg6的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应5分钟。其余操作同实施例19。转化率:96%,Mn=3.80×104g/mol,分子量分布PDI=1.37,等规度Pm=0.68。
实施例44
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol)和0.5mL异丙醇的四氢呋喃溶液。量取催化剂Mg6的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应3分钟。其余操作同实施例19。转化率:95%,Mn=3.74×104g/mol,分子量分布PDI=1.23,等规度Pm=0.64。
实施例45
氩气保护下,在聚合瓶中加入L-丙交酯(0.144g,1.0mmol),用0.5mL异丙醇甲苯溶液溶解。量取催化剂Mg6的甲苯溶液0.5mL加入到聚合瓶中,使得[L-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[L-LA]0=1:1:200。控制反应温度25℃,反应3分钟。其余操作同实施例19。转化率:93%,Mn=2.96×104g/mol,分子量分布PDI=1.15。
实施例46
氩气保护下,在聚合瓶中加入D-丙交酯(0.144g,1.0mmol),用0.5mL异丙醇甲苯溶液溶解。量取催化剂Mg6的甲苯溶液0.5mL加入到聚合瓶中,使得[D-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[D-LA]0=1:1:200。控制反应温度25℃,反应3分钟。其余操作同实施例19。转化率:95%,Mn=3.17×104g/mol,分子量分布PDI=1.21。
实施例47
氩气保护下,在聚合瓶中加入ε-己内酯(0.144g,1.0mmol)和0.5mL异丙醇甲苯。量取催化剂Mg6的甲苯0.5mL加入到聚合瓶中。[ε-CL]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[ε-CL]0=1:1:200。控制反应温度25℃,反应2分钟。其余操作同实施例19。转化率:95%,Mn=1.98×104g/mol,分子量分布PDI=1.19。
Claims (10)
2.根据权利要求1所述的二(2-吡啶基)甲基取代氨基酚氧基镁络合物(I),其特征在于,
R1~R2为C1~C8直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基,C6~C12的芳基;
R3为C1~C8直链、支链或环状结构的烷基;
R4为二(三甲基硅)氨基,二(三乙基硅)氨基,二(二甲基氢硅)氨基。
3.根据权利要求1所述的二(2-吡啶基)甲基取代氨基酚氧基镁络合物(I),其特征在于,R1~R2为甲基、异丙基、叔丁基、枯基、三苯甲基、苯基;R3为甲基、乙基、异丙基、正丁基、叔丁基、金刚基、环戊基、环己基、正己基、正辛基;R4为二(三甲基硅)氨基。
4.权利要求1~3任一项所述的二(2-吡啶基)甲基取代氨基酚氧基镁络合物(I)的制备方法,包括如下步骤:
二(2-吡啶基)甲酮和伯胺R3NH2缩合生成相应亚胺(II),亚胺(II)经硼氢化钠还原生成仲胺(III);仲胺(III)和2-溴甲基取代酚(IV)发生反应,反应温度为25~150℃,反应时间为2~72小时,然后从反应产物中收集目标二(2-吡啶基)甲基取代氨基酚类配体(V);
任选的,将式(V)所示的二(2-吡啶基)甲基取代氨基酚类配体和镁金属原料化合物在有机介质中反应,反应温度为0~100℃,反应时间为2~96小时,然后从反应产物中收集目标二(2-吡啶基)甲基取代氨基酚氧基镁络合物(I);
反应式中取代基R1~R4与权利要求1~3任一项所述的二(2-吡啶基)甲基取代氨基酚氧基镁络合物(I)的各相应基团的要求一致。
5.根据权利要求4所述的方法,其特征在于,镁金属原料化合物为二{二(三甲基硅)氨基}镁;二(2-吡啶基)甲基取代氨基酚类配体(V)与镁金属原料化合物的摩尔比为1:0.5~1.5;所述的有机介质选自四氢呋喃、乙醚、甲苯、苯、石油醚和正己烷中的一种或两种。
6.权利要求1~3任一项所述的二(2-吡啶基)甲基取代氨基酚氧基镁络合物的应用,其特征在于,用于内酯的开环聚合。
7.根据权利要求6所述的应用,其特征在于,内酯选自L-丙交酯,D-丙交酯,rac-丙交酯,meso-丙交酯,ε-己内酯,β-丁内酯。
8.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的二(2-吡啶基)甲基取代氨基酚氧基镁络合物为催化剂,使丙交酯在-40~130℃下聚合,聚合时催化剂与单体的摩尔比为1:1~10000。
9.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的二(2-吡啶基)甲基取代氨基酚氧基镁络合物为催化剂,在醇存在的条件下,使丙交酯在-40~130℃下聚合,聚合时催化剂与醇以及单体摩尔比为1:1~50:1~10000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,苄醇。
10.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的二(2-吡啶基)甲基取代氨基酚氧基镁络合物为催化剂,在醇存在下或不加醇,使ε-己内酯或β-丁内酯在-40~50℃下聚合;所述的醇为C1~C10直链、支链或环状结构的烷基醇,苄醇。
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